Preparation and application of molecularly imprinted polymer solid‐phase microextraction fiber for the selective analysis of auxins in tobacco

As signal molecules, auxins play an important role in mediating plant growth. Due to serious interfering substances in plants, it is difficult to accurately detect auxins with traditional solid‐phase extraction methods. To improve the selectivity of sample pretreatment, a novel molecularly imprinted polymer ‐coated solid‐phase microextraction fiber, which could be coupled directly to high‐performance liquid chromatography, was prepared with indole acetic acid as template molecule for the selective extraction of auxins. The factors influencing the polymer formation, such as polymerization solvent, cross‐linker, and polymerization time, were investigated in detail to enhance the performance of indole acetic acid‐molecularly imprinted polymer coating. The morphological and chemical stability of this molecularly imprinted polymer‐coated fiber was characterized by scanning electron microscopy, infrared spectrometry, and thermal analysis. The extraction capacity of the molecularly imprinted polymer‐coated solid‐phase microextraction fiber was evaluated for the selective extraction of indole acetic acid and indole‐3‐pyruvic acid followed by high‐performance liquid chromatography analysis. The linear range for indole acetic acid and indole‐3‐pyruvic acid was 1–100 µg/L and their detection limit was 0.5 µg/L. The method was applied to the simultaneous determination of two auxins in two kinds of tobacco (Nicotiana tabacum L and Nicotiana rustica L) samples, with recoveries range from 82.1 to 120.6%.     

Nanogram/mL detection of nortriptyline: Preparation of a molecularly imprinted polymer for spectrophotometric determination of nortriptyline based on multivariate optimization methods

In this work, the molecularly imprinted polymer was used as a selective sorbent in solid‐phase extraction method for the spectrophotometric determination of nortriptyline at 239 nm. Molecularly imprinted polymer was synthesized by pyrrole as a functional monomer in the presence of nortriptyline as a template. Several factors, consist of the concentration of the monomer to template ratio, amount of initiator, stirring rate, reaction time, the pH of the buffer solution, amount of sorbent, loading time, shaking rate of loading, extraction time, and shaking rate of extraction were evaluated due to their effectiveness in the preparation and extraction capability of molecularly imprinted polymer. Multivariate optimization methods, such as Plackett‐Burman and central composite designs, were employed to find and optimize the significant factors. Under the selected optimal conditions, molecularly imprinted polymer showed a linear range from 0.1 to 100 µmol/L (0.026 to 26 µg/mL) nortriptyline, a detection limit of 10.3 nmol/L (2.7 ng/mL), a highly repeatable (relative standard deviation of 3.7%) and reproducible response (relative standard deviation of 4.6%), and a good selectivity in the presence of structurally related molecules. Furthermore, molecularly imprinted polymer showed high extraction efficiency and was successfully used for the determination of nortriptyline in real samples.     

Determination of β-Agonists in Porcine Urine by Molecularly Imprinted Polymer Based Chemiluminescence

Isoprenaline was used as the template to synthesize a molecularly imprinted polymer that was able to simultaneously recognize ten β-agonists. The simulation showed that the three-dimensional conformation of the template was the main factor responsible for the polymer’s recognition. The polymer particles were coated in the wells of a conventional microplate as the recognition reagent to prepare a chemiluminescence sensor. The light signal was initiated with a highly effective bis(2,4,6-trichlorophenyl) oxalate-H₂O₂-imidazole system. The assay contained only one sample-loading step followed by immediate data acquisition, so one measurement was complete within 12?min. The sensor was used to determine the ten analytes in porcine urine. The results showed that the senor achieved ultrahigh sensitivity, with limits of detection from 2.0 to 7.0?pg/mL, high recoveries from 78.6% to 99.4%, and satisfactory recycle performance up to seven times. This is the first study reporting a molecularly imprinted polymer based microtiter chemiluminescence sensor for the determination of β-agonists.     

Silver Molecularly Imprinting Polymer for the Determination of p-Nitroaniline by Surface Enhanced Raman Scattering

Molecular imprinting and surface enhanced Raman scattering (SERS) were used to prepare a core-shell Ag@molecularly imprinting polymer (MIP) for the determination of p-nitroaniline. The obtained Ag@MIP exhibits a detection limit of 10^?12 M, which demonstrates higher sensitivity toward p-nitroaniline than conventional approaches. In addition, the Ag@MIP shows good recyclability, and simultaneously offers better stability and high SERS activity for recognizing target molecules. To characterize the high SERS activity of the SERS-MIP hybrid material, a possible mechanism for the SERS substrate is proposed involving enhancement by the MIP. This study is expected to provide an alternative approach for the determination of p-nitroaniline in aqueous environments.     

A new ionic liquid surface‐imprinted polymer for selective solid‐phase‐extraction and determination of sulfonamides in environmental samples

Toward improving the selective adsorption performance of molecularly imprinted polymers in strong polar solvents, in this work, a new ionic liquid functional monomer, 1‐butyl‐3‐vinylimidazolium bromide, was used to synthesize sulfamethoxazole imprinted polymer in methanol. The resulting molecularly imprinted polymer was characterized by Fourier transform infrared spectra and scanning electron microscopy, and the rebinding mechanism of the molecularly imprinted polymer for sulfonamides was studied. A static equilibrium experiment revealed that the as‐obtained molecularly imprinted polymer had higher molecular recognition for sulfonamides (e.g., sulfamethoxazole, sulfamonomethoxine, and sulfadiazine) in methanol; however, its adsorption of interferent (e.g., diphenylamine, metronidazole, 2,4‐dichlorophenol, and m‐dihydroxybenzene) was quite low. ¹H NMR spectroscopy indicated that the excellent recognition performance of the imprinted polymer was based primarily on hydrogen bond, electrostatic and π‐π interactions. Furthermore, the molecularly imprinted polymer can be employed as a solid phase extraction sorbent to effectively extract sulfamethoxazole from a mixed solution. Combined with high‐performance liquid chromatography analysis, a valid molecularly imprinted polymer‐solid phase extraction protocol was established for extraction and detection of trace sulfamethoxazole in spiked soil and sediment samples, and with a recovery that ranged from 93–107%, and a relative standard deviation of lower than 9.7%.     

