从分子运动论看连续介质气体动力学和稀薄气体的新特性

首先，综述了根据分子运动论对连续介质极限气体行为的最近研究，它表明；经典的连续气体动力学是不完整的；用分子运动论分析在连续介质极限时一些重要情况得到氧化的正确行为是必不可免的。即，即作了特殊的情况，甚至在平均自由程变为零的极限下热传导方程不能描述静止气体温度场；文中给出了根据分子运动论导出的温度场的正确方程组和边界条件及其具体应用。     

IRAP: An efficient retrotransposon-based electrophoretic technique for studying genetic variability among geographical isolates of Schistosoma japonicum

In the present study, a inter-retrotransposon-amplified polymorphism (IRAP) technique, based on retrotransposons, was used to examine genetic variability among Schistosoma japonicum isolates from different provinces in mainland China. Of the 15 primers screened, 5 produced highly reproducible IRAP patterns. Using these primers, 54 discernible DNA fragments were generated with 40 (74.07%) being polymorphic, indicating considerable genetic variation among the examined S. japonicum isolates. The primer LTR-11 was found to be able to differentiate male and female parasites, producing one constant specific band for female S. japonicum isolates. The percentages of polymorphic bands (PPB) among all parasites, among isolates from mountainous provinces and among those from the lake/marshland areas were 74.07, 48.15, and 66.67%, respectively. UPGMA analysis revealed that the IRAP profiles could group S. japonicum isolates in mainland China into two clades (mountainous and lake/marshland types), and samples from the same geographical origins clustered together. These results demonstrated that the IRAP technique is suitable for studying genetic diversity and population structures, and also provides an effective technique for studying sex differentiation of S. japonicum.     

Electrodeposited lead dioxide coatings

Lead dioxide coatings on inert substrates such as titanium and carbon now offer new opportunities for a material known for 150 years. It is now recognised that electrodeposition allows the preparation of stable coatings with different phase structures and a wide range of surface morphologies. In addition, substantial modification to the physical properties and catalytic activities of the coatings are possible through doping and the fabrication of nanostructured deposits or composites. In addition to applications as a cheap anode material in electrochemical technology, lead dioxide coatings provide unique possibilities for probing the dependence of catalytic activity on layer composition and structure (critical review, 256 references).     

A modification of the successive projections algorithm for spectral variable selection in the presence of unknown interferents

This work proposes a modification to the successive projections algorithm (SPA) aimed at selecting spectral variables for multiple linear regression (MLR) in the presence of unknown interferents not included in the calibration data set. The modified algorithm favours the selection of variables in which the effect of the interferent is less pronounced. The proposed procedure can be regarded as an adaptive modelling technique, because the spectral features of the samples to be analyzed are considered in the variable selection process. The advantages of this new approach are demonstrated in two analytical problems, namely (1) ultraviolet–visible spectrometric determination of tartrazine, allure red and sunset yellow in aqueous solutions under the interference of erythrosine, and (2) near-infrared spectrometric determination of ethanol in gasoline under the interference of toluene. In these case studies, the performance of conventional MLR-SPA models is substantially degraded by the presence of the interferent. This problem is circumvented by applying the proposed Adaptive MLR-SPA approach, which results in prediction errors smaller than those obtained by three other multivariate calibration techniques, namely stepwise regression, full-spectrum partial-least-squares (PLS) and PLS with variables selected by a genetic algorithm. An inspection of the variable selection results reveals that the Adaptive approach successfully avoids spectral regions in which the interference is more intense.     

A new carotenoid glycoside from Rehmannia glutinosa

A new carotenoid glycoside, namely neo-rehmannioside (1), together with five known compounds, 6-O-seco-hydroxyaeginetoyl ajugol (2), oxyrehmaionoside B (3), ajugol (4), geniposidic acid (5) and geniposide (6) was isolated from the 95% ethanol extract of dry roots of Rehmannia glutinosa. The structure of the new compound (1) was determined based on MS, IR, 1-D and 2-D NMR spectral data.     

