PhI(OAc)_2-promoted umpolung acetoxylation of enamides for the synthesis of α-acetoxy ketones

Umpolung is a fundamental concept in organic chemistry, which provides an alternative strategy for the synthesis of target compounds which were not easily accessible by conventional methods. Herein, a mild and efficient PhI(OAc)_2-promoted umpolung acetoxylation reactions of enamides was developed for the synthesis of α-acetoxy ketones. The reaction tolerates a wide range of functional groups and affords α-acetoxy ketones in good to excellent yields. PhI(OAc)_2 serves as a source of acetoxy in the reaction.     

An unexpected synthesis of an α,β,γ,δ-unsaturated ketone due to an abnormal opening of benzylidene acetal by bromide anion

An unexpected synthesis of an α, β, γ,δ-unsaturated ketone, which embodies a new type of oxy-carbon cyclic structure, was achieved, while we tried to construct the taxane CB-ring system. Also, a series of abnormal reaction phenomena was found to be related to the formation and reaction of seven membered cyclic benzylidene acetal.     

A Stable Vector for High-Level Expression and Secretion of Human Interferon αA in Yeast

Yeast high stable plasmid vector pHC11 was constructed by introducing pEMBL Yi27 cleaved with SmaI into the SnaBI site of intact 2 μm plasmid. The result of plasmid stability assay revealed that 82% of the host cells still harbored the vector after 50-generations growth in non-selective medium, which confirmed the existence of a non-functional region in 2 μm plasmid. The human interferon αA (IFN αA) gene expression-secretion cassette was inserted into pHC11, and the yeast transformant was cultured in complex medium. Tbe data showed that the expressed product was 36.8% of the total protein amount in the culture supernatant and the IFN αA biological activity was 2.6×10~(10) units per liter, demonstrating that high-level expression and secretion of IFN αA were achieved in yeast by using the stable vector pHC11.     

Stereoselective synthesis ofvic-halohydrins and an unusual Knoevenagel product from an organocatalyzed aldol reaction：A non-enamine mode

Stereoselective synthesis by an aldol reaction between chloroacetone and aldehyde was studied using a synthesized chiral organocatalyst and triethylamine. The reaction gave α-chloro-β-hydroxy ketones in excellent yield with highantiselectivity and enantioselectivity. The chiral organocatalyst was also used in the Knoevenagel reaction, which gave α-cyano-β-hydroxy ketones at a low tem-perature and the usual Knoevenagel product at a high temperature. Both products were obtained in good to moderate yield with goodanti selectivity in the case of α-cyano-β-hydroxy ketone deriva-tives.     

非烯胺途径有机催化醛醇缩合反应立体选择性合成邻卤代醇和Knoevenagel产物（英文）

Stereoselective synthesis by an aldol reaction between chloroacetone and aldehyde was studied using a synthesized chiral organocatalyst and triethylamine. The reaction gave α-chloro-β-hydroxy ketones in excellent yield with high anti selectivity and enantioselectivity. The chiral organocatalyst was also used in the Knoevenagel reaction, which gave α-cyano-β-hydroxy ketones at a low temperature and the usual Knoevenagel product at a high temperature. Both products were obtained in good to moderate yield with good anti selectivity in the case of α-cyano-β-hydroxy ketone derivatives.     

Physical and Electrochemical Characterization of Hydrothermal Prepared α'-NaV_2O_5 Crystals

α'-NaV2O5 was prepared by a simple hydrothermal process.X-ray diffraction confirmed the orthorhombic structure of α'-NaV2O5,with preferential growth along the (001) direction.Scanning electron microscopy showed α'-NaV2O5 was composed of flake-shaped crystals.X-ray photoelectron spectroscopy confirmed the co-existence of V4+ and V5+ in α'-NaV2O5,which results in an average V4.5+ oxidation state of α'-NaV2O5.The observed Raman bands are ascribed to different V―O vibrations.α'-NaV2O5 shows a reversible specific capacity of about 100 mA·h·g-1 between 3.5 and 1.0 V,with a good capacity retention.The good electrochemical stability of the material is attributed to its structural stability during Li+ intercalation.     

