分子印迹聚合物固相萃取研究进展

对最新报道的分子印迹聚合物作为固相萃取剂及其在色谱样品前处理方面的应用进行综述和展望,主要包括固相萃取、基质固相分散萃取、固相微萃取、搅拌棒吸附萃取和磁性材料萃取,同时总结了分子印迹聚合物制备技术面临的挑战和问题,提出了可能的解决方案。     

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％．     

印迹分子聚合物结合低共熔溶剂用于山楂中咖啡酸的固相萃取（英文）

在相同的实验条件下,分别合成了以咖啡酸为模板的印迹分子聚合物和无模板分子聚合物。使用场发射扫描电镜法和吸附实验表征这两种聚合物材料的孔状结构和选择性吸附性能。然后利用印迹分子聚合物、无模板分子聚合物、C18萃取小柱这3种材料结合固相萃取法纯化山楂提取物中的咖啡酸,提取率分别为3.46、1.01、1.17μg/g。为了优化固相萃取过程,实验研究了不同洗脱剂的影响。分别利用用氯化胆碱和甘油、氯化胆碱和尿素(摩尔比均为1∶2)合成出两种低共熔溶剂。甲醇与这两种低共熔溶剂分别以不同的体积比混合作为洗脱剂,用于优化咖啡酸的固相萃取过程。实验结果表明,印迹分子聚合物是一种良好的固相萃取材料;当甲醇和甘油基低共熔溶剂在体积比为3∶1混合时,表现出最好的洗脱能力,得到咖啡酸的回收率为82.32%。     

槲皮素分子印迹聚合物的制备及固相萃取性能研究

采用分子印迹技术, 以槲皮素为模板分子, 丙烯酰胺为功能单体, 乙二醇二甲基丙烯酸脂为交联剂, 通过热引发聚合, 制备了槲皮素分子印迹聚合物, 并通过装入固相萃取柱试验了聚合物对槲皮素的选择性能. 结果表明, 该分子印迹聚合物对槲皮素具有高度选择性, 为从天然产物中高效分离富集黄酮活性成分槲皮素提供了一种新材料.     

马拉硫磷分子印迹聚合物的制备及其在固相萃取中的应用

以马拉硫磷为模板分子,采用原位逐步聚合法制备了具有良好识别性能的分子印迹聚合物(MIPs),考察了马拉硫磷、甲基对硫磷、对硫磷及甲胺磷在马拉硫磷聚合物的选择性分离富集特性。用聚合物固相萃取了蜂蜜、蔬菜和天然水中的马拉硫磷。结果表明,聚合物对模板分子产生了印迹效应,对马拉硫磷有明显的选择性。流速为1.0 mL/min,进...     

赛庚啶-分子印迹聚合物的制备及其固相萃取研究

以赛庚啶为模板分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,通过优化致孔剂、单体及模板与单体摩尔比等因素,合成了对赛庚啶具有高选择性的分子印迹聚合物,其表面积达24.9 m2/g。制备的印迹聚合物固相萃取小柱(MISPE)依次以甲醇和水活化小柱,水溶液上样,水和甲醇依次洗涤,氨化甲醇(5∶95,V/V)洗脱,赛庚啶在制备MISPE小柱上的回收率为94.0%,而非分子印迹小柱(NISPE)的回收率仅为38.9%;MISPE结合赛庚啶的容量达8.8 mg/g,印迹因子约为2.32。在优化的固相萃取条件下,10 mg/L赛庚啶、阿米替林、磺胺嘧啶和甲氧苄啶混合标准溶液上样,进行选择性实验。以0.05%戊烷磺酸钠溶液和乙腈为流动相,梯度洗脱,在MISPE小柱上,与CYP化学结构差异较大的磺胺嘧啶和甲氧苄啶回收率均小于10%,结构相似的阿米替林回收率达70%,赛庚啶回收率大于90%;4种分析物在NISPE小柱上的回收率均小于30%。制备的MISPE小柱应用于畜禽饮用水样中赛庚啶的分离富集和分析测定,方法回收率为80.5%~97.7%,检出限达0.01 mg/L。     

