扑热息痛分子印迹聚合物应用于固相萃取的研究

以扑热息痛为印迹分子,丙烯酰胺为功能单体,乙二醇二甲基丙烯酸酯为交联剂合成了棒状的印迹聚合物;把其装于自制的固相萃取柱中,研究了以乙腈和水为溶剂时扑热息痛在柱上的保留行为;通过优化清洗、洗脱条件,使扑热息痛和与其具有相似结构的非那西丁、对叔丁基苯酚在柱上得到了很好的分离;同时也测定了治疗感冒的药物海王银得菲中扑热息痛的含量,其回收率可达94．3％．     

一种高选择性固相萃取吸附剂--分子印迹聚合物

固相萃取是对样品富集、分离的一种有效方法,因而得到广泛应用.分子印迹是近些年发展起来的新技术,由于分子印迹聚合物具有高的选择性,被应用于环境、药物、生物、食品等样品的分析.本文介绍了固相萃取和分子印迹技术的原理以及两者结合用于固相萃取的过程,对近10年来国内外分子印迹聚合物应用于固相萃取的研究工作进行了总结和评述,并对其将来的发展进行了展望.     

Recent Advances in Molecularly Imprinted Polymers for Antibiotic Analysis

The abuse and residues of antibiotics have a great impact on the environment and organisms, and their determination has become very important. Due to their low contents, varieties and complex matrices, effective recognition, separation and enrichment are usually required prior to determination. Molecularly imprinted polymers (MIPs), a kind of highly selective polymer prepared via molecular imprinting technology (MIT), are used widely in the analytical detection of antibiotics, as adsorbents of solid-phase extraction (SPE) and as recognition elements of sensors. Herein, recent advances in MIPs for antibiotic residue analysis are reviewed. Firstly, several new preparation techniques of MIPs for detecting antibiotics are briefly introduced, including surface imprinting, nanoimprinting, living/controlled radical polymerization, and multi-template imprinting, multi-functional monomer imprinting and dummy template imprinting. Secondly, several SPE modes based on MIPs are summarized, namely packed SPE, magnetic SPE, dispersive SPE, matrix solid-phase dispersive extraction, solid-phase microextraction, stir-bar sorptive extraction and pipette-tip SPE. Thirdly, the basic principles of MIP-based sensors and three sensing modes, including electrochemical sensing, optical sensing and mass sensing, are also outlined. Fourthly, the research progress on molecularly imprinted SPEs (MISPEs) and MIP-based electrochemical/optical/mass sensors for the detection of various antibiotic residues in environmental and food samples since 2018 are comprehensively reviewed, including sulfonamides, quinolones, β-lactams and so on. Finally, the preparation and application prospects of MIPs for detecting antibiotics are outlined.     

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。     

大黄酸磁性印迹聚合物的制备及其应用研究

以SiO2包覆的磁性粒子为载体,大黄酸为模板分子,苯基和氨基硅烷偶联剂为二元功能单体,正硅酸乙酯为交联剂制备大黄酸磁性印迹聚合物。采用红外光谱和扫描电镜对该印迹聚合物进行表征。结果表明,该印迹聚合物颗粒分散均匀,呈立方体结构,印迹壳层厚度约75～100nm。结合磁固相萃取技术和高效液相色谱技术对大黄蒽醌类组分进行富集分离,实现猕猴桃根提取液中大黄酸、大黄素、大黄酚和大黄素甲醚等组分的同时分离、富集和检测。     

沙拉沙星分子印迹聚合物的制备及其吸附特性

以沙拉沙星为模板分子、甲基丙烯酸为功能单体和乙二醇二甲基丙烯酸酯为交联剂合成了分子印迹聚合物 ,并用平衡吸附实验研究了其吸附性能。结果表明 :该聚合物对沙拉沙星有较高的亲和性和选择性 ,解离常数Kd=7.2 6× 10 - 7～ 2 .19× 10 - 5mol L。     

分子印迹聚合物微球的制备及应用研究进展

球形分子印迹聚合物具有制备简单、使用方便；分子识别效率高且便于功能设计等优点，近年来成为分子印迹技术领域研究的热点之一。对球形分子印迹聚合物微球的制备及其应用研究进展作了较为详细的介绍。     

Preparation and Application of Molecularly Imprinted Polymers for Flavonoids: Review and Perspective

The separation and detection of flavonoids from various natural products have attracted increasing attention in the field of natural product research and development. Depending on the high specificity of molecularly imprinted polymers (MIPs), MIPs are proposed as efficient adsorbents for the selective extraction and separation of flavonoids from complex samples. At present, a comprehensive review article to summarize the separation and purification of flavonoids using molecular imprinting, and the employment of MIP-based sensors for the detection of flavonoids is still lacking. Here, we reviewed the general preparation methods of MIPs towards flavonoids, including bulk polymerization, precipitation polymerization, surface imprinting and emulsion polymerization. Additionally, a variety of applications of MIPs towards flavonoids are summarized, such as the different forms of MIP-based solid phase extraction (SPE) for the separation of flavonoids, and the MIP-based sensors for the detection of flavonoids. Finally, we discussed the advantages and disadvantages of the current synthetic methods for preparing MIPs of flavonoids and prospected the approaches for detecting flavonoids in the future. The purpose of this review is to provide helpful suggestions for the novel preparation methods of MIPs for the extraction of flavonoids and emerging applications of MIPs for the detection of flavonoids from natural products and biological samples.     