Preparation of porous α-Fe2O3-supported Pt and its sensing performance to volatile organic compounds

Porous α-Fe2O3 was synthesized by a simple hydrothermal treatment of FeCl3 aqueous solution followed by a calcination process. In the synthesis of porous α-Fe2O3, no templates or pore-directing agents were used. The as-prepared porous α-Fe2O3 was further employed as a support for loading Pt nanoparticles. The gas sensing performance of the obtained porous α-Fe2O3-supported Pt to VOCs was investigated. The sensor presented a high response and fast response-recovery characteristic to several VOCs including acetone, ether, methanol, ethanol, butanol and hexanol. Meanwhile, it exhibited a much higher response than the pure α-Fe2O3 at the operating temperature of 260°C. The enhanced sensing properties may be related to the unique porous structure of the α-Fe2O3 support and the promoting effect of active Pt nanoparticles for the sensing reactions.     

CoMFA 3D-QSAR Analysis of Epothilones Based on Docking Conformation and Alignment

Epothilones belong to a class of novel microtubule stabilizing and anti-mitotic agents, which have a paclitaxel-like mechanism of action. A three-dimensional quantitative structure-activity relationship （3D-QSAR） model was built for epothilones by the method of comparative molecular field analysis （CoMFA） combined with the flexible docking technology. The docking CoMFA model gave a good cross-validated value of q2=0.784 with an optimized component of 6 and the conventional correlation coefficient of r^2=0.985. The statistical results show that the model has good ability to predict the activity of the studied compounds. At last, the docking CoMFA model was analyzed through contour maps complemented with MOLCAD-generated active site potential surface in the α,β-tubulin receptor, which can provide important information for the structure-based drug design.     

Assessment of silver(Ⅰ) complexes of salicylaldehyde derivatives—histidine Schiff base as novel a-glucosidase inhibitors

In this study,a novel class of histidine Schiff base silver(Ⅰ) complexes derived from salicylaldehyde,1a-9a,was found to be an effective inhibitor of α-glucosidase.The results of this study showed that the newly synthesized complexes inhibited α-glucosidase through noncompetitive mechanisms;the IC_(50)values were ranging from 0.00431 μmol L ~1 to 0.492 μmol L ~1.The structure-activity relationship was established as well.These results demonstrated that compound 7a,5-nitro salicylaldehyde Schiff base silver complex,is the most promising α-glucosidase inhibitor with the lowest IC_(50) value,which could be exploited as a drug candidate to alleviate postprandial hyperglycemia in the treatment of type II diabetes mellitus.This research provided a catalyst-free,simple,and environmentally benign reaction to synthesize compounds using mechanochemistry.     

STUDIES ON THE PORE FORMATION MECHANISM OF β-CRYSTALLINE POLYPROPYLENE UNDER STRETCHING*

The pore formation mechanism of,β-crystalline polypropylene under stretching was investigated. The porosity of the samples increases rapidly with stretching, having a maximum at draw ratios around 2 and then decreases monotonically. An abrupt formation process of initial micropores at very low draw ratios was evidenced by in situ SAXS measurements. At the same time the phase transition from ,β-crystal to α-crystal proceeds slowly in the whole deformation process up to large draw ratios around 5. Comparative studies of α- and ,β-crystalline polypropylene samples before stretching indicate that in addition to difference in crystal forms the α- and β-crystalline polypropylene samples exhibit quite different morphological features. There are a lot of interfaces in ,β-crystalline polypropylene samples, which may have a lower density value and can be easily etched by argon ions and penetrated by small molecules. It was concluded from these experimental facts that the pore formation and crystal transition are two independent phenomena during the deformation of β-crystalline polypropylene samples, and phase transition from ,β-crystal to α-crystal could hardly be the origin of pore formation. A defect initiation mechanism was proposed to understand the pore formation behavior of β-crystalline polypropylenes.     

The Deactivation of Nickel Hydroxide to Hypophosphite Electrooxidation on a Nickel Electrode

The deactivation of nickel hydroxide to the electrooxidation of hypophosphite on a nickel electrode was studied by means of in situ UV-Vis subtractive reflectance spectroscopy. The experimental results show that when the potential is lower than -1.0 V (SCE), the surface on nickel electrode is free of nickel hydroxide, on which hypophosphite is active. When the potential moves positively to about 0.75V, two absorbency bands around 300nm and 550nm, which were ascribed to the formation of α-nickel hydroxide, were observed, nickel is oxidized to α-nickel hydroxide. Severe deactivation of the surface occurs when the nickel surface is covered with nickel hydroxide, which separates the hypophosphite ion from nickel substrate.     

