分子印迹聚合物在抗生素残留测定中的应用

抗生素的滥用及残留对生物体和环境造成极大危害,其含量低、种类多、基质复杂,通常需要进行样品前处理结合色谱分析以实现灵敏测定。分子印迹聚合物（MIPs）能选择性识别、有效富集目标分析物并消除干扰,已广泛用于抗生素的样品前处理中。该文对MIPs制备中面临的挑战进行了总结;对2016年以来抗生素MIPs的固相萃取应用进行了综述和展望,主要包括固相萃取、分散固相萃取、磁固相萃取、基质固相分散萃取、固相微萃取、搅拌棒吸附萃取。此外,该文重点介绍了抗生素MIPs的印迹新策略,如多模板、多功能单体、虚拟模板、刺激响应、亲水性印迹等。最后,该文对抗生素MIPs的制备和前处理应用进行了展望。     

替代模板分子印迹技术在样品前处理中的应用

分子印迹聚合物具有抗恶劣环境、选择性高、稳定性好等特点,广泛应用于复杂样品的前处理。采用结构类似物作为替代模板分子,可以解决分子印迹聚合物制备时目标物溶解性差的问题,替代模板分子印迹聚合物不仅对目标分析物具有选择性识别能力,还可以避免模板泄露对痕量分析造成的影响。本文综述了替代模板分子印迹技术在样品前处理中的应用进展,包括替代模板分子印迹技术在固相萃取、固相微萃取、色谱固定相、基质固相分散萃取中的应用,最后对替代模板分子印迹技术在未来的样品前处理中的研究进行了展望。     

分子印迹聚合物在核苷类药物分离分析中的应用

核苷类药物在新型冠状病毒肺炎（COVID-19）、艾滋病及肝炎等病毒性疾病治疗方面效果显著,应用广泛,其准确定量具有重要意义。近年来,基于分子印迹技术合成的分子印迹聚合物（MIPs）备受关注。MIPs可模拟酶与底物或抗体与抗原之间的相互作用,对目标物进行高选择性识别。将MIPs应用于核苷类药物分离分析过程,可显著提高选择性和检测灵敏度。本文对近5年MIPs在核苷类药物样品前处理（固相萃取、固相微萃取等）、色谱分离及传感分析等检测中的应用进行综述,总结了检测过程中面临的挑战,并对其应用前景进行了展望。     

水相识别分子印迹聚合物在样品预处理中的应用

分子印迹聚合物(MIPs)是模拟抗原-抗体识别机制,人工构筑的对目标物具有专一识别性的材料,构建具有优异水相识别能力的MIPs是分子印迹领域长期面临的挑战。近年来水相识别MIPs以其优异的抗基质干扰和水中识别能力,引起了分析化学家、材料学家和环境学家的广泛关注。本文综述了近年来水相识别MIPs在样品预处理中的应用研究。首先,简要介绍了MIPs的构筑原理、优势及面临水相识别困难的挑战。其次,介绍了样品前处理技术及其重要性。再次,结合各类新兴材料和MIPs制备技术,从样品前处理技术的角度(包括固相萃取、分散固相萃取、磁固相萃取、固相微萃取、管尖固相萃取和搅拌棒吸附萃取)全面总结了水相识别MIPs在含水样品分析中的应用,并结合材料性能和分析参数讨论了各类方法的分析优势。最后,分别从水相识别MIPs构建和预处理两方面提出了该领域面临的挑战和未来的发展趋势。     

罗丹明B分子印迹固相萃取小柱的研制及应用

研制一种对罗丹明B具有特异性识别性能的分子印迹固相萃取小柱。用沉淀聚合法制备罗丹明B分子印迹聚合物,通过静态平衡吸附实验及固相萃取实验表征其性能,并对市售辣椒样品中的罗丹明B进行测量。罗丹明B模板聚合物的吸附能力明显优于空白聚合物;印迹固相萃取小柱对罗丹明B标准溶液(0.05 mmol/L)一次性萃取率为98.24%,实际样品测量的回收率为90.0%~95.0%,测定结果的相对标准偏差为0.9%~1.7%(n=3)。罗丹明B分子印迹固相萃取小柱选择性好、萃取率高,可应用于食品、化妆品检测等相关领域。     

分子印迹样品前处理技术的研究进展

样品前处理是分析过程的关键环节,直接影响着分析结果的准确度和精密度．分子印迹聚合物具有特异性识别能力,能从复杂样品中选择性分离富集目标物,在复杂样品前处理领域中有重要的发展潜力和应用前景．本文综述了近年来分子印迹样品前处理技术的研究进展,包括分子印迹固相萃取、分子印迹固相微萃取、分子印迹膜萃取等样品前处理技术．     

