Theoretical Researches on the Recognizing Characteristics of Atrazine Imprinted Polymers with Different Functional Monomers

As a widely used herbicide, the threat of atrazine to both environment and health of people has become the focus. Therefore, the research and analysis of atrazine are getting more important. In this work, the MIT was used to detect atrazine theoretically. Atrazine was taken as a template molecule. MAA, MMA and TFMAA were taken as the functional monomers, respectively. The geometry optimization, the nature of hydrogen bonds, the NBO charge, and the binding energies of the imprinted molecule with the functional monomers were investigated at the B3LYP/6-31g(d,p) level. Results indicated that atrazine had the strongest interaction with TFMAA. When the ratio of atrazine and TFMAA was 1:6, the amount of H-bond formed from atrazine and TFMAA was the largest. Moreover, TFMAA owned the largest binding energy with atrazine while MMA owned the smallest. The study is helpful to interpret experiment phenomena of molecular imprinting and select better functional monomers.     

环丙沙星与三氟甲基丙烯酸分子印迹自组装体系的理论研究

采用量子化学长程校正方法, 以环丙沙星(CIP)为印迹分子, 三氟甲基丙烯酸(TFMAA)为功能单体, 研究了CIP与TFMAA单体分子印迹聚合物(MIPs)自组装体系的构型、 成键作用位点、 反应的结合能、 作用机理及其选择性. 计算结果表明, CIP印迹分子与TFMAA单体通过氢键形成分子结构互补的有序排列复合物, 当印迹分子与功能单体配比(印迹比例)为1: 6时, 其复合物能量最低; 通过模拟洗脱CIP后的复合物对恩诺沙星(ENR)、 诺氟沙星(NOR)、 氧氟沙星(OFL)再结合的结合能可以预测MIPs对CIP印迹分子的选择性, CIP与OFL共存时MIPs对CIP的选择性最好. 采用不同印迹比例, 测定聚合物对CIP的吸附量, 结果表明, 印迹比例为1: 6时, 聚合物吸附量最大, 且对OFL的选择因子最大, 实验结果与计算结果一致.     

除草剂青莠定分子印迹聚合物的合成及结合性能研究

采用分子印迹技术,分别以α-甲基丙烯酸和4-乙烯基吡啶为功能单体,合成了两种对除草剂青莠定具有选择性结合能力的分子印迹聚合物．紫外光度法研究显示了模板分子青莠定和4-乙烯基吡啶的离子作用强于它和α-甲基丙烯酸之间的氢键作用,并用平衡结合实验研究了不同功能单体的聚合物对模板分子的结合能力和对底物的选择性,结果表明以4-乙烯基吡啶为功能单体合成的分子印迹聚合物对青莠定表现出更高的结合能力和更优的选择性．这对分子印迹技术用于环境样品中除草剂青莠定的分离和富集具有重要意义。     

Theoretical Researches on the Self-assembly System of Molecularly Imprinted Polymers Formed via Phenobarbital and Acrylamide

For preparing the phenobarbital(PHN) molecularly imprinted polymers(MIPs) with higher adsorption and selectivity properties, we used the M062 X/6-31 g(d,p) method of density functional theory to predict the various properties of PHN-MIPs. Here PHN is as the imprinted molecule and acrylamide(AM) as the functional monomer. The ethylene glycol dimethacrylate,trimethylolpropane trimethacrylate, divinyl benzene, and pentaerythritol trimethacrylate are as the cross-linking agents, respectively. The acetonitrile, chloroform, toluene, and tetrahydrofuran are used as the solvents, respectively. The configurations of the molecular imprinting self-assembly system for PHN and AM have been simulated to study their bonding sites, binding energy, amount of hydrogen bond, and interaction mechanism. The essence of imprinting interaction for PHN and AM has been revealed by the atomic in the molecule theory. Meanwhile, the analogues of PHN were used to discuss the selectivity property of the stable PHN-AM complex. The results show that the PHN interacts with AM through hydrogen bonds. When the imprinting molar ratio of PHN-AM is1:6 and the THF is as the solvent, the amount of their hydrogen bonds is the most, the binding energy is the lowest, and their configuration is the most stable. In comparison with the other cross-linking agents(EGDMA, TRIM, and DVB), the PETA is more suitable for PHN-MIPs. The selective property of PHN-MIP to PHN is excellent when PHN and DMBA exist at the same time.     

