印迹奎宁聚合物的合成及性能研究

以奎宁为模板分子．分别采用光引发和热引发的本体聚合方法制备了印迹奎宁的聚合物。用红外光谱(IR)、热重分析(TG)、电镜扫描(SEM)对聚合物进行了表征,用结合实验研究了聚合物对不同底物的选择性。采用Seatchard方程研究了模板聚合物对奎宁的结合特性。研究了模板聚合物对奎宁的结合量随时间的变化趋势。     

种子溶胀悬浮聚合法制备分子印迹聚合物微球

 以酪氨酸为印迹分子 ,甲基丙烯酸为功能单体 ,三羟甲基丙烷三甲基丙烯酸酯 (TRIM )为交联剂 ,采用种子溶胀悬浮聚合法在水溶液中制备了一系列分子印迹聚合物微球 (MIPMs)。利用扫描电镜 (SEM)对此微球的粒径大小、粒径分布、表面孔与孔径分布等进行了分析研究 ,探讨了影响其形貌的主要因素 ,并将所得微球用作固定相研究了其分子选择吸附性能。研究表明 ,种子溶胀悬浮聚合法能够制得单分散性较好的、表面带有微孔的分子印迹聚合物微球 ,且该微球呈现出较好的特异吸附性能。     

奎宁分子印迹聚合物的合成与性能研究

采用分子印迹技术 ,以 α-甲基丙烯酸为功能单体 ,二甲基丙烯酸乙二醇酯为交联剂 ,合成出以奎宁为模板的分子印迹聚合物。利用荧光法研究了聚合物的吸附性能和选择识别能力。结果表明 ,和化学组成相同的空白聚合物相比 ,印迹聚合物具有高吸附能力和选择识别能力。奎宁分子印迹聚合物与奎宁分子的离解常数达 1 .0 8× 1 0 - 3mol/L,表观最大吸附量为 1 31 .8μmol/g,为理论值的 56.4%。     

种子溶胀悬浮聚合法制备香草醛分子印迹聚合物微球

以分散聚合法制备的聚苯乙烯微球为种子,采用单步溶胀悬浮聚合法,香草醛为模板分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,在水相中成功制备了分子印迹聚合物微球,通过扫描电镜、静态吸附和高效液相色谱手段对其进行表征。结果表明,该微球对香草醛具有较高的吸附能力和良好的特异选择性,用于液相色谱固定相可将其与结构类似物阿魏酸快速基线分离。     

美托洛尔球形分子烙印聚合物的制备及吸附性能考察

以聚苯乙烯乳液为种球，以药品美托洛尔为模板分子，甲基丙烯酸为功能单体，二甲基丙烯酸乙二醇酯为交联剂，采用两步溶胀和种子悬浮聚合方法，通过优化反应条件，制得单分散性优良的球形分子烙印聚合物（molecularly imprinted polymers，MIPs）。重点讨论了致孔剂、分散剂和乳化剂的选择、搅拌速度对聚合物的粒径大小和分布、表观形态及吸附性能等的影响。通过聚合物对几种β-受体类药物分子的平衡吸附实验表明，MIP对模板分子美托洛尔具有良好的识别能力。     

悬浮聚合法合成马拉硫磷分子印迹聚合物的吸附性能研究

基于分子印迹技术,采用悬浮聚合的方法,合成了马拉硫磷分子印迹聚合物。通过优化,确定最佳合成条件为:模板分子(马拉硫磷)∶功能单体(α-甲基丙烯酸)为1∶8,模板分子(马拉硫磷)∶交联剂(乙二醇二甲基丙烯酸酯)为1∶40,温度60℃,引发剂用量为1.0%。吸附性能测试结果表明,印迹聚合物对马拉硫磷的最大吸附量为4.62μg/mg,而非印迹聚合物对马拉硫磷的最大吸附量为2.21μg/mg;通过选择性实验得到印迹聚合物对灭线磷、甲拌磷、特丁硫磷、乐果、马拉硫磷、克线磷的吸附量分别为3.87、3.75、3.57、4.00、4.44、3.61μg/mg,而非印迹聚合物的吸附量分别为1.42、1.37、1.30、1.43、1.12、1.23μg/mg。     

头孢氨苄分子印迹聚合物制备及其性能研究

采用不同合成方法制备了头孢氨苄分子的印迹聚合物,考察了模板分子与功能单体之间的结合作用,测定了其吸附性能,用扫描电镜对其表面做了表征.结果表明:在甲醇体系中,用丙烯酰胺作功能单体,采用本体聚合法制备的印迹聚合物的吸附能力更好,对模板的单位结合量达到29.6mg/g,特异因子达3.29.     

