Enantiomeric Resolution on L-Carnitine Selective Polymers Prepared by Molecular Imprinting

L-carnitine selective polymers were prepared by molecular imprinting using methacrylic acid as the functional monomer. The acid function of the monomer is expected to form hydrogen bond and ionic interactions with the amine function of the target molecule L-carnitine. The imprinted polymers were used as stationary phases in high-performance liquid chromatography (HPLC). It was shown that L-carnitine imprinted polymer exhibited a higher affinity to its template molecule, while the non-imprinted polymer had no affinity to the compounds tested. Racemic carnitine hydrochloride was efficiently resolved on the L-carnitine imprinted polymer, and the separation factor is 1.9.

Tetracycline selective electrode based on molecularly imprinted polymer particles

Tetracycline selective electrode using molecularly imprinted polymer particles as quasi-ionophore was constructed the first time, and its performance was carefully characterized. Due to the specific recognition of tetracycline by the particles, the selectivity coefficients for routine interferences were less than 10-4. Benefited from the absence of tetracycline in the sensitive membrane and the optimized composition of the inner filling solution, the limit of detection of the electrode was reduced to about 2.5 × 10^-8 mol/ L. It exhibited a good electrode slope 57.6 mV/decade near the theoretical Nernstian one, with a wide linear working range from 6.0 × 10^-8 to 1.0 × 10^-3 mol/L. The fabricated electrode should be used in pH 2--4, response time of which was less than 200 s when the concentration of tetracycline was higher than 1.0 × 10^-6 mol/L and no more than 30 min at the concentration of 1.0 × 10^-8 mol/L.

Monocrotophos Molecularly Imprinted Microspheres Prepared by Precipitation Polymerization in Acetonitrile

Molecularly imprinted microspheres (MIP) for monocrotophos have been prepared by precipitation polymerization in acetonitrile (ACN) 60℃,24 h,using methacrylic acid (MAA),ethylene glycol dimethacrylate (EGDMA) and 2, 2-azobisiobutyronitrile (AIBN) as functional monomer,cross-linker and initiator,respectively.The recognition mechanism was elucidated by UV-vis spectra and computer modeling.Equilibrium binding experiment was employed to investigate the rebinding properties,Scatchard analysis showed that specific binding sites formed in the imprinted microspheres,and there were two kinds of binding sites,one was high binding sites,the other was low binding sites.This microspheres can be useful affinity absorbent used for organophosphorus pesticides separation and purification in food and environmental analysis.

Molecularly Imprinted Polymer for Theophylline Retention and Molecular Recognition Properties in Capillary Electrochromatography

Molecular imprinting of theophylline in poly (methacrylic acid- ethylene dimethacrylate) as CEC stationary phases was synthesized by an in situ photo-initiated polymerization reaction. The effect of electrolyte pH on xanthine derivatives and the stability of MIP column performance were investigated. the relative standard deviation (D RS) of migration time of five consecutive runs on MIP column was in the range of 2.2%–3.1%. The reproducibility of migration time column to column of M(A) was in the range of 3.8%–4.9%. The highest column efficiency was more than 140 000 plates per meter. The MIP capillaries had showed better selective for theophylline, which comparing with the reference column. The urine sample was separated by spiked 5×10?4 mol·L?1 theophylline. Key words capillary electrochromatography - molecular imprinting polymers - theophylline CLC number O 657.8 Foundation item: Supported by the National Nature Science Foundation of China (20375028) and the Research Fund for the National High Technology Development “863” of China (2002AA2Z2004)Biography: Cai Ling-shuang (1968-), female, Associate professor, Ph. D, research direction: separation science.

MOLECULAR IMPRINTED POLYMERS——Novel Polymer Adsorbents

Molecular imprinted polymers (MIPs) are novel functional polymer materials and known as specific adsorbents for the template molecules. These novel functional polymers have promised potential applications in racemic resolution, sensor, chromatography, adsorptive separation and other fields. This review exhibits the approach for preparing MIPs, the features of MIPs obtained by different routes and the characteristics of adsorptive separations with MIPs. The molecular recognition mechanism and the idea of the present possibilities and limitations of molecular imprinting polymerization are discussed as well.

