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Portrait of Professor Michael Page Professor Michael Page

m.i.page@hud.ac.uk | 01484 472534



Biography

Mike Page studied Chemistry at the now University of Brighton in 1967 and completed his PhD at the universities of Leicester and Glasgow in 1970. He worked as a postdoctoral research fellow with Professor W P Jencks in the United States between 1970 and 1972 and then with Professor R P Bell in 1972-1973. He was then appointed Lecturer at the now University of Huddersfield where he has been Senior Lecturer, Principal Lecturer, Reader and then Professor in 1985. Mike was Head of the Department of Chemical and Biological Sciences from 1985 until 1997 and Dean of the School of Applied Sciences from 1989 to 2003. He also acted as Dean of Research from 1987-2003. He went on to become the University’s Deputy Vice-Chancellor with responsibility for planning, resources and research, from which he retired in 2009. He was awarded the honorary emeritus professorship by the University the following year and became the first recipient of a new award, Doctor of the University to add to his existing two DSc awards. Since then, Mike has remained an active researcher and is Director of the research unit IPOS. He was recently asked to take up the position of Acting Dean of the School of Applied Sciences as an interim appointment.

Mike Page has been a member of BBSRC and EPSRC committees, including BioMolecular Sciences, Molecular Recognition, chemistry and organic chemistry. He has represented the UK on international committees such as European Union committees and IUPAC. He was Chairman of the Committee of Heads of Polytechnic Chemistry Departments and a member of the CNAA Chemistry Board. He was Chairman of the Royal Society of Chemistry (RSC) Qualifications and Education Board and a member of the Council and a member of several other RSC committees. He is currently Chair of the RSC Disciplinary Committee and member of the Chemistry Biology Interface Division committee. He was a member of the HEFCE Research Assessment Exercise panel for Chemistry in 1992 and was a member of the HEFCE pilot teaching assessment of chemistry. He has been Chairman of the RSC Organic Reaction Mechanisms Group and a member of the Editorial Boards of Chemical Communications, JCS Perkin 2, Natural Products, Biochemical Journal and J. Phys. Org. Chem.

He was awarded the RSC Perkin Transactions 150th Anniversary Prize 1991; RSC Organic Reaction Mechanisms 2003 and SCI R&D for Society Award 2010. Mike Page has published over 200 research papers and supervised over 50 PhD students. He has edited books on The Chemistry of Enzyme Action (Elsevier 1984), Enzyme Mechanisms (Roy. Soc. Chem. 1987) and The Chemistry of β-Lactam Antibiotics (Blackie 1992). He recently co-authored, with Andrew Williams, a postgraduate book on Organic and BioOrganic Mechanisms (Longman 1997). Mike has given many international plenary lectures and contributed many papers at symposia world-wide.

Mike has worked closely with industry, particularly the pharmaceutical sector and has had colloborative research projects with AstraZeneca, GlaxoSmithKline, Avecia, Syngenta, James Robinson, British Biotech, ICI Pharm., Fisons, PanTherix, Proteus and NPilPharma.

Research & Scholarship

His main areas of research interest are:

  • The chemistry of β-lactam antibiotics and their derivatives
  • The mechanism of β-lactamase, proteases and enzyme catalysed reactions
  • Enzymes in synthesis - enantioselective biotransformations
  • Rationalisation of enzyme catalytic power and enzyme specificity
  • Drug design - enzyme inhibitors
  • Kinetics and mechanisms in organic and biochemistry
  • Intramolecular reactions
  • Proton transfer
  • Metal-ion and micelle catalysed reactions
  • Enantioselective synthesis

These areas of research are inter-related by the theme of the mechanisms of reactions.

Publications and Other Research Outputs

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These second-order rate constants are approximately 109 and 107, respectively, greater than those for a similar acyclic sulfonamide. The entropy of activation for the acid-catalysed hydrolysis of the -sultam is –80 J K–1 mol–1 which may be indicative of unimolecular ring opening, whereas that for the base-catalysed reaction, –184 J K–1 mol–1, is consistent with a bimolecular process.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '32', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29960002245', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1996', 'status_changed_hour' => '12', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6243' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6243', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Wood', 'eprintid' => '6243', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'J. 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The rate of inactivation is first order with respect to -sultam concentration and the second order rate constants show a similar dependence on pH to that for the hydrolysis of a peptide substrate. Inactivation is due to the formation of a stable l l enzyme inhibitor complex as a result of the active site serine being sulfonylated by the -sultam. Ring opening of the -sultam occurs by S–N fission in contrast to the C–N fission observed in the acylation of elastase by N-acylsulfonamides. Structure–activity effects are compared between sulfonylation of the enzyme and alkaline hydrolysis. Variation in 4-alkyl and N-substituted -sultams causes differences in the rates of inactivation by 4 orders of magnitude', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '6', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '14', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => '10.1039/b208079f', 'volume' => '1', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => '1 M. I. Page, Enzyme Inhibition in Comprehensive Medicinal Chemistry, ed. P. G. Sammes, Pergamon Oxford, 1990, Vol. 2, pp. 61–87. 2 (a) C. W. Wharton, The Serine Proteinases in Comprehensive Biological Catalysis, ed. M. Sinnott, Academic Press, London, 1997, Vol. 1, Ch. 11, pp. 345–379; (b) D. J. Underwood, B. G. Green, R. Chabin, S. Mills, J. B. Doherty, P. E. Finke, M. MacCoss, S. K. Shah, C. S. Burgey, T. A. Dickinson, P. R. Griffin, T. E. Lee, K. M. Swiderek, T. Covey, W. 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There is no evidence of neighbouring group participation in the hydrolysis of either N-?-carboxybenzylethane-1,2-sultam or N-(hydroxyaminocarbonylmethyl)-2-benzylethane-1,2-sultam. Oxyanions, but not amines or thiols, react with N-benzoylethane-1,2-sultam in water by a nucleophilic ring opening reaction confirmed by product analysis and kinetic solvent isotope effects. A Brønsted plot for this reaction has two distinct correlations with ?nuc = 0.52 and 0.65 for weak and strong bases, respectively, although a statistically corrected plot may indicate a single correlation.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '12', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => undef, 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => '10.1039/b200184e', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => '1 M. Beardsell, P. S. 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The ‘binge drinking’ ethanol rats administered 1 g/kg ethanol showed increased latencies to those of the control rats in their acquisition of spacial navigation in the Morris Water Maze, which was normalised to that of the controls values after ethane-?-sultam administration. 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Pseudo-first-order rate constants were determined in a variety of buffer solutions, and the overall pH?rate profile was obtained by extrapolation to zero buffer concentration. The hydrolysis of 6-epi-ampicillin is subject to acid and hydroxide-ion catalysis and, for a penicillin, an unusual pH-independent reaction. Intramolecular general base-catalyzed hydrolysis by the side chain amido group is proposed to explain the enhanced rate of neutral hydrolysis of 6-epi-ampicillin and cephalosporins. The ?-lactam of 6-epi-ampicillin also undergoes intramolecular aminolysis by nucleophilic attack of the 6-? side chain amino group to give a stable piperazine-2,5-dione derivative. The low effective molarity for intramolecular aminolysis of only 40 M is partly attributed to the unfavorable trans to cis isomerization about the 6-amide side chain required for ring closure. Theoretical calculations show that the intramolecular aminolysis of 6-epi-ampicillin nucleophilic attack occurs from the ?-face of the ?-lactam ring with an activation energy of 14.4 kcal/mol. 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'creators_name_given' => 'Simon J.F.', 'creators_id' => undef }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Sykes', 'eprintid' => '522', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Nicholas O.', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '522', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '2', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2008', 'fileinfo' => '', 'status_changed_second' => '24', 'exhibitors_name_honourific' => 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'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '10', 'event_dates' => undef, 'fulltimestamp' => '20020000', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '9', 'number' => '13', 'rev_number' => '16', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '1', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'QD', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '1', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '11', 'datestamp_day' => '11', 'abstract' => 'A series of bicyclic trans-fused -lactones and -lactams have been previously described for the inhibition of human neutrophil elastase and as possible development candidates. During the discovery program, it had been assumed that their acylating power was due in part to the inherent strain energy in the bicyclic structure that was released upon ring opening. This is now shown not to be the case, and in fact, these compounds are no more reactive than simple but analogous -lactams and -lactones. The strain energy is not released in the transition state for alkaline hydrolysis or alcoholysis because the reaction proceeds with rate-limiting formation of the tetrahedral intermediate. A reactivity index of kOH is proposed as a simple guide to determine the usefulness of a potential inhibitor as an enzyme acylating agent', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '6', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '1', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => '10.1021/jm0111245', 'volume' => '45', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => '(1) Page, M. I. Enzyme Inhibition. In Comprehensive Medicinal Chemistry; Sammes, P. G., Ed.; Pergamon Oxford, 1990; Vol. 2, pp 61-87. (2) (a) Wharton, C. W. The Serine Proteinases. In Comprehensive Biological Catalysis; Sinnott, M., Ed; Academic Press: London, 1997; Vol. 1, Chapter 11, pp 345-379. (b) Underwood, D. J.; Green, B. G.; Chabin, R.; Mills, S.; Doherty, J. B.; Finke, P. E.; MacCoss, M.; Shah, S. K.; Burgey, C. S.; Dickinson, T. A.; Griffin, P. R.; Lee, T. E.; Swiderek, K. M.; Covey, T.; Westler, W. M.; Knight, W. B. Mechanism of inhibition of human leukocyte elastase by beta lactams. 2. Stability, reactivation kinetics, and products of â lactam derived E-I complexes. Biochemistry 1995, 34, 14344-14355. (c) Katzenellenbogen, J. A.; Rai, R.; Dai, W. Enol-lactone derivatives as inhibitors of human neutrophil elastase and trypsin like proteases. Bioorg. Med. Chem. Lett. 2, 1992, 11, 1399-1404. (d) Knight, W. B.; Maycock, A. L.; Green, B. G.; Ashe, B. M.; Gale, P.; Weston, H.; Finke, P. E.; Hagmann, W. K.; Shah, S. K.; Doherty, J. B. Mechanism of inhibition of human leukocyte elastase by two cephalosporin derivatives. Biochemistry 1992, 31, 4980-4986. (e) Kam, C.-M.; Fujikawa, K.; Powers, J. C. Mechanism-based isocoumarin inhibitors for trypsin and blood coagulation serine proteases: new anticoagulants. Biochemistry 1988, 27, 2547-2557. (f) Navia, M. A.; Springer, J. P.; Lin, T. Y.; Williams, H. R.; Firestone, R. A.; Pisano, J. M.; Doherty, J. B.; Finke, P. E.; Hoogsteen, K. Crystallographic study of a beta-lactam inhibitor complex with elastase at 1.84 Å resolution. Nature 1982, 327, 79-82. (g) Copp, L. J.; Krantz, A.; Spencer, R. W. Kinetics and mechanism of human leukocyte elastase inactivation by ynenol lactones. Biochemistry 1987, 26, 169-178. (h) Gelb, M. H.; Abeles, R. H. Substituted isatoic anhydrides: selective inactivators of trypsin like serine proteases. J. Med. Chem. 1986, 29, 585-589. (i) Gelb, M. H.; Abeles, R. H. Mechanism of inactivation of chymotrypsin by 3-benzyl-6-chloro-2-pyrone. Biochemistry 1984, 23, 6569- 6604. (3) Slater, M. J.; Laws, A. P.; Page, M. I. The relative catalytic efficiency of beta lactamase catalysed acyl and phosphyl transfer. Bioorg. Chem. 2001, 29, 77-95. (4) Beardsell, M.; Hinchliffe, P. S.; Wood, J. M.; Wilmouth, R. C.; Schofield, C. J.; Page, M. I. Beta-sultamssa novel class of serine protease inhibitors. Chem. Commun. 2001, 497-498. (5) Page, M. I. Enzyme Catalysis. In Comprehensive Medicinal Chemistry; Sammes, P.,G., Ed.; Pergamon: Oxford, 1990; Vol. 2, pp 45-60. (6) (a) Laws, A. P.; Page, M. I. The effect of the carboxyl group on the chemical and beta-lactamase reactivity of beta-lactam antibiotics. J. Chem. Soc., Perkin Trans. 2 1989, 1577-1581. (b) Laws, A. P.; Layland, N. J.; Proctor, D. G.; Page, M. I. The roles of the carboxy group in beta-lactam antibiotics and lysine- 234 in beta-lactamase I. J. Chem. Soc., Perkin Trans 2 1993, 17-21. (7) Metz, W. A.; Peet, N. P. Elastase inhibitors. Prog. Inflammation Res. 1999, 9, 853-868. (8) (a) Bode, W.; Wei, A. Z.; Huber, R.; Meyer, E.; Travis, J.; Neuman, S. X-Ray crystal structure of the complex of human leukocyte elastase (PMN elastase) and the third domain of the turkey ovomucoid inhibitor. EMBO J. 1986, 5, 2453-2458. (b) Navia, M. A.; McKeever, B. M.; Springer, J. P.; Lin, T. Y.; Williams, H. R.; Fluder, E. M.; Dorn, C. P.; Hoogsteen, K. Structure of human neutrophil elastase in complex with a peptide chloromethyl ketone inhibitor at 1.84 Å resolution. Proc. Natl. Acad. Sci. U.S.A. 1989, 86, 7-11. (9) Bode, W.; Meyer, E., Jr.; Powers, J. C. Human and porcine pancreatic elastase. X-ray crystal structures, mechanism, substrate specificity, and mechanism-based inhibitors. Biochemistry 1989, 28, 1951-1962. (10) (a) Takahashi, L. H.; Radhakrishan, R.; Rosenfeld, R. E., Jr.; Meyer, E. F., Jr.; Trainer, D. A. Crystal structure of the covalent complex formed by a peptidyl R, R-difluoro-â-keto amide with porcine pancreatic elastase at 1.78 Å resolution. J. Am. Chem. Soc. 1989, 111, 3368-3374. (b) Renaud, A.; Lestienne, P.; Hughes, D. L.; Bieth, J. G.; Dimicoli, J.-L. Mapping the S¢ Subsites of porcine pancreatic and human leukocyte elastases. J. Biol. Chem. 1983, 258, 8312-8316. (11) (a) Edwards, P. D.; Meyer, E. F., Jr.; Vijayalakshmi, J.; Tuthill, P. A.; Andisk, D. A.; Gomes, B.; Strimpler, A. Design, synthesis and kinetic evaluation of a unique class of elastase inhibitors. The peptidyl alpha ketobenzoxazoles and the X-ray crystal structure of the covalent complex between porcine pancreatic elastase and Ac-Ala-Pro-Val-2-benzoxazole. J. Am. Chem. Soc. 1992, 114, 1854-1863. (b) Costanzo, M. J.; Maryanoff, B. E.; Hecker, L. R.; Schott, M. R.; Yabut, S. C.; Zhang, H.-C.; Andrade- Gordon, P.; Kauffman, J. A.; Lewis, J. M.; Krishnan, R.; Tulinsky, A. Potent thrombin inhibitors that probe the S1¢ subsite: tripeptide transition state analogues based on a heterocycle activated carbonyl group. J. Med. Chem. 1996, 39, 3039-3043. (c) Bernstein, P. R.; Gomes, B. C.; Kosmider, B. J.; Vacek, E. P.; Williams, J. C. Nonpeptidic inhibitors of human leukocyte elastase. 6. Design of a potent intratracheally active, pyridone based trifluoromethyl ketone. J. Med. Chem. 1995, 38, 212-215. (d) Edwards, P. D.; Andisik, D. W.; Strimpler, A. M.;Gomes, B.; Tuthill, P. A. 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', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '6', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '19', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => '10.1039/b111340m', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => '1 M. I. Page and A. Williams, Organic and Bioorganic Mechanisms, Longman, Harlow, UK, 1997, ch. 7A. Williams, N. Bourne, K. T. Douglas and T. R. Penkava, J. Chem. Soc. Perkin Trans. 2, 1984, 1827; A. Williams, S. Thea, G. Cevasco, G. Guanti, A. Hopkins and N. Kashefi- Naini, J. Org. Chem., 1985, 50, 2158; G. Cevacso and S Thea, J. Chem. Soc., Perkin Trans. 2, 1997, 2215. 2 N. J. Baxter, A. P. Laws, L. J. M. Rigoreau and M. I. Page, J. Am. Chem. Soc., 2000, 122, 3375. 3 P. Proctor, N. P. Gensmantel and M. I. Page, J. Chem. Soc., Perkin 2, 1982, 1135. 4 J. L. Kice and J. D. Campbell, J. Org. 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COMMUN., 2002, 772–773 773', 'date_year' => '2002', 'status_changed_hour' => '12', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '512' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => '1282654489', 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Ahmed', 'eprintid' => '512', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Naveed', 'creators_id' => undef }, '3' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '512', 'creators_name_honourific' => '', 'pos' => '3', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Tsang', 'eprintid' => '512', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Wing Y.', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Hemming', 'eprintid' => '512', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Karl', 'creators_id' => 'k.hemming@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '2', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2008', 'fileinfo' => '', 'status_changed_second' => '44', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Competitive endo- and exo-cyclic C-N fission in the hydrolysis of N-aroyl ?-lactams ', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/05/12', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '57', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1139/v05-153', 'succeeds' => undef, 'datestamp_month' => '2', 'commentary' => undef, 'lastmod_day' => '24', 'publisher' => 'National Research Council Canada', 'pagerange' => '1432-1439', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2008', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Canadian Journal of Chemistry', 'lastmod_second' => '44', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1480-3291', 'datestamp_hour' => '10', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '44', 'note' => undef, 'edit_lock_until' => '0', 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 9, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '512', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2010', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '8', 'event_dates' => undef, 'fulltimestamp' => '20050900', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '12', 'number' => '9', 'rev_number' => '17', 'edit_lock_user' => '6', 'series' => undef, 'creators_name_lineage' => '', 'pos' => '1', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'QD', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '26', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '8', 'datestamp_day' => '8', 'abstract' => 'Abstract: The balance between endo- and exo-cyclic C–N fission in the hydrolysis of N-aroyl ?