Synthesis of Some Novel Phenyl Substituted Oxothiazolidin- 1’’,3’’,4’’-thiadiazolo-[3’,4’-b]thiazoline of 3β-Substituted Cholestane

Three title compounds 4a—4c have been synthesized by the cyclodehydration of 1’-benzylidine-4’-(3β-substituted-5α-cholestane-6-yl)thiosemicarbazones 2a—2c with thioglycolic acid followed by the treatment with cold conc. H2SO4 in dioxane. The compounds 2a—2c were prepared by condensation of 3β-substituted-5α-cholestan- 6-one-thiosemicarbazones 1a—1c with benzaldehyde. These thiosemicarbazones 1a—1c were obtained by the reaction of corresponding 3β-substituted-5α-cholestan-6-ones with thiosemicarbazide in the presence of few drops of conc. HCl in methanol. The structures of the products have been established on the basis of their elemental, analytical and spectral data.     

CHEMISTRY OF DENUDATINE Ⅲ. REARRANGEMENT OF DENUDATINE

Treatment of denudatine 1 with 10％ HCl soln. at 30-40℃ for 1 day leads to another rearrangement product 3 along with a pair of epimers 2A and 2B. Upon adding a little EtOH in the reaction solution, only a pair of epimers 4A and 4B were obtained along with the unchanged starting material.     

Synthesis of a novel cyclodextrin dimer linked by a macrocyclic polyamine

The first example of cyclodextrin dimer appending a macrocyclic polyamine spacer on the primary faces was synthesized via two approaches: 1,a direct reaction of l,7-bis(2'-aminoethyl)-4,10-dimethyl-l,4,7,10-tetraazacyclododecane (1) with an excess of 6-deoxy-6-O-tosyl-β-cyclodextrin; 2,a condensation of 1 with two equivalents of 6-deoxy-6-formyl-β-cyclodextrin,which was followed by a reduction with NaBH4.     

Palladium-catalyzed concerted [4 + 1] cyclization of prop-2-yn-1-ones and isocyanides

A palladium-catalyzed [4+1] cycloaddition of prop-2-yn-1-ones with double isocyanides is developed herein.The transformation worked well to produce a series of 2-amino-4-cyanofurans with high efficiency and a broad reaction scope.Based on mechanism studies,it is believed that the palladiumcatalyzed [4+1] imidoylative cycloaddition of prop-2-yn-1-ones was concerted.Treated with a ryl amine and H_2 O,the [4+1] cycloaddition of prop-2-yn-1-ones with double isocyanides provided 2-amino-4-amidylpyrroles efficiently.     

A water-stable metal-organic framework: serving as a chemical sensor of PO_4~(3–) and a catalyst for CO_2 conversion

A new 2D Eu-BTB framework(1) with stratified gridding structure of about 14.6×16.9was synthesized and characterized.Compound 1 displays excellent water stability with the pH 2–12. The luminescent investigations suggest that 1 could represent a chemical sensor of PO43. with high sensitivity and selectivity. Importantly, 1 as a sensor of PO_4~(3-) can be reused at least five times.On the other hand, the catalytic investigations of 1 were carried out, indicating that 1 could be demonstrated as a recyclable catalyst for CO_2 conversion with epoxides.     

Nitrogen-doped carbon encapsulated in mesoporous TiO_2 nanotubes for fast capacitive sodium storage

Controllable synthesis of insertion-type anode materials with beneficial micro-and nanostructures is a promising approach for the synthesis of sodium-ion storage devices with high-reactivity and excellent electrochemical performance.In this study,we developed a sacrificial-templating route to synthesize TiO₂@N-doped carbon nanotubes(TiO₂@NC-NTs)with excellent electrochemical performance.The asprepared mesoporous TiO₂@NC-NTs with tiny nanocrystals of anatase TiO₂ wrapped in N-doped carbon layers showed a well-defined tube structure with a large specific surface area of 198 m² g^-1 and a large pore size of~5 nm.The TiO₂@NC-NTs delivered high reversible capacities of 158 m A h g^-1 at 2 C(1 C=335 m A g^-1)for 2200 cycles and 146 m A h g^-1 at 5 C for 4000 cycles,as well as an ultrahigh rate capability of up to 40 C with a capacity of 98 m A h g^-1.Even at a high current density of 10 C,a capacity of 138 m A h g^-1 could be delivered over 10,000 cycles.Thus,the synthesis of mesoporous TiO₂@NC-NTs was demonstrated to be an efficient approach for developing electrode materials with high sodium storage and long cycle life.     