Preparation and Electrochemical Characters of Parathion Molecule Imprinted Polymeric Sensors

A sensitive, fast and low-cost molecular imprinted polymeric sensor for quantitative determination of parathion was prepared with chitosan（CS） as function matrix and parathion（PT） as template molecule via constant potential electrochemical deposition. Sensitive response was obtained with a detection limit of 1.0× 10-7 mol/L and an excellent recognition for PT was achieved due to the good memory capacity of the sensor. The developed sensor exhibited good fabrication reproducibility and acceptable stability, which provided a new promising tool for pesticide analysis.

Computer Simulation and Experimental Investigations of Phenobarbital Molecular Imprinting System

The interaction process between the phenobarbital（PHN） and acrylamide（AM） was studied using the M062X/6-31G（d,p） method. The PHN and AM were used as the template and functional monomer,respectively. The molecular electrostatic potential（MEP） was simulated for predicting the reactive sites. The atoms in molecules theory helped to reveal the imprinting mechanism and optimize the molar ratios for PHN and AM. The molecular imprinted polymers（MIPs） containing PHN were synthesized through the precipitation polymerization. The diameter range of the obtained MIPs was from 150 to 390 nm. According to the computational results,MIPs with the molar ratio of PHN and AM equal to 1：6 showed high selective adsorption for PHN. The apparent maximum adsorption quantity（Q_（max）） of MIPs toward PHN was 7.9 mg/g,and the Qmax of nonimprinted polymer microspheres（NIPs） was 3.2 mg/g. Herein,the studies can provide theoretical and experimental references for the controllable fabrication of MIPs.

Preparation and Cyclic Voltammetry Characterization Of Cu-dipyridyl Imprinted Polymer

Polymer capable of specific binding to Cu-dipyridyl complex was prepared by molecular imprinting technology. The binding specificity of the polymer to the template (Cu-dipyridyl complex) was investigated by cyclic voltametric scanning using the carbon paste electrode modified by polymer particles in phosphate buffer solution. Factors that influence rebinding of the imprinted polymer were explored. The result demonstrated that the cyclic voltammetry was an efficient approach to explore interactions between template and imprinted polymers.

Simultaneous Chiral Separation Using a Combinatorial Molecular Imprinting Phase

Molecular imprinting chiral stationary phase against Cbz-L-Serine (Cbz-L-Ser) and Cbz-L-Alaine (Cbz-L-Ala) were prepared utilizing acrylamide + 2-vinylpyridine as combined basic functional monomers. Cross-selectivity was used to obtain simultaneous chiral separations of Cbz-DL-Ser and Cbz-DL-Ala by connecting two columns packed with Cbz-L-Ser and Cbz-L-Ala imprinted chiral stationary phase, respectively.

Template-Monomer Interaction in Molecular Imprinting: Is the Strongest the Best?

Molecularly imprinted polymers (MIPs) represent a new class of materials possessing high selectivity and affinity for the target molecule. They have been utilized as sensors, catalysts, sorbents for solid-phase extraction, stationary phase for liquid chromatography, mimics of enzymes, receptors, and antibodies. In this research, molecular imprinted polymers (MIPs) for luteolin were prepared using acrylamide, 4-vinylpyridine and 1-allyl-piperazine as functional monomers and ethylene glycol dimethacrylate as cross-linker by non-covalent imprinting method. UV-visible spectra were used to evaluate the interaction strength between the template and the monomers. The composites of the polymers were calculated from elementary analysis. The porous properties of the imprinted polymers have been determined from nitrogen adsorption-desorption isotherms. The imprinting efficiency of the prepared MIPs was evaluated by selective adsorption for luteolin and its structural analogues. Although the interaction strength of monomers to the template was in the order 1-ALPP > 4-VP > AA, the binding affinity of the imprinted polymers towards luteolin was in the order MIP 2 > MIP 3 > MIP 1. Our results demonstrated that the imprinting efficiency was depending not only on the interaction strength between the template and the monomer, but also on the fidelity in transferring the complex into the polymer.

