萘酰亚胺类新型手性荧光染料的设计合成及其应用

本文利用较温和的反应条件制备了两个新型萘酰亚胺类手性荧光染料NNH、NNM,测试了其吸收光谱、荧光光谱和圃二色光谱.研究了化舍物NNH与扁桃酸的作用,利用荧光光谱实现了对不同构型的扁桃酸的识别.采用荧光和圆二色两种手段考察了化舍物NNM对pH值的响应,结果表明两种方法得到的pKa值吻合.     

手性酒石酸衍生物DMTA合成工艺研究

研究了手性酒石酸衍生物D-或L-二对甲氧基苯甲酰酒石酸(DMTA)的合成工艺。在三氟化硼-乙醚络合物催化下,D-(或L-)酒石酸与对甲氧基苯甲酰氯和二氯亚砜作用生成D-(或L-)二对甲氧基苯甲酰酒石酸酐,然后酸酐在丙酮-水体系中水解成D-(或L-)二对甲氧基苯甲酰酒石酸,两步总收率82.73%,光学纯度大于99%。     

手性拆分剂L-二苯甲酰酒石酸和L-二乙酰酒石酸的合成工艺研究

研究了手性拆分剂L-二苯甲酰酒石酸和L-二乙酰酒石酸的合成工艺及各种反应条件对收率和产物旋光纯度的影响。在路易斯酸催化下,L-酒石酸与苯甲酰氯及二氯亚砜作用生成L-二苯甲酰酒石酸酐,然后L-二苯甲酰酒石酸酐再水解成L-二苯甲酰酒石酸,二步总收率86%,旋光纯度大于99%;在硫酸催化下,L-酒石酸与乙酐作用生成L-二乙酰酒石酸酐,再水解成L-二乙酰酒石酸,二步总收率为75%,旋光纯度大于99%。     

几种手性二醇的合成

以(+)-酒石酸二乙酯为原料合成了(+)-2,3-O-异丙叉-1,4-丁二醇3、(+)-4,5-异丙叉-3,6-二乙基-3,6-辛二醇4、(+)-2,3-0-亚苄基-1,4-丁二醇5和(-)-1,4-二苄氧基-2,3-丁二醇8。     

手性拆分剂一水合-L-二苯甲酰酒石酸的合成工艺研究

以L-酒石酸、苯甲酰氯为起始原料,甲苯为溶剂,经过酯化、酐化和水解2步反应得到手性拆分剂一水合-L-苯甲酰酒石酸,并优化了工艺条件。结果表明,在n(L-酒石酸)∶n(苯甲酰氯)=1∶3.1、反应温度为120~125℃、反应时间3.5 h及酸酐水解体系为甲苯/水、n(酸酐)∶n(水)=1∶4、反应温度为100~105℃、水解时间3 h的反应条件下,目标化合物的总收率达84.1%,纯度大于99.5%。该方法反应收率高,后处理简便,污染少,工艺条件易于控制,适合工业生产。     

环糊精聚合物键合手性固定相的合成及手性拆分应用

手性固定相是液相色谱手性分离的基础与核心。本文用简单缩聚法合成环糊精聚合物(CDP),并将这种CDP键合到自制二氧化硅微球上,合成了新型的环糊精聚合物键合型手性固定相（CSP）。在合成过程中考察了反应时间,原料比例及原料加入次序对所制CSP的影响。随后,用扫描电镜法检验了所制填料圆整度,用四氮唑蓝法检测环糊精的含量为42.4 μmol/g,其环糊精键合量明显高于CD单体键合硅胶。最后将最优条件下得到的手性填料用高压匀浆法装柱,并进行液相色谱法拆分手性药物。用二者与ODS在相同的色谱条件下进行对比,结果表明：环糊精聚合物键合硅胶手性固定相对所选手性药物拆分能力更强。     

荧光共轭聚合物的结构设计与合成方法研究

荧光共轭聚合物既有机小分子荧光材料优良的光学品质,又具有高分子材料优越的可加工性能,成为了荧光材料的研究热点。因此,荧光共轭聚合物在开发新型化学、生物及爆炸物传感器等方面具有非常广阔的应用前景。本文介绍了几种典型的荧光聚合物,重点介绍了聚合物中荧光发色团的合成,从分子结构设计、应用及优缺点等方面对各种合成方法进行阐述比较。并且展望了今后荧光共轭聚合物的发展前景。     

