THE PRESENCE OF PHOTOREACTIVE β-CARBOLINE FLUOROPHORES IN WEATHERED WOOL KERATIN

Abstract Solvent-cleaned Merino wool, which was enzymatically digested with protease K, displayed a fluorescence maximum at 500 nm when excited at 430 nm. The yield of this emission was approximately 15 times greater for a fiber tips digest than for a digest of the mid-length region of the same fibers.
Separation of the components in the wool tip digest by silica gel thin-layer chromatography revealed the presence of several fluorescent species. The chromatographic mobility of these species was similar to the behavior observed in a preparation of authentic 1-methyltetrahydro-P-carboline, 1,3-dicarboxylic acid.
Mass spectroscopy of the fluorescent compounds in the wool tip digest displayed molecular ions, [M + H]⁺ with m/z = 273.0890 and 257.0560, and molecular weights that define the formulae C₁₄H₁₂N₂O₄ and C₁₁H₈O₄N₂, respectively, which correspond to β-carboline 1,3-dicarboxylic acids. Mass spectral evidence also indicates the presence of two other β-carbolines.     

Use of solvent sorption to detect structural changes in rigid PVC compounds

The effects of type of PVC and its thermal history on solvent sorption behaviour were investigated. Samples were immersed in toluene at 25°C, and the equilibrium solvent uptake and sorption half-times were measured for a variety of samples. The shape of the sorption curve was also observed. Equilibrium sorption was found to decrease with increasing amount of crystallinity in the sample. Sorption half-time increased with increased crystallinity, but minimum equilibrium sorption did not correspond with maximum half-time, possibly due to the type of crystallinity present. The shape of the sorption curve (Fickian or Case II sorption) also depended on the ype of PVC used and is thermal history. The solvent sorption technique was shown to be a sensitive method for detecting small structural changes in PVC.     

organocuprate reactions of enone lactones. I. Synthesis of trans-fused rings via conjugate addition.

Control of the stereochemistry of substituents needed to construct a bicyclic system (e.g. a hydrindanone) is achieved by conjugate addition of an organocuprate to a cyclohexenone made conformationally rigid by the attachment of a 1,3-lactone.     

Molecular approaches to solar energy conversion with coordination compounds anchored to semiconductor surfaces

Strategies toward the realization of molecular control of interfacial charge transfer at nanocrystalline semiconductor interfaces are described. Light excitation of coordination compounds, based on (dpi)6 transition metals, anchored to wide band-gap semiconductors, such as TiO2, can initiate electron-transfer processes that ultimately reduce the semiconductor. Such photoinduced charge-separation processes are a key step for solar energy conversion. The thermodynamics and kinetic rate constants for three different interfacial charge separation mechanisms are discussed. Tuning the energetic position of the semiconductor conduction band relative to the molecular sensitizer has provided new insights into interfacial charge transfer. Supramolecular compounds that efficiently absorb light, promote interfacial electron transfer, and feature additional functions such as intramolecular electron transfer when bound to semiconductor surfaces have also been studied. New approaches for enhancing charge-separation lifetimes for solar energy conversion are presented.     

Synthese und Fluoreszenzeigenschaften von cyansubstituierten 2-Aminopyridinen

The synthesis of several 2-aminopyridines is described. The reaction of tetracyanoethylene with 3-imino-propane-carbonitrile gives 2-amino-3,4,5-tricyano-pyridines with alkyl and aryl-substituents, resp., in position 6. Nucleophilic substitution of 2-amino-6-chloro-3,5-dicyanopyridines and 2-amino-6-chloro-3,4,5-tricyano-pyridines with phenolates leads to a variety of pyridines. Spectroscopical data of absorption and fluorescence are presented and the influence of the cyano groups is discussed. The results are in good agreement with quantum chemical calculations (PPP).

Herrn Univ-Prof. Dr.A. Holasek zum 60. Geburtstag gewidmet.     

Identification of a chemical indicator of the rupture of 1,4-β-glycosidic bonds of cellulose in an oil-impregnated insulating paper system

In this study, headspace gas chromatography/mass spectrometry has been used to assess the volatile by-products generated by the ageing of oil-impregnated paper insulation of power transformers. Sealed-glass ampoules were used to age under oxidative conditions 0.5-g specimens of insulating paper in 9 mL of inhibited mineral oil in a temperature range of 60–120 °C and moisture of 0.5, 1 and 2% (w/w). A linear relationship between one of the oil-soluble degradation by-products, i.e. methanol, and the number of ruptured 1,4-β-glycosidic bonds of cellulose, regardless of the type of paper (ordinary Kraft or thermally-upgraded (TU) Kraft paper), was established for the first time in this field. Ageing at 130 °C of model compounds of the Kraft paper constituents (α-cellulose, hemicellulose and lignin) and two cellulosic breakdown by-products (D-(+)-glucose and 1,6-anhydro-β-d-glucopyranose) confirmed that the α-cellulose degradation was mostly responsible for the presence of this molecule in the system. Furthermore, additional 130 °C-tests with six different papers and pressboard samples under a tight control of initial moisture indicated that at least one molecule of methanol is formed for each rupture of 1,4-β-glucosidic bond of the molecular chains. Stability tests showed that the ageing indicator is stable under the oxygen and temperature conditions of open-breathing transformers. The presence of methanol was detected in 94% of oil samples collected from over than 900 in-service pieces of equipment, confirming the potential for this application. Lastly, the tests have shown that oil-oxidation by-products and TU-nitrogenous agents modify the methanol partitioning coefficients in the paper/oil/air system, which makes their study essential over a range of field conditions encountered by power transformers. Results are presented and discussed in comparison with 2-furfuraldehyde, which is the current reference in the domain.     

Vector-spinor space and field equations

Generalizing the work of Einstein and Mayer, it is assumed that at each point of space-time there exists a vector-spinor space with N_v vector dimensions and N_s spinor dimensions, where N_v=2k and N_s=2 ^k, k3. This space is decomposed into a tangent space with4 vector and4 spinor dimensions and an internal space with N_v–4 vector and N_s–4 spinor dimension. A variational principle leads to field equations for geometric quantities which can be identified with physical fields such as the electromagnetic field, Yang-Mills gauge fields, and wave functions of bosons and fermions.     

Analysis of the degradation products of diproteverine by moving belt LC/MS

Moving belt LC/MS has been used to identify the degradation products of the slow calcium membrane channel inhibitor, Diproteverine, after storage at elevated temperature and humidity. The major products observed result from oxidation. Two of these products, both ketones, yield [M ? 14 + H]⁺ ions by chemical ionization. These unusual ions also occur for some simple aromatic ketones used as model compounds and are shown to arise by reduction of the carbonyl group to a methylene by the reagent gas.