A Novel Molecular Imprinted Polymers-Based Lateral Flow Strip for Sensitive Detection of Thiodiglycol

Traditional detection of thiodiglycol(TDG),a metabolic marker for sulfur mustard poisoning,requires not only professional operators,but also expensive reagents and large instruments.Herein,we developed a novel molecular imprinted polymers(MIPs)-based lateral flow assay(LFA)strategy for the quick,sensitive,and selective detection of TDG.Gold nanoparticles(Au NPs),MIPs,and metallothioneins(MTs)were respectively loaded on the conjugate pad,test line(T line)and control line(C line).After adding TDG,Au NPs on the conjugate pad reacted with TDG through the Au-S bond first.Then,under the action of capillary force,the conjugates of TDG and Au NPs were trapped by the MIPs as they traveled to the T line,and the residual Au NPs bound with the MTs on the C line,exhibiting two obvious red bands on T line and C line,respectively.In contrast,a single red band could be observed on C line without TDG.This method exhibited a wide linear range from 10.0 pg/m L to 10,000.0 ng/m L and its limit of detection(LOD)was as low as 0.41 pg/m L.This method was successfully utilized to detect TDG in human urine,presenting significant potential in the point-of-care testing of TDG in clinical samples of the sulfur mustard poisoning patients.

Molecularly Imprinted Polymer for Solid-Phase Extraction of Ecteinascidin 743 from Sea Squirt

Ecteinascidin 743 from sea squirt is one of the most original anti-tumoral activity compounds, as proven by the Natural Cancer Institute. Ecteinascidin 743 could be obtained with traditional liquid extraction, but it should be purified and separated from the extract. A molecularly imprinted solid-phase extraction procedure was developed for the selective separation. Ecteinascidin 743 was used as the template and the polymer was synthesized in a methanol environment. Water and n-hexane as the washing solvents can eliminate most of the interference. Good linearity and low relative standard deviations （less than 4.39%）justify its continuing development.

Novel polymer system for molecular imprinting polymer against amino acid derivatives

Molecular imprinting polymers (MIPs) against N-Cbz-L-Tyr were prepared utilizing different polymer systems and evaluated in HPLC mode. It was found that MIP utilizing cocktail functional monomers, acrylamide + 2-vinylpyridine showed better molecular recognition and better separation ability for the template molecule than those utilizing other functional monomers. MIP utilizing trimethylolpropane trimethacrylate as cross-linker showed higher load capacity and separation factor than those utilizing ethylene glycol dimethacrylate as cross-linker. Increasing the concentration of competing solvent, acetic acid weakened me ionic interaction and hydrogen bonding between the analyte and the functional monomers, 2-vinylpyridine and acrylamide, when me template enantiomer was separated by HPLC. Therefore increasing of the concentration of acetic acid leads to decreasing of capacity factor, separation factor and resolution.

分子印迹手性整体柱的制备及对非对映异构体的分离

采用原位分子印迹技术 ,单步制备了一种辛可宁印迹的手性整体柱。为了提高柱效和选择性 ,选择了相对低极性的甲苯 /十二醇复合致孔体系。在等度及梯度洗脱条件下 ,非对映异构体辛可宁与辛可尼丁被完全分离。等度洗脱中相对较宽的色谱峰可以在梯度洗脱中得到改善。同时考察了流动相中醋酸浓度、流速以及温度对分离的影响。由于柱中存在大的流通孔 ,大大降低了分离过程中的柱压降 ,从而使这种色谱柱能够在相对高的流速下使用。提高温度可以提高分离因子 ,在 60℃获得最大分离因子 5 40。

苯丙氨酸衍生物分子印迹聚合物的制备及手性拆分研究

以分子印迹技术合成分子印迹聚合物 ,作为手性色谱柱的固定相来拆分苯丙氨酸衍生物的对映异构体。采用了新型的交联剂及光引发剂。模板分子和可聚合的功能单体形成配合物是分子印迹聚合物必不可少的条件。模板分子与功能单体的比例为 1∶4时 ,获得了良好的分离效果 ,分离因子α为 1 .6 9。光聚合方式合成的分子印迹聚合物比热聚合方式合成的拆分能力要高。且聚合的温度越低 ,聚合物分离效果越好。

