毛细管电色谱技术研究进展

毛细管电色谱是一种新型的微分离技术，它结合了毛细管电泳和高效液相色谱的优点，近年来越来越受到分析化学家的关注。本文介绍了近几年来毛细管电色谱技术取得的最新进展，包括填充柱、开管柱、整体柱电色谱的色谱柱制备技术，压力驱动电色谱技术，毛细管电色谱的检测技术及样品预富集技术，指出了存在的问题并展望了电色谱发展前景。     

《毛细管电色谱理论基础》

毛细管电色谱作为一种新型微分离分析技术，其分离过程具有多种机理协同作用的特征。对于毛细管电色谱的理论研究不仅要考虑系统的电属性，还要兼顾溶质的两相分配特征。该书系统地阐述了毛细管电色谱的基本理论，讨论了分离过程中影响峰展宽的因素及其规律。基于作者发展的弛豫理论和唯象的输运过程处理方法，阐述了毛细管电色谱中的动力学和热力学问题，分别就不同的分离模式的选择性规律和柱内富集理论与技术、梯度洗脱的溶质输运特征加以说明。     

《毛细管电色谱理论基础》

毛细管电色谱作为一种新型微分离分析技术，其分离过程具有多种机理协同作用的特征。对于毛细管电色谱的理论研究不仅要考虑系统的电属性，还要兼顾溶质的两相分配特征。该书系统地阐述了毛细管电色谱的基本理论，讨论了分离过程中影响峰展宽的因素及其规律。基于作者发展的弛豫理论和唯象的输运过程处理方法，阐述了毛细管电色谱中的动力学和热力学问题，分别就不同的分离模式的选择性规律和柱内富集理论与技术、梯度洗脱的溶质输运特征加以说明。     

《毛细管电色谱理论基础》

毛细管电色谱作为一种新型微分离分析技术，其分离过程具有多种机理协同作用的特征。对于毛细管电色谱的理论研究不仅要考虑系统的电属性，还要兼顾溶质的两相分配特征。该书系统地阐述了毛细管电色谱的基本理论，讨论了分离过程中影响峰展宽的因素及其规律。基于作者发展的弛豫理论和唯象的输运过程处理方法，阐述了毛细管电色谱中的动力学和热力学问题，分别就不同的分离模式的选择性规律和柱内富集理论与技术、梯度洗脱的溶质输运特征加以说明。     

《毛细管电色谱理论基础》

毛细管电色谱作为一种新型微分离分析技术，其分离过程具有多种机理协同作用的特征。对于毛细管电色谱的理论研究不仅要考虑系统的电属性，还要兼顾溶质的两相分配特征。该书系统地阐述了毛细管电色谱的基本理论，讨论了分离过程中影响峰展宽的因素及其规律。基于作者发展的弛豫理论和唯象的输运过程处理方法，阐述了毛细管电色谱中的动力学和热力学问题，分别就不同的分离模式的选择性规律和柱内富集理论与技术、梯度洗脱的溶质输运特征加以说明。     

《毛细管电色谱理论基础》

毛细管电色谱作为一种新型微分离分析技术，其分离过程具有多种机理协同作用的特征。对于毛细管电色谱的理论研究不仅要考虑系统的电属性，还要兼顾溶质的两相分配特征。该书系统地阐述了毛细管电色谱的基本理论，讨论了分离过程中影嗡峰展宽的因素及其规律。基于作者发展的弛豫理论和唯象的输运过程处理方法，阐述了毛细管电色谱中的动力学和热力学问题，分别就不同的分离模式的选择性规律和柱内富集理论与技术、梯度洗脱的溶质输运特征加以说明。     

《毛细管电色谱理论基础》

毛细管电色谱作为一种新型微分离分析技术，其分离过程具有多种机理协同作用的特征。对于毛细管电色谱的理论研究不仅要考虑系统的电属性。还要兼顾溶质的两相分配特征。该书系统地阐述了毛细管电色谱的基本理论，讨论了分离过程中影响峰展宽的因素及其规律。基于作者发展的弛豫理论和唯象的输运过程处理方法，阐述了毛细管电色谱中的动力学和热力学问题，分别就不同的分离模式的选择性规律和柱内富集理论与技术、梯度洗脱的溶质输运特征加以说明。     

