Molecularly imprinted polymers: towards highly selective stationary phases in liquid chromatography and capillary electrophoresis

Molecularly imprinted polymers (MIPs) are synthetic polymers with a predetermined selectivity for a given analyte, or group of structurally related compounds, that make them ideal materials to be used in separation processes. In this sense, it is not surprising that the first applications of MIPs were as tailor-made chiral stationary phases in liquid chromatography. However, peak broadening and tailing, especially of the more retained enantiomers, were observed. Accordingly, this paper gives an overview of the attempts carried out during the recent years to improve the chromatographic performance of MIPs in liquid chromatography and capillary electrophoresis as well as the more recent applications. We conclude that MIPs are very promising materials to be used as selective stationary phases in chromatography although further developments are necessary in order to fully exploit their potential.     

分子印迹技术在毛细管电色谱中的应用

分子印迹技术是制备具有分子识别功能聚合物，即分子印迹聚合物（MIPs)的一种新技术；毛细管电色谱（CEC）是一个具有发展前途的色谱新技术。将分子印迹技术和毛细管电色谱两种新技术相结合，优势互补，具有极大的发展潜力。本文对分子印迹技术在毛细管电色谱中的应用，以及各类MIPs-CEC毛细管柱的制备方法进行了较为全面的综述，引用文献52篇。     

Development and application of polymeric monolithic stationary phases for capillary electrochromatography

Monolithic columns for capillary electrochromatography are receiving quite remarkable attention. This review summarizes results excerpted from numerous papers concerning this rapidly growing area with a focus on monoliths prepared from synthetic polymers. Both the simplicity of the in situ preparation and the large number of readily available chemistries make the monolithic separation media a vital alternative to capillary columns packed with particulate materials. Therefore, they are now a well-established stationary phase format in the field of capillary electrochromatography. A wide variety of synthetic approaches as well as materials used for the preparation of the monolithic stationary phases are presented in detail. The analytical potential of these columns is demonstrated with separations involving various families of compounds and different chromatographic modes.     

分子印迹聚合物在毛细管电色谱拆分手性药物中的研究进展

手性药物通过与生物体内生物大分子之间的手性匹配与分子识别来发挥药理作用。两个对映体与体内手性环境相互作用的不同导致每个对映体表现出不同的药理活性、代谢过程、代谢速率及毒性等药代动力学特征。因此发展手性药物的拆分方法,对于手性药物的开发和生产过程的质量监控具有重要意义。分子印迹聚合物（MIPs）是以目标分子作为模板而制备的高分子聚合物,它具有特定的空间分子结构和官能团,对目标分子具有高度的特异性识别能力。基于该特点,MIPs非常适合于手性药物的拆分和纯化。毛细管电色谱（CEC）可同时基于毛细管电泳和液相色谱的分离机理对目标物进行分离,因此具有高分离效率和高选择性的特点。将MIPs材料作为CEC的固定相,可将这两种技术的优势结合,从而实现对手性药物的高效拆分。MIPs材料在1994年首次应用于CEC手性拆分,此后该研究领域开始获得关注和发展。MIPs材料主要通过4种模式在CEC中实现手性拆分,分别是作为开管柱、填充柱和整体柱的固定相以及分离介质中的准固定相。该综述以这4种模式作为分类基准,根据MIPs制备所需的材料和分离对象对其在CEC手性拆分中的应用进行了总结,揭示了MIPs在CEC手性拆分中的潜力,同时评述了这4种模式各自的优势与不足,并对将来MIPs在CEC手性拆分中的发展进行了展望。     

Polymeric monolithic stationary phases for capillary electrochromatography

This review summarizes the contributions of a number of groups working in the rapidly growing area of monolithic columns for capillary electrochromatography (CEC), with a focus on those prepared from synthetic polymers. Monoliths have quickly become a well-established stationary phase format in the field of CEC. The simplicity of their in situ preparation method as well as the good control over their porous properties and surface chemistries make the monolithic separation media an attractive alternative to capillary columns packed with particulate materials. A wide variety of approaches as well as materials used for the preparation of the monolithic stationary phases are detailed. Their excellent chromatographic performance is demonstrated by numerous separations of different analytes.     

