Xing-Zhi Song

Nonplanar porphyrins and their significance in proteins

Nonplanar distortions of tetrapyrroles are prevalent in the hemes of hemoproteins, the pigments of photosynthetic proteins, and cofactor F430 of methylreductase. The nonplanarity of these porphyrin cofactors is currently believed to influence factors in the biological activity of the proteins, in part, because the porphyrin deformations are often conserved within functional classes of proteins. The occurrence, classification, and study of nonplanar porphyrins in proteins and synthetic nonplanar porphyrin analogs are reviewed.

Raman dispersion spectroscopy on the highly saddled nickel(II)-octaethyltetraphenylporphyrin reveals the symmetry of nonplanar distortions and the vibronic coupling strength of normal modes

We have measured the polarized Raman cross sections and depolarization ratios of 16 fundamental modes of nickel octaethyltetraphenylporphyrin in a CS2 solution for 16 fundamental modes, i.e., the A1g-type vibrations ν1, ν2, ν3, ν4, ν5, and φ8, the B1g vibrations ν11 and ν14, the B2g vibrations ν28, ν29, and ν30 and the antisymmetric A2g modes ν19, ν20, ν22, and ν23 as function of the excitation wavelength. The data cover the entire resonant regions of the Q- and B-bands. They were analyzed by use of a theory which describes intra- and intermolecular coupling in terms of a time-independent nonadiabatic perturbation theory [E. Unger, U. Bobinger, W. Dreybrodt, and R. Schweitzer-Stenner, J. Phys. Chem. 97, 9956 (1993)]. This approach explicitly accounts in a self-consistent way for multimode mixing with all Raman modes investigated. The vibronic coupling parameters obtained from this procedure were then used to successfully fit the vibronic side bands of the absorption spectrum and to calculate the resonance...

Electron transfer photosensitized by a tin lipoporphyrin in solution, micelles, and at water—organic solvent interfaces

Abstract Electron transfer photosensitized by a tin lipoporphyrin [Sn(IV) octakis((methoxycarbonyl-methyl)-meso-tetrakis-(((eicosanyloxy)carbonyl) phenyl)-porphyrin (SnLipoP)] is investigated under various solution conditions using a donor—SnLipoP—methylviologen (MV2+) ternary system, where the donor is triethanolamine (TEA) or ethylenediaminetetraacetic acid (EDTA). The photoreaction of SnLipoP is compared with the photoreactions sensitized by common Sn porphyrins like tin protoporphyrin IX (SnPP) and octaethylporphyrin (SnOEP). A constant photoreaction rate is observed in a water/organic solvent (hexane, benzene) two-phase system in which the porphyrin (SnLipoP, SnOEP) is in the organic solvent and MV2+ is in the aqueous phase. The rate is monitored by the change in the UV—visible absorption spectra produced by aqueous methylviologen radical MV·+. In contrast with the two-phase system, macroscopically homogeneous solutions (aqueous SnPP and micellar solutions of SnLipoP, SnPP and SnOEP) give pseudo-logarithmic rates. These electron-transfer processes are completely consistent with reductive primary electron transfer to the tin porphyrin and optical shielding effects. Differences in the rates for SnLipoP and the other Sn porphyrins are explained by structural differences in the porphyrins. In particular, the structure of the porphyrin influences the phase in which the porphyrin resides, its location relative to interfacial regions, and the way it interacts with itself and other system components.