Theoretical study of structure,vibrational and electronic spectra of isomers of methyl-3-methoxy-2-propenoate

A systematic quantum mechanical study of the possible conformations, their relative stabilities, vibrational and electronic spectra and thermodynamic parameters of methyl-3-methoxy-2-propenoate has been reported for the electronic ground (S₀) and first excited (S₁) states using time-dependent and time-independent Density Functional Theory (DFT) and RHF methods in extended basis sets. Detailed studies have been restricted to the E-isomer, which is found to be substantially more stable than the Z-isomer. Four possible conformers c′Cc, c′Tc, t′Cc, t′Tc, of which the first two are most stable, have been identified in the S₀ and S₁ states. Electronic excitation to S₁ state is accompanied with a reversal in the relative stability of the c′Cc and c′Tc conformers and a substantial reduction in the rotational barrier between them, as compared with the S₀ state. Optimized geometries of these conformers in the S₀ and S₁ states are being reported. Based on suitably scaled RHF/6-31G^** and DFT/6-311G^** calculations, assignments have been provided to the fundamental vibrational bands of both these conformers in terms of frequency, form and intensity of vibrations and potential energy distribution across the symmetry coordinates in the S₀ state. A complete interpretation of the electronic spectra of the conformers has been provided.     

Dry deposition of elemental iodine on skin,hair, and clothing from air

Hairless rats, clothes, human hair, filter paper and water were exposed to gaseous elemental iodine in a glass chamber for 60–120 minutes. The deposition of gaseous elemental iodine on skin and lung of rats, human hair, water, clothes and paper were investigated by measuring iodine content in the exposed material by epithermal neutron activation analysis (ENAA). For measurement of the iodine concentration in the chamber air, elemental iodine in the air was collected by continuously sucking air through an active charcoal column. The trapped iodine in the active charcoal was then determined by ENAA. The measured deposition velocity in the test chamber of gaseous elemental iodine on skin, clothing, hair and water ranges from 0.006 on filter paper and water to about 0.05 cm/s on skin and clothes. The variation of elemental iodine concentration in air of the glass chamber was investigated by collecting and analyzing air samples at various time intervals. The results show that the variation with time in the concentration of the iodine can be described by an exponential function.     

Determination of traces of bismuth by quenching of solid-substrate room-temperature phosphorescence from morin-labeled silicon dioxide nano-particles

Silicon dioxide nano-particles, diameter 50 nm, containing morin (morin–SiO₂) have been synthesized by the sol–gel method. They emit strong and stable room-temperature phosphorescence (SS-RTP) on filter paper as substrate, and bismuth can quench the intensity of the SS-RTP. On this basis a new morin–SiO₂ solid-substrate room-temperature phosphorescence-quenching method has been established for determination of traces of bismuth. Reduction of phosphorescence intensity (I_p) is directly proportional to the concentration of bismuth in the working range 0.16–14.4 ag spot^–1 (sample volume 0.40 L spot^–1, corresponding to the concentration range 0.40–36.0 fg mL^–1). The regression equation of the working curve is I_p=14.86+5.279×[Bi³⁺] (ag spot^–1) (n=6, r=0.9982). The detection limit of this method is 0.026 ag spot^–1 (corresponding to a concentration of 6.5×10^–17 g mL^–1).This sensitive, reproducible and accurate method has been used for successful analysis of real samples.     

Raman spectroscopic study of the hydration of short-chain poly(oxyethylene)s C <Subscript>1</Subscript>E<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>C <Subscript>1</Subscript> (<Emphasis Type="Italic">n</Emphasis>=1−4)

The hypothesis that the degree of hydration of poly(oxyethylene) (POE) in aqueous solution depends on the mole ratio of water molecules to ether oxygen atoms in the molecule has been verified by studying the isotropic Raman spectra in the O−H stretching region for four short-chain POEs (C ₁E _n C ₁ withn=1−4). Excellent coincidence of the O−H stretching Raman band for all four POEs studied in the range of mole ratio H₂O/O _ether from 25 to 0.6 was observed, thus confirming the assumption stated above. A conclusion that all ether oxygen atoms in the POE molecule participate in hydrogen bonding with water molecules has been made.     

Stabilization of γ‘ phase in Bi<Subscript>4</Subscript>V<Subscript>2-x</Subscript>Fe<Subscript>x</Subscript><Superscript>II</Superscript>O<Subscript>11-1.5x</Subscript> series

Summary This work reports the room-temperature stabilization of the Bi₄V_2-xFe_x^IIO_11-1.5x γ ‘ phase, a promising ionic conductive material that finds application in solid oxide fuel cell and oxygen sensor devices. The Fe(II) cation proved to be a better stabilizer than Fe(III), which was previously used, since a lower substitution degree of V⁵⁺ is needed for the former. Powder X-ray diffraction, Fourier-transform infrared spectroscopy and differential scanning calorimetry were used in these experiments.     