STUDIES ON THE MUNG BEAN TRYPSIN INHIBITOR——REDUCTION AND REOXIDATION OF THE DISULFIDE BONDS OF THE LYS ACTIVE FRAGMENT

Two peptide chains A_1 and A_2 of the Lys active fragment, linked via a couple ofinter-disulfide bonds, could be separated from each other after reduction with dithiothreitoland gel filtration on Sephadex G-25. Reoxidation of the reduced peptide chain A_1 resultedin recovering the inhibitory activity with 25% yield, based on the original activity of theLys fragment. The A_1 active fragment was further purified by affinity chromatographywith immobilized trypsin. Sephadex G-25 gel filtration produced two forms of the A_1 activefragment, the major fraction being a monomer and the minor one being a dimeer with loweractivity. The results obtained offered evidence of the evolution of mung bean inhibitorfrom an ancestral single-headed inhibitor by fused gene duplication with A_2 as a connectingpeptide. The CD spectra of the Lys fragment and the reoxidized peptide chain A_1 werealso compared.     

Synthesis of Some New Heterocycles Derived from Phenylacetyl Isothiocyanate

Phenylacetyl isothiocyanate (1) was reacted with benzoyl hydrazine (2a) in acetonitrile to give thiosemicarbazide derivative 3 which was cyclized by polyphosphoric acid to give 1,2,4-triazoline-5-thione derivative 4. Treatment of 1 with thiosemicarbazide (2b) yielded another 1,2,4-triazoline-5-thione derivative 5. Similar treatment of 1 with phenyl hydrazine (2c) in acetonitrile gave a differently substituted 1,2,4-triazoline-5-thione derivative 6 in one pot-reaction. On the other hand, when the reaction was carried out in acetone, a mixture of 6 and thiadiazolidine derivative 7 was obtained. However, reaction of 1 with hydrazine hydrate (2d) gave hydrazine derivative 8. Reaction of isothiocyanate 1 with anthranilic acid (9) gave benzo[d][1,3,6]oxazin-1-one derivative 10. Treatment of 1 with 2-aminothiophenol (11a), 2-aminophenol (11b) or o-phenylenediamine (11c) produced benzothiazole derivative 12a, benzoxazole derivative 12b and benzimidazole derivative 12c, respectively. The structures of all the products were confirmed by micro-analytical and spectral data.     

DEPENDENCE OF THE DISTRIBUTION OF ACTIVE CENTERS ON MONOMER IN SUPPORTED ZIEGLER-NATTA CATALYSTS

Distribution of active centers(ACD)of ethylene or 1-hexene homopolymerization and ethylene-1-hexene copolymerization with a MgCl_2/TiCl_4 type Z-N catalyst were studied by deconvolution of the polymer molecular weight distribution into multiple Flory components.Each Flory component is thought to be formed by a certain type of active center. ACD of ethylene-1-hexene copolymer with very low 1-hexene incorporation was compared with that of ethylene homopolymer to see the effect of introducingα-olefin on eth...     

Direct observation of uncoated spectrin with atomic force microscope

Spectrin molecules extracted from human blood ceil membrane have been examined by atomic force microscopy (AFM) without using shadowing or staining procedures. A drop of the solution containing spectrin molecules was deposited on the freshly deaved mica substrate. After about 1 min, the residual solution was removed with a piece of filter paper. Afterwards the sample was imaged with a home-made atomic force microscope (AFM) in air in a constant force mode. The obtained AFM images revealed that the spectrin molecules prepared from the above procedures exhibit several kinds of structures as follows: (i) the compact rod-like spectrin heterodimers with a length of around 100 nm; (ii) bent or curved linear tetramers with a length of around 200 nm; (iii) somewhat curved spectrin hexamers, octomers or decamers with lengths of about 300, 400, or 500 nm; and (iv) high oligomers with a length above 1 000 nm.     

