Effect of replacing the primary quinone by different species on the ultrafast photosynthetic electron transfer in bacterial reaction centres

Using picosecond absorption spectroscopy it has been shown that in Rhodobacter sphaeroides reaction centres the substitution of the primary quinone acceptor (QA), ubiquinone-10, by other quinone species (with redox potentials higher or lower than that of ubiquinone-10) has essentially no modifying effect on the reaction centre protein. The molecular relaxation processes that accompany the localization and stabilization of a photo-excited electron on the intermediate acceptor, bacteriopheophytin (I), are not affected, although the subsequent transfer of the electron from I to QA is slowed down. Consequently, this leads to a lower quantum efficiency of high rate of direct I-----QA reaction is normally due to the specificity of the primary quinone species and its binding site in the reaction centre protein which provide optimum steric and chemical conditions for an effective interaction between I and QA.     

Photophysical properties of carborane-containing derivatives of 5,10,15,20-tetra(p-aminophenyl)porphyrin

Absorption, fluorescence emission, fluorescence excitation spectra and fluorescence decay kinetics of carborane derivatives of 5,10,15,20-tetra(p-aminophenyl)porphyrin have been investigated. Carborane derivatives are prepared by acylation of the amino groups of 5,10,15,20-tetra(p-aminophenyl)porphyrin by 9-carboranyl acetyl chloride. From the analysis of the absorption and fluorescence spectra, it is concluded that covalent linking of carborane molecules to the tetraphenylporphyrin molecule significantly changes the self-conjugated pi-system of the porphyrin macrocycle: positions of maxima of absorption and fluorescence spectra shift to the red region by 3-8 nm; the halfwidths of these bands are broadened by 2.5-5.0 nm; the relative intensity of the bands I-IV also changes. The fluorescence decay kinetics of the carborane derivatives are biexponential. According to the experimental data and model simulation, it is concluded that the intramolecular electron transfer proceeds from the porphyrin excited part of the molecule to carboranyls with a rate constant of 415 ps(-1) and efficiency of 0.16-0.8. Recombination of separated charges occurs within 1.4 ns.     

Analysis of fluorescence kinetics upon intense picosecond laser pumping: Excitation dynamics in photosynthesizing systems

A new method for the fluorescence kinetics analysis is presented in this work. It permits one to obtain new information, both quantitative and qualitative, about the processes in any condensed molecular system. As an example, this method was applied to the light-harvesting antenna of photosynthesizing organisms. The time dependence of the bimolecular quenching rate of excitons, γ, was found. The experimental value of γ is obtained without any preliminary theoretical considerations. The character of γ-time dependence permits one to find the values of the coefficient of the diffusion D = 4 × 10^-3cm²s^-1 and Förster annihilation radius $\text{R}{}_0\text{= 100}\text{A}\text{?}$, within the limits of the diffusive model.     

A variable temperature EPR study of Mn-doped NH4Cl0.9I0.1 single crystal at 170 GHz: Zero-field splitting parameter and its absolute sign

EPR measurements have been carried out on a single crystal of Mn(2+)-doped NH(4)Cl(0.9)I(0.1) at 170-GHz in the temperature range of 312-4.2K. The spectra have been analyzed (i) to estimate the spin-Hamiltonian parameters; (ii) to study the temperature variation of the zero-field splitting (ZFS) parameter; (iii) to confirm the negative absolute sign of the ZFS parameter unequivocally from the temperature-dependent relative intensities of hyperfine sextets at temperatures below 10K; and (iv) to detect the occurrence of a structural phase transition at 4.35K from the change in the structure of the EPR lines with temperature below 10K.     

Excitation energy transfer in covalently bonded porphyrin heterodimers

We describe the photophysical properties of heterodimers that are formed by the free base 2-(2-carboxyvinyl)-5,10,15,20-tetraphenylporphyrin and the zinc complex of 5-(p-aminophenyl)-10,15,20-triphenylporphyrin and that are covalently bonded by the amide link. These dimers differ in the configuration of the double bond in the spacer group. We determine fluorescence quantum yields of heterodimers and their porphyrin components. The energy transfer rate constants have been estimated from the measured fluorescence lifetimes and fluorescence excitation spectra and, also, they have been calculated from the steady-state absorption and fluorescence spectra according to the Förster theory. We have found that the efficiency of the intramolecular energy transfer in heterodimers is 0.97–0.99, and the energy migration rate constants have been found to be (1.82–4.49) × 10¹⁰ s^?1. The results of our investigation show that synthesized heterodimers can be used as efficient light-harvesting elements in solar energy conversion devices.     