A new approach in assessing microbiological results in water analysis proficiency testing

Due to the relatively large spread in the results of microbiological proficiency tests, the z-scores are often not able to detect zero or low results as being ‘bad’ results. This paper describes an adapted z-score based on the average or the standard deviation of the 50% ‘highest’ results. The combination of the adapted z-scores of four samples enables a better judgement of the performance of each laboratory. Papers published in this section do not necessarily reflect the opinion of the Editors, the Editorial Board or the Publisher.     

Trennung,Identifizierung und Bestimmung von Bactericiden auf der Basis von halogenierten Aromaten mittels Gas-Chromatographie

The separation of a mixture of 22 bactericides has been achieved by gas chromatography on columns with silicone rubber W-982 as stationary phase with temperatures between 100° and 300°C. The unchanged compounds as well as their silylation products have been used. The latter are more conveniently used especially for the quantitative determination. To be able to calculate the retention indices after Kovats gas chromatography has been performed isothermally at 180°C for the more volatile compounds and at 250°C for all other bactericides.The retention indices obtained under these conditions are tabulated together with the limits of detection.     

Oral aminolevulinic acid induces protoporphyrin IX fluorescence in psoriatic plaques and peripheral blood cells

Photodynamic therapy (PDT) with topical aminolevulinic acid (ALA) has been shown in previous studies to improve psoriasis. However, topical ALA-PDT may not be practical for the treatment of extensive disease. In order to overcome this limitation we have explored the potential use of oral ALA administration in psoriatic patients. Twelve patients with plaque psoriasis received a single oral ALA dose of 10, 20 or 30 mg/kg followed by measurement of protoporphyrin IX (PpIX) fluorescence in the skin and circulating blood cells. Skin PpIX levels were determined over time after ALA administration by the quantification of the 635 nm PpIX emission peak with in vivo fluorescence spectroscopy under 442 nm laser excitation. Administration of ALA at 20 and 30 mg/kg induced preferential accumulation of PpIX in psoriatic as opposed to adjacent normal skin. Peak fluorescence intensity in psoriatic and normal skin occurred between 3 and 5 h after the administration of 20 and 30 mg/kg, respectively. Ratios of up to 10 for PpIX fluorescence between psoriatic versus normal skin were obtained at the 30 mg/kg dose of ALA. Visible PpIX fluorescence was also observed on normal facial skin, and nonspecific skin photosensitivity occurred only in patients who received the 20 or 30 mg/kg doses. PpIX fluorescence intensity was measured in circulating blood cells by flow cytometry. PpIX fluorescence was higher in monocytes and neutrophils as compared to CD4+ and CD8+ T lymphocytes. PpIX levels in these cells were higher in patients who received higher ALA doses and peaked between 4 and 8 h after administration of ALA. There was only a modest increase in PpIX levels in circulating CD4+ and CD8+ T lymphocytes. In conclusion oral administration of ALA induced preferential accumulation of PpIX in psoriatic plaques as compared to adjacent normal skin suggesting that PDT with oral ALA should be further explored for the treatment of psoriasis.     

Tying together the ultrastructural modifications of wood fibre induced by pulping processes with the mechanical properties of paper

The composition and ultrastructural arrangement of cell wall polymers in wood fibres have determining influence on the properties of wood derived materials. It is therefore important to improve our understanding of the relationship between fibres organisation, the modifications induced by pulping treatments, and the resulting paper sheet mechanical properties. The different treatments to which fibres are subjected during the manufacturing of pulps and papers induce morphological and micro-structural alterations due to the removal of wall constituents and of microfibrillar elements. The impact of pulping processes on fibres was investigated at the ultrastructural scale of transmission electron microscopy. Particular attention was given to the effects of beating in refiners at various intensities on the ultrastructure of fibres. The most characteristic effects consisted of delaminations, microfibril disorganisation, and even fractures, of varying importance depending on the intensity of the mechanical refining. The consequences of internal alterations and surface modifications of the fibres were examined in relation to the paper sheet mechanical properties. Correlations between the type of alteration observed in the fibres and its possible impact on a given paper mechanical property are suggested. With similar approaches, the effects of drying and recycling were studied.     

Stereoselectivity of (−)-(1<Emphasis Type="Italic">R</Emphasis>,2<Emphasis Type="Italic">S</Emphasis>)-2-methylamino-1-phenylpropan-1-ol preparation

Stereoselectivity of reductive amination of (R)-1-hydroxy-1-phenylpropan-2-one by methylamine was studied. From the four isomers possible, only two are produced by this reaction. These are marked as (−)-(1R,2S)-ephedrine (desired product) and (+)-(1S,2R)-ephedrine. The reaction stereoselectivity depends both on the type of the catalyst and reaction conditions. The most suitable type is the supported platinum. However, this catalyst rapidly deactivates. With a decreasing activity of Pt catalyst, the stereoselectivity decreases. It is also decreased during the production of the second liquid phase (water) in the reaction mixture.