Nonlinear magneto-optical rotation via alignment-to-orientation conversion

Nonlinear magneto-optical rotation is investigated at high light powers where the rotation is significantly modified by ac Stark shifts. These shifts are shown to change the overall sign of rotation for closed F-->F+1 transitions compared to the low light power limit. The effect is demonstrated by measurements in rubidium and density matrix calculations. The results are important for applications of nonlinear optical rotation such as sensitive magnetometry.     

Supramolecular self-assembly of 5,10,15,20-tetrakis-(3-hydroxyphenyl)porphyrinatozinc with some transition metals and bidentate ligands

Coordination interactions between 5,10,15,20-tetrakis(3-hydroxyphenyl)porphyrinatozinc(II) and transition metal chlorides [La(III), Mn(II), Cr(III), Sn(II)], 1,4-diazabicyclo[2.2.2]octane, and 4,4′-bipyridine were studied. Self-assembly of supramolecular bis-porphyrin structures was developed.     

Gamma Irradiation Effects on Mechanical and Thermal Properties and Biodegradation of Poly(3-hydroxybutyrate) Based Films

Summary: Their biodegradable properties make polyhydroxyalkanoates (PHAs) ideal candidates for innovative applications. Many studies have been primarily oriented to poly(3-hydroxybutyrate) (PHB) and poly(3-hydroxybutyrate-co-3-valerate) (PHBV) and afterwards to blends of PHAs with synthetic biodegradable polymers, such as poly(ε-caprolactone) (PCL). Medical and pharmaceutical devices require sterilization and γ irradiation could provide a proper alternative since it assures storage stability and microbiological safety. This contribution presents the effect of γ irradiation on the mechanical and thermal properties and on the biodegradation of PHB, PHBV and a commercial PHB/PCL blend. Samples, prepared by compression moulding, were irradiated in air at a constant dose rate of 10 kGy/h, from 10 to 179 kGy. Polymer chain scission was assessed by changes in the molecular weight, thermal properties and tensile behaviour. The correlation between absorbed dose and changes in the mechanical properties and biodegradation is discussed in detail. The optimum dose to guarantee microbiological sterilization without damage of the structure or meaningful loss of the mechanical properties is also reported.     

Femtopicosecond relaxation of zinc porphyrinate trimer linked by the triazole bridge

The femtosecond dynamics of excitation relaxation of the zinc porphyrinate trimer was studied by the pumping—scanning method. The obtained results were examined using semi-empirical quantum chemical calculations. The dynamics of excitation relaxation shows that the application of similar systems as models for studying photosystems and development of artificial analogs of natural photosynthetic centers is promising. An explanation for the observed coherent dynamics of exciton bands was proposed.     

Nonradiative deactivation of the electronic excitation energy in cyanine dyes: influence of binding to DNA

The processes of nonradiative deactivation of electronic excitation energy in cyanine dyes determine their quantum yield. Because of that, the study of the influence of cyanines binding to DNA on these processes can provide information on the causes leading to the cyanines fluorescence intensity enhancement in the presence of DNA. In the presented paper, the activation energies of nonradiative degradation of electronic excitation, quantum yields and rate constants of nonradiative transitions of several cyanines in free state and in the presence of DNA were established and compared. The mechanisms of nonradiative deactivation of dye excitation energy were discussed.     

Calculation of the fine structure of the triplet state $$\tilde a^3 A_2 $$ of the ozone molecule by the method of multiconfiguration self-consistent field

The zero-field splitting of the \(\tilde a^3 A_2 \) state of the O₃ molecule is interpreted on the basis of ab initio quantum-chemical calculations. The spin—orbit coupling with the ground X¹A₁ state is shown to make the main contribution to the zero-field splitting of the \(\tilde a^3 A_2 \) term (the state of the ³σπ type). The calculated parameters D and E agree well with experiment.     

Interactions of cyanine dyes with nucleic acids. XXIV. Aggregation of monomethine cyanine dyes in presence of DNA and its manifestation in absorption and fluorescence spectra.

Absorption, fluorescence emission and excitation spectra of benzothiazole cyanine dyes--thiazole orange (TO) and 7-methyl-6-(3-methyl-2,3-dihydro-1,3-benzothiazol-2-ylidenmethyl) [1,3] dioxolo [4',5':4,5] benzo [d] [1,3] thiazolium methylmethosulfate (Cyan 13)--were investigated over a wide concentration range. The dyes form aggregates with a 'sandwich'-like structure in water solution. At low dye to DNA concentrations ratios, Cyan 13 and TO monomers appear to interact with the DNA. On increasing the dye to DNA concentrations ratio, free dye molecules aggregate with the DNA-bound ones. The spectra of the free dye aggregates and the aggregates formed on the DNA, are characterized by an anomalously large (more than 100 nm) Stokes shift. This suggests, that the pi-electron systems of the aggregates undergo substantial changes in excited state, compared to those of the monomers. The formation of aggregates consisting of the free and DNA-bound dye molecules can be explained using the half-intercalation model of the interaction of the cyanine dye monomers with the DNA.     

Thermal explosion of a reactive mixture under conditions of oscillating ambient temperature

The problem of the thermal explosion of a finite volume of a reactive material in a medium with harmonically oscillating temperature is solved in the classical formulation. A kind of resonance is shown to arise when the oscillation period is commensurate with the adiabatic induction period of thermal explosion at the mean ambient temperature. At both high and very low oscillation frequencies, the critical condition parameter and induction period are only slightly affected by ambient temperature oscillations. By contrast, at moderately low frequencies, even small-amplitude oscillations of ambient temperature can strongly influence the critical condition and, especially, induction period of thermal explosion.