非那西汀印迹聚合物固相萃取性能研究

研究非那西汀分子印迹聚合物的固相萃取性能。用本体聚合法制备非那西汀分子印迹聚合物,通过静态平衡吸附试验及固相萃取试验,研究其固相萃取性能。非那西汀模板聚合物的吸附能力明显强于空白聚合物。模板聚合物对浓度为0.03mmol/L的非那西汀标准溶液一次性萃取率为74.2%。非那西汀印迹聚合物对非那西汀具有特异性识别性能,可作为固相萃取固定相的应用研究。     

分子印迹技术在固相萃取中的应用

对2000-2010年间国内外文献报道的有关分子印迹技术在固相萃取中的应用进行了综述。主要内容包括分子印迹技术和固相萃取技术的原理、分子印迹聚合物的制备和分子印迹-固相萃取的两种操作模式,着重介绍了分子印迹-固相萃取在环境、食品、生物医药等领域中的应用(引用文献32篇)。     

分子印迹聚合物在极性农药残留检测中的应用进展

极性农药包括杀菌剂、除草剂、杀虫剂等,种类丰富,成本低廉,在农业中应用广泛,其滥用易导致水资源和土壤等环境污染,人类通过间接接触动植物源性食品和环境中的极性农药残留也增加了农药暴露风险。极性农药的物理化学性质差异大,通常痕量存在于食品和环境样品等复杂基质中,这对其准确检测分析带来了挑战。分子印迹聚合物(MIPs)作为一种人工制备的选择性吸附剂,具有与模板分子在空间结构、大小尺寸和功能基团上互补的特定识别位点,且易于制备,成本低,稳定性好,重复利用率高,已被广泛用于极性农药残留的样品前处理和分析检测中。MIPs可以作为固相萃取(SPE)、固相微萃取(SPME)、磁性固相萃取(MSPE)、搅拌棒固相萃取(SBSE)等前处理方法的吸附剂,还可用于制备光、电、化学传感器,作为质谱检测的离子源基底和拉曼光谱的增强基底。目前针对极性农药残留的检测,已有许多研究报道了多种分子印迹材料用于高效分离分析各种复杂基质中的极性农药残留,但未见此方面的综述报道。该文首先介绍了MIPs的印迹策略、聚合策略,并针对传统MIPs制备和应用中存在的问题,简要概括了一些新型的分子印迹策略和制备技术;然后从极性农药残留分析的角度出发,总结归纳了分子印迹材料近年来特别是近5年来在各种极性农药残留(包括新烟碱类、有机磷类、三嗪类、唑类、脲类等)检测中的应用,并针对现存问题展望了其未来的发展方向和趋势。     

亲水性分子印迹聚合物的制备及其在天麻素分析检测中的应用

以天麻素为模板分子,α-1-烯丙基-2-N-乙酰胺基葡萄糖为新型亲水性功能单体,N,N'-亚甲基双丙烯酰胺为交联剂,合成了对天麻素有高选择性的亲水性分子印迹聚合物(MIPs)。吸附结果表明,MIPs能够特异性识别天麻素。对MIPs吸附剂性能的考察证明,亲水性天麻素MIPs可作为固相萃取(SPE)吸附剂分离纯化天麻素。方法验证实验显示了良好的回收率(90.4%~97.1%)和精密度(3.3%~5.2%,n=5)。该文以新型亲水性功能单体为基础,建立了天麻素的分子印迹固相萃取样品前处理方法。     

Syntheses of molecularly imprinted polymers: Molecular recognition of cyproheptadine using original print molecules and azatadine as dummy templates

The use of custom-made polymeric materials with high selectivities as target molecules in solid-phase extraction (SPE), known as molecularly imprinted solid-phase extraction (MISPE), is becoming an increasingly important sample preparation technique. However, the potential risk of leakage of the imprinting molecules during the desorption phase has limited application. The use of a mimicking template, called a dummy molecular imprinting polymer (DMIP), that bears the structure of a related molecule and acts as a putative imprinting molecule may provide a useful solution to this problem.In the current study, cyproheptadine (CPH) and azatadine (AZA) were used as templates in the development of an MIP and DMIP for acrylic acid and methacrylic acid monomers. Our results indicate that DMIPs have equal recognition of CPH, avoiding the problem of leakage of original template during the desorption phase relative to MIPs synthesized in presence of the print molecule CPH. Examination of the surface structure of the two polymer products by SEM shows appreciable differences in structural morphology and function of the monomers employed. These results are well supplemented by data obtained for swelling ratios and solvent uptake. Molecular modelling of CPH and AZA suggests that both substrates are similar in shape and volume.     

