Synthesis of diastereomeric 3-hydroxy-4-pyrrolidinyl derivatives of nucleobases

The work deals with the synthesis of hydroxypyrrolidine analogs of nucleosides. Starting from the optically pure l- or d-tartaric acid, we improved the synthesis of enantiomeric trans-3,4-dihydroxypyrrolidines and elaborated a procedure for the synthesis of all possible diastereoisomers of 3-hydroxy-4-pyrrolidinyl derivatives of both purine and pyrimidine nucleobases. The prepared compounds were tested for cytostatic and antiviral properties but no significant activity was found.     

取代茚基稀土配合物/添加剂体系催化丙烯腈聚合

研究了取代茚基稀土配合物 /添加剂体系对丙烯腈的聚合 ,发现季胺盐及芳氧钠是取代茚基二价稀土配合物催化丙烯腈聚合的有效添加剂 ,其中Me3NC1 6 H33Br效果最好 ,5种二价稀土配合物 (C5H9C9H6 ) 2 Yb (THF) 2 ,(C5H9C9H6 ) 2 Sm (THF) 2 ,KSm (C5H9C9H6 ) 3(THF) 3,(PhCH2 C9H6 ) 2 Sm(THF) 2 和 (CH3CH2 C9H6 ) 2 Sm (THF) 2 与Me3NC1 6 H33Br构成的催化体系对于丙烯腈聚合都显示出好的催化活性。对(C5H9C9H6 ) 2 Yb(THF) 2 /Me3NC1 6 H33Br体系而言 ,在丙烯腈中当催化剂用量为 2× 10 - 5mol·g - 1时 ,丙烯腈聚合的最大转化率为 61%。     

Synthesis, crystal structure and properties of the Cu complex of a tetradentate imidazole-functionalized diazamesocyclic ligand, 1,4-bis(N-1-methylimidazol-2-yl-methyl)-1,4-diazacycloheptane

A new potential tetradentate ligand, 1,4-bis(N-1-methylimidazol-2-ylmethyl)-1,4-diazacycloheptane (l), together with its Cu^II complex [CulCl]ClO₄ (1), has been reported. The crystal structure of 1, determined by single-crystal X-ray analysis, shows that it is in chiral P2₁2₁2₁ space group. The Cu^II centre is penta-coordinated in square pyramidal geometry and the diazacycloheptane (DACH) ring adopts normal boat configuration. The most striking feature of this complex is the formation of a 3D network bridged through the C-H?Cl hydrogen bonds with the perchlorate anions in the cavities, and stabilized via π-π stacking interactions along the a-direction. The solution behaviour of 1 has been further investigated by UV/Vis and ESR techniques.     

Formation of polymeric micelles with amino surfaces from amphiphilic AB‐type diblock copolymers composed of poly(glycolic acid lysine) segments and polylactide segments

Amphiphilic AB‐type diblock copolymers composed of hydrophobic poly(L ‐lactide) (PLA) segments and hydrophilic poly(glycolic acid lysine) [poly(Glc‐Lys)] segments with amino side‐chain groups self‐associated to form PLA‐based polymeric micelles with amino surfaces in an aqueous solution. The average diameter of the loose core–shell polymeric micelles for poly(Glc‐Lys) [number‐average molecular weight (M_n) = 1240]‐b‐PLA (M_n = 7000) obtained by a dimethyl sulfoxide/water dialysis method was estimated to be about 50 nm in water by dynamic light scattering measurements. The size and shape of the obtained polymeric micelles were further observed with transmission electron microscopy and atomic force microscopy. To investigate the possibility of applying the obtained PLA‐based polymeric micelles as bioabsorbable vehicles for hydrophobic drugs, we tested the entrapment of drugs in poly(Glc‐Lys) (M_n = 1240)‐b‐PLA (M_n = 7000) micelles and their release with doxorubicin as a hydrophobic drug. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1426–1432, 2002     

氟代二苯乙烯氨基酸的合成及性能

以4-碘-L-苯丙氨酸为初始原料,经羧基和氨基的保护得到化合物2;化合物2与4-氟苯乙烯进行Heck反应得化合物3;化合物3脱去保护基得氟代二苯乙烯氨基酸(4,47.4%);其结构经1H NMR,13C NMR,IR和MS(ESI-TOF)确证。光学性质研究结果表明:4的激发、发射波长分别为314 nm和355 nm,斯托克斯位移为41 nm,荧光量子产率为0.22。化合物4在甲醇溶液中存在光致顺反异构现象,反式→顺式结构转变速率常数为0.026 min^-1。     

镧系与二甘醇-二-(邻羟基苯基)醚配合物的合成与表征

本文合成14种镧系高氯酸盐及硝酸盐分别与二甘醇-二-(邻羟基苯基)醚(记为EO_2(HOP)_2,EO=ethylene oxide,HOP为邻羟基苯基)形成的新配合物,确证组成为Ln(ClO_4)_3·EO_2(HOP)_2·nH_2O(Ln:La-Eu,n=10,Ln:Gd,Dy-Tm,Y,n=7),La_3(NO_3)_9·(EO_2(HOP)_2)_2·3H_2O及La(ClO_4)_2·EO_2H(OP)_25H_2O。文中研究了配合物红外,紫外、~1HNMR谱及~(13)C纵向弛豫时间T_1等,并讨论了共存阴离子、溶剂及配体不同端基对成配的影响。     