高岭土磁性复合材料表面印迹聚合物选择性吸附分离环丙沙星

以氨基改性的磁性高岭土为基质材料,利用电子转移产生催化剂的原子转移自由基聚合法制备磁性高岭土表面印迹聚合物（MMIPs）。通过FTIR、TEM、TGA、XRD和VSM等方法对其物理化学性质进行表征,其比表面积112 m²·g^-1,且具有较好的热稳定性、超顺磁性（M_s=13.365 emu·g^-1）。吸附性能研究表明,准二级动力学模型能较好地描述MMIPs对环丙沙星（CIP）吸附动力学行为,Langmuir等温模型能较好地拟合MMIPs对CIP的吸附平衡数据,25℃时MMIPs的单分子层吸附容量为89.36 mg·g^-1。选择性实验研究表明,MMIPs对CIP具有较好地选择识别性。结合高效液相色谱分析技术,MMIPs已成功应用于鲜鱼样品中痕量CIP的分离、富集和回收,CIP的回收率为92.15%。     

药物利多卡因分子印迹聚合物的制备及识别特性

利多卡因与甲基丙烯酸为功能单体分别在低温(0～4℃)紫外光照、加热条件下制备利多卡因分子印迹聚合物,实验结果通过Scatchard方程分析可知,低温紫外光照下制备的利多卡因MIP对利多卡因具有良好的选择性,并可进一步应用于临床利多卡因药物的分离富集和检测.     

高岭土磁性复合材料表面印迹聚合物选择性吸附分离环丙沙星

以氨基改性的磁性高岭土为基质材料,利用电子转移产生催化剂的原子转移自由基聚合法制备磁性高岭土表面印迹聚合物(MMIPs)。通过FTIR、TEM、TGA、XRD和VSM等方法对其物理化学性质进行表征,其比表面积112 m2·g-1,且具有较好的热稳定性、超顺磁性(Ms=13.365 emu·g-1)。吸附性能研究表明,准二级动力学模型能较好地描述MMIPs对环丙沙星(CIP)吸附动力学行为,Langmuir等温模型能较好地拟合MMIPs对CIP的吸附平衡数据,25℃时MMIPs的单分子层吸附容量为89.36 mg·g-1。选择性实验研究表明,MMIPs对CIP具有较好地选择识别性。结合高效液相色谱分析技术,MMIPs已成功应用于鲜鱼样品中痕量CIP的分离、富集和回收,CIP的回收率为92.15%。     

环丙沙星分子印迹聚合物的制备及其吸附特性的研究

以环丙沙星(CIP)为模板分子,α-甲基丙烯酸(MAA)为功能单体,三甲基丙烯酸三羟甲基丙烷酯(TRIM)为交联剂,进行热聚合.通过对于功能单体和交联剂的用量对分子印迹聚合物吸附性能的影响的研究,得到最佳的聚合配比为n(CIP):n(MMA):n(TRJM)=1:6:16,并以此配比制得了对环丙沙星具有特异选择性吸附的分子印迹聚合物.通过静态平衡结合法研究了模板聚合物的结合动力学以及该聚合物的结合能力和选择特性,通过Scatchard分析法研究了印迹聚合物对模板分子的结合特性.结果表明,该印迹聚合物具有良好的吸附能力和吸附选择性,静态吸附分配系数KD为41.64,分离因子α为1.62;该印迹聚合物中形成了2类不同的结合位点,经计算它们的离解常数分别为Kd1=5.249×10-5mol·L-1,Kd2=2.237×10-3mol·L-1.     

阴离子印迹聚合物的制备及其应用研究进展

离子印迹聚合物是利用印迹技术对模板离子进行印迹、聚合进而得到能够选择性吸附该离子的一种特殊聚合物.目前的报道大多是阳离子印迹聚合物,因为阴离子模板结构更复杂多样且电荷尺寸比更小,致使阴离子印迹聚合物的发展相对滞后.为能更有效地指导阴离子印迹聚合物的制备,本文概述了阴离子印迹聚合物的发展现状,介绍了与不同阴离子有相互作用...     