分子烙印传感器的研究进展

分子烙印技术是制备具有选择性分子识别能力的聚合物的新兴技术,其应用之一是将分子烙印聚合物用作分析化学中化学传感器的识别元件。本文综述了分子烙印技术的原理方法及其在传感器方面的应用,评述了分子烙印传感器的发展方向,展望了其在有机磷化合物检测中的应用前景。     

Synthesis and chromatographic evaluation of molecularly imprinted polymers prepared by the substructure approach for the class-selective recognition of glucuronides

Two series of molecularly imprinted polymers (MIPs) for the class-selective recognition of glucuronides have been prepared by using lipophilic substructures of the target analyte as template molecule and potent host monomers against oxyanions, that are expected to establish a strong stoichiometric interaction with the single carboxylic group of the template. The polymers were tested as stationary phases in liquid chromatography for specific recognition. A preliminary investigation of the imprinting properties of eleven MIPs was carried out, by comparing the retention time of the template and of structurally related compounds on the MIP column with that on the corresponding non-imprinted polymer (NIP). The two polymers showing the best performance were selected to further test cotinine, mycophenolic acid, testosterone and their respective glucuronides as model compounds. The high specificity obtained against glucuronides and the different chemical structure of the parent drug make the two MIPs class-selective imprinted receptors, also suitable for SPE application.     

Selective trace analysis of chloroacetamide herbicides in food samples using dummy molecularly imprinted solid phase extraction based on chemometrics and quantum chemistry

A methodology based on chemometrics and quantum chemistry was proposed to design and synthesize dummy molecularly imprinted polymers (DMIPs) capable of extracting chloroacetamide herbicides from food samples. Molecular modeling approach in conjunction with clustering analysis was used to predict the most suitable dummy template. Metolachlor deschloro was selected as the template to synthesize DMIPs, which were used as the solid phase extraction (SPE) materials. The selective adsorption of DMIPs was evaluated by high performance liquid chromatography (HPLC). The retention property of six chloroacetamide herbicides on DMIPs was also predicted using clustering analysis. The optimum loading, washing and eluting conditions for dummy molecularly imprinted solid phase extraction (DMISPE) were established to obtain high selectivity and sensitivity. Water, dichloromethane and methanol were chosen as loading, washing and elution solvent, respectively. Under optimized DMISPE conditions, recoveries of analytes were in the range of 83.4–106.7% with satisfactory precision (RSD% lower than 13%). Compared with other commercial SPE columns, DMISPE exhibited selective binding properties for chloroacetamide herbicides and the matrix effect was significantly decreased.     

Synthetic approaches to parabens molecularly imprinted polymers and their applications to the solid-phase extraction of river water samples

In this paper we describe the synthesis, characterisation and use of two distinct molecularly imprinted polymers (MIPs) prepared using esters of p-hydroxybenzoic acid (parabens) as templates: one MIP was synthesised by precipitation polymerisation using a semi-covalent molecularly imprinting strategy with methyl paraben as the template/target (MIP 1); the second MIP was prepared in monolithic form through a conventional non-covalent molecular imprinting strategy, with butyl paraben as the template (MIP 2). MIP 1 recognized methyl paraben, showed cross-selectivity for other parabens analytes used in the study and higher affinity towards these compounds than did a non-imprinted control polymer. Similarly, MIP 2 demonstrated higher affinity towards paraben analytes than a non-imprinted control polymer.For the analysis of environmental water samples, a solid-phase extraction (SPE) protocol was developed using MIP 2 as sorbent, and results were compared to a SPE using a commercial sorbent (Oasis HLB). With MIP 2 as sorbent and butyl paraben as target, when percolating 500 mL of river water spiked at 1 μg L⁻¹ through the SPE cartridge, and using 1 mL of isopropanol as cleaning solvent, a higher recovery of butyl 4-hydroxybenzoate (butyl paraben) and a cleaner chromatogram where achievable when using the MIP compared to the commercial sorbent.     