Computational Investigation on the Ethylene-induced Esterase from Citrus Sinensis

In order to understand the interaction between ethylene-induced esterase(EIE, EC 3.1.1.) from Citrus sinensis and α-naphthyl acetate, a 3D model of EIE was generated based on the crystal structure of the tobacco salicylic acid binding protein 2(SABP2). With the aid of the molecular mechanics and molecular dynamics methods, the final refined model was obtained and its reliability was further assessed. In this study, the docking results show that the main-chain amide of residue His85 and residue Val18 can form hydrogen bonds to the carbonyl oxygen group of α-naphthyl acetate. MM-PBSA method was applied to calculating the binding free energy between EIE mutants and α-naphthyl acetate. Our calculated binding free energy of each of the two mutant complexes is increased compared with that of the one of the wild type, which is unfavorable to the reaction. It is well consistent with the experimental data. The above results clearly indicate that His85 and Val18 in EIE function as the oxyanion role and take part in the catalytic reaction. The new structural insights obtained from this computational study are expected to stimulate further biochemical studies on the structures and mechanisms of EIE and other members of the plant α/β hydrolases.     

Layered zirconium phosphate-supported metalloporphyrin： Synthesis and catalytic application

This paper reports a new route for the preparation of layered alpha-zirconium phosphate （α-ZrP）-supported metalloporphyrin MnTMPyP. MnTMPyP was intercalated into α-ZrP using α-ZrP.BA （i.e. pre-intercalated bultylamine was arranged by a monolayer mode in α-ZrP） as a starting material. The catalytic activity of the supported material for homovanillic acid （HVA） oxidation was investigated. The results showed a promising layered material-supported catalyst in catalytic system.     

Utilization of α-olefins obtained by pyrolysis of waste high density polyethylene to synthesize α-olefin-succinic-anhydride based cold flow improvers

A new route of utilization of α-olefin rich hydrocarbon fractions obtained by waste polymer pyrolysis was investigated. α-olefin-succinic-anhydride intermediate-based pour point depressant additives for diesel fuel were synthesized, in which reactions needed α-olefins were obtained by pyrolysis of waste high-density polyethylene (HDPE). Fraction of α-olefins was produced by the de-polymerization of plastic waste in a tube reactor at 500℃ in the absence of catalysts and air. C17～22 range of mixtures of olefins and paraffins were separated for synthesis and then, these hydrocarbons were reacted with maleic-anhydride (MA) for formation of α-olefin-succinic-anhydride intermediates. The olefin-rich hydrocarbon fraction contained approximately 60% of olefins, including 90%～95% α-olefins. Other intermediates were produced in the same way by using commercial C20 α-olefin instead of C17～22 olefin mixture. The two different experimental intermediates with number average molecular weights of 1850g/mol and 1760g/mol were reacted with different alcohols: 1-butanol, 1-hexanol, 1-octanol, i-butanol, and c-hexanol to produce their ester derivatives. The synthesized ten experimental pour point depressants were added in different concentrations to conventional diesel fuel, which had no other additive content before. The structure and efficiency of experimental additives were followed by different standardized and non-standardized methods. Results showed that the experimental additives on the basis of the product of waste pyrolysis were able to decrease not only the pour but also the cloud point and cold filter plugging point (CFPP) of diesel fuel, whose effects could be observed even if the concentration of additives was low. Furthermore, all additives had anti-wear and anti-friction effects in diesel fuel.     

SYNTHESIS AND SECRETION OF HUMAN ATRIAL NATRIURETIC PEPTIDE IN Saccharomyces cerevisiae

A chemically synthesized α-hANP gene was inserted into plasmid YFD18, which was an expression-secretion vector of yeast. The recombinant then transformed in the yeast Y33. The expression level of yeast transformants was about 700 μg ANP/L detected by RIA. More than 99% of expression products were secreted in the culture medium. N-terminal analysis of purified product showed that the first 4 amino acid residues of α-hANP were deleted.     

