印迹材料MIP-PDAC/PSA的制备及对谷氨酸对映体识别拆分的研究

以伯胺树脂球为基质,谷氨酸(Glu)的一种对映体L-谷氨酸为模板分子,N,N-亚甲基双丙烯酰胺(MBA)为交联剂,通过接枝交联聚合与印迹过程同步法制备了L-谷氨酸的分子表面印迹材料MIP-PDAC/PSA。以D-谷氨酸为对比物研究MIP-PDAC/PSA对谷氨酸(Glu)对映体进行拆分的可行性。实验结果表明,印迹材料MIP-PDAC/PSA对L-谷氨酸具有良好的识别选择性。相对于D-谷氨酸识别选择性系数为5.92,表现出良好的拆分性能。此外,印迹材料MIP-PDAC/PSA具有良好的解吸性能,解吸率达到98.34%。     

氨基酸对映体的手性拆分

氨基酸对映体的分离是生命科学的基础,主要方法有高效毛细管电泳法、高效液相色谱法、薄层色谱法和气相色谱法等,高效液相色谱法是广泛应用的手性氨基酸拆分方法。本文介绍了间接法和直接法手性拆分的分离机理,并详细介绍了Pirkle手性固定相、胶束手性固定相、包合手性固定相、配体交换手性固定相、蛋白质手性 j固定相等5类手性固定相的应用。     

印迹材料MIP-PAM/PSA的制备及对氧氟沙星的识别与拆分

通过接枝聚合和交联印迹过程同步法,以伯胺树脂微球(PSA)为基质,S-氧氟沙星为模板分子,乙二醇二缩甘油醚(EGDE)为交联剂,制备了 S-氧氟沙星的表面分子印迹材料MIP-PAM/PSA.研究了分子印迹材料MIP-PAM/PSA对氧氟沙星对映体拆分的可行性.采用FTIR、SEM对PSA和印迹材料的结构、形貌进行了表征...     

分子印迹技术手性分离氨基酸衍生物(Ⅱ)—流动相对分子印迹聚合物手性拆分效果的影响

系统研究了乙腈流动相中甲醇、乙酸和水的体积分数变化对分子印迹聚合物手性拆分效果的影响。在流动相乙腈中添加较少量的甲醇或乙酸时〔φ(甲醇)≤8%,φ(乙酸)≤2%〕,随其体积分数的增加,手性分离效果提高;但当其体积分数继续增加,分离效果变差。以水作为添加物质时,当体积分数相对较少〔φ(H2O)≤30%〕,随其体积分数增加,手性分离效果变差;当水体积分数继续增加,拆分效果有所提高,在φ(H2O)=70%时,选择性因子达到1 52。降低流动相的pH值有利于手性拆分。利用梯度洗脱技术可以改善色谱分离中印迹分子洗脱峰的拖尾。     

利用分子印迹聚合物对外消旋药物萘普生的手性拆分

采用丙烯酰胺为功能单体,以二甲基丙烯酸乙二醇酯为交联剂,在模板分子(S)-萘普生的存在下,制备(S)-萘普生的分子印迹聚合物,并对其进行了高效液相色谱评价.结果表明,萘普生的外消旋混合物得到了较好的拆分,而且分离了与萘普生结构相似的布洛芬、酮洛芬,探讨了萘普生手性拆分的机理,考察了流速、流动相中乙酸含量对分离效果的影响.     