An insight into molecularly imprinted polymers for capillary electrochromatography

Molecularly imprinted polymers (MIPs) are actively being developed as a practical tool for affinity chromatographic supports. From the viewpoint of separation science, capillary electrochromatography (CEC) might be one of the more promising chromatographic techniques to be used in combination with the MIPs. However, up to the present, very little MIP work has involved CEC. This review gives a full overview of MIP including current trends in MIP, methods for the characterization of MIP, and methods for the preparation of MIP with particular emphasis on application of the resulting materials in CEC. To prepare MIPs with selectivity predetermined for a particular substance or group of structural analogues is an important factor for the development of a new format of CEC. From the fundamental research with the batch method, a better knowledge of imprint formation and imprint recognition will be helpful for expanding the application area of the combination of MIPs with CEC.     

Analytical application of carbon nanotubes,fullerenes and nanodiamonds in nanomaterials-based chromatographic stationary phases: A review

An overview of the most significative results so far attained in the application of carbon nanotubes, fullerenes and nanodiamonds as chromatographic separation media is presented. In particular, the authors focus on their use in capillary and packed-column gas chromatography, in high performance liquid chromatography and capillary electrochromatography, paying also attention to recently developed stationary phases for fast chromatography and nanochromatography. The performance of the nanomaterials is compared to that of planar and amorphous carbon sorbents and critically discussed in regard to retentive capability and selectivity. A wide part of this review is devoted to the most recent improvements achieved in terms of selectivity by use of functionalized nanotubes and by combination of carbon nanotubes with ionic liquids. Practical aspects of synthetic procedures in preparing novel stationary phases in relationship with their chromatographic behaviour are also commented.     

Approaches to molecular imprinting based selectivity in capillary electrochromatography

The work done during the past decade in order to adapt molecularly imprinted polymers (MIPs) to the capillary format and subsequently use these highly selective matrices for capillary electrochromatography (CEC) are reviewed in this article. MIPs are prepared utilizing a templated polymer synthesis where the template addresses the selectivity of the resulting polymer. These polymers possess binding characteristics that are comparable to the biological antibodies. Due to the polyclonality of the binding sites in the MIP, the separation result in severe peak broadening and tailing when performed in the isocratic mode. This was seen early in the development of MIPs as selective stationary phases in liquid chromatography (LC). As a mean of decreasing these problems, much effort was put into adapting the MIP to fit in CEC systems, that offers an efficiency that is superior to that in LC. Aiming to increase the efficiency of the MIP-CEC systems, different MIP formats have been developed that can be divided into three conceptually different categories, i.e., the monolithic, the microparticle and the coating. The strive for MIP formats that can be used in small bore capillaries has led to the development of MIP formats applicable to miniaturized systems approaching the chip format. Although prepared in order to perform MIP-CEC mediated separations, these formats can be used in a broad range of applications were the characteristics of the MIP, e.g. stability, selectivity and cost efficiency, could offer an interesting solution to cover the needs.     

微波聚合快速制备分子印迹毛细管电色谱整体柱

以甲基丙烯酸为功能单体、己二醇二甲基丙烯酸酯为交联剂、 对羟基苯甲酸为模板分子, 采用微波辐射聚合的方式快速制备了分子印迹毛细管电色谱整体柱, 并取得了较好的印迹效果. 分子印迹材料的原位制备5 min即可完成, 大大快于国内外传统的方法.     