Simultaneous determination of levofloxacin and ciprofloxacin in human urine by ionic‐liquid‐based,dual‐template molecularly imprinted coated graphene oxide monolithic solid‐phase extraction

A novel method was developed to simultaneously determine the ciprofloxacin and levofloxacin levels in human urine using an ionic‐liquid‐based, dual‐molecularly imprinted polymer‐coated graphene oxide solid‐phase extraction monolithic column coupled with high‐performance liquid chromatography. The molecularly imprinted monolithic column was prepared using ciprofloxacin and levofloxacin as templates, 1‐vinyl‐3‐ethylimidazolium bromide as the functional monomer, and graphene oxide as the core material. The resulting imprinted monoliths were characterized by scanning electron microscopy and fourier transform‐infrared spectroscopy. The efficiency and capacity of the ionic‐liquid‐based imprinted monolithic column were investigated by varying the synthesis conditions (ciprofloxacin/levofloxacin ratio and template/functional monomer/cross‐linker ratio). The solid‐phase extraction process was optimized by changing the washing and eluting conditions. The results suggested that the proposed ionic‐liquid‐based molecularly imprinted solid‐phase extraction monolithic‐high‐performance liquid chromatography method could separate ciprofloxacin and levofloxacin efficiently and simultaneously from human urine. The mean recoveries of ciprofloxacin and levofloxacin ranged from 89.2 to 93.8 and 86.7 to 94.6%, respectively. The intra‐ and interday relative standard deviation ranged from 0.9 to 3.2 and 0.8 to 2.9%, respectively. Under the optimized conditions, the recoveries of ciprofloxacin and levofloxacin were more than 93.8%.     

利用分子印迹传感器选择性测定绿麦隆

以绿麦隆为模板分子,邻氨基酚为功能单体,在金电极表面电聚合制得具有特异性识别孔穴的绿麦隆分子印迹膜。采用循环伏安、差分脉冲伏安法研究了印迹膜的性能、结构、分子印迹效应和模板分析物,并比较了传感器对其它结构相似化合物的选择性响应,发现该传感器对绿麦隆检测具有良好的选择性。绿麦隆浓度在3.0×10-7~1.5×10-6mol/L范围内与峰电流呈线性关系,检出限为1.0×10-7mol/L,在干扰物质共存情况下的回收率为105%~116%。     

克百威分子印迹聚合物的合成及其性能评价

以克百威为模板分子,甲基丙烯酸(MAA)为功能单体,二甲基丙烯酸乙二醇酯(EGDMA)为交联剂,采用沉淀聚合的方法制备了克百威分子印迹聚合物。通过红外光谱分析得到模板和功能单体的最佳配比为n(carbofuran)∶n(MAA)=1∶6。印迹聚合物的红外光谱测定结果表明,聚合物中存在与模板分子相互作用的特征基团;从印迹聚合物的扫描电镜图观察到分子印迹聚合物(MIP)与空白聚合物(NIP)的表面形态不同,可推论MIP存在与模板分子相互识别的结合位点。通过静态平衡结合法研究了模板分子聚合物的吸附能力、结合动力学和选择特性。结果表明,与非印迹聚合物相比,印迹聚合物对克百威具有较强的吸附特性和很好的专一选择性,3h后基本达到最大吸附量。采用固相萃取柱预处理样品,用高效液相色谱法测定自来水中10、50、100mg/L克百威的加标回收率为94%～117%,相对标准偏差(n=3)为2.5%～4.7%。     

分子印迹材料研究进展

本文简要综述了分子印迹的原理、制备技术,着重介绍了与膜材料、磁性材料、纳米材料和复合材料相结合的分子印迹技术的应用与发展。     

A new application of imprinted polymers: Speciation of organotin compounds

Molecular imprinting technology has been employed for the first time to prepare a specifically affinity chromatographic stationary phase for speciation purposes. Tributyltin has been chosen as the template molecule and the non-covalent approach has been applied. Three different polymerization methods have been evaluated: (i) a composite material, (ii) a polymer prepared via-Iniferter grafting; (iii) an emulsion polymer. Columns packed with different polymers have been evaluated by liquid chromatography (LC) coupled to inductively coupled plasma mass spectrometry (ICP-MS). The chromatographic conditions as well as the analytical characteristics of the developed method are discussed in this paper. Our findings have shown formation of specific cavities in the grafted Iniferter as well as in the emulsion polymers with the latter achieving resolution of four organotin compounds. Detection limits are similar to those obtained with commercial, but not specific, stationary phases (6 pg for monobutyltin, MBT; 10 pg for both tributyltin, TBT, and triphenyltin, TPhT; and 20 pg for dibutyltin, DBT). The main advantage of this proposed stationary phase is that good recovery is obtained for all species, including MBT. Baseline resolution for TBT and TPhT has also been obtained. The high selectivity of this column prevents matrix interferences. The method has been validated by analyzing two biota reference materials (ERM-CE477 mussel tissue and T-38 oyster tissue).