替米考星分子印迹聚合物的制备及其固相萃取研究

以泰乐菌素为虚拟模板分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,合成了对替米考星具有高选择性的分子印迹聚合物。考察了二甲基甲酰胺、甲醇、丙酮和氯仿4种致孔剂对合成聚合物性能的影响。通过正交实验优化的聚合配方为:1.0mmol泰乐菌素,8.0mmol甲基丙烯酸,20.0mmol乙二醇二甲基丙烯酸酯,6.0mL氯仿,20.0mg偶氮二异丁腈。研究了将该聚合物作为固相萃取填料分离、富集替米考星的萃取条件和萃取性能。当萃取柱依次用甲醇和水(pH9.0)活化,乙腈溶液上样,甲醇和氯仿分别洗涤,3mL氨化甲醇(95:5,V/V)洗脱时,替米考星在分子印迹固相萃取柱上的回收率达到90%以上,而非分子印迹固相萃取柱的回收率仅为32%。     

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。     

吡虫啉分子印迹聚合物的合成及固相萃取性能研究

采用分子印迹技术,以丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,在甲醇溶液中合成了吡虫啉分子印迹聚合物,研究了聚合物的吸附性和选择性,用聚合物固相萃取大蒜中吡虫啉残留量。结果表明,聚合物通过离子键和氢键对模板分子产生了印迹效应,对吡虫啉具有明显的选择性。通过优化淋洗和洗脱条件,对大蒜中的残留吡虫啉富集。     

利多卡因分子印迹聚合物的制备及其在固相萃取中的应用

以利多卡因(LD)分子印迹聚合物为研究体系,利用分子模拟计算功能单体与模板分子之间的相互作用能,并通过作用实验加以验证,确定衣康酸为最佳单体。以乙二醇二甲基丙烯酸酯为交联剂,N,N-二甲基甲酰胺(DMF)为溶剂,采用本体聚合法合成分子印迹聚合物(MIP);采用高效液相色谱检测。实验发现,聚合物具有较高的印迹指数和选择性;在乙腈加载、5%甲醇-乙腈淋洗、5%HCl-甲醇洗脱条件下,聚合物具有最佳印迹效果。通过渗漏实验考察聚合物键合容量。实验发现,在乙腈溶液中每100mg MIP与空白聚合物(NIP)可分别键合1.62和0.92mg LD分子;采用光度法测定牛血清中利多卡因的含量,其平均回收率达到84.6%。     

Ternary choline chloride/caffeic acid/ethylene glycol deep eutectic solvent as both a monomer and template in a molecularly imprinted polymer

A molecularly imprinted polymer based on a ternary deep eutectic solvent comprised of choline chloride/caffeic acid/ethylene glycol was prepared. The caffeic acid in the ternary deep eutectic solvent was used as both a monomer and template. The molecularly imprinted polymer based on the ternary deep eutectic solvent was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, field‐emission scanning electron microscopy, Brunauer–Emmett–Teller surface area analysis, atomic force microscopy, and elemental analysis. A series of molecularly imprinted polymers based on choline chloride/caffeic acid/ethylene glycol with different molar ratios was prepared and applied to the molecular recognition of polyphenols. A comparison of the recognition ability of molecularly imprinted polymers to polyphenols revealed that the choline chloride/caffeic acid/ethylene glycol (1:0.4:1, molar ratio) molecularly imprinted polymer had the best molecular recognition effect with 132 μg/g of protocatechuic acid, 104 μg/g of catechins, 80 μg/g of epicatechin, and 123 μg/g of caffeic acid in 6 h, as well as good molecular recognition ability for polyphenols from a Radix Asteris sample. These results show that the ternary deep eutectic solvent based molecularly imprinted polymer is a potential medium that can be applied to drug purification, drug delivery, and drug analysis.     

A new molecularly imprinted polymer for the on-column solid-phase extraction of diethylstilbestrol from aqueous samples

The estrogenic compound diethylstilbestrol (DES) is widely studied because of its potential endocrine disruption effects. The prohibition of the use of diethylstilbestrol as a growth promoter has not been enough to ensure the total disappearance of this compound from environmental matrices. Due to the low levels of DES present in the environment, preconcentration and clean up methods are necessary for its analysis. This paper describes the synthesis and use of a molecularly imprinted polymer (MIP) as sorbent for on-column solid-phase extraction of DES from aqueous samples. The selectivity of the DES-MIP was evaluated towards several selected estrogens such as hexestrol (HEX), estrone (E1), estriol (E3), estradiol (E2) and ethynylestradiol (EE2). HPLC-DAD was used to quantify all analytes at 230-nm wavelength. The method has been successfully applied to the analysis of DES in spiked river and tap water samples, with recoveries of 72% and 83% respectively.     