-lactams shows that the difference in reactivity between strained ?-lactams and their acyclic analogues is minimal. Attack of hydroxide ion occurs preferentially at the exocyclic acyl centre rather than that of the ?-lactam during the hydrolysis of N-p-nitrobenzoyl ?-lactam. In general, both endo- and exo-cyclic C–N bond fission occurs in the alkaline hydrolysis of N-aroyl ?-lactams, the ratio of which varies with the aryl substituent. Hence, the Brønsted ?-values differ for the two processes: –0.55 for the ring-opening reaction and –1.54 for the exocyclic C–N bond fission reaction. For the pH-independent and acid-catalysed hydrolysis of N-benzoyl ?-lactam, less than 3% of products are derived from exocyclic C–N bond fission. 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'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Capon', 'eprintid' => '6196', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Brian', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Sankey', 'eprintid' => '6196', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'G.H.', 'creators_id' => undef } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '2', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 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OO-benzylidene-2,3-dihydroxybenzoic acid is considerably faster than that of OO-benzylidene-3,4-dihydroxybenzoic acid and OO-benzylidenecatechol. The pH-rate profile is of the form: kobs=k1/(1 +Ka/10–pH). The high rate is associated with the k1-term which probably arises from intramolecular general-acid catalysis. This kinetic parameters of this reaction are compared with those for the formally analogous inter-molecularly general-acid catalysed hydrolysis of benzylidenecatechol. OO-Benzylidene-2,3-dihydroxybenzoic acid is not intramolecularly hydrogen bonded in dilute solutions in carbon tetrachloride', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '51', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29720000529', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1972', 'status_changed_hour' => '8', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6126' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '0' => { 'creators_name_lineage' => 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=> undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '37', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '8', 'datestamp_day' => '8', 'abstract' => 'The rate of aminolysis of benzylpenicillin and cephaloridine by hydroxylamine, unlike other amines, shows only a first order dependence on amine concentration. The rate enhancement compared with that predicted from a Bronsted plot for other primary amines with benzylpenicillin is greater than 106. This is much more than an -effect and is compatible with rate-limiting formation of the tetrahedral intermediate due to a rapid intramolecular general acid catalysed breakdown of the intermediate. For cephaloridine, the rate enhancement is greater than 104 which demonstrates that -lactam C–N bond fission and expulsion of the leaving group at C3 are not concerted. ', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '6', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '37', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => '10.1039/b313900j', 'volume' => '2', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => '1 M. I. Page, Adv. Phys. Org. Chem., 1987, 23, 165; M. I. Page, in The Chemistry of ?-Lactams, ed. M. I. Page, Blackie, Glasgow, 1992, pp. 129–147; M. I. Page, Acc. Chem. Res., 1984, 17, 144. 2 N. P. Gensmantel and M. I. Page, Chem. Commun., 1978, 374; A. F. Martin, J. J. Morris and M. I. Page, Chem. Commun., 1979, 298; J. J. Morris and M. I. Page, J. Chem. Soc., Perkin Trans. 2, 1980, 212. 3 J. J. Morris and M. I. Page, J. Chem. Soc., Perkin Trans. 2, 1980, 220. 4 N. P. Gensmantel and M. I. Page, J. Chem. Soc., Perkin Trans. 2, 1982, 137. 5 A. M. Davis, P. Proctor and M. I. Page, J. Chem. Soc., Perkin Trans. 2, 1991, 1213. 6 A. Llinas, J. Donoso, B. Vilanova, J. Frau, F. Munoz and M. I. Page, J. Chem. Soc., Perkin Trans. 2, 2000, 1521. 7 A. Llinas and M. I. Page, J. Phys. Org. Chem., in press. 8 A. P. Laws and M. I. Page, Chem. Commun, 1998, 1609; S. Bounaga, M. Galleni, A. P. Laws and M. I. Page, Bioorg. Med. Chem., 2001, 9, 503. 9 A. Llinas and M. I. Page, Submitted to Bioorg. Med. Chem. Letts. 10 M. Birus, S. Inic, N. Kujundzic and B. Nigovic, Croat. Chim. Acta, 1998, 71, 807. 11 J. O. Edwards and R. G. Pearson, J. Am. Chem. Soc., 1962, 84, 16. 12 A. Llinas, B. Vilanova, F. Munoz and J. Donoso, J. Mol. Catal. A, 2001, 175, 3. 13 W. S. Faraci and R. F. Pratt, J. Am. Chem. Soc., 1986, 108, 5328; W. S. Faraci and R. F. Pratt, Biochemistry, 1985, 24, 903; S. C. Buckwell, M. I. Page, J. L. Longridge and S. G. Waley, J. Chem. Soc., Perkin Trans. 2, 1988, 1823; E. J. J. Grabowski, A. W. Douglas and G. B. Smith, J. Am. Chem. Soc., 1985, 107, 265.', 'date_year' => '2004', 'status_changed_hour' => '14', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '220' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'O'Gorman', 'eprintid' => '220', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'P.A.', 'creators_id' => 'p.o'gorman@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Hemming', 'eprintid' => '220', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Karl', 'creators_id' => 'k.hemming@hud.ac.uk' }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '220', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '1', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2007', 'fileinfo' => '', 'status_changed_second' => '26', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'The synthesis of azabicyclo[4.2.1]nonenes by the addition of a cyclopropenone to 4-vinyl substituted 1-azetines-isomers of the homotropane nucleus', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/02/20', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '45', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1016/j.tetlet.2005.11.081', 'succeeds' => undef, 'datestamp_month' => '7', 'commentary' => undef, 'lastmod_day' => '17', 'publisher' => 'Elsevier', 'pagerange' => '425-428', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2008', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Tetrahedron Letters', 'lastmod_second' => '3', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '0040-4039', 'datestamp_hour' => undef, 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => undef, 'note' => 'Copyright © 2007 Elsevier B.V. All rights reserved. ScienceDirect® is a registered trademark of Elsevier B.V. ', 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => undef, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '220', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2008', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '10', 'event_dates' => undef, 'fulltimestamp' => '20060000', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '15', 'number' => undef, 'rev_number' => '15', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'QD', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '30', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '22', 'datestamp_day' => '13', 'abstract' => 'The conversion of 4-vinyl substituted ?-lactams into 4-vinyl substituted 1-azetines and their subsequent reaction with diphenylcyclopropenone (DPP) results in the formation of a highly functionalised 7-azabicyclo[4.2.1]nonene. This heterocyclic system is an isomer of the homotropane (9-azabicyclo[4.2.1]nonene) nucleus, which is the core structure of a class of alkaloid natural products that includes anatoxin-a. The key processes involved are two ring expansions, one of which constitutes a formal [3+2] cycloaddition and the other of which is an unusual aza-Cope (amino-Claisen) [3,3]-sigmatropic rearrangement. ', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '12', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => undef, 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => '10.1016/j.tetlet.2005.11.081', 'volume' => '47', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => '1 (a) For relevant reviews, see:J.W. Daly, Cell. Mol. Neurobiol. 25 (2005), pp. 513–552. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (b) H.L. Mansell, Tetrahedron 52 (1996), pp. 6025–6061. Abstract | Abstract + References | PDF (1288 K) | View Record in Scopus | Cited By in Scopus 2 (a) J.P. Devlin, O.E. Edwards, P.R. Gorham, N.R. Hunter, R.K. Pike and B. Stavric, Can. J. Chem. 55 (1977), pp. 1367–1371. (b) P.J. Parsons, N.P. Camp, N. Edwards and L.R. Sumoreeah, Tetrahedron 56 (2000), pp. 309–315. SummaryPlus | Full Text + Links | PDF (160 K) | View Record in Scopus | Cited By in Scopus (c) J.B. Brenneman and S.F. Martin, Org. Lett. 6 (2004), pp. 1329–1331. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (d) T. Hjelmgaard, I. Søtofte and D. Tanner, J. Org. Chem. 70 (2005), pp. 5688–5697. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus 3 (a) D.B. Kanne, D.J. Ashworth, M.T. Cheng, L.C. Mutter and L.G. Abood, J. Am. Chem. Soc. 108 (1986), pp. 7864–7865. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (b) E. Wright, T. Gallagher, C.G.V. Sharples and S. 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Murthy, Synthesis (1986), pp. 437–449. Full Text via CrossRef (d) G.S. Singh, Tetrahedron 59 (2003), pp. 7631–7649. SummaryPlus | Full Text + Links | PDF (973 K) | View Record in Scopus | Cited By in Scopus 11 (a) S. Scheibye, B.S. Pedersen and S.O. Lawesson, Bull. Soc. Chim. Belg. 87 (1978), pp. 229–238. View Record in Scopus | Cited By in Scopus (b) For a review, see:M. Jesberger, T.P. Davis and L. Barner, Synthesis (2003), pp. 1929–1958. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus 12 Fresh Meerwein’s reagent gave yields of 2-ethylthio-1-azetines 8 at the higher end of the range. The conversion of the 4-vinyl ?-lactams 6 into the corresponding 2-ethoxy-1-azetines was unsuccessful. 13 G. Pifferi, P. Consonni, G. Pelizza and E. Testa, J. Heterocycl. Chem. 4 (1967), pp. 619–624. 14 H. Heimgartner, F. Stierli, R. Prewo and J.H. Bieri, Helv. Chim. Acta 66 (1983), pp. 1366–1375. 15 (a) T. Eicher and R. Rohde, Synthesis (1985), pp. 619–625. Full Text via CrossRef (b) T. Eicher, F. Abdesaken, G. Franke and J.L. Weber, Tetrahedron Lett. 16 (1975), pp. 3915–3918. Abstract | Abstract + References | PDF (181 K) (c) T. Eicher, J.L. Weber and G. Chatila, Liebigs Ann. Chem. (1978), pp. 1203–1221. 16 (a) M.A.M. Gomaa, J. Chem. Soc., Perkin Trans. 1 (2002), pp. 341–344. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (b) N. Abe, T. Murafuji, Y. Sugihara and A. Kakehi, Heterocycles 41 (1995), pp. 2289–2298. 17 All new compounds gave satisfactory 1H/13C NMR spectra, mass spectra and HRMS/microanalysis. 18 Typical experimental and spectroscopic details for compounds 12: To a stirred solution of 2-ethylthio-4-vinyl-1-azetine 8 (0.1–0.5 g) in anhydrous acetonitrile (10–20 mL) was added, with stirring and under an atmosphere of dry nitrogen, a solution of diphenylcyclopropenone (1.0 M equiv) in acetonitrile (5–20 mL). The mixture was stirred at room temperature until the reaction was complete (one week) and the solvent was removed by rotary evaporation. The crude product was purified by flash silica column chromatography (petroleum ether–ethyl acetate/2:1). As an example, 6-ethylthio-3,4-dimethyl-1,8-diphenyl-7-azabicyclo[4.2.1]nona-3,7-dien-9-one 12c was obtained as a dark orange solid (0.271 g, 62% yield), mp 177–181 °C, from 1-azetine 8c (0.195 g, 1.16 mmol) and DPP (0.240 g, 1.16 mmol). ?H (400 MHz, CDCl3): 1.28 (3H, t, J = 7.4, CH3CH2), 1.695 (3H, s, Me), 1.700 (3H, s, Me), 2.55 (1H, dq, J = 11.3, 7.4, CH2CH3), 2.66 (1H, dq, J = 11.5, 7.5, CH2CH3), 2.76 (1H, d, J = 16.8, CH2CMe), 2.85 (1H, d, J = 16.8, CH2CMe), 2.97 (1H, d, J = 16.3, CH2CMe), 3.22 (1H, d, J = 16.2, CH2CMe), 7.14 (2H, dd, J = 6.5, 1.6, 2 × ArH), 7.23–7.30 (3H, m, 3 × ArH), 7.32–7.39 (3H, m, 3 × ArH), 7.66 (2H, dd, J = 7.5, 1.0, 2 × ArH). ?C (100 MHz, CDCl3): 14.3 (Me), 23.3 (Me), 23.6 (Me), 23.8 (CH2), 42.5 (CH2), 46.0 (CH2), 63.5 (q), 83.0 (q), 124.0 (q), 125.2 (q), 127.1 (CH), 127.9 (CH), 128.2 (CH), 128.3 (CH), 129.0 (CH), 130.8 (CH), 132.2 (q), 136.7 (q), 173.7 (q), 215.1 (q). ?max (thin film, cm?1): 3057 (m), 2986 (m), 2930 (m), 1737 (s), 1566 (m), 1446 (s), 1374 (m), 1266 (s), 1245 (s), 1046 (m), 739 (s), 700 (s). EI+ mass spectrum (m/z, %): 376 ([M++1], 5%), 375 ([M]+, 10%), 347 (28%), 318 (45%), 293 (50%), 264 (100%), 178 (74%), 105 (25%), 91 (40%), 77 (48%), 41 (38%). HRMS [CI+(NH3)]: Found [M+H+] 376.1730, C24H26NOS requires 376.1732. 19 (a) L. Viallon, O. Reinaud, P. Capdevielle and M. Maumy, Tetrahedron Lett. 36 (1995), pp. 4787–4790. SummaryPlus | Full Text + Links | PDF (193 K) | View Record in Scopus | Cited By in Scopus (b) L. Viallon, O. Reinaud, P. Capdevielle and M. Maumy, Tetrahedron 52 (1996), pp. 13605–13614. Abstract | Abstract + References | PDF (515 K) | View Record in Scopus | Cited By in Scopus ', 'date_year' => '2006', 'status_changed_hour' => '18', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6194' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Gowling', 'eprintid' => '6194', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Eric W.', 'creators_id' => undef }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Gensmantel', 'eprintid' => '6194', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Nigel P.', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6194', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '58', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Metal ion catalysis in the aminolysis of penicillin', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/61/94', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '41', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/P29780000335', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '12', 'publisher' => 'Royal Society of Chemistry', 'pagerange' => '335-342', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Journal of the Chemical Society, Perkin Transactions 2', 'lastmod_second' => '58', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1472-779X', 'datestamp_hour' => '8', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '58', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 4, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6194', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19780400', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '8', 'number' => '4', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '41', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '12', 'datestamp_day' => '12', 'abstract' => 'The copper(II) ion catalysed hydrolysis and aminolysis of benzylpenicillin in water at 30° shows saturation kinetics. A 1 : 1 complex is formed between the metal ion and benzylpenicillin which is attacked by hydroxide ion and amine ca. 107-fold faster than unco-ordinated benzylpenicilin. The Brønsted value for nucleophilic attack by amines is 0.87. The copper(II)ion catalysed reactions of the methyl ester of benzylpenicillin show much smaller rate enhancements indicating that the site of co-ordination for the antibiotic involves the ionised carboxy-group. The mechanism of the catalysed reactions does not involve the intermediate formation of benzylpenicillenic acid or a keten. The reactions are inhibited by buffers which co-ordinate to copper(II)ions. 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This reaction has an unusually small entropy change because of the development in the product of rotational entropy which is absent in the monoatomic reactants. In general, the formation of a transition state or monomolecular product from two molecules of reactant, in the gas phase, results in the loss of about 15 Kcal.mole?1 of translational and rotational entropy. Effective molarities of up to 108 M can be rationalised in terms of entropy changes without the introduction of new chemical concepts or terms. 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'status_changed_day' => '6', 'datestamp_day' => '6', 'abstract' => 'The hydrolysis of benzylpenicillin is catalysed by alkoxide ions and other oxygen bases. Catalysis occurs by a nucleophilic pathway and the intermediate ester can be detected in some cases. The Brønsted nuc for alkoxide ions is 0.97, and is compatible with rate-limiting ring opening of the -lactam. A solvent isotope effect of 3.2 for the trifluoroethanol-catalysed reaction suggests protonation by water occurs to the departing -lactam nitrogen. Penicillin is not a particularly effective acylating agent of alcohols', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '51', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29910001213', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1991', 'status_changed_hour' => '9', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6222' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6222', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '54', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Transition states, standard states and enzymic catalysis', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/62/22', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '14', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1016/0020-711X(80)90301-8', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '12', 'publisher' => 'Pergamon', 'pagerange' => '331-335', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'International Journal of Biochemistry', 'lastmod_second' => '54', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1357-2725', 'datestamp_hour' => '12', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '54', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 8, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6222', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19800800', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '12', 'number' => '5', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '14', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '12', 'datestamp_day' => '12', 'abstract' => '1. 1. Thermodynamic aspects of transition state theory are reviewed with particular reference to enzyme-catalysed reactions. 2. 2. Standard states must be specified when free energy changes of enzyme catalysed reactions are expressed graphically, otherwise false conclusions may be drawn. 3. 