Synthesis and chromatographic study of methyl-2,3-O-isopropylidene-5-dimethyl-arsinoyl-β-d-ribofuranoside and methyl-2,3-O-isopropylidene-5-deoxy-5-dimethyl-thioarsinoyl-β-d-ribofuranoside

The synthesis of two riboside-containing arsenic compounds, methyl-2,3-O-isopropylidene-5-dimethyl-arsinoyl-β-d-ribofuranoside and methyl-2,3-O-isopropylidene-5-deoxy-5-dimethyl-thioarsinoyl-β-d- ribofuranoside is presented in this paper. Intermediates and final products of the synthesis were examined by gas chromatography and thin layer chromatography. The purity of the products was assessed by NMR spectroscopy. Trimethylsilylation was used to volatilise sugar compounds and thus use of the costly HPLC–MS technique was avoided. The results affirmed the presence of tautomers in case of arsenosugars.     

Laser-induced periodic surface structures on different poly-carbonate films

Laser-induced periodic surface structures (LIPSS) were generated on oriented and amorphous thick, as well as on spin-coated thin, poly-carbonate films by polarized ArF excimer laser light. The influence of the film structure and thickness on the LIPSS formation was demonstrated. Below a critical thickness of the spin-coated films the line-shaped structures transformed into droplets. This droplet formation was explained by the laser-induced melting across the whole film thickness and subsequent de-wetting on the substrate. The thickness of the layer melted by laser illumination was computed by a heat-conduction model. Very good agreement with the critical thickness for spin-coated films was found. The original polymer film structure influences the index of refraction of the thin upper layer modified by the laser treatment, as was proven by the dependence of the structure’s period on the angle of incidence both for ‘s’- and ‘p’-polarized beams. The effect of the original surface roughness – grains in thick films or holes in thin films – was studied using atomic force microscopy. It was shown that the oblique incidence of ‘s’-polarized beams results in an intensity confinement in the direction of the forward scattering and in asymmetrical interference pattern formation around these irregularities. A new, two-dimensional grating-like structure was generated on spin-coated films. These gratings might be used as a special kind of mask. Received: 10 July 2001 / Accepted: 23 July 2001 / Published online: 30 August 2001     

Criteria for optimizing dcems

As depth-selective conversion electron Mössbauer-effect measurements present a difficult task in Mössbauer spectroscopy due to the long recording times involved, the shortening of the measuring times is of major practical importance. Possible improvements of the overall experimental performance and measuring time gains due to efficiency increase and back-ground reduction will be analyzed; advantages of a scintillation counter over a channeltron for⁵⁷Fe DCEMS applications will be discussed.     

Zur Kinetik der Peptidspaltung durch Fermente der Hefe

Ohne Zusammenfassung     

AB initio method for treatment of spatially extended systems I vanishing atomic two-electron integrals

Acta Physica Hungarica - The possibility of the calculation of molecular properties on ab initio level for extended systems is investigated in a series of papers. In the first Part the effect of...     

Travelling-wave amplified spontaneous emission excited in a prismatic geometry

A new experimental realisation of the travelling-wave amplified spontaneous emission (TWASE) is described utilising a prismatic arrangement to get the pulse front delay in the pump beam. Rhodamine dye solutions were pumped by the amplified 25 ps long 555 nm pulses of a distributed feedback dye laser. The pulse shortening in the TWASE resulted in 12 ps output pulses with 18% energy efficiency. The observed spectrum showed numerous lines, and it contained the amplified Raman line of the pump beam. Several spots were found in the far-field zone of the generated TWASE.     

A useful ring transformation route to novel thiazepino[7,6-b]indoles from monochloro-β-lactam-fused 1,3-thiazino[6,5-b]indoles,analogues of cyclobrassinin

The Staudinger ketene-imine cycloaddition reactions of cyclobrassinin phytoalexin analogues 2-aryl-4,9-dihydro-1,3-thiazino[6,5-b]indoles with chloroacetyl chloride as a ketene source were investigated under different conditions. Both β-lactam ring formation and the N-chloroacetylation of the indole moiety took place. The indole N-chloroacetyl group can be easily removed by treatment in the presence of silica gel in methanol at reflux temperature. The selective β-lactam formation can be also achieved in certain cases under milder Staudinger conditions. The treatment of azeto[2,1-b]thiazino[6,5-b]indole-1-one derivatives with sodium ethoxide in ethanol provided the novel thiazepino[7,6-b]indole ring systems in a one-step ring transformation. The structures of the new ring systems were determined by means of IR and NMR spectroscopy.     

Mass fragmentation study of the trimethylsilyl derivatives of arctiin,matairesinoside, arctigenin,phylligenin, matairesinol,pinoresinol and methylarctigenin: Their gas and liquid chromatographic analysis in plant extracts

The mass fragmentation patterns and the characteristic behavior of the trimethylsilyl (TMS) derivatives of the dibenzylbutyrolactone-type (arctiin, arctigenin, methylarctigenin, matairesinoside, matairesinol) and those of the diphenylperhydrofurotetrahydrofurane-type (phylligenin, pinoresinol) lignans, obtained by gas chromatography–mass spectrometry (GC–MS), were presented. It was shown that upon acidic hydrolysis the dibenzylbutyrolactone-type lignans are stable while the diphenylperhydrofurotetrahydrofurane-type ones decompose. As a novelty to the field we confirmed that the fragment species of the derivatized lignan glycosides, in the presence of excess hexamethyldisilazane, leaded to their in situ derivatization. Quantification of the selective fragment ions of the TMS derivatives by GC–MS, in respect of the ions found one by one, and concerning the selective fragment ions {SFI(s)} in total, provided acceptable reproducibilities, suitable for quantitation purposes: varying between 1.20% and 6.6% relative standard deviation percentages (RSD%). For characterization of the behavior of various type of lignans, analyses were performed with the untreated and with the trifluoroacetic acid hydrolyzed plant extracts, from the same sample, in parallel, both by GC–MS and by high performance liquid chromatography–mass spectrometry, working in the positive electron ionization mode (HPLC–ESPI-MS). The analysis of lignans in fruit and leaf extracts (obtained from the Arctium, Centaurea and Forsythia plants) was confirmed both by GC–MS and by HPLC–ESPI-MS. Our multicomponent system (including the identification and quantification of sugars, sugar alcohols, and several members of various homologous series of acids, anthraquinones and flavonoids) has been extended to the analysis of lignan glycosides and to the free lignans. Reproducibilities in the quantitation of lignans in plant matrices, as averages on GC and HPLC basis, varied between 0.9% and 11% (RSD). The distribution of the lignan constituents was presented for 5 Arctium, for 8 Centaurea and for 4 Forsythia plant extracts: the total of lignan contents varied between 0.42 and 87.9 mg/g, respectively.