Development of a broad selective molecularly imprinted polymers-based solid phase extraction of contraceptive drug levonorgestrel from water samples

A broad selective molecularly imprinted polymers-based solid phase extraction (MISPE) for levonorgestrel (LNG) from water samples was developed. Using LNG as a template molecule, acrylamide (AA) as functional monomer, ethylene glycol dimethacrylate (EGDMA) as linking agent and bulk polymerisation as a synthetic method, the molecularly imprinted polymers (MIPs) were synthesised and characterised. The MIPs displayed a high specific rebinding for LNG with the imprinting factor of 3.71. The Scatchard analysis showed that there was at least one class of binding site for LNG formed in the MIPs with the dissociation constant of 8.046?µg?mL^?1. The results of selectivity testing indicated that the MIPs also exhibited high cross-reactivity with structurally related compounds (estrone, methylprednisolone and ethinyl estradiol), but no recognition with non-structurally related compound (indomethacin), suggesting that the MIPs could be used as a broad recognition absorbent. MISPE column was prepared by packing MIPs particles into a common SPE cartridge. The MISPE extraction conditions including loading, washing and eluting solutions were carefully optimised. Water samples spiked with LNG were extracted by MISPE column and detected by high-performance liquid chromatography. The recoveries were found to be 79.97?～?132.79% with relative standard deviations (RSD) of 1.92?～?10.43%, indicating the feasibility of the prepared MIPs for LNG extraction.     

Molecularly imprinted polymers for on-line preconcentration by solid phase extraction of pirimicarb in water samples

The synthesis and performance of a molecularly imprinted polymers (MIPs) as a selective solid phase extraction sorbent for the preconcentration of the carbamate pirimicarb from water samples is described. The MIP was prepared using pirimicarb as the template, methacrylic acid as the functional monomer and ethylene glycol dimethacrylate as the cross-linking monomer, and using chloroform as the solvent. The detection of pirimicarb was carried out by differential pulse voltammetry (DPV) at a hanging mercury drop electrode (HMDE) in 0.1 mol l⁻¹ HCl. Solvents of different polarities were checked for the polymer synthesis, and different experimental variables (sample pH, selection of the eluent used, eluent volume, analyte and eluent flow rates and sample volume) associated with the rebinding/extraction process were optimised. For a 25 ml sample, the process took about 13 min and resulted in a nominal enrichment factor of 50 (eluent MeOH:H₂O:HAc, 7:2:1; 0.5 ml) for pirimicarb. A limit of detection of 4.1 μg l⁻¹ was obtained, and a good reproducibility of the measurements using different MIP microcolumns was found. Furthermore, the MIP selectivity was evaluated by checking several substances with similar and different molecular structures to that of pirimicarb. As an application, pirimicarb was determined in water samples of diverse origin which were spiked at a concentration level of 71.5 μg l⁻¹.     

Magnetic molecularly imprinted polymers for recognition and enrichment of polysaccharides from seaweed

New magnetic molecularly imprinted polymers with two templates were fabricated for the recognition of polysaccharides (fucoidan and alginic acid) from seaweed by magnetic solid‐phase extraction, and the materials were modified by seven types of deep eutectic solvents. It was found that the deep eutectic solvents magnetic molecularly imprinted polymers showed stronger recognition and higher recoveries for fucoidan and alginic acid than magnetic molecularly imprinted polymers, and the deep eutectic solvents‐4‐magnetic molecularly imprinted polymers had the best effects. The practical recovery of the two polysaccharides (fucoidan and alginic acid) purified with deep eutectic solvents‐4‐magnetic molecular imprinted polymers in seaweed under the optimal conditions were 89.87, and 92.0%, respectively, and the actual amounts extracted were 20.6 and 18.7 μg/g, respectively. To sum up, the developed method proved to be a novel and promising method for the recognition of complex polysaccharide samples from seaweed.     

Magnetic deep eutectic solvents molecularly imprinted polymers for the selective recognition and separation of protein

A novel and facile magnetic deep eutectic solvents (DES) molecularly imprinted polymers (MIPs) for the selective recognition and separation of Bovine hemoglobin (BHb) was prepared. The new-type DES was adopted as the functional monomer which would bring molecular imprinted technology to a new direction. The amounts of DES were optimized. The obtained magnetic DES-MIPs were characterized with fourier transform infrared spectrometry (FT-IR), thermogravimetric analysis (TGA), field emission scanning electron microscope (FESEM), dynamic light scattering (DLS), elemental analysis and vibrating sample magnetometer (VSM). The results suggested that the imprinted polymers were successfully formed and possessed a charming magnetism. The maximum adsorption capability (Q_max) and dissociation constant (K_L) were analyzed by Langmuir isotherms (R² = 0.9983) and the value were estimated to be 175.44 mg/g and 0.035 mg/mL for the imprinted particles. And the imprinted particles showed a high imprinting factor of 4.77. In addition, the magnetic DES-MIPs presented outstanding recognition specificity and selectivity so that it can be utilized to separate template protein from the mixture of proteins and real samples. Last but not least, the combination of deep eutectic solvents and molecular imprinted technology in this paper provides a new perspective for the recognition and separation of proteins.     