Theoretical Study on the Structures and Properties of Phenobarbital Imprinted Polymers

Recently, the investigation of novel molecularly imprinted polymers（MIPs） has attracted a lot of interest and becomes a fascinating field. The phenobarbital（PHN） was taken as an imprinted molecule and the 2-vinyl-4,6-diamino-1,3,5-triazine（VDAT） was considered as a functional monomer in this study. The geometry optimization, natural bond orbital（NBO） charge, and molecular electrostatic potential（MEP） of PHN and VDAT were studied at the M062 X level belonging to one of the hybrid density functional theories. Furthermore, we discussed the bonding conditions of PHN molecular imprinted polymers（PHN-MIPs） via the hydrogen bond length and atoms in molecules（AIM） theory. The rebinding property of PHN-MIPs was also researched. The results of MEP and NBO charge analysis were coincident. The stability property was excellent when the ratio of PHN and VDAT was 1：4. Except the classic hydrogen bonds, non-classical hydrogen bonds also existed in the imprinted polymers. By simulating the rebinding energies between the pentobarbital（PNT）, barbital（BAR）, and PHN-MIPs after the elution of PHN, the rebinding property of PHN-MIPs to PHN was excellent when PNT and BAR existed all at once. This research can provide theoretical reference for the synthesis and characterization of novel PHN-MIPs.     

乙酰水杨酸分子印迹聚合物的合成及性能研究

采用分子印迹技术,以乙酰水杨酸为模板分子,1,4-二乙烯基苯为交联剂,分别以α-甲基丙烯酸和丙烯酰胺为功能单体,合成了对乙酰水杨酸具有特异性吸附能力的两种分子印迹聚合物;它们对乙酰水杨酸都存在两类不同亲和性的结合位点,其中用丙烯酰胺合成的分子印迹聚合物对模板分子乙酰水杨酸的氢键作用力和结合能力都比用α-甲基丙烯酸合成的聚合物强。这对分子印迹技术用于环境、血液等复杂样品中乙酰水杨酸的分离和富集具有重要意义。     

Plastic Antibodies for Cosmetics: Molecularly Imprinted Polymers Scavenge Precursors of Malodors

Molecularly imprinted polymers (MIPs) are synthetic antibody mimics capable of specific molecular recognition. Advantageously, they are more stable, easy to tailor for a given application and less expensive than antibodies. These plastic antibodies are raising increasing interest and one relatively unexplored domain in which they could outplay these advantages particularly well is cosmetics. Here, we present the use of a MIP as an active ingredient of a cosmetic product, for suppressing body odors. In a dermo‐cosmetic formulation, the MIP captures selectively the precursors of malodorous compounds, amidst a multitude of other molecules present in human sweat. These results pave the way to the fabrication of a novel generation of MIPs with improved selectivities in highly complex aqueous environments, and should be applicable to biotechnological and biomedical areas as well.     

由不同功能单体合成的对羟基苯甲酸分子印迹聚合物识别特性的实验和理论研究

以对羟基苯甲酸(p—HB)为模板分子,以4-乙烯吡啶(4-Vpy)、丙烯酰胺(AM)或二者等摩尔比的混合物为功能单体制备了相应的分子印迹聚合物(Molecularly imprinted polymer,MIP),考察了MIP作为高效液相色谱柱固定相时模板分子及其类似物的保留行为,同时也考察了在乙腈流动相中添加剂乙酸或水对色谱保留的影响．三种MIPs的保留大小顺序为：当功能单体为4-Vpy时,MIP对模板及其类似物的保留最强;当以4-Vpy和AM作为混合单体时,保留次之;而功能单体为AM时,保留最差．以H2O作为添加剂时MIP的识别效果要优于以CH3CO2H为添加剂的情况．使用半经验量化法之一,PM3方法,借助Gaussian94软件对以p—HB与相应的功能单体体系进行了计算模拟．结果表明,聚合前单体与模板复合物结合能量的大小与实验所得的容量因子间具有正相关性．即结合能越高,容量因子k′值越大．     

苄嘧磺隆印迹聚合物的波谱分析及吸附性能研究

以苄嘧磺隆为模板分子, α-甲基丙烯酸为功能单体, 三甲氧基丙烷三甲基丙烯酸酯为交联剂, 二氯甲烷为致孔剂, 在20 ℃温度下, 采用紫外引发沉淀聚合方法制备了苄嘧磺隆分子印迹聚合物. 紫外光谱和核磁共振氢谱实验提示了聚合前模板分子与功能单体之间的相互作用主要是分子间氢键, 分子间氢键相互作用能和双氢键的键距由Hyperchem 7.0和Gaussian 03W软件分别计算为: －28.6163 kJ/mol和0.179～0.181 nm. 制备的印迹聚合物在高效液相色谱和吸附动力学实验中都表现出对模板分子有较强的吸附作用.     