Developments in the use of soluble ionic polymers as pseudo-stationary phases for electrokinetic chromatography and stationary phases for electrochromatography

This article reviews the development, characterization and application of soluble ionic polymeric materials as pseudo-stationary phases for electrokinetic chromatography and as stationary phases for electrochromatography since 1997. Polymeric pseudo-stationary phases for electrokinetic chromatography, including cationic polymers, anionic siloxane and acrylamide polymers, polymerized surfactants (micelle polymers), and chiral polymers are reviewed. Also reviewed are suspended molecularly imprinted polymer micro-particles. Application of polymeric pseudo-stationary phases with electrospray ionization mass spectrometric detection is presented. Recent progress in the development and characterization of physically adsorbed stationary phases for electrochromatography using polymers of the same or similar chemistry is also reviewed.     

Capillary electrochromatography with physically and dynamically absorbed stationary phases

Adsorption is always considered a troublesome effect in capillary electrophoresis (CE) and capillary electrochromatography (CEC). However, the adsorption effect can also be exploited to prepare or optimize the stationary phase in CEC. Compared with the chemical synthesis of new stationary phase materials for CEC, this method is simpler and more convenient. This review is focused on CEC with physically and dynamically adsorbed stationary phases. Separation of some acidic, basic and neutral solutes as well as enantiomers in CEC with dynamically adsorbed stationary phases are presented. The theory for the migration of charged solutes and the stationary phases currently used in CEC are also briefly reviewed.     

基于碳纳米材料的毛细管电色谱固定相研究进展

碳纳米材料由于其具有独特的纳米结构、大的比表面积、较强的热稳定性、良好的导电性以及较好的吸附性能等物理化学性质,因而在分析科学、生命科学、材料科学及环境科学等领域得广泛的应用.结合国内外最新文献,对近5年来碳纳米材料在毛细管电色谱新型固定相的制备研究方面进展进行了评述,包括毛细管电色谱的分类及分离机理、毛细管电色谱柱的制备方法和优缺点,碳纳米材料(石墨烯、碳纳米管、氧化石墨烯、还原氧化石墨烯、富勒烯)的结构性质及制备方法、碳纳米材料在毛细管电色谱柱固定相中的应用及作用机理等,并对其在色谱应用领域的方向进行了展望.     

Recent development trends for chiral stationary phases based on chitosan derivatives,cyclofructan derivatives and chiral porous materials in high performance liquid chromatography

The separation of enantiomers by chromatographic methods, such as gas chromatography, high‐performance liquid chromatography and capillary electrochromatography, has become an increasingly significant challenge over the past few decades due to the demand of pharmaceutical, agrochemical, and food analysis. Among these chromatographic resolution methods, high‐performance liquid chromatography based on chiral stationary phases has become the most popular and effective method used for the analytical and preparative separation of optically active compounds. This review mainly focuses on the recent development trends for novel chiral stationary phases based on chitosan derivatives, cyclofructan derivatives, and chiral porous materials that include metal‐organic frameworks and covalent organic frameworks in high‐performance liquid chromatography. The enantioseparation performance and chiral recognition mechanisms of these newly developed chiral selectors toward enantiomers are discussed in detail.     

Recent developments in the field of monolithic stationary phases for capillary electrochromatography

This review summarizes the contributions to the rapidly growing area of monolithic columns based on both silica and synthetic polymers for capillary electrochromatography and chip electrochromatography, with a focus on those published during the year 2004. A wide variety of both modified approaches to the "old" monoliths and new monoliths have been reported despite the very short period of time covered. This demonstrates that monolithic stationary phases have become a well-established format in the field of electrochromatography. The simplicity of their preparation as well as the good control over their porous properties and surface chemistries make the monolithic separation media an attractive alternative to capillary columns packed with particulate materials.     

Monolithic stationary phases for liquid chromatography and capillary electrochromatography

A monolithic stationary phase is the continuous unitary porous structure prepared by in situ polymerization or consolidation inside the column tubing and, if necessary, the surface is functionalized to convert it into a sorbent with the desired chromatographic binding properties [J. Chromatogr. A 855 (1999) 273]. Monolithic stationary phases have attracted considerable attention in liquid chromatography and capillary electrochromatography in recent years due to their simple preparation procedure, unique properties and excellent performance, especially for separation of biopolymers. This review summarizes the preparation, characterization and applications of the monolithic stationary phases. In addition, the disadvantages and limitations of the monolithic stationary phases are also briefly discussed.     