分子印迹材料在手性拆分中的应用研究进展

拆分手性化合物、提纯有利生物活性的对映异构体在食品、制药、生命科学等领域具有重要意义。分子印迹聚合物(MIP)是一种人工合成的具有对目标物质定向亲和性的聚合物,基于MIP制造的手性选择剂具有更高的亲和力和选择性,同时更易于制备和更为稳定,因此在手性拆分领域得到了广泛应用。综述了MIP材料在手性拆分中用于样品前处理、手性固定相(CSP)、传感器的研究进展,并介绍了提高手性选择能力的新策略,包括手性树状大分子、表面印迹载体、金属离子、纳米MIP、手性功能单体、协同辅助材料等,展望了MIP手性拆分未来的发展方向。     

HPLC手性离子对试剂法拆分普萘洛尔对映体

建立了一种以Nova PakCN HP氰基柱为固定相,以V(二氯甲烷)∶V(乙醇)=97∶3为流动相,添加N 苄氧羰基 S 苯基 L 半胱胺酸甲酯(MBPCE)为手性离子对试剂,拆分普萘洛尔对映体的高效液相色谱的分析方法。当c(MBPCE)=3.5mmol/L,流动相流速为0.5ml/min,检测波长为254nm时,普萘洛尔对映体的分离选择性为1.15,分离度为1.02,线性范围为0.1～4.0mg/ml,浓度测定的变异系数为0.21%～0.86%。     

氟草烟异辛酯对映体的手性拆分

利用高效液相色谱手性固定相法对氟草烟异辛酯对映异构体进行了拆分研究。使用了正己烷和石油醚两种流动相体系,正己烷流动相条件下考察了多种极性改性剂及其含量,以及温度对手性拆分的影响。实验结果显示,以异丙醇为改性剂,在正己烷体系中的分离效果最好,室温下最大分离因子可达到1．2,温度降低有利于对映体的拆分。石油醚体系的分离效果不佳。     

乙氧呋草黄对映体的手性拆分研究

进行了除草剂乙氧呋草黄对映体在自制的纤维素-三(3,5-二甲基苯基氨基甲酸酯)(CDMPC)高效液相色谱手性柱上的拆分研究。使用了两种流动相体系:正己烷-异丙醇;石油醚-异丙醇,并分别考察了流动相中加入的极性改性剂对手性拆分的影响。试验结果显示,乙氧呋草黄在两种流动相体系中都能得到最好的拆分,但正己烷体系优于石油醚体系,流动相中的极性改性剂的含量减少有利于手性拆分。在正己烷流动相条件下考察了柱长、温度对手性拆分的影响。对对映体的拆分机理进行了讨论。     

氨氯地平磁性印迹材料的制备及其性能

为制备一种对氨氯地平的识别选择材料,通过交联聚合与印迹过程同步法,以改性Fe₃O₄磁性纳米微粒为载体,S-氨氯地平为模板分子,乙二醇二缩甘油醚(EGDE)为交联剂制备了S-氨氯地平磁性表面分子印迹材料1MMIP-Fe3O4@SiO2-PAM。研究了磁性分子印迹材料MMIP-Fe₃O₄@SiO₂-PAM对氨氯地平对映体拆分的可行性。通过FTIR光谱、扫描电镜SEM、热重分析仪TGA和磁强计VSM对功能微粒进行表征,结果表明,改性Fe3O4磁性纳米微粒表面出现了印迹空穴,且磁性表面分子印迹材料MMIP-Fe₃O₄@SiO₂-PAM具有良好的磁性和磁响应性。此外,通过静态、动态、选择性吸附和可重用性实验评估MMIP-Fe₃O₄@SiO₂-PAM的手性识别与拆分性能。结果表明印迹材料对模板分子吸附量为243 mg·g^-1,选择性系数为...     

Separation of hydroxybenzoic acid isomers using the molecular imprinting technique

Molecular imprinting polymers (MIPs) for salicylic acid (SA), 3‐hydroxybenzoic acid (3HBA), and 4‐hydroxybenzoic acid (4HBA) were synthesized using styrene and 4‐vinylpyridine (4‐VPy) as functional monomer and divinylbenzene (DVB) as crosslinker. The adsorption characteristics of hydroxybenzoic acid (HBA) isomers on each MIP were investigated. The materials used for the polymerization of each 3HBA and 4HBA‐MIPs were adsorbed relatively well. This verifies that the MIPs that can adsorb template selectively were synthesized. However, SA‐MIP had no molecular imprinting effect. SA has intramolecular hydrogen bond and it is difficult to adsorb on recognition site of SA‐MIP, because its structure differs from that of recognition site of SA‐MIP. It indicates that SA‐MIP had no recognition effect. 1,2,3,4‐Tetrahydro‐1‐naphthol (THN)‐MIP was synthesized, which is similar to SA with intramolecular hydrogen bond. SA was separated selectively using THN‐MIP. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Molecular imprinting polymers for the separation of toluic acid isomers

