Photogeneration and quenching of reactive oxygen species by urocanic acid

Urocanic acid, UCA, is characterized by two electronic transitions in the UV-B (280-320 nm) which comprise its broad absorption spectrum and give rise to wavelength-dependent isomerization quantum yields. The absorption spectrum of UCA extends into the UV-A (320-400 nm). Given the UV-A component of sunlight is significantly greater than the UV-B component it is hypothesized even weak UV-A photochemistry of UCA could be important for in vivo responses to UV radiation. Degenerate pump-probe experiments performed on t-UCA at several wavelengths in the UV-A reveal an excited-state absorption that undergoes a rapid, approximately 1 ps decay. Photoacoustic experiments performed on both the cis and trans isomers reveal the formation of a long-lived intermediate following UV-A excitation. The efficiency and action spectra for this latter photoactive process are presented and are similar for both isomers of UCA. Cholesterol hydroperoxide assays designed to investigate the nature of the UV-A photoreactivity of t-UCA confirm the production of reactive oxygen species. The bimolecular rate constant for the quenching of singlet oxygen by t-UCA is determined to be 3.5 x 10(6) M(-1) s(-1). Taking into consideration recent theoretical calculations and jet expansion studies of the electronic structure of gas-phase t-UCA, a model is proposed to explain the isomerization and photoreactivity of t-UCA in solution over the UV-A region.     

Coherent effects in energy transport in model dendritic structures investigated by ultrafast fluorescence anisotropy spectroscopy

Measurements of ultrafast fluorescence anisotropy decay in model branched dendritic molecules of different symmetry are reported. These molecules contain the fundamental branching center units of larger dendrimer macromolecules with either three (C(3))- or four (T(d), tetrahedral)-fold symmetry. The anisotropy for a tetrahedral system is found to decay on a subpicosecond time scale (880 fs). This decay can be qualitatively explained by F?rster-type incoherent energy migration between chromophores. Alternatively, for a nitrogen-centered trimer system, the fluorescence anisotropy decay time (35 fs) is found to be much shorter than that of the tetramers, and the decay cannot be attributed to an incoherent hopping mechanism. In this case, a coherent interchromophore energy transport mechanism should be considered. The mechanism of the ultrafast energy migration process in the branched systems is interpreted by use of a phenomenological quantum mechanical model, which examines the two extreme cases of incoherent and coherent interactions.     

The polymorphic transformations of cobalt molybdate

Polymorphic transformations of CoMoO₄ were studied by means of high temperature X-ray measurements within the temperature range 25–1200°C. On heating phase a obtained from low temperature modification b a new modification a′ was discovered. Phase a obtained by thermal decomposition of solvated α-CoMoO₄ shows different behaviour. At 700–930°C depending on the conditions of preparation it transforms irreversibly into still another modification a″. On cooling, a mixture of phases a + a″ is obtained, the presence of a″ being responsible for the explosionwise transition into b, observed around the room temperature.     

Prediction of adsorption of organic component and water vapour mixture onto activated carbon

A simple isotherm equation is derived for the adsorption of an organic component onto activated carbon in presence of water vapour. The theoretical results are compared with experimental data for toluene-water vapour-activated carbon, which were published byRipperger andGermerdonk [10].

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Vorhersage der Adsorption einer organischen Komponente und Wasserdampf an Aktivkohle

Zusammenfassung Es wird eine einfache Adsorptionsisotherme abgeleitet, welche die gleichzeitige Adsorption eines organischen Stoffes und Wasser an Aktivkohle beschreibt. Die theoretischen Ergebnisse werden mit experimentellen Resultaten vonRipperger undGermerdonk [10] für Toluol-Wasser-Aktivkohle verglichen.

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Symbols a _i adsorbate concentration in adsorbent, kg/kg of carbon - a _0i monolayer capacity, kg/kg of carbon - b _i kinetic parameter of theLangmuir equation - E _j adsorption energy in thej-th layer - i i-th component (1 — water vapour, 2 — organic compound) - j j-th layer - m number of layers - n number of adsorbed components - p partial pressure, Pa - p* saturation partial pressure, Pa - p _C water vapour partial pressure at begining of capillary condensation, Pa - surface coverage     

The convenient route to cd fragment for the synthesis of vitamin D3 relatives

The efficient degradation of $\text{1}$ to the α-methylene ketone $\text{4}$ is described. Compound $\text{4}$ was then converted to the allylic alcohol $\text{8a}$ - the precursor of vitamin D³ relatives.     

Phase equilibria in the ternary system PbO−P2O5−PbCl2

Journal of Thermal Analysis and Calorimetry - In the ternary system PbO?P2O5?PbCl2, the partial ternary system Pb5Cl2O4?Pb3Cl2O2?Pb10(PO4)6Cl2 was examined by thermal,...     

