气相色谱手性衍生化试剂N－七氟丁酰基－L－脯氨酰氯的合成与应用

合成了用于气相色谱（ＧＣ）的手性衍生化试剂Ｎ－七氟丁酰基－Ｌ－脯氨酰氯（Ｎ－ＨＦＢ－Ｌ－ＰＣｌ）。各种特性试验表明，Ｎ－ＨＦＢ－Ｌ－ＰＣｌ是灵敏的ＧＣ手性衍生化试剂，可直接于水相拆分微量的手性胺对映体。     

气相色谱手性衍生化试剂N－七氟丁酰基－L－脯氨酰氯的合成与应用

 合成了用于气相色谱（ＧＣ）的手性衍生化试剂Ｎ－七氟丁酰基－Ｌ－脯氨酰氯（Ｎ－ＨＦＢ－Ｌ－ＰＣｌ）。各种特性试验表明，Ｎ－ＨＦＢ－Ｌ－ＰＣｌ是灵敏的ＧＣ手性衍生化试剂，可直接于水相拆分微量的手性胺对映体。     

ELECTRODEPOSITION OP Ba－K－Bi－O AND Ba－K－M－Bi－O （M＝Rb， Pb AND La） SINGLE CRYSTALS

ＥＬＥＣＴＲＯＤＥＰＯＳＩＴＩＯＮＯＰＢａ－Ｋ－Ｂｉ－ＯＡＮＤＢａ－Ｋ－Ｍ－Ｂｉ－Ｏ（Ｍ＝Ｒｂ，ＰｂＡＮＤＬａ）ＳＩＮＧＬＥＣＲＹＳＴＡＬＳ￥ＬｉａｎｇＺｈｏｎｇＺＨＡＯ；ＪｉｎＢｉａｏＺＨＡＮＧ；ＷｅｉＨｕａＷＡＮＧＳｈｉＨｏｎｇＬＩＵ；ＤａｏＢｅ...     

氟喹诺酮类药物与牛血清白蛋白作用的研究

用荧光猝灭法研究了ＢＳＡ与ＮＦＬＸ及ＯＦＬＸ之间的相互作用，根据Ｆｏｒｓｔｅｒ的能量转移理论，确定了能量给体－受体间的距离，根据荧光猝灭谐绘制了猝灭曲线，确定其猝灭过程是静态猝灭，用Ｌｉｎｅｗｅａｖｅｒ－Ｂｕｒｋ双倒数曲线测定ＮＦＬＸ－ＢＳＡ和ＯＦＬＸ－ＢＳＡ络合物的离解常数，并详细研究了１０种阳离子，４种阴离子与药物对ＢＳＡ竞争结合的影响，推测了药物与蛋白的主要作用力。     

THE SYNTHESIS OF 4，5－BIS（4＇－BROMOBENZYLTHIO）－1，3－DITHIOLE－2－THIONE WITH ONE DIMENSIONAL INTERMOLECULAR INTERACTIONS

ＴＨＥＳＹＮＴＨＥＳＩＳＯＦ４，５－ＢＩＳ（４＇－ＢＲＯＭＯＢＥＮＺＹＬＴＨＩＯ）－１，３－ＤＩＴＨＩＯＬＥ－２－ＴＨＩＯＮＥＷＩＴＨＯＮＥＤＩＭＥＮＳＩＯＮＡＬＩＮＴＥＲＭＯＬＥＣＵＬＡＲＩＮＴＥＲＡＣＴＩＯＮＳ￥ＦａｎｇＱＩ（Ｉｎｓｔｉｔｕｔｅｏ...     

柱前手性衍生色谱法拆分DL—氨基酸时流动相的影响

本文利用邻苯二甲醛和Ｎ－乙酰－Ｌ－半胱氨酸作柱前手性衍生化试剂，经反相高效液相色谱法拆分ＤＬ－氨基酸对映体，研究了流动相组成对出峰顺序和分离效果的影响。     

交联法固定化米曲霉及拆分反应性能的研究

本文采用戊二醛－明胶－乙二胺交联固定米曲霉，应用正交设计方法优选出相应的固定化条件，制备出拆分ＤＬ－氨基酸反应活性较高的酶催化剂，并对ｐＨ，温度，离子浓度，底物浓度等因素对固定化菌体的反应活性的影响进行了实验研究，用固定化菌体柱对Ｎ－乙酰－ＤＬ－丙氨酸进行连续拆分，结果表明催化剂具有主好的工业应用前景。     