分子印迹球状β-环糊精聚合物的合成及性能研究

利用分子印迹技术,以β-环糊精为功能单体,甲苯-2,4-二异氰酸酯为交联剂,茶碱为模板分子,合成了分子印迹β-环糊精聚合物。采用反相悬浮聚合的方法,以戊二醛为交联剂,用聚乙烯醇(PVA)包埋环糊精聚合物合成了分子印迹球状β-环糊精聚合物(MI-CDPs)吸附剂,对聚合物的合成条件进行了考察,并利用静态吸附方法对球状MI-CDPs的吸附性能进行研究,结果表明,球状MI-CDPs对水溶液中的茶碱分子表现出良好的分子识别能力,实现了对水溶液中茶碱的分子识别,证实在pH=9时,球状MI-CDPs的吸附性能最佳。     

烟酸分子印迹聚合物的制备及分子识别性能的研究

以烟酸(NA)为模板分子、4-乙烯基吡啶(4-VP)为功能单体、二甲基丙烯酸乙二醇酯(EGDMA)为交联剂、偶氮二异丁腈(AIBN)为引发剂,分别采用本体聚合法和溶胀聚合法制备了分子印迹聚合物MIP1及MIP2.静态平衡结合实验表明,MIP1、MIP2对NA的结合量Q分别为193.56、215.35 μmol/g,均大...     

异戊巴比妥分子印迹聚合物的合成和识别性能研究

以异戊巴比妥为模板,分别以丙烯酰胺和甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,偶氮二异丁腈为引发剂,用本体聚合法制备了分子印迹聚合物(molecularly imprinted polymer,MIP)。考察了以不同功能单体合成的MIP对模板分子和结构类似物的识别能力和选择性。表明以丙烯酰胺为功能单体合成得到的MIP比甲基丙烯酸为单体的聚合物具有更好的再识别性和选择性,前者对异戊巴比妥的饱和吸附量可达到28．58μmol／g．为理论吸附量的40．9％。     

Preparation, characterization and properties studies of quinine-imprinted polymer in the aqueous phase

The uniform-sized spherical molecularly imprinted polymers were successfully prepared through molecular imprinting technology by two-step seed swelling and mini-emulsion polymerization in the aqueous condition using quinine as template molecules and methacrylic acid (MAA) as functional monomer. The polymers were characterized by IR spectra, thermal-weight analysis, scanning electron microscope and laser particle size analysis. The properties of imprinted polymers were investigated in different organic phases and aqueous media. In the organic media, results suggested that polar interactions (hydrogen bonding, ionic interactions) between acidic monomer/polymer and template molecules are mainly responsible for the binding and recognition; whereas in the aqueous medium, a considerable recognition effect was also obtained where the ionic (electrostatic) interaction and hydrophobic interaction play an important role. The experiments of binding different substrates indicated that the MIPs possessed an excellent rebinding ability and inherent selectivity to quinine. __________ Translated from Zhongshan Dcocue Xuebao/Acta Scientianum Natralium University Sunyatseni, 2005, 44(3)(in Chinese)     

Preparation of amino group-containing polymers by plasma polymerization

Plasma polymerizations of bis(dimethylamino)methylsilane (BDMAMVS), bis(dimethylamino) methylvinylsilane (BDMAMVS), and trimethylsilyldimethylamine (TMSDMA) were investigated by elemental analysis, IR spectroscopy, and ESCA. Polymer deposition was fairly faster in the BDMAMVS and TMSDMA systems than in the BDMAMS system, indicating that vinyl and methyl substituents contribute to polymer formation, whereas hydrogen substituents disturb the polymer formation. IR and ESCA spectra for these polymers showed that some dependence of the polymers formed in the chemical composition on the nature of the monomers. A part of methylamino groups in these monomers were oxidized to give amido and amine oxide groups. BDMAMVS and TMSDMA yielded polymers with few fragmentations of methylamino groups, whereas the polymers formed from BDMAMS had no methylamino groups.     

