ON THE MECHANISM OF PHOTOSENSITIZING ACTION OF CHLOROPHYLL

Abstract— The paper presents ideas according to which the primary photochemical reaction of chlorophyll and its analogs can be either photooxidation or photoreduction of the pigment sensitizer depending on the reaction conditions. The factors determining the course of the process of photosensitization comprise the nature and state of the pigment and participating reagents, the nature and reaction of the medium, concentration of the oxidant and reductant, their ability to form complexes with the pigment, etc.
The paper presents the results of simple kinetic investigations in which, by means of changing pH of the medium, conditions were created favouring either the primary photo-oxidation or the primary photoreduction of the pigment-sensitizer. These results, as well as the data of experiments on the changes in reagents' concentration show the reality of the above mentioned concepts.
Considerations are presented on the possibility of photochemical interaction of two chlorophyll molecules in vivo during the photosensitization of photosynthesis.     

Electrical properties (dc and ac) of vanadium-borate glass

The results of an investigation into the temperature and frequency dependence of the electrical conductivity [dc and ac (10²–10⁵ Hz)] of glass of the composition 35% B₂O₃-15% CaO-20% V₂O₄-30% V₂O₅ (weight %) are discussed. The resistivity of the glass at T=300°K is =1.2·10¹¹ ·cm. The activation energy of the dc conductivity is E=(0.652±0.004) eV and equal to E for ₂ at high temperatures. The temperature-frequency dependences of the polarization component _p, the dielectric loss coefficient, and the permittivity are explained on the basis of the Fröhlich model proposed for uncoupled relaxation oscillators for which the heights of the potential barriers are uniformly distributed in some range of energies.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika. No. 3, pp. 35–38, March, 1981.     

1H NMR Analysis of Heteroassociation of Caffeine with Mitoxanthrone in Aqueous Solution

Heteroassociation of caffeine (CAF) with the antibiotic mitoxanthrone (novatrone, NOV) in aqueous solution was studied by one-dimensional (1D) and two-dimensional (2D) ¹H NMR spectroscopy (500 MHz). The concentration and temperature dependences of the proton chemical shifts of the molecules in aqueous solution have been measured. The equilibrium constants of heteroassociation between CAF and NOV and the limiting proton chemical shifts of the aromatic ligands of the associates have been determined. The most plausible structure of the 1:1 CAF–NOV heterocomplex in aqueous solution was inferred from the calculated values of the induced proton chemical shifts and quantum-mechanical screening curves for CAF and NOV. The thermodynamic parameters of the formation of the CAF–NOV heterocomplex have been calculated. The relatively high heteroassociation constant (K = 256 ± 31 M^–1, T = 318 K), the positive value of entropy for heteroassociation [ S = 15.3 ± 4.0 J/(moleK)], and the structural features of the chromophore of the novatrone molecule indicate that hydrophobic interactions play a significant role in stabilization of the CAF–NOV heterocomplex.     

An investigation of the change in the electrical conductivity during photochemical reactions in solutions of safranine T

The reduction of electrical conductivity on illumination has been investigated in greater detail for a pyridine solution of safranine, and has also been observed for some dyestuffs of similar structure. It is suggested that the cause of the conductivity reduction is due to a diminution of the mobility of the cation of the dyestuff due to complex-formation between this and the molecules of the reducing agent due to the phototransfer of an electron. It has been shown experimentally that change in conditions may lead to a change in the sign of the effect, giving an increase in conductivity on illumination, which may be explained by the capacity of the molecule to undergo transition from reduction to oxidation under the changed conditions.     

Stochastic nonlinear Perron–Frobenius theorem

We establish a stochastic nonlinear analogue of the Perron–Frobenius theorem on eigenvalues and eigenvectors of positive matrices. The result is formulated in terms of an automorphism T of a probability space and a random transformation D of the non-negative cone of an n-dimensional Euclidean space. Under assumptions of monotonicity and homogeneity of D, we prove the existence of scalar and vector measurable functions α > 0 and x > 0 satisfying the equation αTx = D(x) almost surely. We apply the result obtained to the analysis of a class of random dynamical systems arising in mathematical economics and finance (von Neumann–Gale dynamical systems).     

Specific features of lignin dissolution in aqueous and aqueous-organic media

The solubility of lignin in aqueous NaOH solutions and dioxane-water mixtures was studied. Factors governing the solubility of lignin in these media were determined.     

Aggregation of 1,3,7-trimethylxanthine with methylene blue in aqueous solution

We have studied self-association of aromatic molecules of the thiazine dye methylene blue in aqueous solution, using a dimer model. We have determined the dimerization equilibrium constant for the dye molecules K_D = 3900 ± 800 M⁻¹ at T = 293 K. We have decomposed the experimental spectrum into dimer and monomer components. Using the ratio of the molar absorption coefficients for two absorption bands of the dimer spectrum, we obtained the “average” value of the angle between the electronic transition moments of the molecules in the dimers, α = 48°. We have studied heteroassociation of methylene blue (MB) and 1,3,7-trimethylxanthine (caffeine) molecules in aqueous solution. We have calculated the heteroassociation constant as 200 ± 34 M⁻¹. We conclude that heteroassociation of methylene blue and caffeine molecules leads to a lower effective dye concentration in solution, which hypothetically may affect its biological activity. We have determined the values of the Gibbs free energy, the enthalpy, and the entropy for dimerization of methylene blue molecules: ΔG₂₉₃ = −(20 ± 3) kJ/mol, ΔH = −(25 ± 9) kJ/mol, Δ S₂₉₃ = −(17 ± 6) J/mol·K; and for methylene blue-caffeine heteroassociation: ΔG₂₉₃ = −(13 ± 3) kJ/mol, ΔH = −(14 ± 10) kJ/mol, ΔS₂₉₃ = −(2.4 ± 0.2) J/mol·K, respectively. We have shown that the methylene blue aggregates and the heteroassociates with caffeine are predominantly stabilized by dispersion interactions between the chromophore molecules in the associates. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 158–163, March–April, 2006.     

Structural and thermodynamic analysis of heteroassociation of daunomycin and flavin mononucleotide molecules in water by <Superscript>1</Superscript>H NMR spectroscopy

Heteroassociation of the antitumor antibiotic daunomycin (DAU) with flavin mononucleotide (FMN) has been investigated by one-and two-dimensional ¹H NMR spectroscopy (500 MHz) in a water solution to determine the molecular mechanism of the combined action of the antibiotic and vitamin in the FMN-DAU system. The equilibrium constants of the reactions, induced proton chemical shifts, and thermodynamic parameters (ΔH, ΔS) of heteroassociation were determined from the concentration and temperature dependences of the proton chemical shifts in the interacting aromatic molecules. Analysis of the results indicate that heterocomplexes of riboflavin mononucleotide and daunomycin are formed due to stacking interactions between aromatic chromophores. The most probable spatial structure of the 1:1 DAU-FMN heterocomplex was determined by the molecular dynamics method using the X-PLOR program and the results of the analysis of the induced proton chemical shifts in molecules. Calculation of the relative content of self-and hetero-complexes of daunomycin for different values of the ratio (r) between the concentrations of flavin mononucleotide and daunomycin demonstrated that for r > 3, the contribution of DAU-FMN heterocomplexes to the equilibrium distribution of associates in aqueous solution is dominant. It is concluded that the aromatic molecules of vitamins, in particular, riboflavin, can form energetically strong heteroassociates with antitumor antibiotics in water solution and can thereby affect their medical and biological activity.