3. Enzymes cannot increase the rate of unimolecular reactions if either the transition state and ground state bind equally well to the enzyme or if the enzyme binds the ground state more tightly than the transition state. This is true even if the enzyme changes conformation during the reaction and even if the transition state is different in the presence and absence of enzyme. ', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '14', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1016/0020-711X(80)90301-8', 'volume' => '11', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1980', 'status_changed_hour' => '12', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6123' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6123', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Buckwell', 'eprintid' => '6123', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Stephen C.', 'creators_id' => undef }, '3' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Waley', 'eprintid' => '6123', 'creators_name_honourific' => '', 'pos' => '3', 'creators_name_given' => 'Stephen G.', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Longridge', 'eprintid' => '6123', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Jethro L.', 'creators_id' => undef } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '32', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Hydrolysis of 3-substituted cephalosporins catalysed by ?-lactamases I and II from Bacillus cereus and by hydroxide ion', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/61/23', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '1', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '42', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/P29880001823', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '6', 'publisher' => 'Royal Society of Chemistry', 'pagerange' => '1823-1827', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Journal of the Chemical Society, Perkin Transactions 2', 'lastmod_second' => '32', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1472-779X', 'datestamp_hour' => '10', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '32', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 10, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6123', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19881000', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '10', 'number' => '10', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '42', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '6', 'datestamp_day' => '6', 'abstract' => 'Second-order rate constants for the alkaline hydrolysis of 3-thiol substituted cephalosporins are independent of the pKa of the thiol over a pKa range of 9. If there is a leaving group at C-3 it is expelled after the -lactam ring is opened and the expulsion of the leaving group does not enhance the rate of -lactam C–N bond fission. The zinc enzyme -lactamase II is about a 100-fold better catalyst than the serine enzyme -lactamase I for the hydrolysis of the same cephalosporin. The second-order rate constant kcat/Km for both -lactamase enzymes shows no dependence on the nature of the substituent at C-3 which is not explicable by the different chemical reactivity of the cephalosporins. There is no evidence for a significant recognition site in either enzyme for the C-3 substituent. The kinetic parameters kcat and Km for the -lactamase I-catalysed hydrolysis may be complicated by the formation of intermediates.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '42', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29880001823', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1988', 'status_changed_hour' => '10', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6172' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6172', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Davis', 'eprintid' => '6172', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Andrew M.', 'creators_id' => undef } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '44', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Opening of the thiazolidine ring of penicillin derivatives', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/61/72', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '30', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/C39850001702', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '11', 'publisher' => 'Royal Society of Chemistry', 'pagerange' => '1702-1704', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Chemical Communications', 'lastmod_second' => '44', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1359-7345', 'datestamp_hour' => '12', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '44', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 12, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6172', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19851200', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '12', 'number' => '23', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '30', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '11', 'datestamp_day' => '11', 'abstract' => 'Penicilloic acid derivatives undergo two types of reversible thiazolidine ring opening reactions; in aqueous alkaline solution methyl benzylpenicilloate ring opens to give an enamine intermediate by a base-catalysed elimination process involving C-6-H whereas benzylpenicilloic acid epimerises at C-5 by unimolecular ring opening to form an intermediate iminium ion', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '30', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/C39850001702', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1985', 'status_changed_hour' => '12', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6230' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Jencks', 'eprintid' => '6230', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'William P.', 'creators_id' => undef }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6230', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '48', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Entropic Contributions to Rate Accelerations in Enzymic and Intramolecular Reactions and the Chelate Effect', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/62/30', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '4', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://www.pnas.org/content/68/8/1678.abstract?sid=4932c4c3-274c-4490-b4c3-14d299f92e20', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '12', 'publisher' => 'National Academy of Sciences', 'pagerange' => '1678-1683', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'National Academy of Sciences. Proceedings', 'lastmod_second' => '48', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '0027-8424', 'datestamp_hour' => '13', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '48', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 8, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6230', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19710800', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '13', 'number' => '8', 'rev_number' => '8', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '4', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '12', 'datestamp_day' => '12', 'abstract' => 'It is pointed out that translational and (overall) rotational motions provide the important entropic driving force for enzymic and intramolecular rate accelerations and the chelate effect; internal rotations and unusually severe orientational requirements are generally of secondary importance. The loss of translational and (overall) rotational entropy for 2 ? 1 reactions in solution is ordinarily on the order of 45 entropy units (e.u.) (standard state 1 M, 25°C); the translational entropy is much larger than 8 e.u. (corresponding to 55 M). Low-frequency motions in products and transition states, about 17 e.u. for cyclopentadiene dimerization, partially compensate for this loss, but “effective concentrations” on the order of 108 M may be accounted for without the introduction of new chemical concepts or terms. 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undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19740100', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '8', 'number' => '1', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '34', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '12', 'datestamp_day' => '12', 'abstract' => 'The kinetics of the -chymotrypsin catalysed hydrolysis of p-nitrophenyl acetate and N-acetyl-L-tryptophan methyl ester have been investigated at pH 7·85 and ionic strength 0·2M in solutions containing from 1 to 20% v/v dioxan or propan-2-ol. The solubilities of the two esters in these media were also measured. The ratio of the activity coefficients of the two transition states shows a much smaller variation with the organic solvent content of the medium than does the ratio of the activity coefficients of the substrates in their ground states, from which it is concluded that the substrate undergoes significant desolvation in the activation process. After allowing for the increased stability of the ester brought about by the addition of organic solvent, the inhibitory effect of dioxan can be represented by the simple formation of an inactive 1 : 1 complex of dioxan with the enzyme', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '34', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29740000066', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1974', 'status_changed_hour' => '8', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6163' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => 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'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '43', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '6', 'datestamp_day' => '5', 'abstract' => 'The kinetics of the reversible ionisation of 3-phenylcoumaran-2-one (pKa = 8.9), to form a carbanion, are reported in 50% (v/v) water–dioxane mixtures at 25 °C. Proton abstraction is catalysed by hydroxide ion, water and general bases which generate a Brønsted B of 0.52 indicative of a fairly symmetrical transition state. Rate limiting proton abstraction by hydroxide ion is confirmed by a primary kinetic isotope effect, kH/kD, of 3.81. Protonation of the enolate carbanion occurs by the hydronium ion and general acids but not by water. In acidic solution, below pH 5, O-protonation occurs initially to generate the neutral enol and ketonisation occurs by C-protonation of the minor enolate anion species in an overall pH independent step. The pKa of the enol is 6.0 and the pKE is calculated to be 2.9. The intrinsic rate constant, log (ko/dm3 mol–1 s–1), of 2.60 is similar to those of other carbon acids of pKaca. 9, suggesting that a relatively small amount of molecular and solvent reorganisation is required in order to stabilise the generated charge in the transition state. A rate–equilibrium correlation for proton transfer to hydroxide ion from carbon acids activated by a mono carbonyl group has been extended in the thermodynamically favourable direction to cover pKa units with no signs of significant curvature in the direction predicted by Marcus theory. 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'eprintid' => '511', 'creators_name_honourific' => '', 'pos' => '5', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '2', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2008', 'fileinfo' => '', 'status_changed_second' => '55', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Acylation versus sulfonylation in the inhibition of elastase by 3-oxo-beta-sultams ', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 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'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '37', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '8', 'datestamp_day' => '8', 'abstract' => '-Sultams are the sulfonyl analogues of -lactams, and 3-oxo- -sultams are both -lactams and -sultams and, therefore, susceptible to nucleophilic attack at either the acyl or the sulfonyl center. They are novel inactivators of serine enzymes. The second-order rate constant for the inactivation of elastase at pH 6 by N-benzyl-4,4-dimethyl-3-oxo- -sultam is 768 M-1 s-1, which is 103-fold greater than However, in contrast to N-acyl -sultams, which sulfonylate the active site serine residue to form a sulfonate ester, 3 acylation followed by slow deacylation to regenerate the active enzyme.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '6', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '37', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => '10.1021/ja050787z', 'volume' => '127', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => '(1) Baxter, N. J.; Rigoreau, L. J. M.; Laws, A. P.; Page, M. I. J. Am. Chem. Soc. 2000, 112, 3375-3385; J. Chem. Soc., Perkin Trans. 2 1996, 2245- 2246. (2) Hinchliffe, P. S.; Wood, J. M.; Davis, A. M.; Austin, R. P.; Beckett, R. P.; Page, M. I. Org. Biomol. Chem. 2003, 1, 67-80. (3) Page, M. I. Enzyme Inhibition. In ComprehensiVe Medicinal Chemistry; Sammes, P. G., Ed.; Pergamon: Oxford, 1990; Vol. 2, pp 61-87. (4) Metz, W. A.; Peet, N. P. Prog. Inflammation Res. 1999, 9, 853-868. (5) Bode, W.; Meyer, E., Jr.; Powers, J. C. Biochemistry 1989, 28, 1951- 1963. (6) Macdonald, S. J. F. et al. Bioorg. Med. Chem. Lett. 2001, 11, 895-898. (7) Page M. I., Ed. The Chemistry of â-Lactams; Blackie: Glasgow, 1992. (8) (a) Chabin, R.; Green, B. G.; Gale, P.; Maycock, A. L.; Weston, H.; Dorn, C. P.; Finke, P. E.; Hagmann, W. K.; Hale, J. J.; MacCoss, M.; Shah, S. K.; Underwood, D.; Doherty, J. B.; Knight, W. B. Biochemistry 1993, 32, 8970-8980. (b) Beauve, C.; Bouchet, M.; Touillaux, R.; Fastrez, J.; Marchand-Brynaert, J. Tetrahedron 1999, 55, 13301-13320. (9) Wood, J. M.; Page, M. I. Trends Heterocycl. Chem. 2002, 8, 19-34. (10) Page, M. I. Acc. Chem. Res. 2004, 37, 297-303. (11) Macdonald, S. J. F. et al. Bioorg. Med. Chem. Lett. 2001, 11, 243-246. (12) Sykes, N. O.; Macdonald, S. J. F.; Page, M. I. J. Med. Chem. 2002, 45, 2850-2856. (13) Ahmed, N.; Tsang, W. Y.; Page, M. I. Org. Lett. 2004, 6, 201-203. (14) (a) Eriksson, S. O.; Jakobsson M. Acta Pharm. Suec. 1973, 10, 63-74. (b) Matsui, S.; Aida H. J. Chem. Soc., Perkin Trans. 2 1978, 1277- 1280. (15) Wilmouth, R. C.; Westwood, N. J.; Anderson, K.; Brownlee, W.; Claridge, T. D. W.; Clifton, I. J.; Pritchard, G. J.; Aplin, R. T.; Schofield, C. J. Biochemistry 1998, 37, 17506-17513. (16) Firestone, R. A.; Barker, P. L.; Pisano, J. M.; Ashe, B. M.; Dahlgren, M. E. Tetrahedron 1990, 46, 2255-2262. 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However, the rate of reaction is inhibited by increasing concentrations of hydroxide ion and penicillin anion. A saturation phenomenon is observed with increased concentration of surfactant. Attempts are made to determine the binding- and rate-constants using existing kinetic models. These are not completely satisfactory and a model is proposed which assumes that both hydroxide ion and penicillin have to be bound to the micelle for reaction to occur. Bromide, chloride, acetate, fluoride, and benzylpenicilloate ions all inhibit the micellar catalysis.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '45', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29820000147', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1982', 'status_changed_hour' => '13', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6119' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Webster', 'eprintid' => '6119', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Philip S.', 'creators_id' => undef }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6119', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Ghosez', 'eprintid' => '6119', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Leon', 'creators_id' => undef } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '31', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'The hydrolysis of azetidinyl amidinium salts. Part 2. Substituent effects, buffer catalysis, and the reaction mechanism', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/61/19', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '14', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/P29900000813', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '6', 'publisher' => 'Royal Society of Chemistry', 'pagerange' => '813-823', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Journal of the Chemical Society, Perkin Transactions 2', 'lastmod_second' => '31', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1472-779X', 'datestamp_hour' => '10', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '31', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 5, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6119', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19900500', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '10', 'number' => '5', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '14', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '6', 'datestamp_day' => '6', 'abstract' => 'The hydrolysis of azetidin-2-ylideneammonium salts gives a mixture of -lactams, by exocyclic C–N bond fission, and -amino amides, by endocyclic C–N bond breakage and opening of the four-membered ring. The reaction is general-base catalysed and more -lactam is formed using a less basic buffer. The mechanism of the buffer-catalysed reaction is the general-acid-catalysed breakdown of a reversibly formed neutral tetrahedral intermediate. The Brønsted -values vary with substituents in the amidinium salt so that they decrease with increasing electron withdrawal in the nitrogen amine which is expelled. Electron-withdrawing substituents attached to either nitrogen of the amidinium salt favour expulsion of that leaving-group amine. The Brønsted 1g for endocyclic C–N bond fission and -amino amide formation is –0.52 whereas that for exocyclic C–N bond fission and -lactam formation is –0.83. Substituent effects on the nitrogen amine which is not expelled but forms the product amide or -lactam generate p values of –0.71 and –0.07, respectively. Changes in structure–reactivity relationships with substituents are examined by an analysis of the reaction mechanism', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '14', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29900000813', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1990', 'status_changed_hour' => '10', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '515' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '515', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '2', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2008', 'fileinfo' => '', 'status_changed_second' => '48', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => '?