Facile Formation of Ytterbium Diiodide and Its Use in the Synthesis of Allyl Selenides

Ytterbium metal reacts with iodine to generate ytterbium diiodide directly,which can react with diselenides to form ytterbium selenolates(RSeYbI2).These species reacted smoothly with allyl bromide to give allylselenides in moderato to good yields under neutral conditions.     

Kinetics of Reaction Bisphenol-S Epoxy Resin with Methylacrylic Acid

The reaction kinetics of bisphenol-S epoxy resin with methyl-acrylic acid in the presence of quaternary ammonium salt catalyst was studied. The reaction rate constants at different temperatures were determined. The reaction is first order with respect to epoxy group, zero order with respect to methylacrylic acid and 0.71 order with respect to quaternary ammonium salt catalyst, respectively. The mechanism of this reaction was discussed.     

Lewis Base Organocatalyzed Enantioselective Hydrosilylation of α-Keto Ketimines

A chiral Lewis base organocatalyzed enantioselective hydrosilylation ofa-keto ketimines was investigated.The reactions afforded various enantioenriched a-amino ketones with good yields（up to 95％） in moderate to good enantioselectivities（up to 98％ e.e.）.Furthermore,one of the products was reduced to a chiral 1,2-amino alcohol.Following cyclization of it with triphosgene generated a cannabinoid receptor 1 （CB 1） inhibitor with good diastereoselectivity.     

Kinetics of Reaction of Bromo-epoxy Resin with Oleic Acid catalyzed by Dimethyl benzyl amine

The kinetics of reaction of bromo-epoxy resin with oleic acid in the presence of dimethylbenzylamine catalyst was studied. The reaction is a zero order reaction with respect to oleic acid, first order with respect to epoxy group and 0. 74 order with respect to dimethylbenzylamine. The reaction rate constants at various temperatures and activation energy were determined. The mechanism of this reaction was discussed. Keywords Tetrabromobisphenol-A, Bromo-epoxy resin, Oleic acid kinetics, Reaction mechanism     

HYPERBRANCHED CONJUGATIVE MACROMOLECULES CONSTRUCTED FROM TRIPLE-BOND BUILDING BLOCKS

Polycyclotrimerization and polycoupling of acetylenic monomers respectively furnish hyperbranched polyarylenes and polyynes with high molecular weights(up to 1×10~6)in high yields(up to 99.9%).The polymers possess low intrinsic viscosities and high thermal stabilities,losing little of their weights when heated to＞400℃.Upon pyrolysis at＞800℃,the polymers graphitize with high char yields(up to 86%).Hyperbranched polyarylenes efficiently emit deep-blue to blue-green lights with fluorescence quantum yields up to 98% and strongly attenuate intense laser pulses with optical power-limiting performances superior to that of C_(60),a well-known optical lirniter.Poly(alkenephenylenes),poly(aroylarylenes)and polyynes are readily cross-linkable by UV irradiation,serving as excellent photoresist materials for the generation of patterns with nanometer resolution.Thin films of hyperbranched polyynes exhibit very high refractive indexes(n up to 1.86).The internal and terminal acetylene moieties of the polyynes readily form complexes with cobalt carbonyls,which can be transformed into soft ferromagnetic ceramics with high magnetic susceptibilities(M_s up to ca.118 emu/g)and near-zero magnetic losses.     

TOTAL SYNTHESIS OF YEAST ALANINE TRANSFER RIBONUCLEIC ACID

By a combination of chemical and enzymatic methods, small oligonucleotides with lengths varying from 2 to 8 nucleotides were synthesized from mononucleotides. The small oligonucleotides were then ligated with T_4 RNA ligase into six laxge ligonucleotides (9 to 19 nucleotides long) which were further ligated to form two half molecules with 35 and 41 nucleotides respectively, Finally, the two synthetic half molecules were annealed and ligated to obtain the whole molecule of yeast alanine tRNA (tRNA_y~(Ala)). Prior to this, two semi-syntheses were performed, i. e. ligation of the synthetic 5'-half molecule with the natural 3'-half molecule and that of the natural 5'-half molecule with the synthetic 3'-half molecule.     