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。     

《毛细管电色谱及其在生命科学中的应用》新书问世

毛细管电色谱是近年发展起来的一种新型微分离技术，它整合了毛细管电泳与微径柱液相色谱的优点，通过在填充微细颗粒液相色谱填料的微径柱色谱柱两端施加直流高压电场，达到对痕量复杂生物及化学体系样品良好地分离。该书是作者近年来从事毛细管电色谱领域研究的积累和总结，全面介绍了毛细管电色谱基本原理、分离机理和分离行为，各类毛细管柱的制备方法和性能评价，加压毛细管电色谱仪的研制及应用实例。该书可供化学和生物专业研究生和科研人员参考阅读。     

《毛细管电色谱及其在生命科学中的应用》新书问世

毛细管电色谱是近年发展起来的一种新型微分离技术，它整合了毛细管电泳与微径柱液相色谱的优点，通过在填充微细颗粒液相色谱填料的微径柱色谱柱两端施加直流高压电场，达到对痕量复杂生物及化学体系样品良好地分离。该书是作者近年来从事毛细管电色谱领域研究的积累和总结，全面介绍了毛细管电色谱基本原理、分离机理和分离行为，各类毛细管柱的制备方法和性能评价，加压毛细管电色谱仪的研制及应用实例。该书可供化学和生物专业研究生和科研人员参考阅读。     

Use of on-line mass spectrometric detection in capillary electrochromatography

Capillary electrochromatography (CEC) is a liquid phase analytical separation technique that is generally carried out with packed capillary columns by electroosmotically driven mobile phase at high electric field strength. The analytes are separated by virtue of the differences in their distribution between the mobile and stationary phases and, if charged in their electrophoretic mobilities as well. It is thus considered a hybrid of liquid chromatography and capillary electrophoresis and is expected to combine the high peak efficiency of capillary zone electrophoresis (CZE) with the versatility and loading capacity of HPLC. This review explores the potential use of on-line mass spectrometric detection for CEC. It discusses key design issues that focus on the physical and electrical arrangement of the CEC column with respect to the electrospray orifice inlet. The salient features of the sheathless, sheath flow and liquid junction interfaces that are frequently employed while coupling a CEC column to an electrospray ionization mass spectrometry system are also highlighted. Possible configurations of the CEC column outlet that would obviate the need for pressurizing the capillary column are also presented. While coupling CEC with MS both the nature of the interface and the configuration of the column outlet will determine the optimal arrangement. The review also discusses bandspreading that occurs when a connecting tube is employed to transfer mobile phase from the column outlet to the atmospheric region of the electrospray source with a concomitant loss in sensitivity. Selected examples that highlight the potential of this technique for a wide range of applications are also presented.     

Sol-gel stationary phases for capillary electrochromatography

A review is presented on the current state of the art and future trends in the development of sol-gel stationary phases for capillary electrochromatography (CEC). The design and synthesis of stationary phases with prescribed chromatographic and surface charge properties represent challenging tasks in contemporary CEC research. Further developments in CEC as a high-efficiency liquid-phase separation technique will greatly depend on new breakthroughs in the area of stationary phase development. The requirements imposed on CEC stationary phase performance are significantly more demanding compared with those for HPLC. The design of CEC stationary phase must take into consideration the structural characteristics that will provide not only the selective solute/stationary phase interactions leading to chromatographic separations but also the surface charge properties that determine the magnitude and direction of the electroosmotic flow responsible for the mobile phase movement through the CEC column. Therefore, the stationary phase technology in CEC presents a more complex problem than in conventional chromatographic techniques. Different approaches to stationary phase development have been reported in contemporary CEC literature. The sol-gel approach represents a promising direction in this important research. It is applicable to the preparation of CEC stationary phases in different formats: surface coatings, micro/submicro particles, and monolithic beds. Besides, in the sol-gel approach, appropriate sol-gel precursors and other building blocks can be selected to create a stationary phase with desired structural and surface properties. One remarkable advantage of the sol-gel approach is the mild thermal conditions under which the stationary phase synthesis can be carried out (typically at room temperature). It also provides an effective pathway to integrating the advantageous properties of organic and inorganic material systems, and thereby enhancing and fine-tuning chromatographic selectivity of the created hybrid organic-inorganic stationary phases. This review focuses on recent developments in the design, synthesis, characterization, properties, and applications of sol-gel stationary phases in CEC.     

