Microbiological transformations of steroids

Summary A culture of Actinomyces albus 3006 is incapable of reducing the 20-keto group of 17,21-deoxy-⁴-3-keto steroids except when the substrate contains an oxygen function in the 11-position.We are deeply grateful to Dr. M. Shirasaka (Japan), Dr. P. Djassi (USA), and Dr. B. Camerino (Italy) for kindly providing samples of 7-hydroxyprogesterone, 15-hydroxyprogesterone, and 15-hydroxyprogesterone.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya No. 11, pp. 2008–2015, November, 1964     

X-ray fluorescent spectroscopy study of the charge state of heteroatoms in organic compounds of third row elements. 8. Tin chloride and its complexes

We have established that the total electron density on the chlorine atoms in SnCl₄L₂ complexes remains virtually unchanged compared with the original acceptor in strong complexes, decreases with weak complexes, and markedly increases in all the studied TiCl₄L₂ complexes. We show that the negative charge decreases on the chlorine atoms in the acceptor part of SnCl₄L₂ trans complexes, with square planar SnCl₄, compared with the original tetrahedral configuration.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2522–2525, November, 1989.     

Asymmetric synthesis of 4-amino-γ-butyrolactones via lithium amide conjugate addition

Upon treatment with homochiral lithium (R)-N-benzyl-N-(α-methylbenzyl)amide, γ-benzyloxy but-2-enoates undergo competitive conjugate addition and γ-deprotonation, while γ-tert-butyldimethylsilyloxy but-2-enoates undergo exclusive conjugate addition. Treatment of γ-benzyloxy or γ-tert-butyldimethylsilyloxy but-2-enamides with lithium (R)-N-benzyl-N-(α-methylbenzyl)amide furnishes exclusively the γ-benzyloxy- or γ-tert-butyldimethylsilyloxy-β-amino amide products of conjugate addition in high de. The γ-tert-butyldimethylsilyloxy-β-amino butanoate products of conjugate addition readily undergo O-desilylation and concomitant cyclisation to furnish 4-[N-benzyl-N-(α-methylbenzyl)amino]-γ-butyrolactone, which may be stereoselectively functionalised via deprotonation and alkylation to give the corresponding trans-3-alkyl-4-amino-γ-butyrolactones. Alternatively, stereoselective alkylation of γ-benzyloxy- or γ-tert-butyldimethylsilyloxy-β-amino butanoates and butanamides through enolate formation and alkylation following a tandem (via the (Z)-lithium enolate) or stepwise (via the (E)-lithium enolate) protocol gives a range of separable syn- and anti-α-alkyl-β-amino esters and amides. O-Silyl deprotection of the syn- and anti-α-alkyl-β-amino butanoates with TBAF and concomitant cyclisation provide trans-3-alkyl-4-amino-γ-butyrolactones, consistent with epimerisation to the thermodynamically favoured trans-lactone occurring upon deprotection.     

Preparation and Characterization of Binder for Inorganic Composites Made from Amorphous Mineral Raw Material

The preparation and characterization of a composite binder made through a sol-gel route from an amorphous mineral raw material has been studied. The amorphous mineral raw material is alumino-silicate based but contains also alkaline earth and some transition metal oxides. A stable sol can be prepared by dissolving the raw materials in formic acid. The drying and heat treatment of the subsequent gel has been studied by thermogravimetry, nuclear magnetic resonance, infrared spectroscopy as well as X-ray diffraction studies. The different constituents of the raw material have shown to play a major role during the drying and heat treatment of the gels. The binding effect of the binder was evaluated to be good by studying paper-binder composites as well as wetting properties.     

Weighted integral formulas on manifolds

We present a method of finding weighted Koppelman formulas for (p,q)-forms on n-dimensional complex manifolds X which admit a vector bundle of rank n over X×X, such that the diagonal of X×X has a defining section. We apply the method to ℙ ⁿ and find weighted Koppelman formulas for (p,q)-forms with values in a line bundle over ℙ ⁿ . As an application, we look at the cohomology groups of (p,q)-forms over ℙ ⁿ with values in various line bundles, and find explicit solutions to the -equation in some of the trivial groups. We also look at cohomology groups of (0,q)-forms over ℙ ⁿ ×ℙ ^m with values in various line bundles. Finally, we apply our method to developing weighted Koppelman formulas on Stein manifolds.     

A rigidity theorem for holomorphic generators on the Hilbert ball

We present a rigidity property of holomorphic generators on the open unit ball of a Hilbert space . Namely, if is the generator of a one-parameter continuous semigroup on such that for some boundary point , the admissible limit - , then vanishes identically on .

     

Inelastic hyperspectral lidar for profiling aquatic ecosystems

Monitoring the aquatic environment and the life of free‐floating organisms remains on the borderline of our technical capabilities. Therefore, our insights into aquatic habitats, such as, abundance and behavior of organisms are limited. In order to improve our understanding of aquatic life, we have developed a low‐cost inelastic hyperspectral lidar with unlimited focal depth and enough sensitivity and spatiotemporal resolution to detect and resolve position and behavior of individual submillimeter organisms. In this work, we demonstrate elastic as well as molecular ranging by using the water Raman band, and by observing fluorescence from chlorophyll and from dye‐tagged organisms. We present an aquatic laser‐diode‐based inelastic light detection and ranging (lidar) system with unprecedented sensitivity, spatiotemporal resolution and number of spectral bands. Our system offers new opportunities for quantitative in situ studies of aquatic organisms, and has the potential to considerably advance our understanding of biological life in aquatic systems.

     

地脉动作用下主机装置靶室结构稳定性分析与评估

在大型固体激光器结构稳定性设计中,数值模拟结果是结构稳定性设计的主要依据,故数值模拟的可信度至关重要。为了评估装置稳定性计算结果的可信度,基于现代模型验证与确认技术中关于不确定性源的量化及传播分析方法、模型形式误差与预测推断的叠加方法研究,对靶球结构的最大位移响应进行了预测推断。稳定性分析中为了快速进行不确定性参数的传播和灵敏度分析,使用二次响应面模型作为代理模型,灵敏度分析结果表明模态阻尼比对靶球结构的稳定性影响更大。对关心量的稳定性预测结果表明,靶球结构最大位移响应的上界与稳定性设计指标相比,安全裕度仍大于7,说明主机装置的稳定性设计具有足够的可信度。     

X-Ray determination of the effective charges on sulfur and phosphorus atoms in chemical compounds

The dependencies of Kα line shifts of the P and S atoms on effective charges of the atoms, calculated by CNDO/S, CNDO/2, INDO, and MNDO methods in the minimal and extended basis sets, have been investigated for model compounds. Good linear relationships between Kα shifts and atomic charges have been obtained for all cases investigated except for CNDO/2 and INDO calculations in the extended basis set. It is found that the PS bond ionicity is a nearly constant value, whereas the P S bond ionicity increases linearly with an increase in the positive charge of the central P atom. It is shown that the P and S atom charge in sulfides and phosphines containing no substituents with a strong M-effect at the central atom depend only on inductive substituent effects. Also, the positive charge on the central atom increases with the growth of the π-donor properties of substituents in sulfides and phosphines containing substituents exerting a strong M-effect, as well as in phosphoryl and thiophosphoryl compounds and sulfones.