Hydrogen peroxide assisted photorelease of an anthraquinone-based ligand from [Ru(2,2'-bipyridine)2(9,10-dioxo-9,10-dihydroanthracen-1-olate)]Cl in aqueous solution.

A new class of light-activated ruthenium(ii) complex was designed as a potential blocker of biological functioning, especially for targeting redox reactions within mitochondria under light activation. Based on our concepts the complex [Ru(bipy)2(1-hydroxyanthra-9,10 quinone)]Cl (RU1) was prepared and studied to understand the preliminary reaction mechanisms and its excited state behaviour through a series of stability tests, electrochemistry, UV-Visible kinetics and femtosecond transient absorption spectroscopy experiments. Under white light in the presence of H2O2 two different reactions (fast and slow) appear to take place. The complex loses the quinone-based ligand and a resulting Ru(iii) or Ru(v) species is produced. The complex RU1 shows potential to consume H2O2 from the one carbon metabolism in mitochondria, and hence may cut the energy cycle pathway of tumor cells.

Comparison of electron injection and recombination on TiO2 nanoparticles and ZnO nanorods photosensitized by phthalocyanine.

Titanium dioxide (TiO2) and zinc oxide (ZnO) semiconductors have similar band gap positions but TiO2 performs better as an anode material in dye-sensitized solar cell applications. We compared two electrodes made of TiO2 nanoparticles and ZnO nanorods sensitized by an aggregation-protected phthalocyanine derivative using ultrafast transient absorption spectroscopy. In agreement with previous studies, the primary electron injection is two times faster on TiO2, but contrary to the previous results the charge recombination is slower on ZnO. The latter could be due to morphology differences and the ability of the injected electrons to travel much further from the sensitizer cation in ZnO nanorods.

Effects of orientation at the phthalocyanine-CdSe interface on the electron transfer characteristics.

A phthalocyanine molecule adsorbed on the (101[combining macron]0) surface of wurtzite CdSe is theoretically modeled by the DFT method. We have found that a linker does not affect substantially the redox properties of phthalocyanine, while saturation of the macrocycle with peripheral substituent groups causes a downward shift in the energy position of its frontier orbitals that can hinder electron injection to the CdSe surface. Tilting of the phthalocyanine molecule relative to the surface also leads to the lowering of its molecular electronic levels relative to the bands of CdSe. At a tilting angle of 30°, the LUMO level of the dye appears to be lower than the conduction band minimum of cadmium selenide, which makes the electron transfer to its hybridized surface unfavorable. By contrast, the HOMO level of the phenylbutyric acid linker provides a suitable intermediate channel for the hole transfer from the valence band of CdSe to the phthalocyanine that points to the possible acceptor behavior of the phthalocyanine molecule in its hybrids with CdSe nanostructures.

Photoinduced hole transfer in QD-phthalocyanine hybrids.

A series of CdSe quantum dot (QD)-phthalocyanine (Pc) hybrids were synthesized and their photophysics was studied using steady state and time-resolved spectroscopic methods. Emission of QDs was progressively quenched upon increasing the concentration of Pc in the hybrids. A detailed transient absorption study of the hybrids revealed that the mechanism of quenching is charge separation, resulting in the formation of hybrids with negatively charged QDs and the Pc cation. Direct photo-excitation of Pc did not show any detectable interaction between the excited state of Pc and the QD to which it is attached. An explanation is proposed, based on the suggestion that the energy of the lowest unoccupied molecular orbital (LUMO) of Pc is lower than the lower edge of the QD conduction band, while the energy of the highest occupied molecular orbital (HOMO) of Pc is sufficiently higher than the high energy edge of the QD valence band (VB), thus permitting hole transfer from the QD VB to the Pc HOMO after photo-excitation of QDs.

Compact hematite buffer layer as a promoter of nanorod photoanode performances.

The effect of a thin α-Fe2O3 compact buffer layer (BL) on the photoelectrochemical performances of a bare α-Fe2O3 nanorods photoanode is investigated. The BL is prepared through a simple spray deposition onto a fluorine-doped tin oxide (FTO) conducting glass substrate before the growth of a α-Fe2O3 nanorods via a hydrothermal process. Insertion of the hematite BL between the FTO and the nanorods markedly enhances the generated photocurrent, by limiting undesired losses of photogenerated charges at the FTO||electrolyte interface. The proposed approach warrants a marked improvement of material performances, with no additional thermal treatment and no use/dispersion of rare or toxic species, in agreement with the principles of green chemistry.

Charge separation and charge recombination photophysical studies in a series of perylene-C60 linear and cyclic dyads.