使用含离子涂层柱的毛细管电泳和毛细管电色谱的研究进展

 毛细管电色谱是近年发展起来的高效、高选择性的微分离技术。与一般的毛细管电泳和使用ODS反相填料的毛细管电色谱相比 ,含离子涂层柱的毛细管电泳和毛细管电色谱能提供较大且可控的电渗流 ,便于拓宽分离对象 ,优化分离条件。对使用含离子涂层柱的毛细管电泳和电色谱的特点、发展和应用状况进行了综述。     

分子印迹聚合物颗粒在毛细管电色谱中的应用

依据分子印迹技术(MIT)制备的分子印迹聚合物(MIP)颗粒对模板分子及其结构类似物具有特异性识别和选择性吸附作用,同时具有较大的比表面积和快速的传质动力学特性,因而被广泛用作液相色谱固定相和固相萃取材料。将MIP颗粒作为固定相应用于毛细管电色谱(CEC),结合了CEC的快速、高效和MIP的高亲和性、高选择性的特点,成为分析科学领域最具有发展前景的分离技术之一。MIP颗粒在CEC领域有几种不同的应用形式: 作为填充材料填充到毛细管柱中;作为嵌入材料嵌入到毛细管柱内部不同基质的骨架中;作为准固定相添加到CEC运行缓冲溶液中。本文综述了近几年MIP颗粒在CEC领域应用的发展,对该领域今后的发展前景进行了展望。     

The analysis of basic pharmaceutical compounds by capillary electrochromatography using continuous bed stationary phase

Summary Capillary electrochromatography (CEC) is classed as a hybrid technique between CE and HPLC and it combines the advantages of both these techniques. However, in some cases the disadvantages are also brought to light and some of these are difficult to resolve. For example the analysis of basic compounds using CEC. The problems of tailing peaks during HPLC analysis of basic compounds was resolved by end capping the residual silanol groups, but in CEC these are the groups that generate the electroosmotic flow. The analysis of basic compounds is crucial within the pharmaceutical industry where a high percentage of the drug actives are basic. Specially designed Continuous Beds stationary phases (CB) can mean that each application can have a specific stationary phase. In order to overcome the problem associated with the analysis of basic compounds using electrochromatography, we have designed a CB stationary phase with a positive charge, which could be operated using negative voltage. The resulting chromatography showed almost gaussian peaks for bases like nortriptyline which tail significantly using stationary phase typically used in CEC.     

Capillary electrochromatography-mass spectrometry for the separation and identification of isomeric polyaromatic hydrocarbon DNA adducts derived from in vitro reactions

Capillary electrochromatography (CEC) is an emerging technique that combines features of both micro-capillary high-performance liquid chromatography (microHPLC) and capillary electrophoresis (CE). This separation technique possesses high speed and the efficiency of an electro-driven system, while the selectivity and sample loadability compare to those of a packed capillary LC column. Since the separation mechanism is based on that of HPLC, the concept of isoeluotropic strength and selectivity of solvents as well as the on-column focusing techniques for sample introduction used in LC can be applied in CEC. This article examines some of these features of CEC in the context of our own experiences with the technique. More specifically, emphasis is placed on applications of CEC to the analysis of DNA adducts of polyaromatic hydrocarbons by coupling CEC to mass spectrometry. It is shown that, with proper selection of mixed organic modifiers in the mobile phase, i.e. ternary and quaternary mobile phases, complex DNA adduct mixtures derived from in vitro reactions can be separated isocratically with improved selectivity and much greater speed than by HPLC. Additionally, the speed of the analysis is further enhanced by employing a step gradient. Furthermore, CEC may be easily coupled to mass spectrometry such that the characterization of each isolated component from the mixtures is performed on-line with the separation. By using on-column focusing, the sample loadability onto a CEC column is improved.     