Asymmetric catalytic 1,3-dipolar cycloaddition of α-diazoesters for synthesis of 1-pyrazoline-based spirochromanones and beyond

A highly enantioselective 1,3-dipolar cycloaddition of α-substituted diazoesters with exocyclic enones was achieved with chiral scandium(III)/N,N′-dioxide complex as the catalyst. This protocol provided a facile and efficient route to optically active 1-pyrazoline-based spirochromanones and others with good outcomes(up to 97% yield, 98% ee with 95:5 dr). Moreover,enantioenriched 2-pyrazoline-based spirochromanones were also accessible by switching α-substituted diazoesters to α-diazoacetates. The further specific transformations of chiral pyrazoline-based spiro-compounds to spirocyclopropane derivatives were disclosed as well.     

ROLE OF THIOL-DISULFIDE EXCHANGE IN INSULIN BINDING TO ITS RECEPTOR

The effects of reduction by DTT, oxidation by DTNB and treatment with NEM on the thiol contents and insulin binding to its receptor in mice liver membranes were studied. Reduction with DTT leads to a parallel increase in the thiol content and the speciflc binding of insulin to the membrane. Scatchard analysis of the results shows little change in the number of binding sites but a twofold increase of the binding constant. Washing the membrane with bound insulin by a DTT containing buffer results in a more marked increase in the release of bound insulin than washing with buffer alone, suggesting that part of the insulin is bound to its receptor by covalent disulfide linkages through a thIol-disulfide exchange reaction and reduction with DTT leads to a marked increase in this "disulfide-linked" insulin. Treatment with DTNB or NEM of the DTT-reduced membrane seems to reverse the effect of DTT reduction, although the reaction of the untreated membrane with DTNB or NEM had little or no effect on the specific     

Dyes with high affinity for polylactide

Attempts were made to develop dyes with high affinity for polylactide as an alternative to the existent commercial disperse dyes. The dyes synthesized according to the affinity concept of dye to polylactide exhibited excellent dyeing properties on polylactide compared with the commercial disperse dyes.     

O—Maltosylation of Heterocyclic Ketene Aminals

The stereoselective synthesis of O-maltosides by reacting benzoyl-substituted heterocyclic ketene aminals 1 or 2 with acetylated maltosyl bromide 3 was investigated.Compounds 1 or 2 reacted with 3 in the presence of mercuric cyanide to give O-maltosides 4 or 5 with E-configuration.While 1 reacted with 3 in the presence of calcium hydride to give O-maltosides 6 with Zconfiguration.     

Dye-sensitized solid-state solar cells fabricated by screen-printed TiO_2 thin film with addition of polystyrene balls

The screen-printed nanoporous TiO2 thin film was employed to fabricate dye-sensitized solid-state solar cells using CuI as hole-transport materials. The solar cell based on nanoporous TiO2 thin film with large pores formed by the addition of polystyrene balls with diameter of 200 nm to the TiO2 paste exhibits photovoltaic performance enhancement, which is attributed to the good contact of CuI with surface of dye-sensitized thin film due to easy penetration of CuI in the film with large pores.     

STUDIES ON THE REACTION OF SULFUR,SELENIUM AND TELLURIUM WITH SODIUM HYDROXIDE UNDER PHASE TRANSFER CATALYSIS(Ⅱ).A CONVENIENT METHOD FOR THE SYNTHESIS OF BI(ACYL)DISULFIDES

A simple and general method for the synthesis of bi(acyl)disulfides isreported.Sulfur is allowed to react with sodium hydroxide to give sodium disulfideat 65℃ under PTC,which can react with acyl halides to afford bi(acyl)disulfides ingood to excellent isolated yields.The effects of solvents and phase transfercatalysts are discussed.     

Preface

About 150 years ago, along with the establishment of physical chemistry, chemistry was promoted from an empirical to a highly quantitative science which attempts to understand elementary systems with great theoretical and experimental rigor. Today physical chemistry is distinguished as an ever-evolving discipline to develop new methods, understand fundamental events and tackle grand problems of broad complexity with deep insights.     