-sultams-mechanism of reactions and use as inhibitors of serine proteases ', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/05/15', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '37', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://pubs.acs.org/cgi-bin/abstract.cgi/achre4/2004/37/i05/abs/ar0200899.html', 'succeeds' => undef, 'datestamp_month' => '2', 'commentary' => undef, 'lastmod_day' => '20', 'publisher' => 'American Chemical Society', 'pagerange' => '297-303', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2008', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Accounts of Chemical Research', 'lastmod_second' => '2', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '0001-4842', 'datestamp_hour' => '12', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '48', 'note' => ' ', 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 2, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '515', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2008', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '10', 'event_dates' => undef, 'fulltimestamp' => '20040200', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '9', 'number' => '5', 'rev_number' => '21', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '1', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'QD', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '48', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '8', 'datestamp_day' => '8', 'abstract' => '?-Sultams are reactive sulfonyl analogues of -lactams and show enormous rate enhancements over analogous reactions of sulfonamides. N-Acyl -sultams undergo S-N rather than C-N fission, although -alkenyl substituents direct nucleophilic attack to the acyl center. They also inactivate serine enzymes such as elastase and -lactamase by sulfonylation of the active site serine. Structure-activity relationships are used to identify differences in transition state structures', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '6', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '48', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => '10.1021/ar0200899', 'volume' => '37', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => '(1) Page, M. I.; Williams, A. Organic and Bio-organic Mechanisms; Addison-Wesley Longman: Harlow, U.K., 1997. Williams, A. Concerted Organic and Bio-organic Mechanisms; CRC Press: Boca Raton, FL, 1999. (2) Page, M. I. 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In The Chemistry of Sulfonic Acids, Esters and their Derivatives; Patai, S., Rappoport, Z., Eds.; Wiley: Chichester, U.K., 1991; Chapter 19, pp 789-878. (15) Baxter, N. J.; Laws, A. P.; Rigoreau, L. J. M.; Page, M. I. Evidence for a Trigonal Bipyramidal Intermediate During Nucleophilic Substitution at a Sulfonyl Centre and for a Sulfonylium Cation in the Acid-Catalyzed Reaction. Chem. Commun. 1997, 2037-2038. (16) Webster, P.; Ghosez, L.; Page, M. I. The Hydrolysis of Azetidinyl/ Amidinium Salts. J. Chem. Soc., Perkin Trans. 2 1990, 805-811. Page, M. I. The Energetics of Intramolecular Reactions and Enzyme Catalysis. Philos. Trans. R. Soc. London, Ser. B 1991, 32, 149-156. (17) Proctor, P.; Gensmantel, N. P.; Page, M. I. The Chemical Reactivity of Penicillins. J. Chem. Soc., Perkin Trans. 2 1982, 1185-1192. Cox, R. A.; Yates, K. The Hydrolyses of Benzamides and Lactams in Aqueous Sulfuric Acid. Can. J. Chem. 1981, 59, 2853-2863. Page, M. I.; Laws, A P.; Slater, M. J.; Stone, J. R. 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'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '59', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'The Reactivity of b-Lactams, the Mechanism of Catalysis and the Inhibition of b-Lactamases', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/60/73', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 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'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '39', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '4', 'datestamp_day' => '4', 'abstract' => 'Four membered b-Lactam rings do not show unusual reactivity compared with their acyclic amide analogues and there is no evidence of concerted mechanisms for nucleophilic substitution reactions at the carbonyl centre. The identity of the general base/acid catalyst in the serine b-Lactamases, which catalyse the hydrolysis of b-Lactams, is unknown. There are no ideal transition state analogue inhibitors for these enzymes which involve several intermediates and transition states. The class C serine b-Lactamase enhances the rate of phosphonylation of its active site serine residue by a similar magnitude to the enzyme rate enhancement factor for the hydrolysis of b-Lactams. Comparisons are made between the stereochemical consequences of tetrahedral and trigonal bipyramidal intermediates for hydrolysis and phosphonylation respectively. Class B zinc b-Lactamases are inhibited by thiol dipeptides with a D configuration at the cysteine centre analogous to the L configuration at C6 in penicillins. The mechanism of hydrolysis catalysed by the metallo-b-Lactamases probably involves a di-anionic tetrahedral intermediate stabilised by zinc(II). 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'creators_name_lineage' => '', 'creators_name_family' => 'Martin', 'eprintid' => '6114', 'creators_name_honourific' => '', 'pos' => '3', 'creators_name_given' => 'Frances', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6114', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '26', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Thiazolidine ring opening in penicillin derivatives. Part 2. Enamine formation', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/61/14', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '41', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/P29910001225', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '6', 'publisher' => 'Royal Society of Chemistry', 'pagerange' => '1225-1229', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Journal of the Chemical Society, Perkin Transactions 2', 'lastmod_second' => '26', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1472-779X', 'datestamp_hour' => '9', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '26', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 8, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6114', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19910800', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '9', 'number' => '8', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '41', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '6', 'datestamp_day' => '6', 'abstract' => 'The alkaline hydrolysis of (3S,5R,6R)-methyl benzylpenicilloate, and the corresponding carboxamide and N-ethylamide, is accompanied by an absorbance increase at 285 nm. This is attributed to a competing elimination reaction across C6–C5 to open the thiazolidine ring and reversibly generate an enamine intermediate. Kinetic analysis and hydrolysis in D2O do not indicate a significant build-up of this intermediate during hydrolysis of the methyl ester. However, over the pH range 4–11 the rate of thiazolidine ring opening is competitive with hydrolysis of the ester function. The deuterium solvent kinetic isotope effect on the ring closure reaction is 7.5.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '41', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29910001225', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1991', 'status_changed_hour' => '9', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6088' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Laws', 'eprintid' => '6088', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Andrew P.', 'creators_id' => 'a.p.laws@hud.ac.uk' }, '3' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6088', 'creators_name_honourific' => '', 'pos' => '3', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Bounaga', 'eprintid' => '6088', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Sakina', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Galleni', 'eprintid' => '6088', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Moreno', 'creators_id' => undef } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '51', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'The mechanism of catalysis and the inhibition of the Bacillus cereus zinc-dependent b-lactamase ', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/60/88', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '20', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => 1, 'gscholar_impact' => undef, 'official_url' => 'http://www.biochemj.org/bj/331/bj3310703.htm', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '5', 'publisher' => 'Portland Press', 'pagerange' => '703-711', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Biochemical Journal', 'lastmod_second' => '51', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '0264-6021', 'datestamp_hour' => '11', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '51', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 5, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6088', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19980501', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '11', 'number' => '3', 'rev_number' => '8', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '20', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '5', 'datestamp_day' => '5', 'abstract' => 'The plot of kcat/Km against pH for the Bacillus cereus 569/H b-lactamase class B catalysed hydrolysis of benzylpenicillin and cephalosporin indicates that there are three catalytically important groups, two of pKa 5.6±0.2 and one of pKa 9.5±0.2. Below pH 5 there is an inverse second-order dependence of reactivity upon hydrogen ion concentration, indicative of the requirement of two basic residues for catalysis. These are assigned to zinc(II)-bound water and Asp-90, both with a pKa of 5.6±0.2. A thiol, N-(2´-mercaptoethyl)-2-phenylacetamide, is an inhibitor of the class B enzyme with a Ki of 70 µM. The pH-dependence of Ki shows similar pH inflections to those observed in the catalysed hydrolysis of substrates. The pH-independence of Ki between pH 6 and 9 indicates that the pKa of zinc(II)-bound water must be 5.6 and not the higher pKa of 9.5. The kinetic solvent isotope effect on kcat/Km is 1.3±0.5 and that on kcat is 1.5. There is no effect on reactivity by either added zinc(II) or methanol. The possible mechanisms of action for the class B b-lactamase are discussed, and it is concluded that zinc(II) acts as a Lewis acid to stabilize the dianionic form of the tetrahedral intermediate and to provide a hydroxide-ion bound nucleophile, whereas the carboxylate anion of Asp-90 acts as a general base to form the dianion and also, presumably, as a general acid catalyst facilitating C–N bond fission. ', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '20', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => undef, 'volume' => '331', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1998', 'status_changed_hour' => '11', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6121' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6121', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Laws', 'eprintid' => '6121', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Andrew P.', 'creators_id' => 'a.p.laws@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '5', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'The effect of the carboxy group on the chemical and ?-lactamase reactivity of ?-lactam antibiotics', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/61/21', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '27', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/P29890001577', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '6', 'publisher' => 'Royal Society of Chemistry', 'pagerange' => '1577-1581', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Journal of the Chemical Society, Perkin Transactions 2', 'lastmod_second' => '5', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1472-779X', 'datestamp_hour' => '10', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '5', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 10, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6121', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19891000', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '10', 'number' => '10', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '27', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '6', 'datestamp_day' => '6', 'abstract' => 'Kinetic parameters are reported for the Bacillus cereus-lactamase I and -lactamase II catalysed hydrolysis of esters and lactones of penicillins and cephalosporins. These are compared with the second-order rate constants for the hydroxide-ion catalysed hydrolysis of the same derivatives. The second-order rate constant, kcat/Km for the hydrolysis of the cephalosporin lactone catalysed by -lactamase I is 50 times greater than that for an analogous cephalosporin and is 3 × 104 times greater than that for hydroxide-ion catalysed hydrolysis, a ratio similar to that for cephalosporins with a carboxylate group at C-4. The methyl ester of benzyl penicillin, but not the corresponding cephalosporanate, is a substrate for -lactamase I. All ester derivatives are much poorer substrates for -lactamase II. The cephalosporin lactone and, to a lesser extent, the methyl ester of benzyl penicillin can obviously bind to -lactamase I even though they do not possess a formal anionic site at C-4 and C-3 respectively. The esterification of the carboxy group at C-3 in penicillins induces neighbouring-group participation by the C-6 acylamido side chain to give an oxazolinone intermediate. This is attributed to different Brönsted 1g dependency for alkaline hydrolysis and intramolecular acylamido participation, which exhibits rate limiting C–N bond fission of the -lactam.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '27', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29890001577', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1989', 'status_changed_hour' => '10', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6208' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6208', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => '', 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '34', 'exhibitors_name_honourific' => undef, 'editors_id' => 'm.i.page@hud.ac.uk', 'title' => 'Chapter 7 The mechanisms of chemical catalysis used by enzymes', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => '', 'dir' => 'disk0/00/00/62/08', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '34', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1016/S0167-7306(08)60378-6', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '12', 'publisher' => 'Elsevier BV', 'pagerange' => '229-269', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => 'New Comprehensive Biochemistry', 'thesis_name' => undef, 'event_location' => undef, 'type' => 'book_section', 'publication' => 'New Comprehensive Biochemistry', 'lastmod_second' => '34', 'place_of_pub' 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undef, 'rev_number' => '10', 'edit_lock_user' => undef, 'series' => 'New Comprehensive Biochemistry', 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '34', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '12', 'datestamp_day' => '12', 'abstract' => undef, 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '34', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1016/S0167-7306(08)60378-6', 'volume' => '6', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1984', 'status_changed_hour' => '10', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6358' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => '1308055675', 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Atherton', 'eprintid' => '6358', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'John H.', 'creators_id' => 'j.h.atherton@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Ji', 'eprintid' => '6358', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Pengju', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6358', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '49', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'The kinetics and mechanisms of organic reactions in liquid ammonia', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/63/58', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '52', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/b912261n', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '14', 'publisher' => 'Royal Society of Chemistry', 'pagerange' => '15-25', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Faraday Discussions', 'lastmod_second' => '57', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1359-6640', 'datestamp_hour' => '18', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '49', 'note' => undef, 'edit_lock_until' => '0', 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 1, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6358', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2011', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '6', 'event_dates' => undef, 'fulltimestamp' => '20100100', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '12', 'number' => undef, 'rev_number' => '8', 'edit_lock_user' => '3483', 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'QD', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '26', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '23', 'datestamp_day' => '23', 'abstract' => 'Liquid ammonia is a potentially useful solvent for a variety of organic reactions and so understanding the kinetics and mechanisms of these processes is important. In contrast to the hydrolysis rates of the substituted benzyl halides in water which vary 107-fold, the rates of the solvolysis of substituted benzyl chlorides in liquid ammonia at 25 °C have little or no dependence upon ring substituents and vary only 2-fold between 4-methoxy- and 4-nitro- derivatives. The Hammett -value is practically zero, which suggests there is no significant charge developed on the central carbon in the transition state. Activation energies for solvolysis of 4-nitro-, 4-methoxy-, 4-chloro- and unsubstituted benzyl chloride in liquid ammonia vary from 40.3 to 43.8 kJ mol-1 in the order of NO2 < H < Cl < OMe and entropies of activation (S) are very negative varying from -188 J K-1 mol-1 to -202 J K-1 mol-1. The solvolysis rates of benzyl halides in liquid ammonia increase linearly with increasing concentration of potassium perchlorate and ammonium chloride. All of these observations are indicative of a bimolecular concerted SN2 mechanism proceeding through a transition state structure with complementary charge development on the entering and leaving groups and little or no change in charge on the central benzylic carbon. Benzyl chloride undergoes substitution with oxygen and nitrogen nucleophiles also by an SN2 process as shown by the dependence of the rate on the concentration of the nucleophile. A Brønsted type relationship for a series of amine nucleophiles show a nuc of 0.33 suggesting an early type transition state with a small amount of charge development on the amine nitrogen. Contrary to commonly accepted views, it appears that the liquid ammonia behaves like a dipolar aprotic solvent in nucleophilic substitution reactions. The nucleophilic substitution reaction in liquid ammonia shows high (>99%) selectivity towards O-benzylation of phenoxide ion, and with 1,2,4-triazolate anion gives predominantly (92%) substitution in the 1-position', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3494', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '26', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/b912261n', 'volume' => '145', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '2010', 'status_changed_hour' => '18', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '527' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '4' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Schofield', 'eprintid' => '527', 'creators_name_honourific' => '', 'pos' => '4', 'creators_name_given' => 'Christopher J.', 'creators_id' => undef }, '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Hinchliffe', 'eprintid' => '527', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Paul S.', 'creators_id' => undef }, '3' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Wilmouth', 'eprintid' => '527', 'creators_name_honourific' => '', 'pos' => '3', 'creators_name_given' => 'Rupert C.', 'creators_id' => undef }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Beardsell', 'eprintid' => '527', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Mark', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Wood', 'eprintid' => '527', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'J. 