（E）－β，γ－UNSATURATED NITRILES FROM DIMETHYLSULFONIUM CYANOMETHYLIDE AND 9－ALKENYL－9－BORABICYCLO［3，3，1］NONANES

（Ｅ）－β，γ－ＵＮＳＡＴＵＲＡＴＥＤＮＩＴＲＩＬＥＳＦＲＯＭＤＩＭＥＴＨＹＬＳＵＬＦＯＮＩＵＭＣＹＡＮＯＭＥＴＨＹＬＩＤＥＡＮＤ９－ＡＬＫＥＮＹＬ－９－ＢＯＲＡＢＩＣＹＣＬＯ［３，３，１］ＮＯＮＡＮＥＳＮａｎＳｈｅｎｇＬＩ；ＭｉｎＺｈｉＤＥＮＧ；Ｙ...     

MOLECULAR MECHANICAL AND QUANTUM CHEMICAL CALCULATION ON ACYLATION REACTIVITY FOR 1－（NITRO SUBSTITUTED ANILINO）－4－SUBSTITUTED－2，6－PIPERAZINEDIONES

ＭＯＬＥＣＵＬＡＲＭＥＣＨＡＮＩＣＡＬＡＮＤＱＵＡＮＴＵＭＣＨＥＭＩＣＡＬＣＡＬＣＵＬＡＴＩＯＮＯＮＡＣＹＬＡＴＩＯＮＲＥＡＣＴＩＶＩＴＹＦＯＲ１－（ＮＩＴＲＯＳＵＢＳＴＩＴＵＴＥＤＡＮＩＬＩＮＯ）－４－ＳＵＢＳＴＩＴＵＴＥＤ－２，６－ＰＩＰＥＲＡＺ...     

CONVERSION OF KETONES INTO1，1－DISUBSTITUTED－2，3，3－TRIFLUORO－2－PROPEN －1－OLSWITH1，1－DIBROMO－1，2，2，2－TETRLUORO ETHANE／MAGNESIUM REAGENT

ＣＯＮＶＥＲＳＩＯＮ　ＯＦ　ＫＥＴＯＮＥＳ　ＩＮＴＯ１，１－ＤＩＳＵＢＳＴＩＴＵＴＥＤ－２，３，３－ＴＲＩＦＬＵＯＲＯ－２－ＰＲＯＰＥＮ　－１－ＯＬＳＷＩＴＨ１，１－ＤＩＢＲＯＭＯ－１，２，２，２－ＴＥＴＲＬＵＯＲＯ　ＥＴＨＡＮＥ／ＭＡＧＮＥＳＩＵＭ...     

Optimization of an α‐(Amino acid)‐N‐carboxyanhydride polymerization using the high vacuum technique: Examining the effects of monomer concentration,polymerization kinetics,polymer molecular weight,and monomer purity

l ‐Ornithine‐based poly(peptides) have been widely utilized in the field of drug delivery, however few studies have been conducted examining the details of polymerization. In this article, the effects of monomer concentration, polymerization kinetics, polymer molecular weight and monomer purity were investigated using l ‐carboxybenzyl (Cbz)‐ornithine as a model monomer. The mechanism of polymerization herein follows the normal amine mechanism to produce poly(peptides) having controlled molecular weights, known chain ends and a narrow polydispersity index (PDI). A preferred monomer concentration range was determined, which required minimal polymerization times and allowed for predictable and reproducible molecular weights with narrow PDIs. The impact of monomer purity on the polymerization was established and monomer purification conditions are reported, which produce high‐purity monomer after a single recrystallization. Additionally, the optimized polymerization conditions and monomer purification protocol were combined with a sequential monomer addition technique to produce high molecular weight poly(ornithine) with a narrow PDI and known chain ends. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1385–1391     

SYNTHESIS AND CHARACTERIZATION OF A NOVEL STYRYLTHIOPHENE MONOMER AND CORRESPONDING POLYURETHANE FOR NLO MATERIALS

A novel monomer, (trans)-7-[4-N,N-(di-β-hydroxyethyl) amino-benzene]-ethenyl-3,5-dinitro-thiophene (HBDT), was synthesized and characterized. The details of synthesizing the monomer andprepolymer, polyurethane with the monomer covalently incorporated are presented. The prepolymer andpolyurethane exhibited good solubility in common organic solvents. Molecular nonlinear optical properties ofthe monomer (HBDT) substituted thiophene based stilbenes is presented.     

