Aqueous solutions that model the cytosol: studies on polarity, chemical reactivity and enzyme kinetics

Concentrated solutions of a series of organic compounds have been prepared and the effects of these solutes on the properties of the solvent system assessed as a function of their concentration and nature. Polarity, as measured by Reichardt's E-T(30) probe, exhibits a linear variation with both solute and water concentration for simple solutes. Non-linear behaviour was also observed and is associated with preferential solvation or binding of the E-T(30) probe molecule by the added solute. The observed trends in polarity are mirrored in the effects of these solutes on chemical reactivity and enzyme kinetics. Environmental effects on the kinetics of hydrolysis of 4-nitrophenyl dichloroacetate, the hydronium-ion catalysed hydrolysis of 2-(4-nitrophenoxy)-tetrahydropyran, the acyl transfer reaction between 4-nitrophenyl acetate and TRIS, the Diels-Alder reaction between 1,4-naphthoquinone and cyclopentadiene and the trypsin-catalysed hydrolysis of 4-nitrophenyl acetate are reported and discussed in terms of the properties of the solutes and the mechanistic requirements of these reactions. Linear correlations were observed between the logarithms of the rate constants for the acetal hydrolysis, acyl transfer and Diels-Alder reactions with water concentration. Since the latter varies linearly with E-T(30), this indicates a linear free energy relationship between solution polarity and chemical reactivity.