环糊精聚合物键合手性固定相的合成及手性拆分应用

用简单缩聚法合成β-环糊精聚合物(β-CDP),并将其键合到自制二氧化硅微球上,合成新型的环糊精聚合物键合型手性固定相(CSP)。合成过程中考察了反应时间、原料比例对所制CSP的影响。用扫描电镜法检验了β-CDP键合硅胶圆整度,以四氮唑蓝法检测环糊精的含量为42.4μmol/g,其环糊精键合量明显高于β-CD单体键合硅胶。最后,将最优条件下得到的手性填料用高压匀浆法装柱,并进行液相色谱法拆分手性药物。将二者与ODS在相同的色谱条件下进行对比,结果表明,环糊精聚合物键合硅胶手性固定相对手性药物拆分能力更强。     

L-酒石酸二乙酯的合成

以L-酒石酸和乙醇为原料合成了手性拆分剂L-酒石酸二乙酯,其结构经IR确证.通过正交实验得优化反应条件为: L-酒石酸100 mmol,n(D 酒石酸)∶n(乙醇)=1∶4,四氯化碳30 mL,浓硫酸4 mL,反映温度67 ℃ ,收率达95.35 %.     

水溶性荧光聚合物的合成和应用

综述了丙烯酰胺类水溶性荧光聚合物的合成方法,应用,理论研究及最新进展。这类聚合物可通过可参与聚合的荧光染料及其标记的单体与丙烯酰胺类水溶性单体共聚,或荧光染料与丙烯酰胺类水溶性聚合物及其衍生物反应制得。这类聚合物的荧光检测下限已达到０．１×１０＾＿６－０．０１×１０＾－６ｇ／ｇ。     

Synthesis,characterization and biodegradation studies of chain‐coupled polyesters based on tartaric acid

A series of chain‐coupled polyesters based on tartaric acid was synthesized and characterized following a two‐step procedure. In the first step, tartaric acid based hydroxyl terminated polyesters with various alkane diols were prepared and then, in a second step, a chain‐coupling approach using hexamethylene diisocyanate was employed on the synthesized polyesters to prepare a series of chain‐coupled polyesters. The number‐average molecular weights (M_n) of the polyesters were found to vary in the range (4.8 ? 28.1) × 10³ g mol^?1. Thermomechanical studies demonstrate that the storage modulus of the chain‐coupled polyesters decreases with increasing polymethylene chain length which is attributable to enhanced flexibility. The isolation of bacteria on medium containing polymer as the sole source of carbon indicates the ability of the synthesized polyesters to be taken up by microorganisms for growth. © 2013 Society of Chemical Industry     

Preparation and characterization of fluorescent polymer magnetic particles

Magnetic iron oxide (maghemite, Fe₃O₄) particles were encapsulated with fluorescent polymer phase. The resulting fluorescent magnetic polymer particles were characterized by Fourier transform infrared spectroscopy (FTIR), thermal gravimeter analysis (TGA), reflection optical microscopy, differential scanning calorimeter (DSC), Fritsch particle sizer, scanning electron microscopy (SEM), powder X‐ray diffractometer (XRD), and vibrating sample magnetometer (VSM) measurements. FTIR and XRD confirmed the presence of iron oxide in polymer phase. The TGA and DSC measurements indicated that the magnetic polymer particles have more than 50% iron oxide content and high thermal stability. SEM and reflection optical microscopy under UV light revealed that all maghemite particles were embedded in the polymer spheres and have fluorescent characteristics. The size‐distribution analysis of prepared magnetic particles was shown that the means diameter of the particles slightly increased. According to our magnetometry data, shape of the loops evidences the ferromagnetic character of the material and no evidence of superparamagnetism was seen. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis, characterization and degradability of polyamides derived from tartaric acid and diaminoethers