<Superscript>1</Superscript>H NMR signal at 2.10 ppm in the spectrum of KMnO<Subscript>4</Subscript>-bleached heparin sodium: identification of the chemical origin using an NMR-only approach

The recently revised European Pharmacopeia and US Pharmacopeia heparin sodium monographs include nuclear magnetic resonance (NMR) tests on both identity and purity. In KMnO₄-bleached heparin, an unidentified NMR signal is present at 2.10 ppm at a level of 15–20% of the mean of signal height of the major glucosamine (GlcNAc/GlcNS,6S) anomeric proton signal at 5.42 ppm and of the major iduronic acid (IdoA2S) anomeric proton signal at 5.21 ppm. According to the new monographs, no unidentified signals greater than 4% should be detected at that position. Thus, the material did not meet the acceptance criterion. The signal at 2.10 ppm has been present at the same level in all released MSD KMnO₄-bleached heparin sodium batches analyzed over the past 10 years. The signal is a result of the KMnO₄ bleaching. No (oversulfated) chondroitin sulfate or dermatan sulfate was detected in this material. A comprehensive NMR study using long-range heteronuclear 2D techniques identifies this signal at 2.10 ppm as originating from the acetyl methyl group of (6-sulfated) 2-N-acetyl-2-deoxy-glucono-1,5-lactone. This modified monosaccharide is formed by the KMnO₄ oxidation of the reducing end of a terminal N-acetylglucosamine.     

Application of high-performance liquid chromatography diode array detection and mass spectrometry to the analysis of characteristic compounds in various essential oils

A high-performance liquid chromatography (HPLC) method was established using an analytical reversed-phase column and gradient elution to achieve chromatographic separation of typical compounds in essential oils. For detection, a diode array detector monitoring different wavelengths simultaneously as well as a mass spectrometer (MS) were used. Atmospheric pressure chemical ionization operating in the positive mode turned out to be a suitable tool to detect volatiles of different chemical classes and to identify them in essential oil matrices. Characteristic fingerprints of eucalyptus, lavender, may chang, pine, rosemary, thyme, and turpentine essential oils monitored at a representative wavelength (220 nm) demonstrated the suitability of HPLC in essential oil analysis. Additional monitoring wavelengths (210, 250, and 280 nm) provided useful information about the identity of the specific component and opened the possibility to differentiate presumably coeluting compounds by means of their distinct absorption behavior. Finally, peak assignment in seven essential oils was performed on the basis of characteristic retention times and UV and MS data of a broad set of reference volatiles.     

Coupling of ortho-substituted aryl chlorides with bulky amides

Voluminous amides were coupled with deactivated, sterically hindered aryl chlorides in excellent yields providing products, which have not been efficiently accessible by transition metal catalysis so far. Application of an unsymmetric bisphosphine ligand was critical for the high catalytic activity.     

A simple and green analytical method for determination of glyphosate in commercial formulations and water by diffuse reflectance spectroscopy

This article describes a simple, inexpensive, and environmentally friendly method for the monitoring of glyphosate using diffuse reflectance spectroscopy. The proposed method is based on reflectance measurements of the colored compound produced from the spot test reaction between glyphosate and p-dimethylaminocinnamaldehyde (p-DAC) in acid medium, using a filter paper as solid support. Experimental designs were used to optimize the analytical conditions. All reflectance measurements were carried out at 495 nm. Under optimal conditions, the glyphosate calibration graphs obtained by plotting the optical density of the reflectance signal (AR) against the concentration were linear in the range 50-500 μg mL(-1), with a correlation coefficient of 0.9987. The limit of detection (LOD) for glyphosate was 7.28 μg mL(-1). The technique was successfully applied to the direct determination of glyphosate in commercial formulations, as well as in water samples (river water, pure water and mineral drinking water) after a previous clean-up or pre-concentration step. Recoveries were in the ranges 93.2-102.6% and 91.3-102.9% for the commercial formulations and water samples, respectively.     

Ionic liquids as recycling solvents for the synthesis of magnetic nanoparticles

This work describes an easy synthesis (one pot) of MFe(2)O(4) (M = Co, Fe, Mn, and Ni) magnetic nanoparticles MNPs by the thermal decomposition of Fe(Acac)(3)/M(Acac)(2) by using BMI·NTf(2) (1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) or BMI·PF(6) (1-n-butyl-3-methylimidazolium hexafluorophosphate) ionic liquids (ILs) as recycling solvents and oleylamine as the reducing and surface modifier agent. The effects of reaction temperature and reaction time on the features of the magnetic nanomaterials (size and magnetic properties) were investigated. The growth of the MNPs is easily controlled in the IL by adjusting the reaction temperature and time, as inferred from Fe(3)O(4) MNPs obtained at 150 °C, 200 °C and 250 °C with mean diameters of 8, 10 and 15 nm, respectively. However, the thermal decomposition of Fe(Acac)(3) performed in a conventional high boiling point solvent (diphenyl ether, bp 259 °C), under a similar Fe to oleylamine molar ratio used in the IL synthesis, does not follow the same growth mechanism and rendered only smaller NPs of 5 nm mean diameter. All MNPs are covered by at least one monolayer of oleylamine making them readily dispersible in non-polar solvents. Besides the influence on the nanoparticles growth, which is important for the preparation of highly crystalline MNPs, the IL was easily recycled and has been used in at least 20 successive syntheses.