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Chem., in press.', 'date_year' => '2001', 'status_changed_hour' => '14', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '3378' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Ahmed', 'eprintid' => '3378', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Naveed', 'creators_id' => undef }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Tsang', 'eprintid' => '3378', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Wing Y.', 'creators_id' => undef }, '3' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '3378', 'creators_name_honourific' => '', 'pos' => '3', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Hemming', 'eprintid' => '3378', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Karl', 'creators_id' => 'k.hemming@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '2', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '41', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Reactivity and selectivity in the inhibition of elastase by 3-oxo-?-sultams and in their hydrolysis', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/33/78', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '2', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/b713899g', 'succeeds' => undef, 'datestamp_month' => '2', 'commentary' => undef, 'lastmod_day' => '13', 'publisher' => 'The Royal Society of Chemistry', 'pagerange' => '3993-4000', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Organic and Biomolecular Chemistry', 'lastmod_second' => '41', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1477-0539', 'datestamp_hour' => '13', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '41', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 12, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '3378', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '2', 'event_dates' => undef, 'fulltimestamp' => '20071200', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '13', 'number' => '24', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '2', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '13', 'datestamp_day' => '13', 'abstract' => '3-oxo-?-sultams are both -sultams and -lactams and are a novel class of time-dependent inhibitors of elastase. The inhibition involves formation of a covalent enzyme–inhibitor adduct with transient stability by acylation of the active-site serine resulting from substitution at the carbonyl centre of the 3-oxo-?-sultam, C–N fission, and expulsion of the sulfonamide. The lead compound, N-benzyl-4,4-dimethyl-3-oxo--sultam 1 is a reasonably potent inhibitor against porcine pancreatic elastase with a second-order rate constant of 768 M–1 s–1 at pH 6, but also possesses high chemical reactivity with a half-life for hydrolysis of only 6 mins at the same pH in water. Interestingly, the hydrolysis of 3-oxo-?-sultams occurs at the sulfonyl centre with S–N fission and expulsion of the amide leaving group, whereas the enzyme reaction occurs at the acyl centre. Increasing selectivity between these two reactive centres was explored by examining the effect of substituents on the reactivity of 3-oxo-?-sultam towards hydrolysis and enzyme inhibition. The inhibition activity against porcine pancreatic elastase has a much higher sensitivity to substituent variation than does the rate of alkaline hydrolysis. A difference of 2000-fold is observed in the second-order rate constants, ki, for inhibition whereas there is only a 100-fold difference in the second-order rate constants, kOH, for alkaline hydrolysis within the series. The higher sensitivity of enzyme inhibition to substituents than that of simple chemical reactivity indicates a significant degree of molecular recognition of the 3-oxo-?-sultams by the enzyme.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3494', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '2', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/b713899g', 'volume' => '5', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '2007', 'status_changed_hour' => '13', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6093' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' 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'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '8', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'A highly diastereoselective synthesis of tricyclic lactams and their application as novel N-acyl iminium ion precursors in the synthesis of isoindolinone derivatives', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/60/93', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 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'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 5, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6093', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19970519', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '12', 'number' => '20', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '6', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '5', 'datestamp_day' => '5', 'abstract' => 'Condensation of 2-formylbenzoic acid with ?-amino alcohol substrates proceeds with extremely high diastereoselectivity to produce tricyclic ?-lactam products. The relative stereochemistry of the major diastereoisomer has been determined by X-ray crystal analysis and a mechanism suggested to explain the stereochemical outcome. Further, we report that this class of heterocycle can act as an N-acyl iminium ion precursor in the synthesis of substituted isoindolinone derivatives. ', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '6', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1016/S0040-4039(97)00686-2', 'volume' => '38', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1997', 'status_changed_hour' => '12', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6188' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6188', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Morris', 'eprintid' => '6188', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Jeffrey J.', 'creators_id' => undef } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '43', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Hydroxy-group participation in the hydrolysis of amides and its effective concentration in the absence of strain effects', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/61/88', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '19', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/P29800000679', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '12', 'publisher' => 'Royal Society of Chemistry', 'pagerange' => '679-684', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Journal of the Chemical Society, Perkin Transactions 2', 'lastmod_second' => '43', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1472-779X', 'datestamp_hour' => '8', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '43', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 4, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6188', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19800400', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '8', 'number' => '4', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '19', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '12', 'datestamp_day' => '12', 'abstract' => 'Rate constants are reported for the alkaline- and acid-catalysed hydrolysis of endo-6-hydroxybicyclo[2.2.1]-heptane-endo-2-carboxamides in aqueous solution. The product of the acid-catalysed reaction is endo-6-hydroxybicyclo[2.2.1]heptane-endo-2-carboxylic acid lactone and this lactone is also formed as an intermediate in alkaline solution before giving the hydroxy-acid anion as the product. The effective concentration of the intramolecular alkoxide ion group is ca. 108M. This is in good agreement with the maximum entropic advantage predicted for intramolecular reactions as the system is thought to be free of major strain energy and solvation effects. Variation of substituents in the amine leaving group gives a 1g value of +0.30 for the hydroxide-ion-catalysed lactonisation reaction. This is interpreted in terms of rate-limiting breakdown of the tetrahedral intermediate in which there is considerable positive charge on the amine nitrogen. Mechanisms consistent with this involve either proton transfer from water to the amine nitrogen occurring synchronously with carbon–nitrogen bond fission or a stepwise process in which the nitrogen of the tetrahedral intermediate is fully protonated and the rate-limiting step is either diffusion apart of this intermediate and hydroxide ion or collapse of this intermediate with hydroxide ion acting as a spectator. The 1g value for the acid-catalysed lactonisation reaction is 0.0.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '19', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29800000679', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1980', 'status_changed_hour' => '8', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6231' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6231', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Capon', 'eprintid' => '6231', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Brian', 'creators_id' => undef } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '2', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'The kinetics and mechanism of the hydrolysis of esters of cis- and trans-2-hydroxycyclopentanecarboxylic acid and 3-hydroxybutyric acid', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/62/31', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '42', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/J29710000741', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '12', 'publisher' => 'Royal Society of Chemistry', 'pagerange' => '741-744', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Journal of the Chemical Society B, physical organic', 'lastmod_second' => '2', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1472-779X', 'datestamp_hour' => '13', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '2', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 6, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6231', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19710600', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '13', 'number' => undef, 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '42', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '12', 'datestamp_day' => '12', 'abstract' => 'The hydrolysis of ethyl cis-2-hydroxycyclopentanecarboxylate is 1·8 to 11 times faster than that of ethyl cyclopentanecarboxylate in 0·1 M-sodium hydroxide in aqueous dioxan (mole fraction of dioxan 0 to 0·329). This is probably not the result of intramolecular hydrogen bonding since ethyl trans-2-hydroxycyclopentanecarboxylate for which such bonding is not possible reacts as fast or faster than the cis-ester. It is tentatively suggested that the smaller dependence of the rates of hydrolysis of the hydroxy-esters on dioxan concentration compared to the unsubstituted ester is the result of solvent sorting. Similar behaviour is found for the hydrolysis of the 2-naphthyl esters and for the ethyl and 2-naphthyl esters of 3-hydroxybutyric acid.The rates of hydrolysis of the hydroxy-esters are enhanced in borate buffers possibly as a result of borate-ester formation followed by intramolecular nucleophilic catalysis.I.r. spectroscopic studies show that the esters of cis-2-hydroxycyclopentanecarboxylic acid are strongly intramolecularly bonded in carbon tetrachloride solution and that those of 3-hydroxybutyric acid are weakly intramolecularly hydrogen bonded. The esters of trans-2-hydroxycyclopentanecarboxylic acid are not intramolecularly hydrogen bonded.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '42', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/J29710000741', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1971', 'status_changed_hour' => '13', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '3356' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Laws', 'eprintid' => '3356', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Andrew P.', 'creators_id' => 'a.p.laws@hud.ac.uk' }, '3' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '3356', 'creators_name_honourific' => '', 'pos' => '3', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Russell', 'eprintid' => '3356', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Mark A.', 'creators_id' => 'm.a.russell@hud.ac.uk' }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Atherton', 'eprintid' => '3356', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'John H.', 'creators_id' => 'j.h.atherton@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '2', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '56', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'The kinetics and mechanism of the acid-catalysed detritylation of nucleotides in non-aqueous solution', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/33/56', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '12', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/b816235b', 'succeeds' => undef, 'datestamp_month' => '2', 'commentary' => undef, 'lastmod_day' => '2', 'publisher' => 'The Royal Society of Chemistry', 'pagerange' => '52-57', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Organic and Biomolecular Chemistry', 'lastmod_second' => '5', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1477-0539', 'datestamp_hour' => '16', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '56', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 1, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '3356', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '6', 'event_dates' => undef, 'fulltimestamp' => '20090100', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '10', 'number' => '1', 'rev_number' => '11', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '1', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'bmsrc', 'institution' => undef, 'subjects' => 'QD', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '13', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '12', 'datestamp_day' => '12', 'abstract' => 'The kinetics and mechanism of the deprotection (detritylation) of 5-O-(4,4-dimethoxytrityl)-2-deoxythymidine nucleoside catalysed by dichloroacetic acid to give a 4,4-dimethoxytrityl carbocation have been studied in toluene, dichloromethane and acetonitrile. There is little or no effect of solvent polarity on the equilibrium and rate constants. Entropies of activation are highly negative -105 J K-1 mol-1 and similarly show little variation with solvent. Addition of small amounts of water to the reaction medium reduces the detritylation rate, presumably through its effect on the solution acidity. All observations are compatible with detritylation occurring through a concerted general acid-catalysed mechanism rather than a stepwise A1 process.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3494', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '13', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/b816235b', 'volume' => '7', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '2009', 'status_changed_hour' => '16', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '7323' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '7323', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '4', 'editors_name_honourific' => '', 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2010', 'fileinfo' => '', 'status_changed_second' => '18', 'exhibitors_name_honourific' => undef, 'editors_id' => 'm.i.page@hud.ac.uk', 'title' => 'The mechanisms of reactions of(beta)lactams', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => '', 'dir' => 'disk0/00/00/73/23', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '29', 'refereed' => undef, 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => undef, 'succeeds' => undef, 'datestamp_month' => '4', 'commentary' => undef, 'lastmod_day' => '1', 'publisher' => 'Blackie Academic and Professional', 'pagerange' => '129-147', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2010', 'book_title' => 'The chemistry of Beta lactams', 'thesis_name' => undef, 'event_location' => undef, 'type' => 'book_section', 'publication' => undef, 'lastmod_second' => '18', 'place_of_pub' => 'London', 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => 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The rates of inactivation show a similar pH-rate dependence as that exhibited by the ?-lactam antibiotics and with ESIMS data it is suggested that ?-sultams sulfonylate the active site serine residue to form a sulfonate ester. ', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '6', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '28', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => '10.1016/j.bmcl.2003.08.082', 'volume' => '13', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => '1. Waley, S. G. In The Chemistry of -Lactams; Page, M. I., Ed.; Blackie: Glasgow, 1992; p 198. Fre` re, J.-M. Mol. Microbiol. 1995, 16, 385. 2. Payne, D. J. J. Med. Microbiol. 1993, 39, 93. Nordmann, P.; Mariotte, P. S.; Naas, T.; Labia, R.; Nicolas, M. H. Antimicrob. Agents Chemother. 1993, 37, 939. Naas, T.; Vandel, L.; Sougakoff, W.; Livermore, D. 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'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'bmsrc', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '17', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '10', 'datestamp_day' => '10', 'abstract' => 'The ability of a taurine prodrug, ethane ?