The preparation of sterically stabilized polymer dispersions

The emulsion polymerizations of styrene (St) and butyl acrylate (BA) stabilized by nonionic polyoxyethylene type emulsifiers did not show the long stationary rate interval. This was discussed in terms of two opposing effects: 1) the decreased monomer concentration at the reaction loci due to the depletion of monomer droplets or depressed monomer droplet degradation and 2) the increased number of polymer particles with increasing conversion. The continuous particle nucleation is attributed to the continuous release of emulsifier from the emulsifier saturated monomer droplets and/or the presence of monomer swollen micelles (microdroplets). The limited particle flocculation operative at lower emulsifier concentrations increases the nonstationary-state polymerization. The particle agglomeration is accompanied by the increased reaction order x (N_p vs. [E]^x) above 0.6. The increased uniformity of monomer emulsion stabilized by Tween 20 by homogenization of monomer emulsion increased the final conversion and the polymerization rate as well. The polymerization rate vs. conversion curve of the homogenized emulsion characterized with broader stationary rate interval reminds the four rate intervals system typical for miniemulsion. The accumulation of polymer and nonionic emulsifier within the monomer phase preserves the monomer droplets up to high conversion. The decreased monomer droplet degradation rises the monomer-starved condition or the depressed transport of both monomer and emulsifier to the reaction loci.     

Study on functionalization of metal surfaces. III. Photopolymerization of monomer films on metal surfaces

The three kinds of monomer films on metal surfaces were deposited by adsorption from a solution of 6-polymerizable substituents-1,3,5-triazine-2,4-dithiol monosodium salts (RTDN); the polymerizable substituents such as cis-9-octadecenylamino, di(cis-9-octadecenyl)amino, and p-vinylbenzyl(cis-9-octadecenyl)amino groups were selected in view of the polymerization activity of unsaturated groups in the substituents and the packing degree of monomer molecules. The monomer films were estimated to consist of mainly 6-substituents-1,3,5,-triazine-2,4-dithione (3H, 5H) and to be multimolecular layers that are considerably cross-packed and ordered. The monomer films on metal surfaces were polymerizable under a UV light irradiation in air atmosphere to give polymer films. In the photopolymerization, azobis(isobutyronitrile) (AIBN) was very effective for increasing the monomer conversion and the polymerization rate. The optimum concentration of AIBN in monomer films was very small, about 0.025 mol %. The monomer conversion was influenced by the kind of monomers, namely, the polymerization activity and the packing degree. The effect of the packing degree was especially remarkable. The monomer conversion decreased with an increase in the thickness of monomer films. This is because the polymerization was initiated by oxygen and AIBN, which were diffused into the inner of monomer films. The possibility of polymerization of the unsaturated groups and the thione groups in monomer molecules under UV light irradiation is discussed.     

硫酸铵水溶液中分散聚合法制备两性共聚物P(AM-co-AA-co-DAC-co-DMC)

利用分散聚合技术,在硫酸铵水溶液中以丙烯酰胺(AM)、丙烯酸(AA)、丙烯酰氧乙基三甲基氯化铵(DAC)、甲基丙烯酰氧乙基三甲基氯化铵(DMC)为单体,合成了两性共聚物P(AM-co-AA-co-DAC-co-DMC).用FTIR,13C-NMR,TEM等方法表征了聚合物的结构和组成.考察了不同分散稳定剂、正负离子单体配比和pH对分散聚合的影响,并对P(AM-co-AA-co-DAC-co-DMC)水基分散聚合条件及稳定性进行了一些探讨.实验表明,在硫酸铵水溶液中制得较稳定的P(AM-co-AA-co-DAC-co-DMC)分散体系,应选用非离子型或阳离子型的分散稳定剂,如聚乙烯吡咯烷酮(PVP)、聚甲基丙烯酰氧乙基三甲基氯化铵(PDMC)、聚丙烯酰氧乙基三甲基氯化铵(PDAC),而其pH应在2到4之间.当选用占总质量1.5%的聚乙烯吡咯烷酮(PVP)为分散稳定剂,引发温度为40℃,正负离子单体物质的量比值大于1,pH=3时,可以制得总离子度超过25%的纳米级两性聚合物.     

