Yu. P. Tsentalovich

Cross-relaxation in nuclear polarization. A flash-CIDNP study

Abstract CIDNP with microsecond time resolution was used to study the kinetics of nuclear polarization formation during the photolysis of acetone in isopropanol over a wide temperature range. The coincidence of signs of multiplet effects of CIDNP (A/E) for cage and escape reaction products as well as the presence of net polarization (E) changing its sign with decreasing temperature have been revealed. The account of scalar electron-nuclear cross-relaxation has been shown to be necessary for the interpretation of the results obtained.

Pyrene fluorescence quenching by aromatic azides

Pyrene fluorescence quenching by phenylazide derivatives with donor and acceptor substituents has been studied by fluorescence spectroscopy and flash photolysis. The rate constants of quenching (kq) in acetonitrile ((0.2–1.2) × 1010 l mol−1 s−1) are found to be close to a diffusion limit; the rate constants were somewhat higher for perfluoro-substituted arylazides. It is found that kq does not depend on solvent polarity; the formation of the pyrene cation in the course of pyrene fluorescence quenching by tolylazide was not detected. Pyrene fluorescence quenching occurred by an energy-transfer mechanism; this is supported by the coincidence of the quantum yields of the direct and sensitized photodecomposition of tolylazide. As estimated, energy transfer in rigid media occurs at characteristic distances of about 10 Å.

CROSS-RELAXATION MECHANISM FOR THE FORMATION OF NUCLEAR POLARIZATION : A QUANTITATIVE TIME-RESOLVED CIDNP STUDY

Abstract The kinetics of the nuclear polarization formed during the photolysis of acetone in isopropanol- d 8 were analyzed quantitatively. Model calculations show that the spin-selective recombination of radicals gives rise to the electron polarization and, with regard to the electron-nuclear cross-relaxation, are adequate to describe the formation of the net nuclear polarization of the reaction products even if the solution contains only one type of radical. For the 2-hydroxy-2-propyl radicals at a magnetic field of 7 T, fitting the theoretical results to the experimental data gives the electron relaxation time T 1 e = 1.0 ± 0.2 μ s and the cross-relaxation time T x = 92 ± 18 μ s.

Laser flash photolysis of fluorinated aryl azides in neutral and acidic solutions

Laser flash photolysis of perfluoro-4-biphenyl azide andN-propyl-4-azido-2,3,5,6-tetrafluorobenzylamide in acetonitrile, water-acetonitrile mixtures, and HCl-containing solutions was studied. The absorption spectra of primary intermediates, singlet arylnitrenes(2a(S) and2b(S), respectively), were recorded. The absolute rate constants of their intersystem crossing in MeCN were measured, and the corresponding Arrhenius parameters were found from the temperature dependences of the rate constants of isomerization of singlet arylnitrenes2a(S) and2b(S) to azirines. Protonation of singlet arylnitrenes2a(S) and2b(S) was observed, the rate constants of their protonation were measured, and the transient absorption spectra of arylnitrenium ions were recorded. It was shown by quantum-chemical calculations (the hybrid B3LYP method) that the arylnitrenium ions that formed have the singlet ground state and the singlet-triplet gap is ∼20 kcal mol−1.

Influence of medium viscosity on photophysical properties of kynurenic acid and kynurenine yellow

Dependences of the fluorescence and triplet state quantum yields of kynurenic acid (1) and kynurenine yellow (2) in water—glycerol mixtures on medium viscosity have been studied. The main channel of the singlet excited state decay of compound 1 is the intersystem crossing, which rate weakly depends on the viscosity; only a small (approximately 1.5-fold) increase in the fluorescence yield was found for this compound with the increase of the solution viscosity from 0.84 cP (aqueous solution) to 78 cP (86% glycerol). The deactivation of the S1 state of compound 2 is caused mainly by the internal conversion, and a noticeable increase of the fluorescence yield (approximately 3-fold), as well as the change in the photolysis product yields, was observed with the increasing percentage of glycerol in the mixture. The triplet state quantum yields for compounds 1 and 2 remained unchanged with the variation of the glycerol content in the mixture.

A Laser Flash-Photolysis Study of the Bimolecular Reactions of Singlet Fluorinated Arylnitrenes

The kinetics and mechanisms of the reactions of singlet perfluoro-4-biphenylnitrene and N-propyl-4-nitreno-2,3,5,6-tetrafluorobenzylamide with various amines, pyridine, and dimethylsulfoxide were studied by laser flash photolysis. The reactions of singlet arylnitrenes with amines are two-step processes. The primary step of the process is adduct formation; the rate constant of this reaction is high and lies within the range 4 × 107–2 × 108l mol–1s–1for the tested secondary amines. The second step (1,2-hydrogen shift) was accelerated in the presence of water.

Application of microbial alkaloid prodigiosin as a potent matrix for the MALDI mass spectrometry analysis of low-molecular-weight plant antioxidants

Microbial alkaloid prodigiosin is proposed as a new effective matrix for the analysis of low-molecular- weight plant antioxidants by MALDI mass spectrometry in the negative ion detection mode. It is demonstrated that the physicochemical characteristics of prodigiosin, such as ability to activate ionization/ desorption of analyte, high absorption coefficient at the working wavelengths of lasers, good solubility in solvents used for analytes, uniformity of crystallization on the target, stability under working conditions, and the absence of interfering peaks of fragment and cluster ions, are consistent with the recommendations for effective matrices. Prodigiosin as a matrix ensures the high-resolution detection of various plant antioxidants in complex mixtures. The obtained mass spectra of flavonoid aglycones were characterized by high quality (signal-to-noise ratio higher than 103) and reproducibility. The use of prodigiosin for analyzing a complex preparation of plant antioxidants ensures the simultaneous recording and interpretation of more than two dozens of ions corresponding to various antioxidants with the molecular weights of 100–500 Da.

Effect of the excitation wavelength and the structure of nitrated 1,2-dyhydroquinolines on dynamics of primary photophysical and photochemical processes

Dynamics of transformations of excited states and active transient species generated in the photolysis of nitrated 1,2-dihydroquinolines (N-DHQ) has been studied by femto- and nanosecond laser pulse photolysis. Spectral and kinetic parameters of primary photophysical and photochemical processes have been determined, and their dependence on the substituent position at the aromatic ring of 1,2-dihydroquinoline (DHQ) and on the wavelength of excitation light has been established. The lifetime of the excited singlet state S1 in N-DHQ is ca. 100 and 500 fs for 8- and 6-nitro-substituted DHQ, respectively, which is shorter in comparison with DHQ without the nitro group by a factor of 104 and more. The major decay channel of the S1 state is the successive formation of three transient species with lifetimes of 0.5 to 16 ps. A triplet state is generated only upon excitation of the short-wavelength band by UV light. The quantum yield of the triplet state depends on the structure of N-DHQ.

Effect of medium on the rate constant of decarbonylation of phenylacetyl radical

The rate constant kCO of decarbonylation of phenylacetyl radicals generated by photolysis of dibenzyl ketone was measured by laser flash photolysis technique in six solvents in a wide temperature range. The pre-exponential factors A and activation energies Ea of decarbonylation were found for all solvents. The kCO value decreases with an increase in the dielectric constant ε of the solvent, whereas an increase in the ability of the solvent for hydrogen bonding increases kCO. The results of quantum-chemical calculations confirm the mutual compensation of the contributions of specific and nonspecific solvations to the activation energy of decarbonylation in alcohols.