Capillary electrochromatographic chiral separations with potential for pharmaceutical analysis

The use of capillary electrochromatography as a chiral separation technique for pharmaceutical applications is reviewed. Publications of the past 10 years that provide a potential practical application in pharmaceutical analysis are considered. Method development or validation, separation strategies, and potential routine analysis by the methods/applications cited are the main subjects on which we focused our attention. The indirect chiral separation method was only used once in CEC mode. In the direct chiral separations, the use of chiral stationary phases was obviously preferred over the use of chiral mobile phases with non-chiral stationary phases. Amongst the chiral stationary phases, those based on macrocyclic antibiotics and polysaccharide selectors were the most frequently used. Monolithic stationary phases also have several applications, but not so extended as those with packed capillary electrochromatography. The considered papers not only describe the applicability of the technique for relatively large sets of chiral analytes, they also showed that various types of stationary phases can be produced in-house in a simple manner. However, to survive as a mature separation technique, considerable time and effort are still needed to solve some disadvantages currently characterizing capillary electrochromatography.     

Monolithic enantiomer-selective stationary phases for capillary electrochromatography

Monolithic materials have become a well-established format for stationary phases in the field of capillary electrochromatography. Four types of monoliths, namely particle-fixed, silica-based, polymer-based, and molecularly imprinted monoliths, have been utilized as enantiomer-selective stationary phases in CEC. This review summarizes recent developments in the area of monolithic enantiomer-selective stationary phases for CEC. The preparative procedure and the characterization of these columns are highlighted. In addition, the disadvantages and limitations of different monolithic enantiomer-selective stationary phases in CEC are briefly discussed.     

Enantiomer separation of chiral pharmaceuticals by capillary electrochromatography

Enantiomer separation of chiral pharmaceuticals by capillary electrochromatography (CEC) is achieved with open-tubular capillaries (o-CEC), with packed capillaries (p-CEC) or with monolithic capillaries. In o-CEC, capillaries are coated with a thin film containing cyclodextrin derivatives, cellulose, proteins, poly-terguride or molecularly imprinted polymers as chiral selectors. In p-CEC, typical chiral HPLC stationary phases such as silica-bonded cyclodextrin or cellulose derivatives, proteins, glycoproteins, macrocyclic antibiotics, quinine-derived and 'Pirkle' selectors, polyacrylamides and molecularly imprinted polymers are used as chiral selectors. Chiral monolithic stationary phases prepared by in situ polymerization into the capillary were also developed for electrochromatographic enantiomer separation.     

Role of molecularly imprinted polymers for selective determination of environmental pollutants--a review

The molecularly imprinted polymers (MIPs) are synthetic polymers possessing specific cavities designed for a target molecule. By a mechanism of molecular recognition, the MIPs are used as selective tools for the development of various analytical techniques such as liquid chromatography, capillary electrochromatography, solid-phase extraction (SPE), binding assays and biosensors. This review describes the application of MIPs to the determination of environmental pollutants in these different analytical approaches with a special emphasis on their potential as selective SPE sorbent for the selective extraction of target analytes from complex matrices.     

Recent highlights in stationary phase design for open-tubular capillary electrochromatography

This review examines the most recent innovations made to achieve high performance in open-tubular capillary electrochromatography (OT-CEC) separations, focusing on the ingenious chemical and physical solutions made to increase the surface area and equip the stationary phase with exploitable selectivity. Among the approaches taken are chemically bonded ligands, etching with chemical bonding, sol-gels, molecularly imprinted polymers, porous layers, physically attached or adsorbed phases, and nanoparticle coatings. Particularly noteworthy are modern developments with macrocyclic receptor ligands, nanoparticles and open channel electrochromatography on-chip.