Magnetic molecularly imprinted polymers based on silica modified by deep eutectic solvents for the rapid simultaneous magnetic‐based solid‐phase extraction of Salvia miltiorrhiza bunge,Glycine max (Linn.) Merr and green tea

Novel magnetic molecularly imprinted polymers (MMIPs) with multiple‐template based on silica were modified by four types of deep eutectic solvents (DESs) for the rapid simultaneous magnetic solid‐phase extraction (MSPE) of tanshinone Ⅰ, tanshinone ⅡA, and cryptotanshinone from Salvia miltiorrhiza bunge; glycitein, genistein, and daidzein from Glycine max (Linn.) Merr; and epicatechin, epigallocatechin gallate, and epicatechin gallate from green tea, respectively. The synthesized materials were characterized by Fourier transform infrared spectroscopy and field emission scanning electron microscopy. Single factor experiments were to explore the relationship between the extraction efficiency and four factors (the sample solution pH, amount of DESs for modification, amount of adsorbent, and extraction time). It was showed that the DES4‐MMIPs have better extraction ability than the MMIPs without DESs and the other three DESs‐modified MMIPs. The best extraction recoveries with DES4‐MMIP were tanshinone Ⅰ (85.57%), tanshinone ⅡA (80.58%), cryptotanshinone (92.12%), glycitein (81.65%), genistein (87.72%), daidzein (92.24%), epicatechin (86.43%), epigallocatechin gallate (80.92%), and epicatechin gallate (93.64%), respectively. The novel multiple‐template MMIPs materials modified by DES for the rapid simultaneous MSPE of active compounds were proved to reduce the experimental steps than single‐template technique, and increase the extraction efficiency.     

Ternary deep eutectic solvent magnetic molecularly imprinted polymers for the dispersive magnetic solid‐phase microextraction of green tea

Ternary deep eutectic solvent magnetic molecularly imprinted polymers grafted on silica were developed for the selective recognition and separation of theophylline, theobromine, (+)‐catechin hydrate, and caffeic acid from green tea through dispersive magnetic solid‐phase microextraction. A new ternary deep eutectic solvent was adopted as a functional monomer. The materials obtained were characterized by FTIR spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, NMR spectroscopy, and powder X‐ray diffraction. The practical recovery of the theophylline, theobromine, (+)‐catechin hydrate, and caffeic acid isolated with ternary deep eutectic solvent magnetic molecularly imprinted polymers in green tea were 91.82, 92.13, 89.96, and 90.73%, respectively, and the actual amounts extracted were 5.82, 4.32, 18.36, and 3.69 mg/g, respectively. The new method involving the novel material coupled with dispersive magnetic solid‐phase microextraction showed outstanding recognition, selectivity and excellent magnetism, providing a new perspective for the separation of bioactive compounds.     

Molecularly imprinted polymer surfaces as solid-phase extraction sorbents for the extraction of 2-nitrophenol and isomers from environmental water

The novel surface molecularly imprinted polymer (MIP) with 2‐nitrophenol (2‐NP) as the template has been prepared and used as the adsorbent for the solid‐phase extraction (SPE). The selectivity of the polymer was checked toward several selected nitrophenols (NPs) such as 2‐NP, 3‐nitrophenol (3‐NP), 4‐nitrophenol (4‐NP) and 2,4,6‐trichlorophenol (2,4,6‐TCP). Under the optimized conditions, high sensitivity (detection limits: 0.07–0.12 ng/mL) and good reproducibility of analytes (2.3–4.8% for four cycles) were achieved. Then, the method was applied for the analysis of selected phenols in spiked tap, lake and river water samples. High recoveries (>83.3%) for nitrophenols (NPs) were obtained, but lower recoveries (<63.4%) were achieved for 2,4,6‐TCP. The method was found to be linear in the range of 1–300 ng/mL with correlation coefficients (R²) greater than 0.99 and repeatability relative standard deviation (RSD) below 7.2% in all cases. For analysis of 120 mL water samples, the method detection limits (LODs) ranged from 0.10 to 0.22 ng/mL and the limit of quantification (LOQs) from 0.33 to 0.72 ng/mL. These results showed the suitability of the MIP‐SPE method for the selective extraction of a group of structurally related isomeric compounds.     

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。