[Interpretation of the resonance Raman spectrum of cytochrome P-450]. / Interpretatsiia spektrov rezonansnogo kombinatsionnogo rasseianiia tsitokhroma P-450.

Normal coordinate analysis has been carried out for the Fe(III) protoporphyrin IX dimethyl ester molecule and its vinyl deuterated analogs. All atoms of substituents were included explicitly in the calculations. On the basis of the calculation results the assignment of the resonance Raman active modes of cytochrome P-450 is given. Attention is mainly devoted to the assignment of vinyl and methyl propionate ester modes. It is shown that methyl propionate ester coordinates take part to a certain extent in the number of modes with frequencies below 1300 cm-1. The frequencies have been found which depend on the angle between the vinyl and macrocycle planes. In passing from perpendicular to in-plane conformation the theoretical frequencies of the delta (Cb C alpha C beta and delta (CCb C alpha) modes shift down by 70 and 220 cm-1 and the value of the last one is only about 110 cm-1.

[Interpretation of the resonance Raman spectra of hemoproteins]. / Interpretatsiia spektrov rezonansnogo kombinatsionnogo rasseianiia gemoproteinov.

The interpretation of the resonance Raman spectra of hemoproteins is given based on the normal coordinate analysis of model compounds (Cu octamethylporphin and Cu octaethylporphin). The correlation between the form of normal vibrations and the sensitivity of vibrational frequencies to the valence and spin state of the Fe atom is discussed.

[Effect of further complexing on the spectral-luminescent properties of Mg-porphyrins]. / Vliianie dopol'nitel'nogo kompleksoobrazovaniia na spektral'no-liuminestsentnye svoistva Mg-porfirinov.

It has been shown by investigations of polarization spectra and the dependence of the degree of fluorescence and phosphorescence polarization on emission wavelength that in non-polar solvents at 77 degrees K the molecules of Mg porphin and Mg tetraphenylporphin possess true symmetry D4h. When polar molecules (water, alcohols, pyridine) are present in the solution further complexing of the magnesium complexes with extra-ligands takes place and the polarization data indicate that D4h symmetry is absent which leads to splitting of the doubly degenerate states by 100-150 cm-1. It has been established that on further complexing the S1 and T1 levels are lowered by approximately 500 and 700 cm-1, respectively, the probability of intercombinational degradation T1 leads to S0 increases in this case. It follows from the data obtained that the extra-ligands do not essentially influence spin-orbit interaction.

[Effect of molecular structures on the probabilities of radiating and non-radiating transitions in molecules derived from chlorophyll]. / Vliianie molekuliarnoi struktury na veroiatnosti izluchatel'nykh i bezyzluchatel'nykh perekhodov v molekulakh proizvodnykh khlorofilla.

The values of luminescence quantum yield and duration have been measured for rhodoporphyrin XV, deoxophyllerythrin, phyllerythrin, etiochlorin, chlorin e6 and their zinc complexes as well as for bacteriochlorin and isobacteriochlorin. The effect of the structural elements, which are characteristic of the chlorophyll molecule, on the probabilities (rate constants) of primary photophysical processes has been traced. It has been shwon, in particular, that all these elements enhance the radiationless de-excitation of the lowest triplet state.

[Quenching of triplet states by Fe(II)- and Fe(III)-porphyrins]. / Tushenie tripletnykh sostoianii Fe(II)- i Fe(III)-porfirinami.

The quenching of triplet states of metalloporphyrin molecules differing in the position of the lowest triplet state (from 9.000 to 15.000 cm-1) by ion complexes of octaethylporphin (OEP) has been investigated. High-spin ferric complex FeCl-OEP in dimethylformamide, toluene and ethanol, low-spin ferric complex FeCl(imidazole)2-OEP in toluene and diamagnetic ferrous complex Fe(piperidine)2-OEP in pyridine-piperidine (25:1) were used as quenchers. It has been found that all iron complexes investigated are effective quenchers of triplet states. The values of bimolecular quenching constants fall within the limits of (1 divided by 4) X 10(9) M-1 sec-1. Energy transfer to low-lying excited levels of iron porphyrins which are due to the presence of 3d electrons of ferric (ferrous) ion has been shown to play an essential role in the quenching process.

[Phosphorescence of octaethylchlorine, isobacteriooctaethylchlorine and their metal complexes]. / Fosforestsentsiia oktaétilkhlorina, izobakteriooktaétilkhlorina i ikh metallokompleksov

The phosphorescence of dihydrooctaethylporphin (octaethylchlorin or OEC), of its complexes with magnesium, zinc, copper and palladium, and of zinc and palladium complexes of isobacteriooctaethylchlorin (5,6,7,8-tetrahydrooctaethylporphin with adjacent hydrogenated pyrrole rings or THOEP-ADJ) has been investigated. The phosphorescence spectra and phosphorescence excitation spectra as well as the ratio of fluorescence and phosphorescence yields and the triplet state lifetume have been measured. It has been shown that the singlet-triplet interval is about 4100 cm-1 for OEC complexes and about 4300 cm-1 for THOEP-ADJ complexes, and depends wealky on the nature of the metal atom forming the complex. The triplet level position of chlorophyll alpha is discussed. It is concluded that the maximum of chlorophyll alpha phosphorescence spectrum must be located at 895 nm.