A Novel Pharmacophore Model Derived from a Class of Capsid Protein Enterovirus 71 Inhibitors

Capsid protein enterovirus 71 (EV71) is one of the major viruses that cause the severe encephalitis and thus result in a high mortality in children less than 5 years of age.In an effort to discover new potent inhibitors against EV71,a novel three-dimensional pharmacophore model was developed on 24 inhibitors with different molecular structures and bioactivities.The best hypothesis (Hypo1) has a high predictive power and consists of four features,namely,one hydrophobic point (HY) and three hydrogen-bond acceptors (HA).Two key features of the best Hypo1,HY1 and HA3 match well with an important narrow hydrophobic canyon and with the surface of LYS274 in the target EV71 active site,respectively.The more versatile feature,HA1,is firstly found to be very influential on these compounds' bioactivities,which may interact with the other side of the active site in the EV71 receptor.The application of the model is successful in predicting the activities of 30 known EV71 inhibitors with a correlation coefficient of 0.831.Furthermore,Hypo1 demonstrates a superior screening capability for retrieving inhibitors from the database with a high enrichment factor of 70.This study provides some important clues in search for more potent inhibitors against EV71 infection.     

An Improved Synthesis of Brodimoprim

Brodimoprim (1) is a new antibacterial benzylpyrimidine with a broad spectrum of antimicrobial activities. An improved synthetic method of (1) was reported in this paper from 4-bromo-3,5-dimethoxybenzaldehyde (2) through Knoevenagel condensation, 1,3-prototropic isomerization and cyclization with overall yield of 53.8% which was 40.2% in the early report. As a key intermediate, cinnamonitrile (3) was prepared by the condensation of 2 with 3- methoxypropan-enitrile, which was generated in situ from acrylonitrile with methanolic sodium methoxide. It was found that 3 could be converted easily into the corresponding benzyl isomer 4 by reacting with ethylene glycol monomethyl-ether. 4 reacted with guanidine to give 1 without isolation and purification.     

Structural study on a bioactive fructan from the root of Achyranthes bidentata Blume

The structure of a saccharide component (Abs),with pronounced activity of improving immunity system,isolated from the root of Achyranthes bidentata Blume,a traditional Chinese herbal medicine,was studied.Based on 13C NMR,HPLC,and methylation analyses,Abs was shown to be a mixture of short-chain fructans with an average dp of 8,containing more (2→6) than (2→1) linked β-D-fructofuranosyl residues,with branching at O-6 or O-1 of 18% of the D-fructofuranoeyl residues.     

FREQUENCY DEPENDENCE OF THE DIELECTRIC RELAXATION OF 1,2-POLYBUTADIENES

The dielectric loss factor and permittivity of a series of 1, 2-polybutadienes with different contents of 1, 2-units and different contents of syndiotactie 1, 2-units were determined over a frequency range from 30Hz to 100KHz at different temperatures. The WLF equation was evaluated for various samples with T_θat 100KHz as a reference temperature and the master curves of various samples have been constructed, which are in accordance with those calculated by Havriliak-Negami equation. The frequency dependence of the dielectric relaxation of 1, 2-polybutadienes was investigated over a frequency range from 10~0 Hz to 10~(12) ZHz in terms of the experimental data and the master curves.     

COULOMETRIC TITRATION OF MYLIS

A method for the determination of Mylis by coulometrictitration was developed.The titration was carried out in a mixture of1 mol/L KBr-2 mol/L HCl(1:1)and bromine was generated at the anode,Mylis reacted with one mole of bromine with a n value of 2.The advantages of this method are simple and rapid,it can be used toanalyze small amount of sample.     