-sultam, to reduce cellular inflammation has been investigated, in vitro, in primary cultures of alveolar macrophages and an immortilised N9 microglial cell line and in vivo in an animal model of inflammation and control rats. Ethane ?-sultam showed enhanced ability to reduce the inflammatory response in alveolar macrophages, as assayed by the lipopolysaccharide-stimulated–nitric oxide release, (LPS stimulated-NO), in comparison to taurine both in vitro (10 nM, 50 nM) and in vivo (0.15 mmol/kg/day by gavage). In addition, ethane ?-sultam, (50, 100 and 1000 nM) significantly reduced LPS-stimulated glutamate release from N9 microglial cells to a greater extent than taurine. The anti-inflammatory response of taurine was shown to be mediated via stabilisation of IkB?. The use of a taurine prodrug as therapeutic agents, for the treatment of neurological conditions, such as Parkinson's and Alzheimer's disease and alcoholic brain damage, where activated phagocytic cells contribute to the pathogenesis, may be of great potential. 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Ring opening of the -lactam requires protonation of the -lactam nitrogen by a general acid catalyst. The general acid/base catalyst in -lactamases is probably a glutamate and a tyrosine residue in class A and C enzymes, respectively. Phosphonamidates inactivate class C -lactamases by phosphonylation of the active site serine, the rate of which is enhanced by a factor of at least 106. The enzyme s catalytic machinery used for hydrolysis is also used for phosphonylation. The rate enhancement may be greater than 109 if the mechanism occurs by an inhibitor assisted reaction involving intramolecular general acid catalysis. Class B metallo- -lactamases are inhibited by thiol derivatives with Ki as low as 10 µM. The mechanism of hydrolysis of the metallo- -lactamase involves a dianionic tetrahedral intermediate stabilised by zinc(II). 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'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '20130900', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '11', 'number' => '21', 'rev_number' => '9', 'edit_lock_user' => '116', 'series' => undef, 'creators_name_lineage' => '', 'pos' => '1', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'QD', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '21', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '26', 'datestamp_day' => '26', 'abstract' => '1,1?-Methylenebis-pyridinium dication (MDP) is an unusual salt with two formal positively charged substituents attached to a central carbon and yet is remarkably stable to hydrolysis at pH < 8. However above this pH it undergoes a biphasic reaction liberating two moles of pyridine sequentially. The rate of the first phase is second order in hydroxide-ion, whilst the second is pH independent. The first phase is also accompanied by the generation of a chromophore at 366 nm which is identified as a pyridine ring opened unsaturated imino-aldehyde, formed by an ANRORC-type mechanism. This intermediate then ring closes to give the second mole of pyridine and formaldehyde. Below pD 8 there is a very slow alternative pathway for degradation which is first order in hydroxide-ion, liberates only one mole of pyridine and forms N-hydroxymethyl pyridinium ion. Rates of deuterium exchange of the central methylene in D2O are faster than those of the breakdown of MDP and are predominantly OD- catalysed with a small amount of buffer catalysis. The estimated pKa of MDP dication in H2O is unexpectedly high at 21.2 at 25degC and I = 1.0 M (KCl), but is about 9 units lower than the mono-cationic N-methylpyridinium ion. Deuterium exchange also occurs in the 2 and 6 positions of the pyridinium rings, but at a slower rate which is first order in deuteroxide ion and only competitive with the breakdown of MDP below pD 11.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '21', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1021/jo401587w', 'volume' => '78', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '2013', 'status_changed_hour' => '9', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6077' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 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'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '38', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '4', 'datestamp_day' => '4', 'abstract' => 'A new approach for the synthesis of non-racemic 3-substituted isoindolin-1-one targets has been developed through application of a tricyclic ?-lactam substrate as an N-acyliminium ion precursor. 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undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '5', 'publisher' => 'Royal Society of Chemistry', 'pagerange' => '535-540', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Journal of the Chemical Society, Perkin Transactions 2', 'lastmod_second' => '26', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1472-779X', 'datestamp_hour' => '11', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '26', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 3, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6091', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19980300', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '11', 'number' => '3', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '47', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '5', 'datestamp_day' => '5', 'abstract' => 'The hydrolysis of coumaran-2-one and 5-substituted 3-phenylcoumaran-2-ones is preceded by a pre-equilibrium involving the formation of an enolate anion at high pH. The pKa of 3-phenylcoumaran-2-one is 8.39 in water at 25 °C and the 3-phenyl substituent increases the carbon acidity by 104. However, despite this ready carbanion formation, the conventional addition–elimination mechanism for hydrolysis of 3-phenylcoumaran-2-ones is confirmed by a solvent kinetic isotope effect of 0.63 and a Brønsted 1g of –0.6. This is compatible with rate limiting formation of a tetrahedral intermediate.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '47', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/a707946j', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1998', 'status_changed_hour' => '11', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6112' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Layland', 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'scopus_id' => undef, 'eprintid' => '6112', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19930100', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '9', 'number' => '1', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '2', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '6', 'datestamp_day' => '6', 'abstract' => 'The replacement of the C3 carboxylate in phenoxymethylpenicillin by a hydroxymethyl group and of the C4 carboxylate in cephalosporins by both a lactone and an aldehyde gives derivatives which are still good substrates for Bacillus cereus 569/H -lactamase I. The enzyme rate-enhancement factors for the hydrolysis of the modified -lactams vary from 104 to 106. All three modified substrates show bell-shaped (kcat/Km)–pH profiles indicative of two catalytically important ionising residues on the protein of pKa, about 5 and 9. Although lysine 234 is a highly conserved residue in class A -lactamases and has been traditionally thought to interact with the carboxylate of the -lactam antibiotic, it is not responsible for the decrease in enzyme activity at high pH corresponding to the pKaof about 9.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '2', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29930000017', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1993', 'status_changed_hour' => '9', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6074' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => 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'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '4', 'datestamp_day' => '4', 'abstract' => 'Although b-lactamases have generally been considered as being devoid of peptidase activity, a low but significant hydrolysis of various N-acylated dipeptides was observed with representatives of each class of b-lactamases. The kcat/Km values were below 0.1 M-1·s-1, but the enzyme rate enhancement factors were in the range 5000–20000 for the best substrates. Not unexpectedly, the best 'peptidase' was the class C b-lactamase of Enterobacter cloacae P99, but, more surprisingly, the activity was always higher with the phenylacetyl- and benzoyl-D-Ala-D-Ala dipeptides than with the diacetyl- and a-acetyl-L-Lys-D-Ala-D-Ala tripeptides, which are the preferred substrates of the low-molecular-mass, soluble DD-peptidases. A comparison between the b-lactamases and DD-peptidases showed that it might be as difficult for a DD-peptidase to open the b-lactam ring as it is for the b-lactamases to hydrolyse the peptides, an observation which can be explained by geometric and stereoelectronic considerations. ', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '19', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => undef, 'volume' => '341', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1999', 'status_changed_hour' => '12', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6177' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Morris', 'eprintid' => '6177', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Jeffrey 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'title' => 'Intra-and inter-molecular general base catalysis in the aminolysis of benzylpenicillin', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/61/77', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '15', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/C39760000495', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '11', 'publisher' => 'Royal Society of Chemistry', 'pagerange' => '495-496', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' 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'fulltimestamp' => '19760700', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '13', 'number' => '13', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '15', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '11', 'datestamp_day' => '11', 'abstract' => 'The rate law for the aminolysis of benzylpenicillin is obtained and Brønsted -values indicate that the general-base-catalysed reaction occurs with a stepwise proton-transfer step; intramolecular general base catalysis occurs in the reaction of ethylenediamine with penicillin.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '15', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/C39760000495', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1976', 'status_changed_hour' => '13', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6125' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6125', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Buckwell', 'eprintid' => '6125', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Stephen C.', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Longridge', 'eprintid' => '6125', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Jethro L.', 'creators_id' => undef } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '10', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Hydrolysis of 6-alkyl penicillins catalysed by ?-lactamase I from Bacillus cereus and by hydroxide ion', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/61/25', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '19', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/P29880001809', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '6', 'publisher' => 'Royal Society of Chemistry', 'pagerange' => '1809-1813', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Journal of the Chemical Society, Perkin Transactions 2', 'lastmod_second' => '10', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1472-779X', 'datestamp_hour' => '11', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '10', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 10, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6125', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19881000', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '11', 'number' => '10', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '19', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '6', 'datestamp_day' => '6', 'abstract' => 'Second-order rate constants for the hydroxide ion-catalysed hydrolysis of 6-alkyl penicillins are independent of the length of the alkyl side-chain and replacement of the amido by an amino group decreases the susceptibility to nuclephilic attack on 6-aminopenicillanic acid only three-fold. B. cereus-lactamase I catalyses the hydrolysis of 6-alkyl penicillins with values of Kcat/Km which are at least 50-fold greater than that shown by 6-aminopenicillanic acid. For the enzyme-catalysed reaction Kcat/Km increases with increasing chain length, reaching a maximum with hexylpenicillin, and then decreases. The binding energy of the alkyl group is weak, only 1.45 kJ mol–1 per methylene residue. Although there appears to be a recognition site for the amido group there is no specific pocket in -lactamase I for the recognition of hydrophobic residues in the 6-acylamido side-chain of penicillins.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '19', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29880001809', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1988', 'status_changed_hour' => '11', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6184' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Proctor', 'eprintid' => '6184', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Philip', 'creators_id' => undef }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Gensmantel', 'eprintid' => '6184', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Nigel P.', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6184', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '48', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Metal-ion catalysed hydrolysis of some ?-lactam antibiotics', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/61/84', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '53', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/P29800001725', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '11', 'publisher' => 'Royal Society of Chemistry', 'pagerange' => '1725-1732', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Journal of the Chemical Society, Perkin Transactions 2', 'lastmod_second' => '48', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1472-779X', 'datestamp_hour' => '13', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '48', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 11, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6184', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19801100', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '13', 'number' => '11', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '53', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '11', 'datestamp_day' => '11', 'abstract' => 'The metal(II)-ion catalysed hydrolysis of some pencillin and cephalosporin derivatives in water at 30° shows saturation kinetics. A 1 : 1 complex is formed between the metal ion and penicillin which is attacked by hydroxide ion up to 108 fold faster than the unco-ordinated compound. The site of co-ordination of the penicillins and copper(II) ions is the -lactam nitrogen and the carboxylate group. The association constants for the cephalosporins and metal ions are greater than those for the penicillins but the transition states for the cephalosporin reaction with hydroxide ion bind less tightly to metal ions. The order of rate enhancement brought about by the metal ion is CuII > ZnII > NiII CoII. The metal ions are thought to stabilise the tetrahedral intermediate formed by hydroxide ion attack on the -lactam. Some comments are made about metal ions as electrophilic catalysts in enzymes.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '53', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29800001725', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1980', 'status_changed_hour' => '13', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '15438' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => '1349433050', 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Atherton', 'eprintid' => '15438', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'John H.', 'creators_id' => 'j.h.atherton@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Ji', 'eprintid' => '15438', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Pengju', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '15438', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '10', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2012', 'fileinfo' => '/style/images/fileicons/application_pdf.png;/15438/1/Click_reactions.pdf', 'status_changed_second' => '33', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Copper catalysed azide–alkyne cycloaddition (CuAAC) in liquid ammonia', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/01/54/38', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'restricted', 'lastmod_minute' => '37', 'refereed' => 'TRUE', 'contact_email' => 'j.h.atherton@hud.ac.uk', 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/c2ob26213d', 'succeeds' => undef, 'datestamp_month' => '10', 'commentary' => undef, 'lastmod_day' => '5', 'publisher' => 'Royal Society of Chemistry', 'pagerange' => '7965-7969', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2012', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Organic & Biomolecular Chemistry', 'lastmod_second' => '33', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1477-0520', 'datestamp_hour' => '10', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '33', 'note' => undef, 'edit_lock_until' => '0', 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 8, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '15438', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2012', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '10', 'event_dates' => undef, 'fulltimestamp' => '20120800', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '10', 'number' => '39', 'rev_number' => '8', 'edit_lock_user' => '116', 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'QD', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '37', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '5', 'datestamp_day' => '5', 'abstract' => 'Copper(I) catalysed azide–alkyne cycloaddition reactions (CuAAC) occur smoothly in liquid ammonia (LNH3) at room temperature to give exclusively 1,4-substituted 1,2,3-triazoles with excellent yields (up to 99%). The CuAAC reactions in liquid ammonia require relatively small amounts of copper(I) catalyst (0.5 mole%) compared with that in conventional solvents. The product can be obtained conveniently by simply evaporation of ammonia, indicating its potential application in industry. The rate of the CuAAC reaction in liquid ammonia shows a second order dependence on the copper(I) concentration and the reaction occurs only with terminal alkynes. Deuterium exchange experiments with phenyl acetylene-d1 show that the acidity of the alkyne is increased at least 1000-fold with catalytic amounts of copper(I) in liquid ammonia. The mechanism of the CuAAC reaction in liquid ammonia is discussed.