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。     

核-壳型分子印迹聚合物的制备与应用

分子印迹聚合物是具有与模板分子形状、大小及官能团完全匹配的特异识别位点的高分子聚合物,能选择性识别、有效富集目标分析物(模板分子)并去除干扰物,已广泛应用于样品前处理、化学/生物传感、药物输送等领域.然而,在合成过程中,仍存在模板分子洗脱困难、有效识别位点少、结合容量低、传质速率慢等问题.核-壳型分子印迹聚合物即在核层颗粒表面进行分子印迹,即表面印迹,印迹位点仅存在于壳层结构中,利于模板分子洗脱及扩散,能够增加有效识别位点并提高印迹容量.依据核层材料的不同,本文详细介绍了以磁性材料及非磁性材料为核的核-壳型分子印迹聚合物的合成与应用,探讨了中空核-壳分子印迹聚合物的制备与发展,并对核-壳印迹聚合物的发展前景进行了展望.     

Magnetic Molecularly Imprinted Polymers for the Rapid and Selective Extraction and Detection of Methotrexatein Serum by HPLC-UV Analysis

In this work, novel selective recognition materials, namely magnetic molecularly imprinted polymers (MMIPs), were prepared. The recognition materials were used as pretreatment materials for magnetic molecularly imprinted solid-phase extraction (MSPE) to achieve the efficient adsorption, selective recognition, and rapid magnetic separation of methotrexate (MTX) in the patients’ plasma. This method was combined with high-performance liquid chromatography–ultraviolet detection (HPLC–UV) to achieve accurate and rapid detection of the plasma MTX concentration, providing a new method for the clinical detection and monitoring of the MTX concentration. The MMIPs for the selective adsorption of MTX were prepared by the sol–gel method. The materials were characterized by transmission electron microscopy, Fourier transform-infrared spectrometry, X-ray diffractometry, and X-ray photoelectron spectrometry. The MTX adsorption properties of the MMIPs were evaluated using static, dynamic, and selective adsorption experiments. On this basis, the extraction conditions were optimized systematically. The adsorption capacity of MMIPs for MTX was 39.56 mgg⁻¹, the imprinting factor was 9.40, and the adsorption equilibrium time was 60 min. The optimal extraction conditions were as follows: the amount of MMIP was 100 mg, the loading time was 120 min, the leachate was 8:2 (v/v) water–methanol, the eluent was 4:1 (v/v) methanol–acetic acid, and the elution time was 60 min. MTX was linear in the range of 0.00005–0.25 mg mL⁻¹, and the detection limit was 12.51 ng mL⁻¹. The accuracy of the MSPE–HPLC–UV method for MTX detection was excellent, and the result was consistent with that of a drug concentration analyzer.     

分子印迹磁固相萃取/气相色谱法分析环境水样中5种酰胺类除草剂残留

以丁草胺为假模板分子,丙烯酰胺为功能单体,利用四氧化三铁磁性纳米微球成功制备了具有特异性识别能力的磁性分子印迹聚合物。采用透射电子显微镜、红外光谱和振动样品磁强计对印迹聚合物进行表征,结果显示,分子印迹聚合物成功包裹在四氧化三铁表面。印迹聚合物对5种酰胺类除草剂均有特异性识别作用。以磁性分子印迹聚合物为基础,建立了酰胺类除草剂的气相色谱检测方法。方法学验证表明该方法具有良好的回收率(85.0%~99.5%)和精密度(RSD为2.8%~5.0%,n=5),线性范围为0.1~500μg·L~(-1),检出限为0.02~0.05μg·L~(-1)。该方法能够应用于农田灌溉用水等环境水样的测定。     

安定分子印迹聚合物的制备及应用

以安定为模板分子,通过本体聚合和沉淀聚合的方法合成了分子印迹聚合物材料,考察了交联剂、致孔剂及温度等条件对聚合物材料性能的影响。电镜扫描图片显示本体聚合得到的聚合物呈不规则形状,而沉淀聚合得到的则是微球颗粒,形状规则。吸附实验表明,聚合物微球对安定的最大吸附量约为130μg/g,对奥沙西泮和硝西泮的吸附量约为110μg/g,对安定类化合物具有较高的吸附性能和选择性。通过对比合成现象和聚合物性能,最终选用以DVB为交联剂、乙腈为致孔剂合成的聚合物微球为固相萃取材料填充固相萃取小柱,从饲料及猪尿样品中选择性地分离、富集痕量安定类药物。结合高效液相色谱法检测,奥沙西泮、硝西泮和安定3种药物在0.1～20 mg/L范围内线性良好,相关系数为0.999 6～0.999 9,检出限(S/N=3)为0.03～0.08 mg/L,加标回收率为66%～79%。该方法为安定类药物的检测提供了一种新途径。     