Molecular imprinting polymers (MIPs) were prepared with styrene, 4‐vinyl pyridine, and divinylbenzene for the separation of toluic acid isomers. The uptake and selectivity were investigated, with respect to how they were governed by the swelling degree of a soft MIP that contained a small amount of crosslinker. The optimum swelling range led to high uptake and the easy removal of the template without sacrificing the selectivity, which was controlled by the shape and size of the imprinting cavity under the same functional monomer, to the guest molecule. The original imprinting cavities were reversibly maintained within the range of 200% swelling and shrinking of MIPs throughout the template extraction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 650–654, 2005     

用电渗析法从谷氨酰胺模拟发酵液中脱除谷氨酸

为改进微生物发酵法生产谷氨酰胺的流程,提出用电渗析方法来分离谷氨酰胺和谷氨酸。在对混合氨基酸溶液中离子成分进行分析的基础上,预测了此方法的可行性,并通过电渗析方法对模拟发酵液进行实验来验证此预测结果。还考察了在混合物中含有硫酸铵时的情况。通过理论预测和实验验证,可以用电渗析法直接分离谷氨酰胺和谷氨酸,且原料中少量的硫酸铵有利于分离过程的进行。     

五种黄酮类分子印迹分离技术研究及应用进展

分子印迹技术用于从复杂的结构类似物混合物中选择性提取黄酮类化合物已经引起近年来的广泛关注。采用传统方法所制备的分子印迹聚合物（MIP）存在诸多缺点,限制了其应用发展。本文主要对5种典型黄酮类化合物（槲皮素、芦丁、异槲皮苷、葛根素、山奈酚）在分子印迹分离方面的研究及应用情况进行综述;对MIP的模拟、合成、表征、应用及优化进行了讨论;采用可逆加成-断裂链转移自由基聚合（RAFT）技术、磁功能化、计算机模拟、优化固相萃取性能参数等措施可以增强MIP印迹结合容量、选择性、传质和分离的程度;指出了开发新单体,引入新聚合方法,提高MIP制备效率,开发大分子检测MIP,使用MIP作为微流体工具,提出合成MIP的新配置,优化MIP的合理设计,探索MIP的大规模合成方法等发展趋势,可为黄酮类化合物及其类似物的分子印迹分离研究提供参考。     

Surface molecular imprinting of nylon fibers for chiral recognition of d‐phenyllactic acid

In the current work, synthetic polyamide nylon fibers were modified via the strategy of surface molecular imprinting to develop enantio‐selective adsorbent fabrics for chiral recognition of d ‐phenyllactic acid (d‐ PhLA). The nylon fibers were first modified by grafting of polyacrylamide and then the incorporated amide groups were converted into functional amino groups via treatment with NaOCl (Hofmann degradation). The amino‐functionalized nylon fibers (Ny‐NH₂) were interacted with the targeted d‐ PhLA enantiomer before crosslinking the amino‐containing grafted chains with glutaraldehyde crosslinker followed by leashing the template d‐ PhLA out of the formed surface polymeric matrix by lowering the pH to 1 to finally produce the desired enantio‐selective adsorbent fibers DP‐Ny. Different instrumental methods such as elemental analysis, Fourier transform infrared spectroscopy, XRD and TGA were employed to examine all the synthetic procedures. SEM was also utilized to observe the morphological appearances of both native and modified nylon fibers. Moreover, the optimum extraction of d‐ PhLA was found to occur at pH 7. Isotherm studies of the prepared DP‐Ny fibers obeyed the common Langmuir linear equation with q_m values 130 ± 2 and 75 ± 1 mg g^?1 in the case of d‐ PhLA and l‐ PhLA, respectively. Furthermore, the enantiomeric resolution of (±)‐PhLA racemate was successfully carried out by a column technique with enantiomeric excess reaching approximately 78%. © 2019 Society of Chemical Industry     

