Volume and compressibility changes of complex formation between 18-Crown-6 and NaCl,KCl, and CsCl in water

The apparent molal volumes and compressibilities of NaCl, KCl, and CsCl in mixtures of 18-Crown-6 and water have been calculated from density and speed-of-sound measurements at 25°C. The partial molal volumes and compressibilities of the salts when all cations have formed complexes with 18-Crown-6 molecules have been evaluated. The sign and magnitude of the volume and compressibility changes of complex formation strongly suggest that the charge of the cation becomes very effectively screened by the crown ether.     

Interactions of D-Maltose and Sucrose with Some Amino Acids in Aqueous Solutions

Calorimetric titrations have been performed at 298.15 K in aqueous solutions to derive the stability constants and thermodynamic parameters of the interactions of D-maltose and sucrose with some amino acids (glycine, DL-alanine, DL-leucine, and L-serine). The apparent molal volumes of the disaccharides in dilute aqueous solutions of the amino acids have been determined from density measurements at 298.15 K. In contrast to D-maltose, sucrose was found to associate with the amino acids and these associated species are preferentially entropy stabilized. These results are interpreted in terms of the influence of the nature of the solutes, their specific conformations, and hydration, on the ability of the disaccharides to form associated complexes with the amino acids.     

Stability of the FID sensitivity during an analysis in capillary GC

The sensitivity of an FID may change when the carrier gas flow rate changes during a chromatographic run. Sample parts which are eluted at reduced FID sensitivity produce a reduced peak area, hence are discriminated as compared to other components. Sensitivity changes were studied for hydrogen as carrier gas. For the detector tested, differences in the carrier gas flow rates of 1 ml/min shifted the FID sensitivity by 1 to 5% (depending on the fuel gas supply). Thus the stability of the sensitivity is no longer ensured as soon as the carrier gas flow rate is changed manually or by an automatic programmer during an analysis. Sensitivity drifts may also occur during temperature programmed runs with a pressure regulated carrier gas supply since the gas flow through the capillary drops with increasing temperature. Such shifts in the response became noticeable as soon as relatively high carrier gas flow rates combined with long range temperature programmes were used. The typical patterns of such discriminations are shown, closing with a discussion on the possibilities for minimizing such undesired effects.     

Small-angle X-ray scattering studies of the open and closed conformations of aspartate aminotransferase

Summary Aspartate aminotransferase was investigated by X-ray small-angle scattering. A small difference was found between the open (active) and the closed (liganded) conformation of the enzyme. The results were compared with X-ray crystallography data.

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Untersuchungen zur Röntgenkleinwinkelstreuung der offenen und geschlossenen Konformation von Aspartat-Aminotransferase

Zusammenfassung Aspartat-Aminotransferase wurde mittels Röntgenkleinwinkelstreuung untersucht. Ein kleiner Unterschied zwischen der offenen (aktiven) und der geschlossenen (ligandierten) Konformation wurde gefunden. Die Ergebnisse wurden mit Röntgenkristallstrukturdaten verglichen.

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Abbreviations AspAT aspartate aminotransferase     

Strukturelle Abwandlungen anN-Acetylneuraminsäure, 3

From methyl-5-acetylamino-7,8-anhydro-4,9-O-bis-(t-butyldimethylsilyl)-3,5-dideoxy--D-glycero-D-galacto-2-nonulopyranosidonic acid methylester (1) the derivatives1 a and1 b were obtained by removing the 9-O-(t-butyldimethylsilyl)group withBu ₄NF, followed by acetylation. Treatment of1 b with 80% acetic acid and acetanhydride/pyridine yields the 8-epi-N-acetylneuraminic acid derivative2 a and the 7-epi-N-acetylneuraminic acid derivative3 a in a ratio of 3:1 (Scheme 1). The structure elucidation of2 b was achieved by converting2 b via the 4,9-bis-O-(tBDMSi)-8-O-tosyl-derivative2 d into the epoxide1 (Scheme 2). Using the same sequence the epoxides4 and5 were transformed into theN-acetylneuraminic acid derivative6 a and the 7,8-bis-epi-N-acetylneuraminic acid derivative7 a (Scheme 3). After treatment with sodium hydroxide and 0.025m HCl and Dowex 50 H⁺ the 8-epi-, 7-epi- and 7,8-bis-epi-N-acetylneuraminic acids2,3, and7 were obtained. These three compounds were tested withCMP-N-acetylneuraminic acid synthetase.

Herrn KollegenK. Schlögl mit den besten Wünschen zum 60. Geburtstag.     