STUDY ON THE CONDUCTIVITY OF A COMPLEX INORGANIC ION EXCHANGER—α—ZIRCONIUM PHOSPHATE MIXED WITH SILICA

The composite of α-ZrP and fumed silica was prepared by dispersing predetermined molar ratios of polycrystalline α-ZrP in water.Admittance measurement of the samples was made in the frequence range from 5Hz to 1MHz and the temperature range from -20℃ to 20℃.The activation energy in conduction of the composites,with different molar fraction of α-ZrP,is about 5.9KJ/mol at 60% and 40% relative humidities.The results show that the charge transport mechanism was not changed after mixing fumed silica into α-ZrP and the charge transport medium is water in α-ZrP and the composites.     

Synthesis of a New Cerebroside Isolated from Typhonium giganteum Engl

The stereoselecfive synthesis of typhoniside, a new cerebroside isolated from Typhonium giganteum Engl. was accomplished.Cerebrosides are a kind of glycolipids highly enriched on the surface of myelin-producing cells and are composed by C18-4,8-sphingadienine, a-hydroxy acid and a saccharide head. It was the first time that cerebrosides were isolated from this traditional Chinese medicine (TCM) by us. In this paper, C18-4,8-sphingadienine was synthesized from D-xylose via a SN2 type reaction, α-Hydroxy acid was prepared from (R)-4-hydroxyte-trahydrofuran-2-one, which in turn could be obtained from Lascorbic acid.     

a,a,a,b-ZnT(o-BocThr)APP对咪唑衍生物和氨基酸酯的分子识别研究

Molecular Recognition of α,α,α,β-ZnT（o-BocThr）APP （1） toward a series of imidazole derivatives and amino acid esters was investigated. Association constants were determined in chloroform by means of UV-Vis titration method. The association constants of 1 with imidazole derivatives are larger than those of 1 with amino acid esters. 1H NMR spectra were investigated to describe the binding mode of the recognition system, showing that all the protons of the guests were shifted to upfield. The circular dichroism spectra of 1-L-/D-ValOMe showed a split cotton effect in Soret region, while those of 1-L-/D-PheOMe showed no split cotton effect. Molecular modeling was performed to understand chiral recognition on a molecular level. Quantum chemical calculation was carried out based on the stable conformations of these recognition systems, which gave a reasonable explanation for the behavior of molecular recognition. The results indicated that the conformation of 1-D-ValOMe was more stable than that of 1-L-ValOMe.     

STRUCTURAL EFFECT ON VINYL POLYMERIZATION INITIATED WITH AROMATIC TERTIARY AMINE

The polymerization mechanism of various vinyl monomers in the presence of aromatic tertiary amines has been studied. It was found that the mechanisms of different monomers are varied with the structures of monomers. Those monomers, such as methacrylic esters containing α-CH_3 group on the double bond could be polymerized with aromatic tertiary amine in the absence of light, while the monomers without α-CH_3 group, such as methyl acrylate, acrylonitrile etc. would polymerize only under light.The structural effects, both of the monomer and the amine, on the rate of photopolymerization were studied. The activities of monomers and amines may be arranged in the following orderMonomer: AN>MA>VA>St Amine: DMT>DMA>DMB>DNAIt is revealed that both the electro-negative group on the double bond of monomer which acts as an acceptor and the electro-positive group on the nitrogen atom of amine which acts as a donor would effectively increase the rate of photopolymerization.     

Synthesis and Bioactivity of Isosteviol Derivatives： A Facile Method for Preparation of Ent-16α-hydroxy-15β-hydroxymethylbeyeran-19-oic Acid

In this paper, two new compounds, ent-16α-hydroxy-15β-hydroxymethylbeyeran-19-oic acid 4 and its ethyl ester 5 were synthesized in good yield with a facile method that has never been reported. The mechanism of this reaction was discussed and the mono-hydroxymethylation of carbonyl compound with two α-hydrogens via Tollens＇ reaction was firstly achieved. Compounds 2-5 were tested for activity of inhibition against glycosidases, among which 5 displays good inhibition of β-glucosidase and α-mannase, respectively.