乙酰二茂铁谷氨酸Schiff碱的合成

由乙酰二茂铁和谷氨酸合成乙酰二茂铁谷氨酸Schiff碱,优化了反应条件。实验结果表明,当原料物质的量比为1∶1.5、反应温度为50℃、反应时间为7h、pH值为7～8时,产品收率最高。     

三唑酮对映体的手性拆分研究

合成了纤维素—三(3，5-二甲基苯基氨基甲酸酯)(CDMPC)，涂敷于氨基丙烷化硅胶上制备成涂敷量15％的手性固定相。以正己烷-异丙醇为流动相，在高效液相色谱上实现了对三唑酮光学异构体的直接拆分，研究了流动相中异丙醇的比例对分离效果的影响，优化了色谱拆分条件。     

分子印迹技术的研究进展及其在分离中的应用

分子印迹技术（MIT）是一种新的、很有发展潜力的分离技术。分子印迹聚合物因其具有预定性、识别性和实用性的优点,已广泛应用于分离技术中,显示出良好的应用前景,引起了人们的广泛关注。介绍了分子印迹技术的产生、原理及其在分离技术方面的应用,并对其进行了展望。     

Molecular imprinted material prepared by novel surface imprinting technique for selective adsorption of pirimicarb

In this paper, a molecular imprinted material with high performance for recognizing pirimicarb, which is a kind of carbamate pesticide, was prepared by adopting the novel surface molecular imprinting technique put forward by us previously. Firstly, the functional macromolecule poly(methacrylic acid) (PMAA) was grafted on the surface of silica gel particles in the manner of “grafting from” using 3-methacryloxypropyl trimethoxysilane (MPS) as an intermediate, and the grafted particle PMAA/SiO₂ was formed. Afterwards, the molecular imprinting was carried out towards the macromolecule PMAA grafted on the surface of silica gel particles using pirimicarb as template and ethylene glycol diglycidyl ether (EGGE) as crosslinking agent via the intermolecular hydrogen bond and electrostatic interaction, and pirimicarb imprinted material MIP-PMAA/SiO₂ was obtained. The combining characteristic of MIP-PMAA/SiO₂ for pirimicarb was studied profoundly with static method. The experimental results show that the surface-imprinted material MIP-PEI/SiO₂ has excellent combining affinity and recognition selectivity for the template molecules of pirimicarb. Before imprinting, PMAA/SiO₂ has greater adsorption capacities for pirimicarb as well as for the contrast substances, atrazine and propoxur, whose structures are similar to pirimicarb, and the selectivity coefficients of PMAA/SiO₂ for pirimicarb with respect to atrazine and propoxur are only 1.523 and 0.612, respectively. However, after imprinting, the combining capacities of MIP-PMAA/SiO₂ towards atrazine and propoxur decrease remarkably, whereas that of MIP-PMAA/SiO₂ for pirimicarb still remains higher. The coefficients of MIP-PMAA/SiO₂ for pirimicarb with respect to atrazine and propoxur were enhanced greatly, and they are 12.20 and 14.15, respectively. Besides, MIP-PMAA/SiO₂ adsorbing pirimicarb in a saturated state has fine elution and reuse properties.     

HPLC手性流动相拆分法在分离药物对映体中的应用

高效液相色谱是拆分手性药物的重要手段。简要介绍了不同的手性流动相添加剂及其拆分机理,综述了2000年以来高效液相色谱手性流动相拆分法在分离药物对映体中的应用。