Enthalpy and volume changes accompanying electron transfer from P-870 to quinones in Rhodopseudomonas sphaeroides reaction centers.

A capacitor microphone was used to measure the enthalpy and volume changes that accompany the electron transfer reactions, PQAhv leads to P+Q-A and PQAQBhv leads to P+QAQ-B, following flash excitation of photosynthetic reaction centers isolated from Rhodopseudomonas sphaeroides. P is a bacteriochlorophyll dimer (P-870), and QA and QB are ubiquinones. In reaction centers containing only QA, the enthalpy of P+Q-A is very close to that of the PQA ground state (delta Hr = 0.05 +/- 0.03 eV). The free energy of about 0.65 eV that is captured in the photochemical reaction evidently takes the form of a substantial entropy decrease. In contrast, the formation of P+QAQ-B in reaction centers containing both quinones has a delta Hr of 0.32 +/- 0.02 eV. The entropy change must be near zero in this case. In the presence of o-phenanthroline, which blocks electron transfer between Q-A and QB, delta Hr for forming P+Q-AQB is 0.13 +/- 0.03 eV. The influence of flash-induced proton uptake on the results was investigated, and the delta Hr values given above were measured under conditions that minimized this influence. Although the reductions of QA and QB involve very different changes in enthalpy and entropy, both reactions are accompanied by a similar volume decrease of about 20 ml/mol. The contraction probably reflects electrostriction caused by the charges on P+ and Q-A or Q-B.