Preparation of thiophilic paramagnetic adsorbent for separation of antibodies

The micron-sized microspheres with superparamagnetic property were synthesized with vinyl acetate and divinylbenzene by microsuspension polymerization. After the complete alcoholysis, these hydroxyl-functionalized microspheres were activated by divinylfone and modified with mercaptoethanol to prepare the thiophilic magnetic adsorbent, which was used to specifically isolate immunoglobulin G （IgG） from human serum. This thiophilic magnetic adsorbent performed an evident salt-dependent adsorption behavior for IgG. Due to their salt-promoted adsorption towards IgG under high salt concentration, the absorbed antibodies could be extracted in low salt concentration with high purity.     

Preface

<正>About 150 years ago, along with the establishment of physical chemistry, chemistry was promoted from an empirical to a highly quantitative science which attempts to understand elementary systems with great theoretical and experimental rigor. Today physical chemistry is distinguished as an ever-evolving discipline to develop new methods, understand fundamental events and tackle grand problems of broad complexity with deep insights.     

N-磺化手性β-氨基醇修饰的钛试剂催化下的酮的不对称炔基化反应研究

The easily prepared and recoverable chiral N-sulfonylated fl-amino alcohol 2 in combination with Ti（OPr-i）4 was found to be an effective chiral catalyst for the enantioselective addition of alkynylzinc to ketones, which gave the useful products, i.e. chiral tertiary propargyl alcohols, with the ee up to 92%.     

Stimuli-responsive organic chromic materials with near-infrared emission

Some organic chromic materials responding to external stimuli, mainly to mechanical forces, with a near-infrared (NIR) emission are discussed. In line with reported cases, there is a conclusion that subtle changes in conformations and packing modes are the primary elements contributing to the optical properties changes.     

Evaluation of 1,2-Diaminoanthraquinone (DAA) as a Potential Reagent System for Detection of NO

The reaction of 1,2-diaminoanthraquinone (DAA) with NO has been investigated for potential development into an optical fibre chemical sensor. In aqueous solutions a linear calibration was obtained between 0 and 40 μM NO with a calculated detection limit of about 5 μM (s/n = 3). DAA was shown to be pH independent between 6 and 10 with a pK_a of ∼5.5 making it a suitable reagent for detection of physiological NO. NO was shown to quench the fluorescence of DAA and this was due to a static quenching mechanism. The effects of nitrite, peroxynitrite, superoxide and hydrogen peroxide were investigated. Peroxynitrite did not react with DAA and nitrite did not interfere with the reaction of NO with DAA. Though attempts to immobilize DAA in silicone rubber and nafion were successful, exposure to NO gas did not result in a significant response.     

Studies on nitramide and its methyl derivatives with ab initio calculations——Ⅳ.The harmonic force field and vibrational spectra of dimethylnitramine and its isotopic derivatives

The complete harmonic vibrational force field of dimethylnitramine has been calculatedat the Hartree-Fock level using 4-21G basis set.The harmonic force field was then scaled with scalefactors previously derived from N-methylnitramine,and the vibrational spectrum of dimethylnitraminewas computed.This apriori prediction,made with no reference to observations on dimethylnitramine,agrees with the experimental IR spectrum in gas phase with a mean deviation of 8.4 cm~(-1).Some of thescale factors were reoptimized by fitting of the computed force field to experimental data.The newset of scale factors reduced the mean deviation to 4.5 cm~(-1),and was used to predict the vibrationalspectrum of deuterated form of dimethylnitramine(-6D).Dipole moment derivatives were also cal-culated and used to predict infrared intensities which are comparable with experimental values.     

SYNTHESIS OF POLY ( ETHER-URETHANE) CONTAINING PENDANT AMINO GROUP

This paper is concerned with the synthesis of poly (ether-urethane) with pendant amino groups. The copolyether produced by ring opening copolymerization of tetrahydrofuran and epibromohydrin was treated with sodium azide in dimethylformamide to form azido substituted copolyether. The poly (ether-urethane) made from it was subjected to reduction reaction to convert azido group to amino group. The stress-strain behavior and dynamic-mechanical properties of poly (ether-urethane) containing pendant amino groups were studied.