磁性碳纳米管表面多金属离子印迹聚合物制备及应用

以磁性碳纳米管为载体,Co~(2+)、Cu~(2+)及Cd~(2+)等多种金属离子为模板和多巴胺为功能单体,研制一种对多种重金属离子具有高选择性吸附性能的磁性离子印迹聚合物(MIIPs)。采用红外光谱仪、透射电子显微镜、扫描电子显微镜和振动样品磁强计等技术手段对MIIPs进行了表征。采用原子吸收光谱详细研究了MIIPs的吸附性能,结果表明,MIIPs不仅具有优异的磁性能,而且对Cu~(2+)、Co~(2+)及Cd~(2+)具有快速、高效的选择识别能力,最大吸附量分别为46.08、36.35和30.65 mg/g。结合磁固相萃取和原子吸收光谱,MIIPs成功用于淤泥中Cu~(2+)、Co~(2+)及Cd~(2+)的同时分离富集,富集因子分别为18.6、13.4以及10.9。     

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。     

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分子印迹聚合物微球的合成及其在固相萃取中的应用

以罗丹明B为模板分子,丙烯酰胺为功能单体,乙二醇二甲基丙烯酸酯为交联剂,采用沉淀聚合法制备了罗丹明B分子印迹聚合物(MIP)微球,并用扫描电子显微镜表征。 采用紫外分光光度法测定了印迹分子罗丹明B与功能单体丙烯酰胺二者之间的结合常数(K=5.303×103 (mol/L)-1)和化学计量比(n=1)。 考察了沉淀剂的种类和用量对聚合物微球的影响。 将分子印迹聚合物微球应用于固相萃取材料自制固相萃取柱,从加标罗丹明B的红椒粉中萃取罗丹明B。 本文优化了固相萃取条件,高效液相色谱检测表明,在一定的萃取条件下,分子印迹聚合物对加标量为0.479 mg/kg的辣椒中罗丹明B的萃取加标回收率可达91.7％～103.5%。     

羟丙哌嗪分子印迹的固相萃取

以L-羟丙哌嗪为模板分子, α-甲基丙烯酸为功能单体, 三羟甲基丙烷三甲基丙烯酸酯为交联剂, 合成了羟丙哌嗪分子印迹聚合物, 利用该聚合物进行羟丙哌嗪固相萃取应用研究. 实验证明, 所合成的分子印迹聚合物具有良好的识别萃取模板分子羟丙哌嗪的能力, 能够用于羟丙哌嗪的富集浓缩, 而空白聚合物却不具备这样的特性. 考察了模板分子与其结构类似物苄基哌嗪、N-异丙基哌嗪和乙氧基羰基哌嗪的固相萃取分离情况, 研究表明, 虽然其中的苄基哌嗪在印迹材料上具有最强的保留, 但是通过先后使用不同的洗脱溶液实现了模板分子与苄基哌嗪的选择性分离.探讨了印迹识别机理,并用PM3 半经验计算机模拟方法进行了辅助分析验证.     

An Update on the Use of Molecularly Imprinted Polymers in Beta-Blocker Drug Analysis as a Selective Separation Method in Biological and Environmental Analysis

Beta-blockers are antihypertensive drugs and can be abused by athletes in some sport competitions; it is therefore necessary to monitor beta-blocker levels in biological samples. In addition, beta-blocker levels in environmental samples need to be monitored to determine whether there are contaminants from the activities of the pharmaceutical industry. Several extraction methods have been developed to separate beta-blocker drugs in a sample, one of which is molecularly imprinted polymer solid-phase extraction (MIP-SPE). MIPs have some advantages, including good selectivity, high affinity, ease of synthesis, and low cost. This review provides an overview of the polymerization methods for synthesizing MIPs of beta-blocker groups. The methods that are still widely used to synthesize MIPs for beta-blockers are the bulk polymerization method and the precipitation polymerization method. MIPs for beta-blockers still need further development, especially since many types of beta-blockers have not been used as templates in the MIP synthesis process and modification of the MIP sorbent is required, to obtain high throughput analysis.     

克百威分子印迹固相萃取微球的制备及性能

以偶氮二异丁腈为引发剂,2~3μm的聚苯乙烯微球为种球,克百威为模板分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,采用单步溶胀法制备粒径均一的克百威分子印迹聚合物微球(MIPMs)。通过扫描电镜(SEM)、吸附平衡实验和竞争吸附实验分析了克百威MIPMs的形貌及其对克百威的结合特性及吸附选择性,并比较了克百威分子印迹固相萃取柱(MISPE)与C18固相萃取柱(C18SPE)富集水中克百威的效果。结果表明:合成的MIPMs粒径约10μm,表面呈蜂窝状;在90min内可达到饱和吸附,最大吸附量为25.94mg/g;在克百威、灭多威和三羟基克百威共存的条件下,克百威MIPMs可实现对克百威的专一性吸附;与C18SPE相比,克百威MISPE重复使用6次后加标回收率仍在85%以上,可用于水体中痕量克百威的检测。