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '116', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '37', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/c2ob26213d', 'volume' => '10', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '2012', 'status_changed_hour' => '10', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6205' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6205', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => '', 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '10', 'exhibitors_name_honourific' => undef, 'editors_id' => 'm.i.page@hud.ac.uk', 'title' => 'Chapter 1 The energetics and specificity of enzyme—substrate interactions', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => '', 'dir' => 'disk0/00/00/62/05', 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'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1984', 'status_changed_hour' => '10', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6179' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Cox', 'eprintid' => '6179', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Graham', 'creators_id' => undef }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Agathocleous', 'eprintid' => '6179', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'D.', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' 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'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '30', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '11', 'datestamp_day' => '11', 'abstract' => 'The cycloaddition of succinimido ketene to 2,3-dihydrofuran yields P- -succinimido bicyclo [3.2.0] 2-oxoheptan-6-one. This unusual stereochemistry is confirmed by 1H NMR and X-ray crystallography. The cyclobutanone product undergoes ring opening in concentrated hydrochloric acid to give 1-succinimido-5-chloro-2-pentanone. 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P.', 'creators_id' => 'a.p.laws@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '10', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2008', 'fileinfo' => '', 'status_changed_second' => '41', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Reactivity and Mechanism in the Hydrolysis of ?-Sultams', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/22/62', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 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undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '53', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '17', 'datestamp_day' => '17', 'abstract' => '-Sultams show extraordinary rate enhancements of 109- and 107-fold, respectively, compared with the acid- and base-catalyzed hydrolysis of corresponding acyclic sulfonamides. They are about 103-fold more reactive than analogous -lactams. The alkaline hydrolysis of some -sultams shows a rate term that is second-order in hydroxide ion concentration, which is indicative of a stepwise mechanism involving a trigonal bipyramidal intermediate (TBPI). The Brnsted lg value for the alkaline hydrolysis of N-aryl--sultams is -0.58 and the kinetic solvent isotope effect / is 0.60, compatible with rate-limiting formation of the TBPI. Conversely, / for N-alkyl--sultams is 1.55, indicative of rate-limiting breakdown of the TBPI. The acid-catalyzed hydrolysis of -sultams is strongly retarded by electron-withdrawing groups to the sulfonyl group, and it is suggested that the mechanism may involve unimolecular ring opening to generate a sulfonylium ion. The Brnsted lg value for the acid-catalyzed hydrolysis of N-benzyl--sultams is 0.32. The general-acid-catalyzed hydrolysis of N-benzyl--sultam by carboxylic acids shows a Brnsted value of 0.67 and is attributed to a specific acid-nucleophilic mechanism with the formation of a mixed-anhydride intermediate. 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They sulfonylate the active site serine residue to form a sulfonate ester which subsequently undergoes C-O bond fission and formation of a dehydroalanine residue by elimination of the sulfonate anion as shown by electrospray ionization mass spectroscopy. The analogous N-acyl ?-lactams are substrates for ?-lactamase and undergo enzyme-catalyzed hydrolysis presumably by the normal acylation-deacylation process. The rates of acylation of the enzyme by the ?-lactams, measured by the second-order rate constant for hydrolysis, kcat/ Km, and those of sulfonylation by the ?-sultams, measured by the second-order rate constant for inactivation, ki , both show a similar pH dependence to that exhibited by the ?-lactamase-catalyzed hydrolysis of ?-lactam antibiotics. Electronwithdrawing groups in the aryl residue of the leaving group of N-aroyl ?-lactams increase the rate of alkaline hydrolysis and give a Bronsted ?lg of -0.55, indicative of a late transition state for rate-limiting formation of the tetrahedral intermediate. Interestingly, the corresponding Bronsted ?lg for the ?-lactamase-catalyzed hydrolysis of the same substrates is -0.06, indicative of an earlier transition state for the enzyme-catalyzed reaction. By contrast, although the Bronsted ?lg for the alkaline hydrolysis of N-aroyl ?-sultams is -0.73, similar to that for the ?-lactams, that for the sulfonylation of ?-lactamase by these compounds is -1.46, compatible with significant amide anion expulsion/S-N fission in the transition state. 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'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'QD', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '37', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '17', 'datestamp_day' => '17', 'abstract' => 'Thiolysis of benzylpenicillin has been investigated by HPLC and 1H-NMR techniques. Thiols catalyse the hydrolysis of benzylpenicillin through the formation of a thioester intermediate. The catalytically reactive form of the thiol has been demonstrated to be the thiolate anion. Variation of reactivity with changing basicity of the thiolate anion generates a Brønsted nuc value of 0.96, indicating that the breakdown of the tetrahedral intermediate is the rate-limiting step, as occurs in aminolysis and alcoholysis. Solvent kinetic isotope effects of 2.2–2.4 indicate that the solvent, water, probably acts as a general acid catalyst in the breakdown of the tetrahedral intermediate. PM3 theoretical calculations support the proposal that breakdown of the tetrahedral intermediate is rate-limiting. The experimental activation energies for the thiolysis of benzylpenicillin vary from 6.9 to 10.4 kcal mol–1', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '6', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '37', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/b001091j', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '2000', 'status_changed_hour' => '10', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6154' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '0' => { 'creators_name_lineage' => '', 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'referencetext' => undef, 'date_year' => '1988', 'status_changed_hour' => '9', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '502' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => ' ', 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Ahmed', 'eprintid' => '502', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Naveed', 'creators_id' => undef }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Tsang', 'eprintid' => '502', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Wing Y.', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '502', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '1', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2008', 'fileinfo' => '', 'status_changed_second' => '5', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'The aminolysis of N-Aroyl ?-Lactams occurs by a concerted mechanism ', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/05/02', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 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undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '5', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => undef, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '502', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2008', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '10', 'event_dates' => undef, 'fulltimestamp' => '20070000', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '9', 'number' => '3', 'rev_number' => '25', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '1', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'QD', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '24', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '25', 'datestamp_day' => '25', 'abstract' => 'N-Aroyl -lactams are imides with exo- and endocyclic acyl centres which react with amines in aqueous solution to give the ring opened -lactam aminolysis product. Unlike the strongly base catalysed aminolysis of -lactam antiobiotics, such as penicillins and cephaloridines, the rate law for the aminolysis of N-aroyl -lactams is dominated by a term with a first-order dependence on amine concentration in its free base form, indicative of an uncatalysed aminolysis reaction. The second-order rate constants for this uncatalysed aminolysis of N-p-methoxybenzoyl -lactam with a series of substituted amines generates a Brønsted nuc value of +0.90. This is indicative of a large development of positive effective charge on the amine nucleophile in the transition state. Similarly, the rate constants for the reaction of 2-cyanoethylamine with substituted N-aroyl -lactams gives a Brønsted lg value of –1.03 for different amide leaving groups and is indicative of considerable change in effective charge on the leaving group in the transition state. These observations are compatible with either a late transition state for the formation of the tetrahedral intermediate of a stepwise mechanism or a concerted mechanism with simultaneous bond formation and fission in which the amide leaving group is expelled as an anion. Amide anion expulsion is also indicated by an insignificant solvent kinetic isotope effect, kH2ORNH2/kD2ORNH2, of 1.01 for the aminolysis of N-benzoyl -lactam with 2-methoxyethylamine. The Brønsted lg value decreases from –1.03 to –0.71 as the amine nucleophile is changed from 2-cyanoethylamine to propylamine. The Brønsted nuc value is more invariant although it changes from +0.90 to +0.85 on changing the amide leaving group from p-methoxy to p-chloro substituted. The sensitivity of the Brønsted nuc and lg values to the nucleofugality of the amide leaving group and the nucleophilicity of the amine nucleophiles, respectively, indicate coupled bond formation and bond fission processes.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '6', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '24', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => '10.1039/b616420j', 'volume' => '5', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => '1 M. I. Page, Adv. Phys. Org. Chem., 1987, 23, 165. 2 M. I. Page, Acc. Chem. Res., 1984, 17, 144. 3 A. F. Martin, J. J. Morris and M. I. Page, J. Chem. Soc., Chem. Commun., 1979, 298; N. P. Gensmantel and M. I. Page, J. Chem. Soc., Perkin Trans. 2, 1982, 147. 4 M. I. Page, in The Chemistry of b-lactams, ed. M. I. Page, Blackie, Glasgow, 1992, pp. 129-147. 5 A. M. Davis, P. Proctor andM. I. Page, J. Chem. Soc., Perkin Trans. 2, 1991, 1213. 6 K. Bowden andK. Bromley, J. Chem. Soc., Perkin Trans. 2, 1990, 2111. 7 H. Bundgaard, Arch. Pharm. Chemi. Sci. Ed., 1976, 4, 91. 8 M. I. Page, The mechanisms of chemical catalysis used by enzymes, The Chemistry of Enzyme Action, ed. M. I. Page, Elsevier, Amsterdam, 1984, pp. 229-269. 9 J. J. Morris and M. I. Page, J. Chem. Soc., Perkin Trans. 2, 1980, 212. 10 A. Tsuji, T. Yamana, E.Miyamoto and E. Kiya, J. Pharm. Pharmacol., 1975, 27, 580. 11 W. Y. Tsang, N. Ahmed, K. Hemming and M. I. Page, Can. J. Chem., 2005, 83, 1432–1439. 12 M. I. Page and P. Proctor, J. Am. Chem. Soc., 1984, 106, 3820–3825. 13 G. M. Blackburn and J. D. Plackett, J. Chem. Soc., Perkin Trans. 2, 1973, 981–985. 14 N. P. Gensmantel andM. I. Page, J. Chem. Soc., Perkin Trans. 2, 1979, 137–142. 15 M. I. Page and J. P. Jencks, J. Am. Chem. Soc., 1972, 94, 3263–3264. 16 A. Llinas and M. I. Page, Org. Biomol. Chem., 2004, 2, 651–654. 17 M. I. Page and A. Williams, Organic and Bioorganic Mechanisms, Longman, Singapore, 1997. 18 W. Y. Tsang, N. Ahmed, P. S. Hinchliffe, J. M. Wood, L. P. Harding, A. P. Laws andM. I. Page, J. Am. Chem. Soc., 2005, 127, 17556–17564. 19 M. Eigen, Angew. Chem., Int. Ed. Engl., 1964, 3, 1–19. 20 D. Stefanidis, S. Cho, S. Dhe-Paganon and W. P. Jencks, J. Am. Chem. Soc., 1993, 115, 1650–1656. 21 E. A. Braude and F. C.Nachod, in Determination of Organic Structures by Physical Methods, Academic Press, New York, 1955. 22 G. M. Blackburn and J. D. Plackett, J. Chem. Soc., Perkin Trans. 2, 1972, 1366–1371. 23 W. P. Jencks, Acc. Chem. Res., 1980, 13, 161. 24 A. K. Covington, R. A. Robinson and R. G. Bates, J. Phys. 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dm–3 and kcat/Km= 4.5 × 105 dm3 mol–1 s–1 at pH 7. With B. cereus 569/H -lactamase I as a catalyst, kcat/Km= 1.87 × 104 dm3 mol–1 s–1 at pH 7 and shows a bell-shaped dependence on pH with apparent pKas of 4.76 and 9.72. Any close proximity between the penicillin 3-aldehyde and a lysine amino group on the protein does not result in iminine formation and inhibition of the enzyme', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '21', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29950000869', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1995', 'status_changed_hour' => '13', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '2259' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Laws', 'eprintid' => '2259', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Andrew P.', 'creators_id' => 'a.p.laws@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '2259', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '10', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2008', 'fileinfo' => '', 'status_changed_second' => '49', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'The Chemical Reactivity of ?-Lactams, ?-Sultams and ?-Phospholactams', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/22/59', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '26', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1016/S0040-4020(00)00412-9', 'succeeds' => undef, 'datestamp_month' => '10', 'commentary' => undef, 'lastmod_day' => '20', 'publisher' => 'Elsevier Science', 'pagerange' => '5631-5637', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2008', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Tetrahedron', 'lastmod_second' => '17', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '0040-4020', 'datestamp_hour' => '15', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '49', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => undef, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '2259', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2008', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '10', 'event_dates' => undef, 'fulltimestamp' => '20000000', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '8', 'number' => '31', 'rev_number' => '11', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '44', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '16', 'datestamp_day' => '16', 'abstract' => '?-Lactam antibiotics display a range of biological activities. The origin of this diverse biological activity is discussed with reference to the chemical reactivity of the small ring system. The reactions of ?-sultams and ?-phospholactams with simple nucleophiles are reported and their potential as mechanism based inhibitors of bacterial and mammalian serine proteases is described.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '6', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '44', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1016/S0040-4020(00)00412-9', 'volume' => '56', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '2000', 'status_changed_hour' => '15', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6158' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 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However, the similarly substituted acyclic ester analogues of the lactone do not exhibit enantioselectivity suggesting that the acylation step shows the selectivity. Racemic spirodilactone can be converted, in principle, entirely into one of its enantiomers.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '29', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29930002317', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1993', 'status_changed_hour' => '8', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '1445' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Tsang', 'eprintid' => '1445', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Wing Y.', 'creators_id' => undef }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Ahmed', 'eprintid' => '1445', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Naveed', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '1445', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '8', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2008', 'fileinfo' => '', 'status_changed_second' => '13', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Acyl vs Sulfonyl Transfer in N-Acyl ?-Sultams and 3-Oxo-? sultams ', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/14/45', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '1', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '47', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1021/ol0361305', 'succeeds' => undef, 'datestamp_month' => '8', 'commentary' => undef, 'lastmod_day' => '19', 'publisher' => 'American Chemical Society', 'pagerange' => '201-203', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2008', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Organic Letters', 'lastmod_second' => '42', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '15237060', 'datestamp_hour' => '9', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '13', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => undef, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '1445', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2010', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '1', 'event_dates' => undef, 'fulltimestamp' => '20040000', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '4', 'number' => '2', 'rev_number' => '14', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '8', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '11', 'datestamp_day' => '11', 'abstract' => 'N-Acylsulfonamides usually react with nucleophiles by acyl transfer and C-N bond fission. 