Quantum-chemical study of spectral and luminescent properties and photochemistry of polyatomic molecules

The potential of a package of quantum-chemical software programs for exploring physicochemical problems pertaining to polyatomic organic molecules is highlighted. The results of investigation into the spectral, luminescent, and photochemical properties of molecules are discussed. The necessity of development of target-oriented models for studying the problems of physics and chemistry of molecules is emphasized.     

Retention characteristics of volatile compounds on tenax TA

The chromatographic separation properties of long, thin adsorption tubes enable substance-specific quantitative enrichment and reduction to be achieved when sampling and thermal desorption are carried out in the same flow direction. The specific retention volumes, and also the breakthrough and peak end volumes, of 69 compounds in the boiling range between-164 and 126°C and of a relative molecular mass between 16 and 119 were determined at temperatures between 30 and 130°C: normal alkanes, isoalkanes, cycloalkanes, alkenes, polyenes, alkynes, aromatics, ethers, alcohols, aldehydes, ketones, carboxylic acids and their esters, nitroalkanes, O-heterocycles, S-heterocycles, chloroalkanes, water, nitrogen monoxide, nitrogen dioxide, carbon dioxide, and sulfur dioxide. The correlation between adsorbent temperature and specific retention volume of these components, presented in the form of diagrams, permits the required quantity of adsorbent to be determined for a given sample volume. Contrary to literature sources, even extremely volatile compounds such as propane, propene, methanol, formaldehyde, formic acid, and chloromethane can be quantitatively retained on Tenax provided the operating conditions are appropriately selected.     

The effect of the source pressure on the abundance of ions of noncovalent protein assemblies in an electrospray ionization orthogonal time-of-flight instrument

The effect of elevating the pressure in the interface region of an electrospray ionization orthogonal time-of-flight mass spectrometer on the ion intensity of different noncovalent protein assemblies has been investigated. Elevating the pressure in the interface region generally led to an enhanced detection of high m/z ions. The optimum pressure was found to be dependent on the m/z value of the ions. This pressure effect should be carefully addressed when relating ion abundance in the mass spectra to solution phase abundance of noncovalent protein assemblies.     

Indications for the Occurrence of Nitric Oxide Synthases in Fungi and Plants and the Involvement in Photoconidiation of Neurospora crassa*

Indications for the occurrence of nitric oxide synthases in Dictyostelium, Neurospora, Phycomyces and the leguminous plant Mucuna hassjoo as well as a physiological role of nitric oxide in Neurospora crassa are demonstrated. An exogenous nitric oxide donor, sodium nitroprus-side, inhibited light-stimulated conidiation in N. crassa. Specific inhibitors of nitric oxide synthase, like the arginine derivatives N^G-nitro-L-arginine (L-NA) and N^G-nitro-L-arginine-methyl ester (L-NAME), enhanced conidiation in darkness and in the light, whereas the stereo-isomer D-NAME was inactive. This communication reports to our knowledge the first time the presence of enzymatic activity of nitric oxide synthase in fungi and a higher plant and an effect of nitric oxide in fungal photophysiology.     

Phototransformations of Phenols in Aqueous Solutions under Different Excitation Modes

The photolysis of aqueous solutions of two widespread environmental organic ecotoxicants—phenol and 4-chlorophenol—on excitation by UV radiation from a KrCl exciplex laser and a glow-discharge KrCl excilplex lamp was studied. The irradiated solutions were studied by spectroscopic techniques. The laser and lamp photolyses were compared.     

Separation of enantiomers: needs, challenges, perspectives

Chiral drugs, agrochemicals, food additives and fragrances represent classes of compounds with high economic and scientific potential. First the present implications of their chiral nature and necessity of separating enantiomers are summarised in this article. In the following a brief overview of the actual approaches to perform enantioseparations at analytical and preparative scale is given. Challenging aspects of these strategies, such as problems associated with data management, choice of suitable chiral selectors for given enantioseparations and enhanced understanding of the underlying chiral recognition principles, are discussed. Alternatives capable of meeting the requirements of industrial processes, in terms of productivity, cost-effectiveness and environmental issues (e.g., enantioselective membranes) are critically reviewed. The impact of combinatorial methodologies on faster and more effective development and optimisation of novel chiral selectors is outlined. Finally, the merits and limitations of most recent trends in discrimination of enantiomers, including advances in the fields of sensors, microanalysis systems, chiroptical methods and chemical force microscopy are evaluated.     

Bromsuperoxid: Bildung und Photoisomerisierung zu Bromdioxid

Bromine Superoxide: Generation and Photoisomerization into Bromine Dioxide Flash pyrolysis of a gas mixture containing bromine, oxygen and argon yields bromine superoxide, which can be identified IR- and UV-spectroscopically after trapping the pyrolysate at 12 K. Matrix irradiation transfers bromine superoxide into bromine dioxide. The backreaction can be induced by changing the wavelength. Even at room temperature a detectable amount of bromine superoxide is formed upon preparing a mixture of gaseous bromine, oxygen and argon.