Glutamate nonenzymic

The rate constant = VN/ (CHaOH) (Eo) is 0.47 M1 sec-1 at 25° and pH 5.0, a value which may be compared to that for the virtual hydrolysis of glutamic acid fc0/(H20) of 91.5 M 1 sec1. Thus, from the ratio kK (H2O)/fc0J it is seen that the rate with methanol is some 194 times slower on a molar basis than that with water even though methanol is generally observed to be a somewhat better nucleophile than water in similar nonenzymic substitution reactions (14)- These results indicate that the enzyme shows a large preference kinetically for water over hydroxylamine or methanol compared to what would be expected on the basis of the intrinsic reactivities of these substances. 

IV. Nonenzymic Formation of Pyrrolidone Carboxylic Acid from Glutamic Acid, Glutamine, and Other Compounds... 

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