By Th. J. De Boer
Read or Download Physical Organic Chemistry–2. Specially Invited Lectures Presented at the Second IUPAC Conference on Physical Organic Chemistry Held at Noordwijkerhout, Netherlands, 29 April–2 May 1974 PDF
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Extra resources for Physical Organic Chemistry–2. Specially Invited Lectures Presented at the Second IUPAC Conference on Physical Organic Chemistry Held at Noordwijkerhout, Netherlands, 29 April–2 May 1974
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These processes can be written as B + H+-BH+ BH + + OH" - B + H 2 0 (6) (7) By analogy with the earlier discussion of hydrogen bonding, the fact that these rates are diffusion-controlled implies that the actual proton transfer is fast compared with diffusion apart of the reactants—that is, the specific rate constant for intramolecular proton transfer in water is about 10 12 s~ *. This rate is very fast because of the rapid proton conduction which can occur through structured water. Marked deviations from diffusion control occur if the water structure is perturbed—for example, by internal hydrogen bonding or by an unusually high charge density.
Chem. Soc. 95, 6134 (1973). H. A. Staab and J. Ber. 101,1457 (1966) ; Tetrahedron Letters, 483,583 (1966). J. Kolc, Tetrahedron Letters, 532 (1972). R. S. Berry, G. N. Spokes and M. Stiles, J. Amer. Chem. Soc. 84, 3570 (1962); 82, 5240 (1960). C. L. Mclntosh and O. L. Chapman, Chem. Commun. Ill (1971). M. Chedekel and O. L. Chapman, unpublished observations. O. L. Chapman, M. R. Engel, J. P. Springer and J. C. Clardy, J. Amer. Chem Soc. 93, 6696 (1971). C. Y. Lin and A. Krantz, Chem. Commun. 1111 (1972).
REGULATION Although the regulation of enzyme activity by switching the enzyme between active and inactive forms has features in common with catalysis, namely 536 ELEMENTARY STEPS IN ENZYME CATALYSIS AND REGULATION Figure 2. A pictorial representation of the first half of the ribonuclease reaction. The free enzyme (A) can exist in two conformations differing by small movements about the hinge region joining the two halves of the molecule ; the substrate is bound (B) and a conformational change occurs bringing Lys 41 close to the active site (C); acid-base catalysis occurs (D); products are formed (E); a conformational change occurs (F); and the product dissociates to give the free enzyme (A) ligand binding and conformational changes, a number of distinct differences in the elementary steps exist.