具有聚集诱导发光效应的咔唑基三苯乙烯衍生物单体及聚合物

合成了一类新的咔唑基三苯乙烯衍生物单体及其聚合物.利用示差扫描量热法(DSC)、热重分析法(TGA)、紫外可见分光光度法和荧光分光光度法等对单体和聚合物的性能进行了初步的表征.实验结果表明,该单体和聚合物具有较高的玻璃化转变温度(Tg),分别为210℃和229℃;单体和聚合物均具有很高的热稳定性,热失重5%的温度分别为466℃和467℃;单体具有明显的聚集诱导发光性能(AIE),而聚合物则具有聚集诱导增强发光性能(AIEE);所合成的单体和聚合物有望在OLED器件以及化学传感器上得到应用.     

Experimental and Modeling Investigation of Radical Homopolymerization of 2‐(Methacryloyloxyethyl) Trimethylammonium Chloride in Aqueous Solution

The radical homopolymerization kinetics of 2‐(methacryloyloxyethyl) trimethylammonium chloride (TMAEMC) in aqueous solution is investigated across a wide range of initial monomer contents (5–35 wt%), ionic strengths, and pH levels using an in‐situ NMR technique to track monomer consumption over the complete conversion range. Molar mass distributions (MMD) of the final homopolymers are also examined, with additional batch and semi‐batch experiments conducted in a stirred vessel. The rates of monomer conversion and polymer MMDs are dependent on initial monomer content but almost entirely independent of pH and the presence of salts, with some acceleration of rate observed for low monomer levels at very high salt concentration. To aid with the interpretation of these results, the conductivity and counterion activity of monomer and polymer mixtures are measured to determine the extent of electrostatic interactions at various levels of conversion. These results are combined with recently reported measurements of TMAEMC homopropagation kinetics to develop a TMAEMC homopolymerization model that captures the systematic decrease in rates of monomer conversion observed with increased initial monomer content during batch polymerization as well as provides a good representation of semi‐batch polymerization.     

Functionalization of polypropylene by grafting with itaconic acid

Grafting of polypropylene was carried out in both boiling xylene and decalin as solvent medium with itaconic acid (2-methylenesuccinic acid) as functional polar monomer using 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (Lupersol 101) as radical initiator. It was found that the temperature influenced the percentage of monomer grafted onto polypropylene and that the amount of monomer incorporated was practically constant after 5 min. The results also show that the amount of monomer incorporated is proportional to the initial monomer concentration used in the grafting reaction, although for higher initiator concentrations a reduction in the percentage of grafting was found.     

疏水缔合聚丙烯酰胺在表面活性单体胶束溶液中的制备及其流变特性

配制了表面活性单体2-丙烯酰胺基十二烷磺酸钠(NaAMC12S)与十二烷基硫酸钠(SDS)的胶束溶液,分别测定了强疏水单体N-正十二烷基丙烯酰胺(C12AM)在两种胶束溶液中的增溶性能;在此基础上,于两种胶束溶液中分别进行了丙烯酰胺(AM)与C12AM的胶束共聚合,制备了疏水缔合聚丙烯酰胺(HAPAM),它们分别为二元共聚物C12AM/AM与三元共聚物C12AM/NaAMC12S/AM;测定了两种共聚物的红外光谱;采用荧光探针法与表观粘度法重点研究了它们的疏水缔合性与流变性能.结果表明,在表面活性单体NaAMC12S的胶束溶液中,可顺利地实现AM与疏水单体的胶束共聚合,由于表面活性单体也参与了共聚合,故制得的产物为三元共聚物C12AM/NaAMC12S/AM;与在SDS胶束溶液中制备的二元共聚物C12AM/AM相比,前者的疏水缔合性更强,其强疏水缔合性以强疏水单体C12AM的贡献为主,以表面活性单体NaAMC12S的贡献为辅.     

Synthesis and helical properties of N‐substituted p‐benzamide random copolymers possessing chiral/achiral and (S)/(R) side chains

Random copolymers of poly(p‐benzamide)s having a methyl‐substituted tri(ethylene glycol) unit as a chiral side chain and a nonsubstituted tri(ethylene glycol) or branching alkyl unit as an achiral side chain were synthesized by copolymerization of N‐substituted 4‐aminobenzoic acid ester monomers with a base in the presence of an initiator. Copolymerizations of the chiral (S)‐monomer with N‐tri(ethylene glycol) achiral monomer and with the racemic monomer were carried out by the addition of a mixture of two monomers and an initiator to a solution of a base all at once, affording the corresponding random copolymers. On the other hand, random copolymerization of the chiral monomer with monomer having an achiral branching alkyl side chain required dropwise addition of the achiral monomer to a mixture of the chiral monomer, the initiator, and the base. These copolymers formed helical structures, but analysis of the CD spectra indicated the absence of cooperativity between the monomer units along the copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011