Ab initio calculation of stationary points for the ground and the first excited state of HCO

SCF and single-reference ACPF calculations were performed in order to determine the structure, stability, and harmonic vibrational frequencies of stationary points for the HCO radical in the ground (²A′) and first excited (²A″) states. Very large and flexible basis sets including two f functions on the heavy atoms and two d functions on hydrogen were used. The calculated geometries and vibrational frequencies are in good agreement with available experimental data. The relative stabilities are now also much better balanced compared to previous theoretical results. © 1995 John Wiley & Sons, Inc.     

Physicochemical aspects of the liposome-wool interaction in wool dyeing

Despite the promising application of liposomes in wool dyeing, little is known about the mechanism of liposome interactions with the wool fiber and dyestuffs. The kinetics of wool dyeing by two dyes, Acid Green 27 (hydrophobic) and Acid Green 25 (hydrophilic), were compared in three experimental protocols: (1) without liposomes, (2) in the presence of phosphatidylcholine (PC) liposomes, and (3) with wool previously treated with PC liposomes. Physicochemical interactions of liposomes with wool fibers were studied under experimental dyeing conditions with particular interest in the liposome affinity to the fiber surface and changes in the lipid composition of the wool fibers. The results obtained indicate that the presence of liposomes favors the retention of these two dyes in the dyeing bath, this effect being more pronounced in case of the hydrophobic dye. Furthermore, the liposome treatment is accompanied by substantial absorption of PC by wool fibers with simultaneous partial solubilization of their polar lipids (more evident at higher temperatures). This may result in structural modification of the cell membrane complex of wool fibers, which could account for a high level of the dye exhaustion observed at the end of the liposome dyeing process.     

Increased structural complexity leads to higher activity: peptides as efficient and versatile catalysts for asymmetric aldol reactions

[reaction: see text] Peptides containing a secondary amine and a carboxylic acid in a specific orientation to each other are presented as highly efficient catalysts for asymmetric aldol reactions: (1) their activity is considerably higher compared to that of proline, and (2) the enantioselectivity of the peptidic catalysts can be changed from (R)- to (S)-selectivity by simple modifications of the secondary structure.     

Determination of trace elements in the Lavender inflorescence (Lavandula angustifolia Mill.) — Lavender oil system

Bulgaria is a famous world producer of essential oils. Quality control of the lavender oils produced is an important analytical task in view of their wide use in perfumery and cosmetics, the food industry and aromatherapy. The present paper studies the relationship between the trace elements content in lavender inflorescence (Lavandula angustifolia Mill.) and in lavender oil derived from this inflorescence. Three model regions were investigated: two of them are situated far from industrial areas — the village of Zelenikovo and the town of Pavel Banya, and one region is located near the Plovdiv Non-Ferrous Metallurgical Plant. The content of the elements Cd, Cr, Cu, Fe, Mn and Pb in plants was determined after acid digestion by flame and electrothermal atomic absorption spectrometry (ETAAS). Lavender oils were analyzed directly by ETAAS. The results undoubtedly show that there is no strong correlation between the trace elements content in inflorescence and in essential oils. It might be assumed that the trace elements present and accumulated in the inflorescence do not pass in lavender oil during the production by steam distillation.     

Deposition of copper films by unbalanced d.c. magnetron sputtering

The electrical resistivity of as deposited polycrystalline copper thin films as a function of varying the process parameters has been investigated. Trying to minimize the resistivity of the copper thin films is important in the semiconductor industry, due to the fact that low resistivity copper can be employed to great advantage for new metallization schemes in advanced ultralarge scale integrated circuits. This paper presents the optimum choice of parameters that are necessary to achieve low resistivities of the thin films in reproducible experiments. All the depositions were performed using an unbalanced d.c. planar magnetron sputtering source (consisting of a circular copper target (98% purity, 0.01% Fe, 0.005% Ni, 0.005% Si) with a diameter of 100mm fitted with two electromagnets). The copper thin films were deposited onto glass substrates with argon being used as the sputtering gas. The resistivity was studied as a function of the pressure of the sputtering gas, the substrate bias, the substrate to target distance, the magnetron power, and the substrate temperature. It was found that depositions producing thin films with a resistivity of that approaching the bulk material (1.7×10^–8m) were obtained if the sputtering gas pressure was below 0.2 Pa. The effect of the substrate bias was insignificant at these pressures. The crystallographic structure of the copper thin films, determined by X-ray diffraction, is also reported.The authors would like to thank Dr. Soukup for his support during this research. We would also like to express our gratitude to Mr. A. Rajský for improving the design of the sputtering device. This work was partially financed by a grant from the Grant Agency of the Czech Republic No. 202/93/0508.     