Toward rapid preparation of capillary columns for electrochromatography use

CEC is a high performance electrodriving liquid phase separation technique. It does not need complex and sophisticated high pressure instrumentation for nanoflow driving. This is attractive for parallel multicolumn analysis. To this end, high throughput methods for column preparation are needed to support the use of multiple columns. In this study, we directly used CEC mobile phase solution as the packing solvent, and realized rapid preparation of capillary columns based on a single particle fritting technology. The method presented high preparation throughput compared with other reported methods based on various fritting technologies. The single particle fritting approach promoted column preparation throughput to 1 column/h, including all the fritting, packing and conditioning steps. The rapidly prepared columns showed consistently high efficiency of up to 150 000 plates per meter, and usefulness in reversed phase CEC of neutral, charged and biomolecules. With standard peptides as the sample, excellent long term reproducibility (better than 0.8%RSD, ten days, for retention times) was observed.     

Porous membrane structures as stationary phase for capillary electrochromatography

This work presents the application of membrane technology for the fabrication of stationary phase for CEC columns using the technique based on phase inversion of polymer solution. A blend of polyimide P84 and sulphonated poly(ether ether ketone was processed via immersion precipitation dry‐wet spinning into small‐bore porous fiber. The morphology, zeta potential, and performance of the porous structure in the CEC separation were investigated. Noncharged molecules (as markers of the electroosmotic flow) and small organic compounds were injected into the column, driven under the application of voltage, and detected on the electropherogram. The proof of concept of applying porous membrane structure as stationary phase for CEC was shown and possible optimization to improve efficiency and selectivity was suggested.     

手性有机聚合物毛细管电色谱整体柱研究进展

毛细管电色谱具有高分离效率、多种保留机制和高选择性的优点。近年来,利用毛细管电色谱进行对映异构体的手性拆分受到了广泛关注。相对于传统的填充柱和开管柱,整体柱在手性拆分方面具有显著优势。与手性硅基整体柱相似,手性有机聚合物整体柱由于具有大孔,可产生较高的流速而压降较小。该文综述了近十年手性有机聚合物整体柱制备方法的研究进展,将手性有机聚合物整体柱的制备方法分为"原位聚合法"和"手性修饰法"两种,虽然前者制备简单并广泛应用于早期研究,但聚合混合液成分的微小改变即可引起最终聚合物的形态变化,并且大部分带丙烯基的手性选择剂较难从市场购买。因此,手性修饰法因作为手性选择剂基质的整体柱制备且优化只需进行一次的优势而受到普遍关注。亲核取代、杂环开环和点击化学是常用的修饰手段。该文总结了这两种制备方法的应用,同时对未来的研究方向提出参考性意见。     

Microemulsion electrokinetic chromatography versus capillary electrochromatography-UV-mass spectrometry for the analysis of flunitrazepam and its major metabolites

Benzodiazepines, namely flunitrazepam and its three major metabolites, were successfully separated by microemulsion electrokinetic chromatography. Separation was achieved using an untreated fused-silica capillary (48 cm (effective length 40 cm) x 50 num) at 25 kV; detection was performed by UV at 220 nm. The microemulsion system consisted of 70 mM octane, 800 mM 1-butanol, 80 mM sodium dodecyl sulfate (SDS) and 10 mM borate buffer, pH 9. Very high efficiencies (up to 400 000 plates) and resolution better than 3 were achieved. Since this technique is not compatible with mass spectrometry (MS) detection, a capillary electrochromatographic (CEC) method was developed to separate flunitrazepam and its metabolites. The effects of mobile phase composition and pH as well as voltage and temperature were systematically investigated. The optimized CEC method allowed the baseline separation of the investigated compounds. For the on-line coupling of CEC with electrospray ionization-mass spectrometry, the column was connected to a void fused-silica capillary using a Teflon connection. This configuration was found efficient and suitable for hyphenation of commercial CEC and MS instrumentation using commercially available CEC columns.