Über eine neue automatische Apparatur zur Zentigramm-Bestimmung von Kohlenstoff und Wasserstoff in organischen Substanzen

Zusammenfassung Das vom Verfasser undE. Sucharda schon 1928 angewandte Prinzip, die durch das Verhalten der Substanz beim Erhitzen bewirkten Druckschwankungen im Verbrennungsrohre zum Zwecke der automatischen Regulierung der Vergasungsgeschwindigkeit der Substanz bei der Elementaranalyse auszunutzen, wurde bei der Konstruktion einer neuen, elektrisch betriebenen, automatischen Apparatur angewandt. Hierbei wird das mit der Substanz gefüllte Mikroschiffchen mittels eines elektrischen Hochfrequenzgenerators erhitzt. Der Stromzufluß zu dem Hochfrequenzgenerator wird durch die erwähnten Druckschwankungen einoder ausgeschaltet. Die Verbrennung verläuft dann bei praktisch konstantem Druck im Verbrennungsrohre, also auch bei konstantem Sauerstoffüberschuß. Die neue Apparatur wird an Hand beigefügter Abbildungen beschrieben. Als Absorptionsmittel für Stickstoffoxyde werden 1 bis 2 g Bleidioxyd in einem 12 cm langen Porzellanschiffchen bei 190° angewandt. Die Absorption des Wassers erfolgt durch wasserfreies Kobaltchlorid, die der Kohlensäure ausschließlich durch Ascarit. Die Sauerstoffgeschwindigkeit im Verbrennungsrohre beträgt 8 ml pro Minute. Bei Substanzen, die mehr als 10% N enthalten, wird zwischen den Kohlensäureabsorptionsapparat und den Wasserabsorptionsapparat ein mit Mangandioxyd gefüllter Apparat eingeschaltet.

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Summary The principle used by the author andE. Sucharda as early as 1928, which employs the variations in pressure in the combustion tube resulting from the behavior of the substance when heated, for automatically regulating the rate of gasifying the substance was applied in the construction of a new electrically operated automatic apparatus. The micro boat charged with the sample is heated by means of a high frequency generator. The flow of current to the high frequency generator is switched on and off by the variations in pressure mentioned above. The combustion then proceeds at practically constant pressure in the combustion tube, and even when there is a constant excess of oxygen. The new apparatus is described in the accompanying figures. The nitrogen oxides are absorbed in 1 to 2 grams of lead dioxide contained in a porcelain boat (12 cm long) at 190°. The absorption of the water is by means of anhydrous cobalt chloride, while the carbon dioxide is taken up in ascarite. The speed of the oxygen in the combustion tube is 8 ml per minute. In the case of samples that contain more than 10% nitrogen, an apparatus filled with manganese dioxide is placed between the carbon dioxide absorber and the apparatus for taking up the water.

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Résumé Le principe de l'utilisation des variations de pression qui se produisent dans un tube à combustion en analyse élémentaire, lors du chauffage de la substance, a été utilisé dès 1928 par l'auteur etE. Sucharda pour la régulation automatique de la gazéification de cette substance. Il a été appliqué à la construction d'un nouvel appareil automatique commandé électriquement. La micronacelle qui contient la substance est chauffée électriquement à l'aide d'un générateur de courant de haute fréquence. Les variations de pression pendant la combustion provoquent l'ouverture ou la fermeture du circuit d'alimentation de ce générateur. Il en résulte que la combustion est effectuée à pression pratiquement constante ainsi qu'à excès d'oxygène constant. Ce nouvel appareil est décrit sur les figures de la publication.On utilise 1 à 2 grammes de bioxyde de plomb disposés dans une nacelle de porcelaine de 12 cm de longueur, portée à 190° pour absorber les oxydes de l'azote. L'eau est absorbée par du chlorure de cobalt anhydre et l'anhydride carbonique exclusivement par de l'ascarite. Le débit du courant d'oxygène dans le tube de combustion est de 8 ml par minute. Pour les substances contenant plus de 10% d'azote, on intercale un absorbeur à bioxyde de manganèse entre l'absorbeur à anhydride carbonique et l'absorbeur à eau.

     

A novel synthesis of racemic and enantiomeric forms of prostaglandin B1 methyl ester

3-(Dimethoxyphosphorylmethyl)cyclopent-2-enone was converted into (+/-)-prostaglandin B1 methyl ester in two steps involving regioselective alkylation at C(2) with methyl 7-iodoheptanoate and subsequent Horner-Wittig reaction with dimer of 2-hydroxyheptanal (42% overall yield). The use of (R)- and (S)-2-(tert-butyldimethylsilyloxy)heptanal for the Horner olefination reaction gave, after deprotection of the hydroxy group, the enantiopure forms of the title compound in 28% overall yield.     

Numerical method of non-isothermal curve analysis by means of electrical resistance measurement during cooling

The temperature-dependence of the electrical resistance of Al-Zn 78 wt.% was measured during linear cooling of the samples in the range of eutectoidal decomposition. The resulting resistancevs. temperature curves were analysed by:

deriving the temperature-dependence of the volume fractionx(T) of theη precipitate;

fitting the theoretical functionx(T)=x _h (T)+x _c (T) following from numerical integration of the reaction rate equations for the simultaneously occurring homogeneous (H) and cellular (C) precipitation processes.

As a result, the activation energiesE _h andE _c , the JMA exponentsn _h andn _c , the rate constantsk _h andk _c , and the critical temperaturesT _o of the two processes were estimated.     

Effect of Mobile Phase pH* on Chromatographic Behaviour in Chiral Ligand-Exchange Thin-Layer Chromatography (CLETLC) of Amino Acid Enantiomers

The enantiomers of some amino acids have been separated on commercial chiral TLC plates in reversed-phase mode. The effect of the pH* of the aqueous-organic mobile phase on the retention and mobility of the enantiomers and on selectivity was investigated. It was shown that for most of the amino acids investigated the highest enantioselectivity was obtained at pH* 3–4 or 6–7. The drift and disturbance of the baseline on the chromatograms were also much smaller at pH* 3–4 and 6–7.