Application of capillary electrochromatography using macroporous polyacrylamide columns for the analysis of lignans from seeds of Schisandra chinensis

Capillary electrochromatography (CEC) using polymer-based monolithic stationary phase has been developed as a promising method for the determination of lignans of Schisandra chinensis. The columns were prepared by in situ copolymerisation of acrylamide, N,N'-methylenebisacrylamide, vinylsulfonic acid and lauryl acrylate in presence of poly(ethylene glycol) as a porogenic agent. The columns [33 cm (24.5 cm effective length) x 75 microm I.D.] were successfully used to analyse and quantify the major lignans in extract of the seeds of Schisandra chinensis. Good separations were achieved in less than 35 min. The calibration graphs were linear in the range 0.025-1.0 mg/ml of given lignan with correlation coefficients between 0.9951 and 0.9996. The inter-day reproducibility of the peak area were below 3.9% and the inter-day reproducibility of the migration time were below 4.2%. The results of quantitative CEC analyses were compared with those obtained by reversed-phase HPLC, the levels of schizandrin, gomisin A, gomisin N and wuweizisu C determined by CEC were in a good agreement with those determined by HPLC.     

Einfache Natriumbestimmung durch Ionenaustauscher Lewatit S 100

Zusammenfassung Es wird eine Methode zur Bestimmung von Natrium mittels Tetraphenyloborat angegeben. Mit Hilfe eines stark sauren Kationaustauschers in der Kaliumform wird das Natrium quantitativ und stöchoimetrisch gegen Kalium ausgetauscht und dieses mit Kalignost bestimmt.Durch Verwendung einer neuartigen Säule wird das Volumen des Filtrats gering gehalten.Eine Natriumgesamtbestimmung erfordert etwa eine Stunde Zeitdauer. Die reine Arbeitszeit beträgt 25 min.Herrn Prof. Dr. A. Kurtenacker zum 70. Geburtstag gewidmet.     

Longest cycles in generalized Buckminsterfullerene graphs

It is shown that every regular 3-valent polyhedral graph whose faces are all 5-gons and 6-gons contains a cycle through at least 4/5 of its vertices.     

Time-resolved and steady-state fluorescence spectroscopic studies of the human lens with comparison to argpyrimidine,pentosidine and 3-OH-kynurenine

The intrinsic fluorescence from the human lens on excitation in the UV region, referred to as blue lens autofluorescence, increases with age or in the presence of diabetes. The present study reveals that the relative contribution of compounds responsible for the blue autofluorescence appears to be a constant with age. Three potential candidates for the blue fluorescence were also studied with respect to fluorescence spectroscopic properties. These were argpyrimidine and pentosidine, both advanced glycation end products, and 3-hydroxykynurenine (3-OH-kynurenine), a photooxidative derivative of tryptophan. It was shown that the spectral properties of argpyrimidine and pentosidine are compatible with the observed blue fluorescence of the human lens, whereas the fluorescence from 3-OH-kynurenine is negligible.     

Configuration and E/Z interconversion mechanism of O(S)-allyl-S(O)-methyl-N-(acridin-9-yl) iminothiocarbonate

The configuration and dynamic behavior of O-allyl-S-methyl-N-(acridin-9-yl)iminothiocarbonate (1) and its S-allyl-O-methyl regioisomer (2) were studied using quantum chemical calculations and by applying a novel graphical method to scatter maps obtained from MD simulations for evaluation of an NOE-weighted internuclear distance (r(NOE)). Energy calculations indicated that the Z configuration was predominant for each compound and, further, this was supported both by the calculated chemical shifts and the r(NOE). Both N-inversion- and rotation-type transition-state structures were also calculated for the E/Z isomerization process, the results indicating that the preferred interconversion mechanism for 1 is N-inversion, but contrastingly, interconversion via rotation is equally as probable as N-inversion for 2. This supports the notion that one or the other or both pathways can be active and each system needs to be assessed on a case-by-case basis.