Design of molecular imprinted polymers compatible with aqueous environment

The main problem of poor water compatibility of molecularly imprinted polymers (MIPs) was addressed in examples describing design of synthetic receptors with high affinity for drugs of abuse. An extensive potentiometric titration of 10 popular functional monomers and corresponding imprinted and Blank polymers was conducted in order to evaluate the subtleties of functional groups ionisation under aqueous conditions. It was found that polymers prepared using 2-trifluoromethacrylic acid (TFMAA) in combination with toluene as porogen possess superior properties which make them suitable for effective template recognition in water. The potential impact of phase separation during polymerisation on formation of high quality imprints has been discussed. Three drugs of abuse such as cocaine, deoxyephedrine and methadone were used as template models in polymer preparation for the practical validation of obtained results. The polymer testing showed that synthesized molecularly imprinted polymers have high affinity and selectivity for corresponding templates in aqueous environment, with imprinting factors of 2.6 for cocaine and 1.4 for methadone and deoxyephedrine. Corresponding Blank polymers were unable to differentiate between analytes, suggesting that imprinting phenomenon was responsible for the recognition properties.     

Approaches to the rational design of molecularly imprinted polymers

In our experience the efficient design of molecularly imprinted polymer (MIPs) for novel templates has proved difficult. Following commonly used imprinting protocols, MIPs designed against one template show both a lack of capacity and poor specificity for rebinding either the template or structurally similar analytes. Optimisation methods that involve changing one factor at a time can be laborious.A novel approach for the optimisation of MIPs using chemometrics is described. Sulfonamides, common drug residues in foodstuffs, were used as the model analytes with a methacrylic acid/ethylene glycol dimethacrylate MIP. To avoid the inaccuracies in measurement caused by template bleed a multi-analyte competition rebind assay was developed to select suitable sulfonamides to be used as the template for the MIP, and for the rebind analyte in the chemometric optimisation study. The rebinding efficiencies were monitored by HPLC. The template sulfonamide was selected as sulfamethazine (SMZ), and the rebind analyte as sulfadimethoxine (SDIM). The template:monomer:cross-linker (T:M:X) ratio of the SMZ block MIP was then optimised using a three-level full factorial design to predict a MIP with the highest rebind capacity. On synthesis this was 38.8% for SDIM in a solid phase extraction (SPE) application agreeing with the predication. The factorial design was further utilised to predict an optimum T:M:X ratio for the production of a class specific MIP, capable of binding a range of sulfonamides simultaneously. The predicted optimum T:M:X ratios of (1:10:55) and (1:10:10) were found to be different to commonly used ratios from the MIP literature.     

Surface-imprinted polymers in microfluidic devices

Molecularly imprinted polymers are generated by curing a cross-linked polymer in the presence of a template. During the curing process, noncovalent bonds form between the polymer and the template. The interaction sites for the noncovalent bonds become "frozen" in the cross-linking polymer and maintain their shape even after the template is removed. The resulting cavities reproduce the size and shape of the template and can selectively reincorporate the template when a mixture containing it flows over the imprinted surface. In the last few decades the field of molecular imprinting has evolved from being able to selectively capture only small molecules to dealing with all kinds of samples. Molecularly imprinted polymers (MIPs) have been generated for analytes as diverse as metal ions, drug molecules, environmental pollutants, proteins and viruses to entire cells. We review here the relatively new field of surface imprinting, which creates imprints of large, biologically relevant templates. The traditional bulk imprinting, where a template is simply added to a prepolymer before curing, cannot be applied if the analyte is too large to diffuse from the cured polymer. Special methods must be used to generate binding sites only on a surface. Those techniques have solved crucial problems in separation science as well as chemical and biochemical sensing. The implementation of imprinted polymers into microfluidic chips has greatly improved the applicability of microfluidics. We present the latest advances and different approaches of surface imprinting and their applications for microfluidic devices.     

模板结构与分子印迹效果间关系的研究

以一些分子量和体积都较小的简单化合物作为模板分子,合成分子印迹聚合物 。通过总结43种化合物的分子印迹聚合物的色谱数据,来研究模板分子的分子量、 作用位点数目、分子刚性等因素与印迹效果的关系。根据免疫学中免疫原性的定义 ,我们提出“印迹原性”的概念,即,化合物能够产生印迹效应的性质称为印迹原 性;具有印迹原必的化合物称为印迹原;并讨论了具有较强选择性的印迹原的化学 基础。所得到的结论将有助于对分子印迹聚合物的识别机理的进一步理解,并且对 于根据模板分子性质预测MIP分子识别能力将具有一定的指导意义。