Preparation and characterization of SiO2 two-step aerogels

Aerogels are well suited as transparent insulation materials in solar architecture and collector systems. Their nanoporous structure provides a high solar transmittance and a low thermal conductivity, generally below 0.02 W m^–1 K^–1. Transparent aerogels with densities above 80 kgm^–3 can easily be prepared at room temperature via a one-step sol-gel process with subsequent supercritical drying. Separating hydrolysis and condensation via a two-step method allows the preparation of transparent ultra-low density SiO₂-aerogels. To optimize the optical properties, characterized by the scattering coefficient of the gels, we have investigated the influence of preparation parameters, such as pH-value of the sol-gel starting solution and macroscopic density, on the gel structure. To determine the nanostructure we performed spectral light scattering as well as small angle X-ray scattering (SAXS) measurements.     

Preparation of crosslinked polymers with increased modulus by high-pressure polymerization

p-Divinylbenzene has been polymerized by heating at pressures ranging from atmospheric to 2.5 GN/m², and the moduli (Young's, shear, and bulk), density, and residual unsaturation of the products have been determined. The results show a marked effect of polymerization pressure upon density and upon the degree of conversion of the second double bond. Linear relations are indicated between modulus and either density or an intermolecular force function based on a 6–12 potential field. These results and others on the densification of polystyrene are discussed and it is concluded that the moduli of the poly-p-divinylbenzene samples prepared under these conditions are still at a level largely determined by intermolecular forces.     

Preparation and characterization of erythromycin molecularly imprinted polymers based on distillation–precipitation polymerization

Erythromycin‐imprinted polymers with excellent recognition properties were prepared by an innovative strategy called distillation–precipitation polymerization. The interaction between erythromycin and methacrylic acid was studied by ultraviolet absorption spectroscopy, and the as‐prepared materials were characterized by Fourier‐transform infrared spectroscopy and scanning electron microscopy. Moreover, their binding performances were evaluated in detail by static, kinetic and selective sorption tests. It was found that the molecularly imprinted polymers afforded good morphology, monodispersity, and high adsorption capacity when the fraction of the monomers was 7 vol% in the whole reaction system, and the adsorption data for imprinted polymers correlated well with the Langmuir model. The maximum capacity of the imprinted and the non‐imprinted polymers for adsorbing erythromycin is 44.03 and 19.95 mg/g, respectively. The kinetic studies revealed that the adsorption process fitted a pseudo‐second‐order kinetic model. Furthermore, the imprinted polymers display higher affinity toward erythromycin, compared with its analogue roxithromycin.     

Preparation of hole transporting polymers by condensation polymerization of triphenylamine derivatives

Hole transporting polymers were prepared by condensation polymerization of triphenylamine and N,N,N',N'‐tetraphenylbenzidine (TPD) having alkyl group with aldehydes in the presence of p‐toluenesulfonic acid. The obtained polymers had molecular weight higher than 10,000 and good film formation ability. It was found that the aromatic amine monomers were connected with aldehyde monomer at the p‐position of the phenyl group. TPD‐aldehyde polymers had almost the same UV absorption and redox potentials as those of TPD monomer indicating that the electronic structure of amine unit did not change by the polymerization. The hole transporting mobility was in the range of 10⁻³‐10⁻⁶cm²/Vs. The electroluminescent device consisting of ITO/TPD polymer/Alq/Mg‐Ag had a maximum luminance of 9000 cd/m².     

