计算生物催化的平衡电位..docVIP

计算生物催化的平衡电位 　　Biochemists Use E0’ 　　Perhaps the most important redox reaction in living organisms are involved in respiration, in which molecules of food are oxidized by O 2 to yield energy or metabolic intermediates. The standard reduction potentials that we have been using so far apply to systems in which all activities of reactants and products are unity. If H+ is involved in the reaction, E 0’ applies when pH=0.Whenever H + appears in a redox reaction, or whenever reactants or products are acids or bases, reduction potentials are pH dependent. 　　Because the pH inside a plant or animal cell is in the neighborhood of 7, reduction potentials that apply at pH 0 are not particularly appropriate. For example, at pH 0, ascorbic acid (vitamin C) is a more powerful reducing agent than succinic acid (琥珀 酸, 丁二酸) is. However, at pH 7, this order in reversed. It is the reducing strength at pH 7, not at pH 0, that is relevant to a living cell. 　　The standard potential for a redox reaction is defined for a galvanic cell(原电池) in which all activities are unity. The formal potential is the reduction potential that applies under a specified set of conditions (including pH, ionic strength, and concentration of complexing agents), Biochemists call the formal potential at pH 7 E 0’ (read “E zero prime”). 　　Example Finding the Formal Potential 　　Find E0’ 　　for the reaction 　　O 　　+2H+(Z) 　　HO 　　+2H2O 　　Dehydroascorbic acid(oxidized) 　　Ascorbic acid(Vitimin C)(reduced) 　　pK 1=4.10 pK2=11.79 　　E 0=0.390v 　　　　SOLUTION Abbreviating dehydroascorbic acid as D, and ascorbic acid as H2A, we rewrite the reduction as 　　O H A H e H D 2222+?++?+ 　　for which the Nernst equation is 　　2 　　20] 　　][[][log 205916. 0+? 　　=H D A H E E (14-33) D is not an acid or a base, so its formal concentration equals its molar concentration: FD = [D].For 　　the diprotic acid H 2A, we use Equation 2 　　11222][][][][2K K K H H F 　　H F A H A H ++==+ 　　++αto express [H2A] in terms of FH2A : 　　2 　　112 　　22][][