近30年海南岛橡胶林时空变化分析

【目的】 海南岛为中国第二大植胶区和仅有的两大热区之一,揭示其橡胶林的时空变化规律,对促进我国天然橡胶产业可持续发展有重要意义。【方法】 在Google Earth Engine(GEE)云计算平台上结合Landsat和Sentinel-2系列时间序列影像和橡胶林物候等信息,以5 a为步长提取了海南岛1990—2020年间7期橡胶林分布图,分析了海南岛橡胶林的时空变化规律。【结果】 ①近30年橡胶林面积增长趋势明显,从1990年的34.44万hm²增长至2020年的58.58万hm²,净增70.11%,且整体上呈现 “北增南减”的空间变化趋势;②在市/县尺度,橡胶林面积最大的主要市/县依次是儋州市、白沙县、澄迈县和琼中县,2020年占全岛橡胶林总面积的51.58%,而三亚市、东方市、文昌市及陵水县的橡胶林面积相对较小,2020年橡胶林总面积占比为5.22%;③近30年来,海南岛91.24%的橡胶林都种植在海拔300 m以下地区,97.75%种植地在25°坡度以下,海拔600 m以上几乎没有橡胶林分布,在海拔50~200 m和坡度0~5°的区域橡胶林增长幅度最大;④海南四大国家级自然保护区的实验区或缓冲区内均有少量橡胶林分布,但面积在逐渐下降。其中,霸王岭保护区内橡胶林面积最大,五指山保护区内面积最小,近30年四大保护区内橡胶林面积累计减少了68.02%,保护效果显著。虽然研究期海南岛的橡胶林面积增长非常显著,但集中在低海拔和相对平缓的区域,没有对位于中高海拔地区的热带雨林造成影响;四大国家级自然保护区内虽均有少量橡胶林分布,但递减趋势明显。【结论】 总体而言,海南橡胶林的发展模式良好,没有以牺牲大量热带森林为代价,尚未对当地的生态环境造成严重影响。     

水分在季节性冻土中的运动

季节性冻土是一种冰水共存的特殊土水体系,在分析冻土中水分运动的驱动力及其影响因素,冻土介质的物理特性（热特性和水力特性）及其参数测定方法的基础上,综述了水分在冻土中运动的基本规律及定量研究水分运动的试验与数值模拟方法。     

Light induced refractive index changes in PMMA films doped with styrene

Solutions of poly(methyl methacrylate) in styrene are used to produce thin polymer films (1m–20m) saturated with styrene monomer. In the illuminated areas refractive index changes up to 10^–2 are achieved by photoinduced polymerisation. The index patterns may be fixed by annealing treatments removing the residual monomer.We thank P. Hertel, M. Kopietz, M. D. Lechner and D. Steinmeier for valuable discussions. Financial support of the Stiftung Volkswagenwerk is gratefully acknowledged.     

Comparison of quantitative methods for analysis of polyphasic pharmaceuticals

Adequate very sensitive quantification methods are needed for the development and are also now required for the monitoring of undesirable solid form(s) as routine tests. The pre-requisite for quantitation are selectivity, sensitivity and most important the purity of standards and their proper storage, what is a challenge for metastable forms. Several analytical techniques are available such as X-ray diffraction, spectroscopy, thermal analysis and microcalorimetry. The different steps of the validation of the analytical methods and problems to be solved are discussed. Examples illustrate the different techniques and compare their possible advantages and limits. The relative standard deviation of measurements should allow for checking the homogenization procedure of mixtures for calibration. The validation should be carried out following ICH guidelines for validation of analytical methods. Comparison of different techniques in adequate concentration range add confidence in the analytical results.     

Molar excess heat capacities and volumes for mixtures of alkanoates with cyclohexane at 25°C

Molar excess volumes V ^E at 25°C have been determined by vibrating-tube densimetry, as a function of mole fraction x for different series of an alkanoate (H _2m+1 C _m COOC _n H _2n+1 )+cyclohexane. Three types of alkanoates were investigated, i.e., methanoates (m=0, with n=3 and 4), ethanoates (m=1, with n=2, 3, and 4) and propanoates (m=2, with n=1, 2, and 3). In addition, a Picker flow calorimeter was used to obtain molar excess heat capacities C _p ^E at constant pressure at the same temperature. V ^E is positive for all systems and rather symmetric, with V ^E (x=0.5) amounting to almost identical values in a series of mixtures containing an alkanoate isomer of same formula (say C₄H₈O₂, C₅H₁₀O₂, or C₆H₁₂O₂). The composition dependence of C _p ^E is rather unusual in that two more or less marked minima are observed for most of the mixtures, especially when the alkanoate is a methanoate or an ethanoate. These results are discussed in terms of possible changes in conformation of both the ester and cyclohexane.