A new donor­acceptor doubly bridged perylenediimide­fullerene dyad (PDI­C60, DB-3), where the perylenediimide (PDI) acts as a donor, has been synthesized and studied by time-resolved absorption spectroscopy. The DB-3 undergoes an electron transfer (ET) in both polar and non-polar media under photo-excitation. Structurally the DB-3 dyad resembles four other recently studied dyads (R. K. Dubey et al., Chem. Eur. J., 2013, 19, 6791­6806). Analysis of the ET reactions in this series of dyads was carried out in frame of both classic and semi-quantum ET theories. The result of the analysis for DB-3 suggests that the electronic coupling for the ET reaction is roughly 0.005 eV, internal reorganization energy is 0.16 eV, and outer sphere or solvent reorganization energy is 0.5 and 0.3 eV in benzonitrile and toluene, respectively.

Electronic energy harvesting multi BODIPY-zinc porphyrin dyads accommodating fullerene as photosynthetic composite of antenna-reaction center.

Efficient electronic energy transfer (EET) in the newly synthesized dyads comprised of zinc porphyrin covalently linked to one, two or four numbers of boron dipyrrin (BDP) entities is investigated. Both steady-state and time-resolved emission as well as transient absorption studies revealed occurrence of efficient singlet-singlet energy transfer from BDP to zinc porphyrin with the time scale ranging between 28 and 48 ps. A decrease in time constants for energy transfer with increasing the number of BDP units is observed revealing better antenna effect of dyads bearing higher number of boron dipyrrin entities. Further, supramolecular triads to mimic the 'antenna-reaction center' functionality of photosynthetic reaction center have been successfully constructed by coordinating fulleropyrrolidine appended with an imidazole ligand to the zinc porphyrin. The structural integrity of the supramolecular triads was arrived by optical, computational and electrochemical studies. Free energy calculations revealed possibility of photoinduced electron transfer from singlet excited zinc porphyrin to fullerene, and the preliminary transient absorption studies involving pump-probe technique are supportive of occurrence of electron transfer from (1)ZnP* to fullerene in the supramolecular triads.

[Optimization of directed training loads on the respiratory system].

Potentiality of an increased elastic resistance to respiratory movements in improving the functional conditioning of young athletes was evaluated. Training with increased elastic resistance to respiration brought about gains in strength and endurance of the respiratory muscles, growth of the maximal oxygen consumption, work ability, and special physical fitness of athletes.

Charge-transfer emission of compact porphyrin-fullerene dyad analyzed by Marcus theory of electron-transfer.

A porphyrin-fullerene dyad, which is characterized by a close proximity of the porphyrin donor and the fullerene acceptor, was found to undergo a photoinduced electron transfer both in solutions and in solid films. Near-infrared charge-transfer (CT) emission was observed and analyzed in frame of the semi-classical Marcus electron-transfer theory yielding values for the reaction free energy, -deltaG degrees = 1.75 eV, the internal reorganization energy, lambdav = 0.05 eV, and the donor-acceptor vibrational energy, hv(v) = 0.14 eV, both in solution and in solid film. The influence of the environment on the CT properties of the dyad is described by a single parameter, the outer-sphere reorganization energy, lambdas, which varies from 0.05 eV in non-polar solvents and films to 0.13 eV in solvents of moderate polarity. At low temperatures (T< 200 K), the CT emission consists of distinct bands shifted from each other by value hv(v). This is the first direct observation of the vibrational frequencies of a porphyrin-fullerene donor-acceptor system.

Kinetics of photo-active bacteriorhodopsin analog 3,4-didehydroretinal.

Kinetics of the photo-induced processes of the transient states of the 3,4-didehydroretinal (3,4-dhr) modified bacteriorhodopsin (bR) was studied by a flash photolysis method in a water suspension at room temperature. The excitation initiated a photocycle with several transient intermediates similar to the trans photocycle of native bR. The main observation of the study was that although major part (80%) of the population of the M state relaxed via the O intermediate as in natural bR, 20% relaxed directly to the bR ground state in 200 ms.

[Folic acid in the combined treatment of patients with disseminated sclerosis and chronic gastritis]. / Folievaia kislota v kompleksnom lechenii bol'nykh rasseiannym sklerozom s khronicheskim gastritom.

Folic acid was used for the complex treatment of patients with multiple sclerosis. The doses employed were 200-300 mcg daily. It was established that folic acid improved the reparative processes in the gastric mucosa and produced a pronounced therapeutic effect on the neurological status of the patients, favoured improvement of their general condition.