Bidirectional electron transfer in photosystem I: direct evidence from high-frequency time-resolved EPR spectroscopy

Efficient charge separation occurring within membrane-bound reaction center proteins is the most important step of photosynthetic solar energy conversion. All reaction centers are classified into two types, I and II. X-ray crystal structures reveal that both types bind two symmetric membrane-spanning branches of potential electron-transfer cofactors. Determination of the functional roles of these pairs of branches is of fundamental importance. While it is established that in type II reaction centers only one branch functions in electron transfer, we present the first direct spectroscopic evidence that both cofactor branches are active in the type I reaction center, photosystem I.     

LASER SPECTROSCOPY OF MODEL PHOTOSYNTHETIC SYSTEMS

Abstract— The goal of the present work was to create and investigate a model system, using a dye imbedded into polymer structure, and to examine characteristics which would provide low heat dissipation and excitation diffusion characteristics approaching those seen in the "antenna" of the photosynthetic apparatus. Zinc tetraphenoxyphtalocyanine served as a dye, and different types of polyvinyl pyridine polymers and polystyrene were used as polymer matricies. Measurements of the absorption, fluorescence and Raman spectra of the polymeric films with dye molecules show that along with Van der Waals interactions of the dye molecules with the side aromatic groups of the polymer there is a coordination interaction between the metal atoms of Zinc phtalocyanine and the nitrogen atoms of the pyridine group of the polymer. A model system shows low heat losses of excitation energy, when the dye concentration does not exceed 10^-2 M (mean distances between molecules of about 34 Å). Electronic excitation diffusion characteristics appeared to be close to those of the light harvesting antenna of the photosynthetic apparatus, indicating high efficiency of the energy migration in it.     

Influence of disorder on superconductivity in non-magnetic rare-earth nickel borocarbides

The effect of substitutional disorder on the superconducting properties of YNi₂B₂C was studied by partially replacing yttrium and nickel by Lu and Pt, respectively. For the two series of (Y, Lu)Ni₂B₂C and Y(Ni, Pt)₂B₂C compounds, the upper critical field H _c2(T) and the specific heat c _p(T, H) in the superconducting mixed state have been investigated. Disorder is found to reduce several relevant quantities such as T _c, the upper critical field H _c2(0) at T=0 and a characteristic positive curvature of H _c2(T) observed for these compounds near T _c. The H _c2(T) data point to the clean limit for (Y, Lu) substitutions and to a transition to the quasi-dirty limit for (Ni, Pt) substitutions. The electronic specific heat contribution γ(H) exhibits significant deviations from the usual linear γ(H) law. These deviations reduce with growing substitutional disorder but remain even in the quasidirty limit which is reached in the Y(Ni_1−x , Pt _x )₂B₂C samples for x=0.1.     

Photosystem 2 effective fluorescence cross-section of cyanobacterium Synechocystis sp. PCC6803 and its mutants

The effective fluorescence cross-section of photosystem 2 (PS2) was defined by measurements of chlorophyll a fluorescence induction curves for the wild type of the unicellular cyanobacterium Synechocystis sp. PCC6803, C-phycocyanin deficient mutant (CK), and mutant that totally lacks phycobilisomes (PAL). It was shown that mutations lead to a strong decrease of the PS2 effective fluorescence cross-section. For instance, the effective fluorescence cross-section of PS2 for wild type, CK and PAL mutants excited at λ(ex)=655 nm were found to be 896, 220 and 83 ?(2) respectively. Here we present an estimation of energy transfer efficiency from phycobilisomes to the pigment-protein complexes of PS2. It was shown that the PS2 fluorescence enhancement coefficient reaches a maximum value of 10.7 due to the energy migration from phycobilisomes. The rate constant of energy migration was found to be equal to 1.04 × 10(10) s(-1).