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Ohne Zusammenfassung     

OXIDATION OF ASCORBIC ACID AS AN INDICATOR OF PHOTOOXIDATIVE STRESS IN THE EYE

When whole retinal pigmented epithelium (RPE) cells isolated from bovine eyes are incubated with 14C-labeled ascorbic acid and exposed to a visible laser, the ascorbic acid is oxidized to dehydro-L-ascorbic acid (DHA). The amount of ascorbic acid which is oxidized is proportional to the radiant exposure of the sample (i.e. the total amount of radiation per unit area delivered over the exposure time). Blue light is more effective than red light in driving the reaction. The amount of label appearing in the DHA fraction is increased if unlabeled DHA is present in the reaction mixture, indicating that some redox cycling of ascorbate is occurring in the RPE cells. The ascorbic acid oxidizing activity does not depend on intact cells, is not inactivated by heating the cells to 80 degrees C, and appears to reside mainly in the subcellular fraction which contains melanin pigment granules. The ascorbic acid oxidation may be caused by free radicals formed when melanin is illuminated with light. This reaction appears to be a useful method for quantifying the production of free radicals during photooxidative stress.     

Solvent effects in the fluorination of 1,2-dichloro-1,1-difluoroethane (R-132b) to 2-chloro-1,1,1-trifluoroethane (R-133a)

Trichloroethylene has been found to act as a rate enhancing co-factor in the liquid phase, tantalum (V) halide catalyzed, fluorine-for-chlorine exchange reaction of 1,2-dichloro-1,1-difluoroethane (R-132b) to 2-chloro-1,1,1-trifluorethane (R-133a). Several trifluoromethyl substituted benzenes have also been found to be rate-enhancing solvents.     

DNA electrophoresis in agarose gels: a simple relation describing the length dependence of mobility

Electrophoretic mobilities of DNA molecules ranging in length from 100 to 10 000 base pairs (bp) were measured in gels of eleven concentrations of agarose from 0.5 to 1.5%. Excellent fits of the dependence of mobility on DNA length were obtained with the relationship [equation: see text] showing an e(-L/gamma) crossover, where L is the length of a DNA fragment and gamma is a crossover length ranging from 8000 to 12000 bp. The other parameters in the fit are mu(s) the mobility of short DNA with unit charge in the limit as length is extrapolated to zero, and muI, the mobility of long DNA as length is extrapolated to infinity. This exponential relationship should be a useful interpolation function for determining DNA lengths over a wide range. The simplicity of this relationship may be of more fundamental significance and suggests that some common feature dominates the electrophoresis of double stranded DNA fragments in agarose gels, regardless of length.     

Reconstructing visible regions from visible segments

An algorithm is presented for reconstructing visible regions from visible edge segments in object space. This has applications in hidden surface algorithms operating on polyhedral scenes and in cartography. A special case of reconstruction can be formulated as a graph problem: Determine the faces of a straight-edge planar graph given in terms of its edges. This is accomplished inO(n logn) time using linear space for a graph withn edges, and is worst-case optimal. The graph may have separate components but the components must not contain each other. The general problem of reconstruction is then solved by applying our algorithm to each component in the containment relation.Research of this author is supported by the National Science Foundation under grant no. ECS-8351942, and by the Schlumberger-Doll Research Labs, Ridgefield, Connecticut.     

Intra- and intermolecular fluorescence quenching in 7-(pyridyl)indoles

Three isomeric 7-(pyridyl)indoles reveal very different, solvent-dependent photophysical properties. Due to rapid excited state depopulation involving intramolecular hydrogen bonding, 7-(2′-pyridyl)indole is practically nonfluorescent at room temperature. In nonpolar and polar aprotic solvents, 7-(3′-pyridyl)indole and 7-(4′-pyridyl)indole fluorescence strongly, but the emission is quenched in alcohols. Syn and anti rotameric forms of 7-(3′-pyridyl)indole are detected, each quenched to a different degree. This differential quenching is interpreted as evidence of enhanced S₁ → S₀ internal conversion being more efficient in cyclic solvates, with alcohol molecules forming a bridge between the proton donor and acceptor groups of an excited chromophore.     

2,2';9',2''-Ter[1,10]phenanthroline

The title molecule, 2,2';9',2'-ter[1,10]phenanthroline can be prepared from 2,9-dichloro-1,10-phenanthroline in three steps through the corresponding diacetyl intermediate. The ligand acts as a hexadentate with K+, while two molecules form a trinuclear, helical complex with Cu(I), which evidences pi-stacking interactions and Cu-Cu distances of 3.01-3.04 A. Electrochemical analysis shows a strong interaction between the Cu(I) centers.     

Konstitution und physikalische Eigenschaften von Äthern, 8. Mitt.: Über die Viskositäts-Temperatur-Abhängigkeit von Äthern und einigen strukturanalogen Kohlenwasserstoffen

Zusammenfassung Unter Verwertung des Versuchsmaterials von 24 nach bestimmten Gesichtspunkten ausgewählten Glykol- und Pentaerythritäthern³, früheren Ergebnissen⁴ und strukturanalogen Kohlenwasserstoffen wird der Einfluß von Strukturmerkmalen, wie Äthergruppen, Verzweigungen, alicyclischen und aromatischen Ringen auf das Viskositäts—Temperatur-(-T)-Verhalten untersucht. Abnehmende Verzweigung hat Absinken der Steilheiten und Zunahme derT ₁-Werte zur Folge, wie man sie in homologen Reihen bei Kettenverlängerung beobachtet. Die Wirkung der Einführung des Cyclopentan-, Cyclohexan-und Benzolringes in Äther und Kohlenwasserstoffe wird diskutiert. Bei den Phenyl-und Benzylglykoläthern zeigen sich Besonderheiten, die durch Assoziation der Moleküle erklärt werden.Mit 4 Abbildungen7. Mitt., Mh. Chem.93, 911 (1962).     

Conformational equilibria and photoinduced tautomerization in 2-(2′-pyridyl)pyrrole

Depending on the polarity and protic abilities of the solvent, 2-(2′-pyridyl)pyrrole can exist in either syn or anti rotameric forms. In nonpolar solvents, intramolecular excited state single proton transfer is observed, manifested by the appearance of low-energy tautomeric emission. The solvent-assisted excited state double proton transfer reaction is also detected. DFT calculations confirm low barriers for both single and double proton transfer processes in the lowest excited singlet state and show different character of the tautomerization in both cases: in the intramolecular reaction, mutual approach of two nitrogen atoms plays an important role.