Asymmetric Catalytic Approach to Multilayer 3D Chirality

The first asymmetric catalytic approach to multilayer 3D chirality has been achieved by using Suzuki-Miyaura cross-couplings. New chiral catalysts were designed and screened under various catalytic systems that proved chiral amide-phosphines to be more efficient ligands than other candidates. The multilayer 3D framework was unambiguously determined by X-ray structural analysis showing a parallel pattern of three layers consisting of top, middle and bottom aromatic rings. The X-ray structure of a catalyst complex, dichloride complex of Pd-phosphine amide, was obtained revealing an interesting asymmetric environment nearby the Pd metal center. Three rings of multilayer 3D products can be readily changed by varying aromatic ring-anchored starting materials. The resulting multilayer products displayed strong luminescence under UV irradiation and strong aggregation-induced emission (AIE). In the future, this work would benefit not only the field of asymmetric synthesis but also materials science, in particular polarized organic electronics, optoelectronics and photovoltaics.     

Synthesis of 2-amino-3-cyano-4H-chromen-4-ylphosphonates and 2-amino-4H-chromenes catalyzed by tetramethylguanidine

Synthesis of 2-amino-4H-chromen-4-ylphosphonates and 2-amino-4H-chromenes has been accomplished by the reaction of salicylaldehyde, malononitrile, dialkyl/diphenylphosphites catalyzed by 1,1,3,3-tetramethylguanidine (TMG) under neat conditions at room temperature. The applicability of catalytic TMG for the synthesis of 2-amino-4H-chromenes also has been described. The mild reaction conditions, simple work-up procedure, and use of TMG as an inexpensive catalyst provides an economical protocol for the preparation of important phosphorus-containing compounds.     

机载平台式惯导系统导电环故障机理分析及解决措施

导电环是平台式惯导系统惯性平台的重要组成部分,主要承担惯性平台台体内各种信号与系统的传输和交联,导电环发生故障直接会导致惯导系统失效。针对导电环三种故障模式:接触电阻变大、绝缘强度降低以及烧坏,本文采用微动磨损和电接触理论,结合作者的实际工作经验,对故障机理进行了分析,提出了相应的改进措施。这些措施均在生产中得到落实。落实措施后的故障统计表明,采取的改进措施有效,导电环的故障率与原来相比降低了38%。     

Facile and efficient synthesis of quinoline-4-carboxylic acids under microwave irradiation

<正>A facile and efficient method for the preparation of 2-non-substituted quinoline-4-carboxylic acids is described via the Pfitzinger reaction of isatins with sodium pyruvate following consequent decarboxylation under microwave irradiation.     

Chemoselective and enantioselective transfer hydrogenation of β,β-disubstituted nitroalkenes catalyzed by a water-insoluble chiral diamine–rhodium complex in water

Asymmetric transfer hydrogenation of β,β-disubstituted nitroalkenes catalyzed by a chiral diamine–rhodium complex in combination with HCO₂Na–HCO₂H as a hydrogen source in water was successfully realized with high reactivity, excellent chemoselectivity and good enantioselectivity. The metal precursor and pH value of the aqueous solution have a large influence on the reactivity and chemoselectivity. The substituents on the benzene rings and the sulfonyl groups of TsDPEN have significant effects on the enantioselectivity. This catalytic asymmetric transformation is one of the most practical pathways to obtain optically active nitroalkanes.     

An Oxidant- and Organic Solvent-Resistant Alkaline Metalloprotease from Streptomyces olivochromogenes

Organic solvent- and detergent-resistant proteases are important from an industrial viewpoint. However, they have been less frequently reported and only few of them are from actinomycetes. A metalloprotease from Streptomyces olivochromogenes (SOMP) was purified by ion exchange with Poros HQ and gel filtration with Sepharose CL-6B. Apparent molecular mass of the enzyme was estimated to be 51 kDa by sodium dodecyl sulfate–polyacrylamide gel electrophoresis and gelatin zymography. The activity was optimum at pH 7.5 and 50 °C and stable between pH 7.0 and 10.0. SOMP was stable below 45 °C and Ca²⁺ increased its thermostability. Ca²⁺ enhanced while Co²⁺, Cu²⁺, Zn²⁺, Mn²⁺, and Fe²⁺ inhibited the activity. Ethylenediaminetetraacetic acid and ethylene glycol-bis (β-aminoethyl ether)-N,N,N′,N′-tetraacetic acid, but not phenylmethylsulfonyl fluoride, aprotinin, and pefabloc SC, significantly suppressed the activity, suggesting that it might be a metalloprotease. Importantly, it is highly resistant against various detergents, organic solvents, and oxidizing agents, and the activity is enhanced by H₂O₂. The enzyme could be a novel protease based on its origin and peculiar biochemical properties. It may be useful in biotechnological applications especially for organic solvent-based enzymatic synthesis.     

Simultaneous determination of phthalates and adipates in human serum using gas chromatography–mass spectrometry with solid‐phase extraction

A gas chromatography–mass spectrometry assay was developed and validated for the simultaneous determination of phthalates and adipates in human serum. The phthalates and adipates studied were dimethyl phthalate, diethyl phthalate, dibutyl phthalate, benzylbutyl phthalate, di‐2‐ethylhexyl phthalate, di‐n‐octyl phthalate, diethyl adipate, dibutyl adipate, diisobutyl adipate, bis(2‐butoxyethyl) adipate and di‐2‐ethylhexyl adipate, with diisooctyl phthalate as internal standard. The extraction and cleaning up procedure was carried out with solid‐phase extraction cartridges containing dimethyl butylamine groups, which showed extraction efficiencies over 88% for each analyte and the internal standard. The calibration curves obtained were linear with correlation coefficients greater than 0.98. For all analytes, the assay gave CV% values for intra‐day precision from 4.9 to 13.3% and mean accuracy values from 91.4 to 108.4%, while inter‐day precision was 5.2–13.4% and mean accuracy 91.0–110.2%. The limits of detection for the assay of phthalates and adipates were in the range 0.7–4.5 ng/mL. The method is simple, sensitive and accurate, and allows for simultaneous determination of nanogram levels of phthalates and adipates in human serum. It was successfully applied to an investigation on the level of phthalates and adipates in a non‐occupationally exposed population.     

The graph and range singularity spectra of b-adic independent cascade functions

With the “iso-Hölder” sets of a function we naturally associate subsets of the graph and the range of the function. We compute the Hausdorff dimension of these subsets for a class of statistically self-similar multifractal functions, namely the b-adic independent cascade functions.