壳聚糖-g-水杨酸的合成

合成了壳聚糖-g-水杨酸,用1^H NMR,IR和热重分析等对结构进行了表征。接枝反应的最佳条件为：壳聚糖12．5mmol,n（水杨酸）：n（壳聚糖）=0．75,于55℃～65℃反应1h,水杨酸接枝率为20％。     

Synthesis of anti-Alzheimer (R)-arundic acid

The asymmetric synthesis of the anti-Alzheimer agent (R)-arundic acid has been performed via a diastereoselective photodeconjugation reaction as the key-step. The synthetic approach involves a readily available chiral auxiliary, diacetone-d-glucose, and allows access to either enantiomer as illustrated by the synthesis of (S)-arundic acid. Both enantiomers were obtained in 88% ee using the same chiral auxiliary.     

Synthesis of (aminomethylene)bisphosphonic acid derivatives

Amino derivatives of methylenebisphosphonic acids were synthesized by phosphorylation of formamide, nitriles or hydrochlorides of alkyl imidates with H₃PO₃—PCl₃—(Me₃Si)₂NH.     

聚(苯乙烯-丙烯酸)-氯化铜配合物膜的合成及表征

将聚(苯乙烯-丙烯酸)(PSAA)(MW＝3500)与氯化铜在异丙醇溶液中反应得到一种配位聚合物膜--聚(苯乙烯-丙烯酸)-氯化铜(PSAA-Cu(Ⅱ))．以ESR，FT-IR，XPS，电导率，元素分析及DMTA等方法对此配合物膜进行表征，确定了组成与结构．结果表明，配位聚合物的中心离子Cu^2 与二个链节单元上的羧基发生配位，从而引起进一步的交联作用，导致玻璃化转变温度和耐热性能的提高．     

铪催化合成聚3-羟基丙酸

以3-羟基丙酸(3-HP)为单体,金属铪(Ⅳ)催化合成了高纯度的聚3-羟基丙酸[P(3-HP)]。3-HP和P-(3-HP)的结构经NMR,FT-IR和GPC等表征。     

Synthesis of n-(jasmonoyl)amino acid conjugates

Both racemic jasmonic acid [(±)-JA] and the naturally occurring (-)-enantiomer [(-)-JA] have been reacted with aliphatic, aromatic as well as acidic amino acids to form amide-linked derivatives. The diastereoigomeric products of (±)-jasmonic acid with S-Val, S-Leu, S-Ile, S-Phe, S-Trp, R-Val, and R-Phe could be separated by silica gel chromatography. The synthesized N-(jasmonoyl)-conjugates have been structurally characterized by MS, ¹H NMR, IR and ORD.     

聚(乙烯基四唑-co-丙烯酸)的合成与表征

以聚丙烯腈为原料,首先通过部分腈基的[3+2]合环反应转化为聚(乙烯基四唑-co-丙烯腈)[Poly(VT-co-AN)],再通过碱性水解反应将剩余的腈基转化为羧基,合成出聚(乙烯基四唑-co-丙烯酸)[Poly(VT-co-AA)]。 采用傅里叶红外变换光谱仪(FT-IR)、核磁共振碳谱仪(¹³C NMR)、酸碱滴定等方法对Poly(VT-co-AN)和[Poly(VT-co-AA)的结构进行了表征,结果表明,Poly(VT-co-AN)的分子链中含有腈基、四唑基团和部分羧基,四唑基团的含量为68.6%,与酸碱滴定法测定的四唑基团的含量相近,[Poly(VT-co-AA)中含有四唑基团和羧基,不含有腈基,酸值高于Poly(VT-co-AN),四唑基团的含量为67.6%,与叠氮化钠与聚丙烯腈的摩尔比相近。 热失重分析结果显示[Poly(VT-co-AA)的热分解速率加快,在270~285 ℃的温度区间内分解完全。     

由(1S)-cis-菊酸合成(1R)-cis-二溴菊酸

拟除虫菊脂是在研究天然除虫菊脂化学的基础上发展起来的一类高效低毒,广谱杀虫剂。其中,溴氰菊脂是活性较高,光稳定性较好的一种菊脂类杀虫剂, 它是具有(IRcis.αs) 构型的单一光学异构体。 生产溴氰菊脂的关键中间体是IR-cis-)二溴菊脂。本文报道利用化学剪切法将(is)-cis-菊脂转化为(IR-cis-)二溴菊脂的新方法。     

Synthesis of (1,6-alpha,alpha'-diaminosuberic acid)oxytocin ('dicarba-oxytocin')

Starting from a selectively protected derivative of α,α′-diaminosuberic acid ( 3 ) the linear protected peptide 11 has been obtained. Cyclisation to 12 followed by removal of the protecting groups by hydrogenolysis afforded the ‘dicarba’ analogue of oxytocin, 1 c , which showed about 5 IU/μmol of uterotonic activity in vitro.     

Poly(lactic acid) Synthesis in Solution Polymerization

The step-growth polymerization of L-lactic acid in solution was studied in this work. In order to attain a polymer with high molecular weight, the water formed during the polymerization must be continuously removed. The use of organic solvents with high boiling point, drying agents and reduced pressure led to poly(lactic acid) (PLA) with high molecular weight, directly from the monomer. Tin (II) chloride dihydrate, SnCl₂.2H₂O, was the best of the catalysts tested as it allowed achieving PLA with a molecular weight close to 80 000 g.mol⁻¹. However, the stereoregurarity control is a severe problem in PLA synthesis by step-growth due to transesterification reactions, which lead to an inversion of the conformation and a decrease of the optical purity of the polymer. Specific rotation measurements were used in this work and showed to be a powerful technique to evaluate the racemization extent. The thermal stability of the PLA samples was evaluated by DSC which exhibits a thermal behaviour similar to the commercial Polylactide.     