Optically clear simultaneous interpenetrating polymer networks based on poly(ethylene glycol) diacrylate and epoxy. I. Preparation and characterization

Poly(ethylene glycol) diacrylate was synthesized from poly(ethylene glycol) of molecular weight 600 with acryloyl chloride in a molar ratio of 1:2. Poly(ethylene glycol) diacrylate (PEGDA) was then blended with diglycidyl ether of bisphenol A (DGEBA) in various ratios, followed by curing with 2,2′-azobisisobutyronitrile (AIBN) and isophronediamine (IPDA) simultaneously. Viscosity changes before and during IPN formation were examined with a Brookfield viscometer. Formation of H-bonding and functional group changes were investigated with FTIR. Exothermic curing thermograms were recorded with dynamic DSC. Optically clear IPNs thus obtained were characterized with rheometric dynamic spectroscopy (RDS) and scanning electron microscopy (SEM) to check possible compatibility of the two networks. Experimental results revealed that during IPN formation hydrogen bonds between PEGDA and DGEBA and interlock of networks had profound effect on viscosity change and pot-life. Complete compatibility of the IPNs was found as DGEBA content was higher than 50% by weight. The compatibility between PEGDA and DGEBA networks was evidenced from inner shift of a single damping peak in RDS. In the meantime, SEM micrographs confirmed the coincidence with the result of RDS © 1992 John Wiley &Sons, Inc.     

The simultaneous saccharification and fermentation of pretreated woody crops to ethanol

Four promising woody crops (Populusmaximowiczii x nigra (NE388), P.trichocarpa x deltoides (Nll), P.tremuloides, and SweetgumLiquidambar styraciflua) were pretreated by dilute sulfuric acid and evaluated in the simultaneous saccharification and fermentation (SSF) process for ethanol production. The yeastSaccharomyces cerevisiae was used in the fermentations alone, and in mixed cultures with β -glucosidase producingBrettanomyces dausenii. Commercial Genencor 150L cellulase enyme was either employed alone or supplemented with β- glucosidase. All SSFs were run at 37 …C for 8 d and compared to saccharifications at 45…C under the same enzyme loadings.S. cerevisiae alone achieved the highest ethanol yields and rates of hydrolysis at the higher enzyme loadings, whereas the mixed culture performed better at the lower enzyme loadings without β -glucosidase supplementation. The best overall rates of fermentation (3 d) and final theoretical ethanol yields (86–90%) were achieved with P.maximowiczii x nigra (NE388) and SweetgumLiquidambar styraciflua, followed by P.tremuloides and P.trichocarpa xdeltoides (N1l) with slightly slower rates and lower yields. Although there were some differences in SSF performance, all these pretreated woody crops show promise as substrates for ethanol production.     

Synthesis of oligosaccharides catalyzed by thermostable β-glucosidase fromPyrococcus furiosus

Focusing on CO₂ fixation, photoautotrophic cultivation of the red algaPorphyridium cruentum was investigated by means of a batch culture under a 5% CO₂-enriched atmosphere. The algal growth kinetics was successfully described with a logistic model, and simulation of a continuous culture under the optimum growth conditions (30°C, 12 klux and 1.18 g-cells/L) showed that the algal CO₂-fixation activity could reach 0.66 g-CO₂/(L X d). Under the same growth conditions, eicosapentaenoic acid (20:5 n-3, EPA) and arachidonic acid (20:4 n-6, ARA) yields were similarly calculated to be 3.6 mg-EPA/(L X d) and 6.5 mg-ARA/(L X d), respectively.     

Micro-Determination of Protein Containing SH– and –S–S– Groups Based on the Polarographic wave of an Electroactive Derivative

This paper presents a new simple and sensitive method for the micro-determination of protein containing SH– and –S–S– groups based on the single sweep polarographic wave of an electroactive derivative. In 0.04molL^–1 Na₃PO₄ and 0.2% ascorbic acid solution, protein is heated in a boiling water bath for 15min, the reaction product giving a sensitive reduction wave at –0.70V (vs. SCE). The wave height is linearly proportional to the concentration of protein. The calibration curves of bovine serum albumin (BSA), human serum albumin (HSA), ovalbumin (OVA) and lysozyme (Lyso) are constructed under the optimal conditions. For BSA and HSA, the linear ranges and detection limits are 0.05–24mgL^–1 and 0.02mgL^–1, respectively. The method has been applied to the determination of protein in human serum samples with satisfactory results. The mechanism of the polarographic wave was also studied, and the results show that S^2– ion is released from the protein molecule during the derivatization reaction, the wave being attributed to the reduction of HgS.