Long-Distance Electron Transfer Coupled to Proton Pumping and Energy Transduction in Biological Systems: A Semiempirical First-Principles Approach

摘要

The first-principles method of electron tunneling currents for electron transfer was previously used to compute the electron coupling matrix in the Marcus theory as well as the tunneling pathway at the extended Huckel level of theory of electronic structure for the redox centers in some living systems such as cytochrome c oxidase. We present here the work in recent development of electron tunneling currents theory that implements in its formalism the inherent systematic ZDO approximation used in ZINDO/S quantum chemical model of electronic structure. Together with the molecular orbitals so calculated semiempirically we develop an approach that is consistent in its approximation, more accurate than the previous methodology and particularly applicable to large biological systems which cannot yet be fully treated ab initio. We calibrate this approach with ab initio results for a small model system of protein, the donor-bridge-acceptor complex of (His)_2 (Met)Cu~+ -(Cys)-(Gly_5)-(His)Ru~(3+)bpy_5Im, and make predictive calculations for the real biological electron transfer systems of His~(126) Ru-modified blue copper protein Pseudomonas aeruginosa azurin and cytochrome c oxidase. Furthermore, the coupling between electron transfer and energy transfer is demonstrated with the thermal motion in protein dynamics for the case of DNA repair by photolyase. Continuing work is underway on the newly crystallized structure of NADH dehydrogenase, the electron entrance to the cellular electron transport respiratory chain. Combining both the rigor of tunneling currents theory and the expedience of ZINDO/S quantum chemical model our approach offers a useful computational method for long-distance electron transfer in biological systems.