Electrochemical polymerization of fluoranthene and characterization of its polymers

A novel inherently conducting polymer, high-quality polyfluoranthene (PFA) film with electrical conductivity of 10(-2) S cm(-1), was first synthesized electrochemically by direct anodic oxidation of fluoranthene in a middle strong Lewis acid-boron trifluoride diethyl etherate. The oxidation potential onset of fluoranthene in this medium was measured to be only 1.07 V vs SCE, which was much lower than that in acetonitrile + 0.1 mol L(-1) tetrabutylammonium tetrafluoroborate (1.68 V vs SCE). This PFA film showed good redox activity and stability even in concentrated sulfuric acid. Moreover, the fluorescence properties of PFA were greatly improved in comparison with those of the monomer. Dedoped PFA films were partly soluble in polar solvents such as CH(2)Cl(2), acetone, tetrahedrofuran, and dimethyl sulfoxide. The structure and morphology of the polymer were investigated by UV-vis spectroscopy, infrared spectroscopy, and scanning electron microscopy, respectively. The results of quantum chemistry calculations of fluoranthene monomer and (1)H NMR spectroscopy of dedoped PFA films indicated that the polymerization mainly occurred at C((3)), C((4)), C((13)), and C((14)) positions.     

Investigation of two-step polymerization reactions by DSC

A light-induced thiol-ene addition was combined with a thermally activated amine-epoxide addition. The two-step character of the polymerization in this resin system was proved by DSC measurements. The energies of the light-activated and the thermally activated reactions were determined.

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Zusammenfassung Die lichtinduzierte Thiol-en-Addition wurde mit der thermisch aktivierten Amin-Epoxid-Addition kombiniert. Der zweistufige Ablauf der Polymerisation in einem derartigen Harzsystem wurde mittels DSC nachgewiesen. Die Energien beider Teilschritte, der lichtinduzierten und der thermisch aktivierten Reaktion, wurden bestimmt.

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Synthesis and characterization of amphiphilic triblock polymers by copper mediated living radical polymerization

2-Dimethylaminoethyl methacrylate (DMAEMA) and 2-diethylaminoethyl methacrylate (DEAEMA) block copolymers have been synthesized by using poly(ethylene glycol), poly(tetrahydrofuran) (PTHF) and poly(ethylene butylenes) macroinitiators with copper mediated living radical polymerization. The use of difunctional macroinitiator gave ABA block copolymers with narrow polydispersities (PDI) and controlled number average molecular weights (M_n’s). By using DMAEMA, polymerizations proceed with excellent first order kinetics indicative of well-controlled living polymerization. Online ¹H NMR monitoring has been used to investigate the polymerization of DEAEMA. The first order kinetic plots for the polymerization of DEAMA showed two different rate regimes ascribed to an induction period which is not observed for DMAEMA. ABA triblock copolymers with DMAEMA as the A blocks and PTHF or PBD as B blocks leads to amphiphilic block copolymers with M_n’s between 22 and 24 K (PDI 1.24-1.32) which form aggregates/micelles in solution. The critical aggregation concentrations, as determined by pyrene fluorimetry, are 0.07 and 0.03 g dm⁻¹ for PTHF- and PBD-containing triblocks respectively.     

Preparation of molecularly imprinted polymers for strychnine by precipitation polymerization and multistep swelling and polymerization and their application for the selective extraction of strychnine from nux‐vomica extract powder

Monodisperse molecularly imprinted polymers for strychnine were prepared by precipitation polymerization and multistep swelling and polymerization, respectively. In precipitation polymerization, methacrylic acid and divinylbenzene were used as a functional monomer and crosslinker, respectively, while in multistep swelling and polymerization, methacrylic acid and ethylene glycol dimethacrylate were used as a functional monomer and crosslinker, respectively. The retention and molecular recognition properties of the molecularly imprinted polymers prepared by both methods for strychnine were evaluated using a mixture of sodium phosphate buffer and acetonitrile as a mobile phase by liquid chromatography. In addition to shape recognition, ionic and hydrophobic interactions could affect the retention of strychnine in low acetonitrile content. Furthermore, molecularly imprinted polymers prepared by both methods could selectively recognize strychnine among solutes tested. The retention factors and imprinting factors of strychnine on the molecularly imprinted polymer prepared by precipitation polymerization were 220 and 58, respectively, using 20 mM sodium phosphate buffer (pH 6.0)/acetonitrile (50:50, v/v) as a mobile phase, and those on the molecularly imprinted polymer prepared by multistep swelling and polymerization were 73 and 4.5. These results indicate that precipitation polymerization is suitable for the preparation of a molecularly imprinted polymer for strychnine. Furthermore, the molecularly imprinted polymer could be successfully applied for selective extraction of strychnine in nux‐vomica extract powder.