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undef, 'gscholar_datestamp_day' => undef, 'issn' => '0960-894X', 'datestamp_hour' => '11', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '32', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => undef, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '2267', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2008', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '10', 'event_dates' => undef, 'fulltimestamp' => '20010000', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '9', 'number' => '2', 'rev_number' => '11', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '1', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'QD', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '13', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '17', 'datestamp_day' => '17', 'abstract' => 'Several cysteinyl peptides have been synthesised and shown to be reversible competitive inhibitors of the Bacillus cereus metallo-?-lactamase. The pH dependence of pKi indicates that the thiol anion displaces hydroxide ion from the active site zinc(II). , -Peptides bind to the enzyme better than other diastereoisomers, which is compatible with the predicted stereochemistry of the active site', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '6', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '13', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1016/S0968-0896(00)00257-1', 'volume' => '9', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '2001', 'status_changed_hour' => '11', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6197' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 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=> '12', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'The kinetics and mechanism of the hydrolysis of 2,3-(phenylmethylenedioxy)benzene (Oo'-benzylidenecatechol) and benzaldehyde diphenyl acetal', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/61/97', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '57', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/P29720000522', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '11', 'publisher' => 'Royal 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undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '3', 'event_dates' => undef, 'fulltimestamp' => '19720500', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '13', 'number' => '5', 'rev_number' => '10', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '55', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '12', 'datestamp_day' => '12', 'abstract' => 'General-acid catalysis has been detected in the hydrolysis of OO-benzylidenecatechol with a Brønsted -value of 0·47 for catalysis by carboxylic acids. There is also a relatively fast spontaneous hydrolysis with k(H2O)/(D2O)= 1·61 and S=–21·1 cal deg–1 mol–1 at 75°. The entropy of activation for the hydronium-ion catalysed reaction is –8·78 cal deg–1 mol–1 and the isotope effect k(H3O+)/k(D3O+)= 0·92 at 75°. These reactions are thought to proceed via A-SE2 mechanisms.The hydrolysis of benzaldehyde diphenyl acetal is much faster than that of benzylidenecatechol and in 20%(w/w) dioxan–water mixtures is also general-acid catalysed with approximately 1 and k(H3O+)/k(D3O+)= 0·67 at 15°. An A-SE2 mechanism was also favoured for this reaction', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '55', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/P29720000522', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1972', 'status_changed_hour' => '8', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '3381' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '3381', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Badarau', 'eprintid' => '3381', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Adriana', 'creators_id' => undef } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '2', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '18', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Loss of enzyme activity during turnover of the Bacillus cereus ?-lactamase catalysed hydrolysis of ?-lactams due to loss of zinc ion', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/33/81', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '37', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1007/s00775-008-0379-2', 'succeeds' => undef, 'datestamp_month' => '2', 'commentary' => undef, 'lastmod_day' => '13', 'publisher' => 'Springer', 'pagerange' => '919-928', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'JBIC Journal of Biological Inorganic Chemistry', 'lastmod_second' => '18', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '09498257', 'datestamp_hour' => '13', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '18', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 8, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '3381', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '2', 'event_dates' => undef, 'fulltimestamp' => '20080800', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '13', 'number' => '6', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '37', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '13', 'datestamp_day' => '13', 'abstract' => 'Metallo-?-lactamases are zinc-ion-dependent and are known to exist either as mononuclear or as dinuclear enzymes. The kinetics and mechanism of hydrolysis of the native zinc Bacillus cereus metallo-?-lactamase (BcII) have been investigated under pre-steady-state conditions at different pHs and zinc-ion concentrations. Biphasic kinetics are observed for the hydrolysis of cefuroxime and benzylpenicillin with submicromolar concentrations of enzyme and zinc. The initial burst of product formation far exceeds the concentration of enzyme and the subsequent slower rate of hydrolysis is attributed to a branched kinetic pathway. The pH and metal-ion dependence of the microscopic rate constants of this branching were determined, from which it is concluded that two enzyme species with different metal-to-enzyme stoichiometries are formed during catalytic turnover. The dizinc enzyme is responsible for the fast route but during the catalytic cycle it slowly loses the less tightly bound zinc ion via the branching route to give an inactive monozinc enzyme; the latter is only catalytic following the uptake of a second zinc ion. The rate constant for product formation from the dinuclear enzyme and the branching rate constant show a sigmoidal dependence on pH indicative of important ionizing groups with pK as of 9.0 ± 0.1 and 8.2 ± 0.1, respectively. The rate constant for the regeneration of enzyme activity depends on zinc-ion concentration. This unusual behaviour is attributed to an intrinsic property of metallo hydrolytic enzymes that depend on a metal bound water both as a ligand for the second metal ion and as the nucleophile which is consumed during hydrolysis of the substrate and so has to be replaced to maintain the catalytic cycle.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3494', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '37', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1007/s00775-008-0379-2', 'volume' => '13', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '2008', 'status_changed_hour' => '13', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6174' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Morris', 'eprintid' => '6174', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Jeffrey J.', 'creators_id' => undef }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Martin', 'eprintid' => '6174', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Anthony F.', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6174', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '58', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Intramolecular general acid catalysis in the aminolysis of benzylpenicillin. A preferred direction of nucleophilic attack', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/61/74', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '42', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1039/C39790000298', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '11', 'publisher' => 'Royal Society of Chemistry', 'pagerange' => '298-299', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Chemical Communications', 'lastmod_second' => '58', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1359-7345', 'datestamp_hour' => '12', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '58', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 3, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6174', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19790300', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '12', 'number' => '6', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '42', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '11', 'datestamp_day' => '11', 'abstract' => 'The reaction of 1,2-diaminoethane monocation with benzylpenicillin shows a rate enhancement of ca. 100-fold compared with a monoamine of similar basicity; this is attributed to intramolecular general acid catalysis which in turn indicates that nucleophilic attack takes place from the least hindered -side in disagreement with the prediction of the theory of stereoelectronic control', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '42', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1039/C39790000298', 'volume' => undef, 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1979', 'status_changed_hour' => '12', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '15510' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => '1349941869', 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Powles', 'eprintid' => '15510', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Nicholas', 'creators_id' => 'n.t.powles@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Ji', 'eprintid' => '15510', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Pengju', 'creators_id' => undef }, '3' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '15510', 'creators_name_honourific' => '', 'pos' => '3', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Atherton', 'eprintid' => '15510', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'John H.', 'creators_id' => 'j.h.atherton@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '10', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2012', 'fileinfo' => '', 'status_changed_second' => '44', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Ionization of Carbon Acids in Liquid Ammonia', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/01/55/10', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '2', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1021/ol2026153', 'succeeds' => undef, 'datestamp_month' => '10', 'commentary' => undef, 'lastmod_day' => '11', 'publisher' => 'American Chemical Society', 'pagerange' => '6118-6121', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2012', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Organic Letters', 'lastmod_second' => '44', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '1523-7060', 'datestamp_hour' => '8', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '44', 'note' => undef, 'edit_lock_until' => '0', 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 11, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '15510', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2012', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '10', 'event_dates' => undef, 'fulltimestamp' => '20111100', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '8', 'number' => '22', 'rev_number' => '7', 'edit_lock_user' => '3494', 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'QD', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '2', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '11', 'datestamp_day' => '11', 'abstract' => 'The acidities of various carbon acids in liquid ammonia (LNH3) at room temperature were determined by NMR and rates of D-exchange. There is a reasonable linear correlation of the pKas in LNH3 with those in water and DMSO of slope 0.7 and 0.8, respectively. Carbon acids with an aqueous pKa of less than 12 are fully ionized in liquid ammonia. Nucleophilic substitution of benzyl chloride by carbanions in liquid ammonia generates a Brønsted ?nuc = 0.38.', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3494', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '2', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1021/ol2026153', 'volume' => '13', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '2011', 'status_changed_hour' => '8', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '6226' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '6226', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Jencks', 'eprintid' => '6226', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'William P.', 'creators_id' => undef } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 'status_changed_month' => '11', 'editors_name_honourific' => undef, 'admin_note' => undef, 'event_title' => undef, 'date_type' => 'published', 'pres_type' => undef, 'longitude' => undef, 'creators_name_honourific' => '', 'include_in_hebci' => 'no', 'producers_name_honourific' => undef, 'scopus_citation_count' => undef, 'datestamp_year' => '2009', 'fileinfo' => '', 'status_changed_second' => '35', 'exhibitors_name_honourific' => undef, 'editors_id' => undef, 'title' => 'Orbital steering, entropy, and rate accelerations', 'corp_creators' => undef, 'contributors_name_given' => undef, 'alt_title' => undef, 'contributors_name_family' => undef, 'sponsors' => undef, 'output_media' => undef, 'editors_name_lineage' => undef, 'dir' => 'disk0/00/00/62/26', 'overlay_journal_id' => undef, 'gscholar_datestamp_year' => undef, 'ispublished' => 'pub', 'item_issues_count' => '0', 'conductors_name_given' => undef, 'sword_depositor' => undef, 'full_text_status' => 'none', 'lastmod_minute' => '36', 'refereed' => 'TRUE', 'contact_email' => undef, 'copyright_holders' => undef, 'date_day' => undef, 'gscholar_impact' => undef, 'official_url' => 'http://dx.doi.org/10.1016/0006-291X(74)90629-9', 'succeeds' => undef, 'datestamp_month' => '11', 'commentary' => undef, 'lastmod_day' => '12', 'publisher' => 'Elsevier', 'pagerange' => '887-892', 'include_in_pedagogical' => 'no', 'task_purpose' => undef, 'status_changed_year' => '2009', 'book_title' => undef, 'thesis_name' => undef, 'event_location' => undef, 'type' => 'article', 'publication' => 'Biochemical and Biophysical Research Communications', 'lastmod_second' => '35', 'place_of_pub' => undef, 'contributors_name_honourific' => undef, 'gscholar_datestamp_day' => undef, 'issn' => '0006-291X', 'datestamp_hour' => '12', 'exhibitors_name_given' => undef, 'creators_name_family' => 'Page', 'composition_type' => undef, 'producers_id' => undef, 'datestamp_second' => '35', 'note' => undef, 'edit_lock_until' => undef, 'editor_note' => undef, 'pedagogic_type' => undef, 'date_month' => 4, 'rights' => undef, 'contributors_type' => undef, 'scopus_id' => undef, 'eprintid' => '6226', 'producers_name_given' => undef, 'thesis_type' => undef, 'projects' => undef, 'lastmod_year' => '2009', 'data_type' => undef, 'gscholar_datestamp_minute' => undef, 'editors_name_given' => undef, 'isbn' => undef, 'include_in_cv' => 'yes', 'editors_name_family' => undef, 'lastmod_month' => '11', 'event_dates' => undef, 'fulltimestamp' => '19740400', 'learning_level' => undef, 'conductors_name_lineage' => undef, 'pages' => undef, 'source' => undef, 'lastmod_hour' => '12', 'number' => '3', 'rev_number' => '9', 'edit_lock_user' => undef, 'series' => undef, 'creators_name_lineage' => '', 'pos' => '0', 'metadata_visibility' => 'show', 'eprint_status' => 'archive', 'creators_name_given' => 'Michael I.', 'exhibitors_name_lineage' => undef, 'divisions' => 'sas', 'institution' => undef, 'subjects' => 'Q1', 'gscholar_datestamp_hour' => undef, 'producers_name_lineage' => undef, 'lyricists_name_given' => undef, 'completion_time' => undef, 'status_changed_minute' => '36', 'conductors_name_honourific' => undef, 'exhibitors_name_family' => undef, 'lyricists_name_honourific' => undef, 'event_type' => undef, 'importid' => undef, 'status_changed_day' => '12', 'datestamp_day' => '12', 'abstract' => 'Some important conceptual and quantitative differences are described between the “orbital steering” and entropy descriptions of the rate accelerations in intramolecular and enzymic reactions that may be brought about by geometric constraints other than distortion. The treatments differ by a factor of 103 – 104 in the maximum rate acceleration that may be obtained from these constraints. The estimation of a “proximity factor” without taking adequate account of the translational and overall rotational entropy terms gives a misleading value for this factor. The conclusion is reaffirmed that increasing the probability of reaction by restricting the free translational and rotational movement of reacting groups can play a large role in the catalytic power of enzymes', 'creators_id' => 'm.i.page@hud.ac.uk', 'contributors_name_lineage' => undef, 'userid' => '3483', 'patent_applicant' => undef, 'monograph_type' => undef, 'datestamp_minute' => '36', 'lyricists_name_family' => undef, 'sword_slug' => undef, 'id_number' => 'doi:10.1016/0006-291X(74)90629-9', 'volume' => '57', 'gscholar_datestamp_month' => undef, 'conductors_id' => undef, 'suggestions' => undef, 'referencetext' => undef, 'date_year' => '1974', 'status_changed_hour' => '12', 'gscholar_cluster' => undef, 'producers_name_family' => undef }, '2265' => { 'funders' => undef, 'conductors_name_family' => undef, 'num_pieces' => undef, 'department' => undef, 'contributors_id' => undef, 'gscholar_datestamp_second' => undef, 'keywords' => undef, 'lyricists_name_lineage' => undef, 'lyricists_id' => undef, 'edit_lock_since' => undef, 'creatorlist' => { '1' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Northfield', 'eprintid' => '2265', 'creators_name_honourific' => '', 'pos' => '1', 'creators_name_given' => 'Christopher J.', 'creators_id' => undef }, '0' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Allin', 'eprintid' => '2265', 'creators_name_honourific' => '', 'pos' => '0', 'creators_name_given' => 'Steven M.', 'creators_id' => undef }, '3' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Slawin', 'eprintid' => '2265', 'creators_name_honourific' => '', 'pos' => '3', 'creators_name_given' => 'Alexandra M.Z.', 'creators_id' => undef }, '2' => { 'creators_name_lineage' => '', 'creators_name_family' => 'Page', 'eprintid' => '2265', 'creators_name_honourific' => '', 'pos' => '2', 'creators_name_given' => 'Michael I.', 'creators_id' => 'm.i.page@hud.ac.uk' } }, 'exhibitors_id' => undef, 'latitude' => undef, 'replacedby' => undef, 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