A series of novel polyamides derived from l or d-tartaric acid and α,ω-diaminoethers containing 1, 2, 3 or approximately 70 oxyethylene units in the main chain were synthesized and characterized. Polycondensation in solution of the diaminoethers with di-O-methyl tartaric acid activated as pentachlorophenyl ester was used for the synthesis of these poly(ether tartaramide)s. Polymerization degrees oscillated between 10 and 140 depending on the length of the oxyethylene segment. These polyamides are highly hygroscopic and soluble in water. They are semicrystalline with melting temperatures ranging from 50 to 190 °C, and thermally stable up to 250 °C. Chiro-optical properties were found to depend on the configuration of tartaric acid showing both high specific rotations and characteristic circular dichroism ellipticities. Definite X-ray diffraction patterns consistent with the crystalline nature of these polyamides were recorded. Racemates made of enantiomeric pairs were also examined and some evidence indicative of the existence of a crystalline structure different from that present in the optically pure components was found.     

荧光高分子应用研究进展

介绍了荧光高分子近年来在理论研究中与作为一种新型功能材料在实际中的应用研究进展。在理论研究中 ,它主要是以荧光探针技术来研究聚合物的微相动力学和构象 ,聚合物相转移和聚集行为 ,聚合物能量转移及光聚合过程。它作为功能材料 ,主要用于荧光化学传感器、非线性光学装置中 ,以及用作光导树脂等材料。     

The structure of tartaric acid adsorbed over nickel catalyst observed by FT-IRAS

The structure of the L-tartaric acid adsorbed on the surface of a nickel metal catalyst with or without NaBr was studied by FT-IRAS. The carboxylic acid and carboxylate type adsorbed species were observed on nickel surface which was treated with only tartaric acid, while only one type of carboxylate ion was observed on the nickel surface which was treated with tartaric acid and NaBr.     

顺丁烯二酸酐催化氧化合成酒石酸

以纳米TiO₂为载体,通过浸渍法制备得到负载型催化剂W/TiO₂,通过催化氧化顺丁烯二酸酐合成酒石酸,研究了催化剂的催化性能。考察了反应温度、反应时间、反应物配比和催化剂用量等反应条件对氧化反应的影响。结果表明,反应温度70 ℃,反应时间6 h,掺杂钨质量分数为10％的W/TiO₂催化剂用量为顺丁烯二酸酐质量的4%和n（H₂O₂）∶n（顺丁烯二酸酐）＝3时,顺丁烯二酸酐转化率达90%。     

Macromolecular and supramolecular chirality: a twist in the polymer tales

Significant advances have been made recently in generating chiral polymer surfaces and materials using a range of methods such as block copolymer self‐assembly, layer‐by‐layer assembly and surface functionalization by polymer brushes. This paves the way for novel chiral materials that can harness and tailor chiral interactions for specific functionalities and properties in a range of biomedical and bioanalytical applications. This paper reviews these advances and speculates on the future of chiral surfaces. © 2013 Society of Chemical Industry     

L-(-)-二对甲氧基苯甲酰酒石酸的合成

以对甲氧基苯甲酸、二氯亚砜、L-酒石为原料,经过生成酰氯、酯化、酐化和水解反应得到L-(-)-二对甲氧基苯甲酰酒石酸。研究了对甲氧基苯甲酰氯的用量、反应时间和酸酐水解体系、水解时间等因素对产率的影响。确定了最佳工艺条件。结果表明,L-酒石酸与对甲氧基苯甲酰氯的摩尔比为1∶2.4,反应时间4 h及酸酐水解体系为丙酮-水(V/V=1∶1),水解时间3 h,目标产物的产率为88.0%。     

酒石酸根阴离子柱撑Mg-Al-LDHs水滑石的合成

采用共沉淀法制备纳米Mg-Al-LDHs水滑石,并以纳米Mg-Al水滑石为前体,采用返混沉淀法进行插层组装,合成酒石酸根阴离子柱撑水滑石。采用红外光谱、X射线衍射对样品进行了表征。结果表明,酒石酸根阴离子可以插入纳米Mg-Al水滑石层间,完全取代CO32-,形成具有超分子结构的稳定酸根阴离子柱撑水滑石,其尺寸达到纳米级。