农药久效磷分子印迹聚合物合成及其亲合性评估

Uniformly imprinted polymer microspheres were prepared by precipitation polymerization in chloroform.MCP（monocrotophos）,MAA（methacrylic acid）,EGDMA（ethylene glycol dimethacrylate） and AIBN（azobisisobutyronitrile） were used as template,functional monomer,crosslinker and initiator,respectively.UV and IR spectra were used to demonstrate the mechanism of the interaction between MCP and MAA.It was found that one MCP was entrapped by three MAA molecules in chloroform.Langmuir model was used to fit the adsorption data,the results showed that the MCP imprinted polymer microspheres showed specific binding sites to the MCP.The data obtained in equilibrium adsorption experiments were processed by Scatchard analysis,the dissociation contents(KD1) and the apparent maximum binding capacity (Bmax1) were KD1=0.062?mmol/L,Bmax1=3.26?μmol/g for high affinity binding sites and KD2=3.03?mmol/L,Bmax2=65.70?μmol/g for low affinity binding sites,respectively.The MCP imprinted polymers have showed higher affinity to MCP than to the other organophosphorus pesticide used.So the imprinted polymers microspheres can be used for trace pesticide residue separation,enrichment and analysis.

微囊藻毒素分子印迹传感器的制备与应用

以邻氨基酚为单体,微囊藻毒素(MC-LR)为模板,采用循环伏安法在金电极的表面电聚合成膜分子印迹材料,制备了传感器。采用安培法对MC-LR进行检测。在制备影响条件最佳值(pH=4.5;单体/模板=1.4×108∶1;洗脱时间10 min)的基础上,对该传感器的线性范围、使用寿命、选择性等进行了研究,并与液相色谱方法进行对比,结果表明:该传感器对MC-LR具有良好的选择性和灵敏度,线性范围为0.05～0.35 mg/L;加标回收率为80%～105%;检出限为7.3μg/L。与液相色谱方法对比,当置信度为99%时,无系统误差。

L-色氨酸分子印迹传感器敏感膜的制备与性能

以L-色氨酸(L-Trp)为模板分子,邻苯二胺(o-PD)为功能单体,在金电极表面原位合成了分子印迹聚合物敏感膜;通过循环伏安法(CV)、差示脉冲伏安法(DPV)和电化学阻抗谱法(EIS)考察了该电极的性能.DPV测试结果表明,在1×10-8～2×10-7mol/L范围内,峰电流与L-Trp的浓度呈线性关系,检出限为0.3×10-8mol/L;选择识别性实验结果表明,L-Trp印迹敏感膜的印迹因子达到3.72,相对于干扰物的选择因子均大于1,对与L-Trp结构相似的L-酪氨酸(L-Tyr)的选择因子也达到2.30,说明该印迹膜对L-Trp具有良好的选择性;识别过程动力学研究结果表明,印迹膜对L-Trp的识别是一个两步连续发生的过程,即快结合过程和慢吸附过程.

悬浮聚合法制备磁性分子印迹聚合物微球

以苯胺和二甲基苯胺为模板分子、甲基丙烯酸(MAA)为功能单体、三羟甲基丙烷三丙烯酸酯(TRIM)为交联单体、Fe3O4为磁性组分,采用悬浮聚合法制备了磁性分子印迹聚合物微球(MMIPMs)。结果表明,改性Fe3O4微粒在MMIPMs中分散较好,MMIPMs在水性介质中对模板分子的选择吸附性较差,但在有机介质中有较好的选择吸附性。

水杨酸分子印迹膜电化学传感器的制备

以水杨酸为模板分子,采用循环伏安法电聚合形成聚吡咯膜,以固定电位过氧化法去除印迹分子,制备了水杨酸分子印迹膜电极。本印迹电极能促进水杨酸电氧化过程,有效地避免结构类似物(如苯甲酸)对其测定的干扰。循环伏安法用于电化学检测,当富集时间为10min,磷酸盐缓冲溶液的pH=6.86时,在1.0×10-6～2.0×10-3mol/L浓度范围内,水杨酸氧化峰电流与其浓度呈良好的线性关系,检出限为0.8μmol/L,用分子印迹膜电极对加标样品进行分析,回收率为94.6%～103.4%。