A gram-scale laboratory synthesis of Annonaceous acetogenin mimic AA005

AA005(1),a potent anticancer mimicking molecule of natural Annonaceous acetogenin,features a central C₂-symmetric triglycol moiety and three stereogenic centers.To support ongoing animal studies,a scalable 10-step synthesis of AA005(1) has been studied,optimized and accomplished in this work,starting from commercially available economic materials ethylene glycol and(R)-epichlorohydrin.A regio-and stereo-controlled BF₃·Et₂O-promoted epoxide opening of(R)-epichlorohydrin with ethylene glycol was investigated,optimized and successfully applied to the scalable preparation of the crucial fragment 6 a with C₂-symmetry.Further successive epoxide openings elaborated both two side chains and the whole skeleton with proper nucleophiles and electrophiles.Comparison and optimization of the reaction sequences finally led to completion of a new multi-gram synthesis ofAA005(1) with satisfactory enantiomeric and diastereomeric purity.     

Extractive Spectrophotometric Determination of Fluconazole by Ion-pair Complex Formation with Bromocresol Green

An extraction-spectrophotometric method for the determination of trace amounts of fluconazole was described. Fluconazole was effectively extracted as a 1 ： 1 ion-pair complex with bromocresole green （BCG） at pH 3.0 into chloroform, followed by spectrophotometric determination at 420 nm. Beer＇s law was obeyed over the range of 4-50 μg.mL^-1 of fluconazole with a detection limit of 3.7 μg.mL^-1 . The method is simple, rapid and sensitive. The procedure was applied to the determination of fluconazole in pharmaceutical preparations as well as its recovery from a blood serum sample.     

EFFECT OF MOLYBDENUM PROMOTER ON THE Cu-Co BASED CATALYSTS

The synthesis of mixed alcohols (C1-C5) from syngas has been studied at 6. 0 MPa over modified Co/CuLaZr catalysts. The molybdenum addition enhanced greatly the activity and the selectivity to alcohols. The improvement of hydrogenation capacity of the system via a reversible spillover effect of hydrogen could explain this effect, together with a great capacity of CO insertion, illustrated by the effect of C2H4 addition as a probe to syngas. Under our experimental conditions, a mixed alcohol production of 147.1g/kg. cat/h containing a proportion of 33. 1% of higher alcohols (C2 OH) was obtained with a selectivity to ROH of 52. 8%.     

Direct Electrochemical Evidence of the Dissociation and Adsorption Behavior of Acetonitrile at Gold Electrodes by Ultrafast Voltammetry

Ultrafast cyclic voltammetry was used to study the redox behavior of a gold electrode in acetonitrile. The direct electrochemical evidence of the dissociation and adsorption behavior of acetonitrile at gold electrodes was found. It could be stated that two consecutive redox paths are involved, each with a special adsorption state acting as the reaction intermediate. The mean value, obtained of the electron-transfer rate constant of the second path, was 1.3 × 105 s-1 with a standard deviation of 0.24 × 105 s-1.     

SUBUNIT STOICHIOMETRY AND INTERACTION OF F_1-ATPase OF BEEF HEART MITOCHONDRIA

By incubating soluble F_1 of the beef heart mitochondria with radio active 7-chloro-4-nitro-2, 1, 3-benzoxadiazole (~(14)C)-NBD-C1 in the dark, a labeled F_1 with NBD/F1 molar ratio of 1: 1 (0.995: 1) wasobtained, but 98% of the ATPase activity was inhibited. The inactivated ATPase activity of the NBD-labeled F_1 may be restored by DTT, suggesting that an essential tyrosine residue of F_1 (O-NBD-F_1) maybe labeled. By exposure of O-NBD-F_1 to reflected light, the NBD label can be transferred to an aminogroup, forming an N-NBD-F_1 with 0.83 NBD label per F_1 molecule and a stable 82.5% inhibition ofthe ATPase activity even in the presence of DTT. Urea PAGE analysis clearly showed that a 63.4% ofthe total radio activity was associated with the β-subunit. In the β-fraction from N-NBD-F_1 only a 19.9-20% of the labeling was detected. It is calculated that F_1 of the beef heart mitochondria contains 3(2.63-2.64) β-subunits. The results obtained are discussed in connection with the subunit-subunit andsite-