莠去津分子印迹聚合物的合成及识别性能研究

以莠去津为模板分子,α-甲基丙烯酸为功能单体,在氯仿溶剂中合成了莠去津分子印迹聚合物．紫外光谱研究表明莠去津与功能单体α-甲基丙烯酸之间确实存在作用力,通过红外光谱分析了聚合物结构,可以确定模板分子与功能单体之间的作用力为氢键．利用透射电镜表征了溶剂用量对印迹聚合物微观形貌的影响,综合利用平衡结合实验考察了不同溶剂用量...     

Molecularly Imprinted Polymer with Calix[4]arene Derivative for the Recognition of Acetanilide

Two molecularly imprinted polymers binding to analgesic acetanilide were prepared using either dual functional monomers of calix[4]arene derivative and acrylamide or single monomer acrylamide, respectively. The polymers were ground, sieved and investigated by equilibrium binding experiment to evaluate their recognition properties for the template and other substrates. Scatchard analysis showed that homogeneous recognition sites were formed in the imprinted polymer matrix. Our results demonstrated that the polymer using two functional monomers exhibited better selectivity for the template. This study may open new frontiers for the development and application of imprinted polymers, such as drug separation and purification.     

有机高分子与聚合硫酸铁的复配特性

研究了水溶性有机高分子(OP)与聚合硫酸铁(PFS)的复配特点,从分子结构和溶剂化角度探讨了OP在PFS中的稳定机制,并采用FT-IR、SEM和X射线衍射探讨了OP与PFS的相互作用.结果表明:具有吡咯环结构的聚二甲基二烯丙基氯化铵、聚二乙基二烯丙基氯化铵和聚乙烯吡咯烷酮能与PFS复配,且具有较好的稳定性;OP与PFS形成了互相融合的复合体系,主要与PFS中Fe4.67(SO4)6(OH)2.20H2O物相发生相互作用.     

光响应性有机-无机杂化分子印迹聚合物的制备及表征

以4-硝基苯酚、 2,4-二氯苯氧乙酸和3-氯丙基三乙氧基硅烷为原料, 经氧化偶合、 酰化、 酯化反应合成了共价结合模板分子2,4-二氯苯氧乙酸(2,4-D)的光响应性含有机硅的偶氮苯功能单体, 通过溶胶-凝胶法制备了光响应性的有机-无机杂化分子印迹聚合物(OIHMIP). 研究了该分子印迹聚合物光响应性能、 对2,4-D的吸附性能和选择识别及光控释放与吸收能力, 用原子力显微镜对其形貌进行了表征. 结果表明, 制得的OIHMIP具有规则的球形, 粒径介于150～200 nm之间. OIHMIP对2,4-D具有良好的吸附和选择识别能力, 在365和440 nm的紫外-可见光交替照射下, 可控制2,4-D的释放与吸收.     

胆甾基功能高分子研究进展

简要评述了胆甾基功能高分子的分子设计与合成研究进展,着重对侧基型高分子胆甾进行论述.     

以混旋邻氯扁桃酸为模板的分子印迹聚合物的制备及拆分性能研究

以混旋邻氯扁桃酸为模板分子和合成的(S)-(1-萘乙基)-丙烯酰胺为手性功能 单体制备分子印迹聚合物作为色谱固定相，对混旋邻氯扁桃酸有较好的拆分能力， 分离因子α达到1.36。但对模板分子的类似物混旋扁桃酸和对氯扁桃酸没有拆分能 力。用Hyperchem软件模拟了(S)-邻氯扁桃酸与(S)-(1-萘乙基)-丙烯酰胺形成的复 合物的结构模型，其在聚合物母体中留下的具有立体构型和作用力双重识别的S-S 型空穴，对(S)-邻氯扁桃酸有较强的保留作用，从而达到对混旋物拆分的目的。