PMAA纳米水凝胶的水相制备

利用表面活性剂间的疏水作用以及表面活性剂与单体间的氢键作用,促使甲基丙烯酸(MAA)单体在原位生成的聚甲基丙烯酸甲酯(PMMA)种子乳胶表面的选择性聚合,实现了PMAA纳米水凝胶的水相"绿色"制备。利用动态光散射、傅里叶红外光谱、透射电子显微镜表征了PMAA纳米水凝胶的尺寸、组成、形貌和pH响应性。研究了聚氧乙烯失水山梨醇单月桂酸酯(吐温20)的用量、N,N’-亚甲基双丙烯酰胺(MBA)的用量、MAA的用量和加入方式、十二烷基硫酸钠(SDS)的补加速率等对PMAA纳米水凝胶的尺寸和溶胀性能的影响。结果表明:PMAA纳米水凝胶为核-壳结构;随着MBA用量的减小、吐温20用量的增加、MAA用量的增加,PMAA纳米水凝胶的尺寸和溶胀比均增大;当采用半连续加入MAA时,PMAA纳米水凝胶的尺寸和溶胀比变小;当SDS的补加时间由60min延长到100min时,PMAA纳米水凝胶的尺寸逐渐变小。PMAA纳米水凝胶具有良好的pH响应性,当介质的pH从1增加到6时,其流体力学体积扩张了64倍。     

Synthesis and Characterization of Chitosan-grafl-Poly（lactic acid） Copolymer

Chitosan-graft-poly(lactic acid)(CS-g-PLA) copolymer was synthesized through emulsion self-assembly in a water-in-oil(W/O) microemulsion. The water phase was composed of CS aqueous solution, while the oil phase was made up of PLA in chloroform. The W/O microemulsion was fabricated in the presence of surfactant span-80 and the self-assembly was performed between PLA and CS under the effect of N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride(EDC·HCl). FTIR and1H-NMR analysis indicated PLA was grafted onto the backbone of CS via the reaction between the carboxyl groups in PLA and the amino groups in CS.1H-NMR characterization further revealed the grafting content of PLA was 16%. The obtained CS-g-PLA could self-assemble to form micelles, their size distributed in the range of 125 375 nm with average diameter of 142 nm. The present design integrates the favorable biological properties of CS and the excellent mechanical properties of PLA, which makes CS-g-PLA copolymer a promising candidate as a carrier for targeted bioactive molecules delivery.     

Synthesis and properties of poly(5-ethynyluridylic acid)

5-Ethynyluridine 5'-diphosphate has been synthesised from 5-ethynyluridine under carefully controlled conditions to prevent any reaction with the ethynyl group. The compound is a substrate for polynucleotide phosphorylase from Micrococcus luteus and has been polymerised to give poly(5-ethynyluridylic acid). The polymer has a stable secondary structure with a T_m of 76° accompanied by a 16% hyperchromicity in solutions of high ionic strength and forms a 1:1 complex with poly(A) with a T_m of 78°. Thus the presence of the ethynyl group in the pyrimidine ring causes the polymer to have and to form much more stable secondary structures than the corresponding unsubstituted polynucleotide poly(U).     

Synthesis and characterization of poly(vinylpyrrolidone-co-vinylphosphonic acid) copolymers

Radical copolymerizations of 1-vinyl-2-pyrrolidone (VP) with vinylphosphonic acid (VPA) at different feed ratios were investigated. The copolymers were characterized by ¹H-NMR, ¹³C-NMR and FT-IR. The copolymer composition was determined from the elemental analysis. Thermogravimetric analysis (TG) illustrates that the copolymers are stable up to 200 °C. Temperature dependence of the alternating current (AC) conductivities were investigated by means of impedance spectroscopy. The direct current (DC) conductivities of the samples are derived from the AC conductivity data.     

白花丹酸的合成

白花丹酸[β-(2,3-二羟基苯甲酰基)丁酸](1)是一个新的天然产物.本文以邻香草醛为原料,经七步反应,得到总收率为21%的产品,其光谱数据与1完全一致.     

Synthesis of poly(glycolic acid) in ionic liquids

The synthesis of poly(glycolic acid) (PGA) by polyesterification of glycolic acid was studied using ionic liquids, mainly 1,3‐dialkylimidazolium salts, as reaction media. The ¹H NMR spectra of PGA oligomers were assigned and end‐group signals were used to follow the reaction. Low PGA yields were obtained by the direct polyesterification of glycolic acid at 200–240 °C, because of monomer evaporation during the reaction. On the other hand, PGAs of DP _n up to 45 were obtained by the postpolycondensation of a preformed oligomer in 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)amide (BMIm⁺Tf₂N^?). The precipitation of PGA in reaction medium at long reaction times limited the achievable molar mass. Rate constants were determined for catalyzed and noncatalyzed reactions, assuming a second‐order reaction mechanism. The efficiency of esterification catalysts such as Zn(OAc)₂ was low in these media, as only about twofold increases in reaction rate were observed. This was assigned to the preferential interaction of Zn²⁺ with ionic liquid anion instead of the polymer carboxylic acid end‐groups. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3025–3035, 2006     

端羟基聚乳酸的合成与表征

采用共沸除水与醇酸缩合反应相结合的方法合成端羟基聚乳酸。通过L9(3^4)正交实验对合成工艺进行了研究,分析了抗氧剂TPP对反应的影响,并用^1H-NMR和DSC对产物结构进行表征。结果表明,产物主要为聚乳酸-1,4-丁二醇(PIA-1,4-BD)。和分子量相同的聚乳酸-1,4-丁二醇．聚乳酸(PLA-1,4-BD-PLA)比较,PLA-1,4-BD具有较高的Tg。