By Imran N Hosein

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30 Introduction 30 ............................................ 2 C l a s s i f i c a t i o n o f Zinc Sites in Zinc E n z y m e s . . . . . . . . . 3 Catalytic . . . . . . . . . . . . . . . . . . . . . . . . Cocatalytic .............................................. Structural ............................................... 31 32 32 I n f l u e n c e o f P r o t e i n Scaffolding o n Zinc B i n d i n g a n d C a t a l y t i c P r o p e r t i e s o f Zinc .

53. 54. 55. 56. 57. 58. 59. 60. 61. 62. 63. 54. 65. 66. 57. 58. 69. 70. 71. 72. 49 Kiefer LL, Paterno, SA, Fierke CA (1995) J Amer Chem Soc 117:6831 Lesburg CA, Christianson DW (1995) J Amer Chem Soc 117:6844 Silverman DN, Lindskog S (1988) Acc Chem Res 21:30 Crowder MW, Wang Z, Franklin EP, Zovinka EP, Benkovic SJ (1996) Biochemistry 35:12126 Concha NO, Rasmussen BA, Bush K, Herzberg O (1996) Structure 4:823 Hooper NM (1994) FEBS Letters 354:1 Rawlings ND, Barrett AJ (1995) Methods in Enzymology 248:183.

14c), and destabilises the HCA II-HCO; complex (see Fig. 14d). An inverse correlation was discovered between logarithmic values of the second-order rate constant for CO2 hydration and the pKa values of zinc(II)bound H20. This is a very unusual result. Br6nsted correlations with positive slopes are observed for most nucleophilic reactions. The observed slope of -1 for CO2 hydration indicates that interactions which destabilise zinc(II)-OH- relative to zinc(II)-OH2 also destabilise the transition state for CO2 hydration relative to zinc(II)-OH-.

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