二维气相色谱技术及其在烟草行业中的应用

二维气相色谱的应用大大提高了分析能力,而与飞行时间质谱的联用更使其达到一个新的高度。介绍了二维气相色谱的原理、优越性及不足,以及与飞行时间质谱联用的技术进展。综述了近年来该技术在各行业特别在烟草行业中的应用,展望了二维气相色谱在烟草行业中的应用前景。     

在线二维液相色谱技术在中药研究中的应用进展

中药的组成复杂,其化学成分的表征和识别一直是中药研究的基础和关键。在线二维液相色谱是基于两种分离模式构建的色谱分析技术,主要包括中心切割二维液相色谱和全二维液相色谱两种模式,因二者具有更高的峰容量而在中药研究中备受青睐。该文对在线二维液相色谱技术的概念和特点进行了讨论,并对二维液相色谱在中药研究中的应用进行了综述,以期为该技术在中药质量控制、物质基础表征、活性成分筛选等研究方面提供一定参考。     

二维液相色谱切换技术及其应用

多维液相色谱已成为复杂样品研究的重要工具。本文在介绍多维液相色谱原理与方法的基础上,重点讨论了二维液相色谱接口切换技术的近期发展,并对其应用现状进行了总结分析。     

强阳离子交换毛细管液相色谱-反相加压毛细管电色谱二维系统的构建及其在中药黄柏提取物分离中的应用

加压毛细管电色谱(pCEC)具有电泳和液相色谱的双重分离机理,其柱效高、选择性强、分辨率高和分离速度快并可进行梯度洗脱。我们在此基础上加入离子交换色谱模式,构建了强阳离子交换-反相加压毛细管液相色谱(micro strong cation exchange liquid chromatography/reversed phase pressurized capillary electrochromatography, μ-SCXLC/RP-pCEC)二维系统,并对中药黄柏的提取物进行了优化分离。第一维μ-SCXLC采用线性盐梯度分离,样品被切割成11个馏分洗脱收集后进入第二维,第二维脱盐后,采用RP-pCEC进行分离分析,梯度洗脱。以中药黄柏提取物为样品,此二维系统的分辨率和峰容量都较一维系统有很大提高,理论峰容量可达900左右,证明构建的二维体系非常适合复杂样品的分离分析。     

离线二维反相液相色谱/超临界流体色谱在瓜蒌子分离中的应用

发展了离线二维反相液相色谱/超临界流体色谱(2D RPLC/SFC)分离瓜蒌子的方法。实验在第一维采用反相色谱,按色谱峰收集从瓜蒌子样品中制备得到的12个组分(F_1~F_(12)),并将得到的组分在第二维使用SFC分离。这些组分在RPLC和SFC的分离对比说明,该二维方法具有良好的分离正交性,可至少检测到150个色谱峰,对于解决结构相似物质的分离、微量成分的富集表现出了明显的优势。SFC方法采用了乙醇-正己烷(3∶7,v/v)的混合溶剂作为改性剂,既提供了适当的洗脱能力,也保证了在上样量增加时满足样品溶解的要求。此二维分离体系可放大到制备水平用于化合物的制备,为瓜蒌子化学成分的纯化制备提供技术支持,为其物质基础研究提供参考。     

二维卷积及其在色谱峰纯度鉴定中的应用

光电二极管阵列检测器与色谱仪的联用 ( HPLC- DAD)为复杂体系中多组分的定性定量分析提供了可能 .Savitzky等 [1]提出了以简单的卷积运算完成数值微分方法 .Gorry等 [2 ]曾以 Gram正交多项式替代幂级数拟合 ,让卷积技术可以覆盖到谱图包括起讫部分的任一点 .Edwards[3]与 Kuo[4 ]等提出的二维卷积法对处理和利用二变量数据矩阵具有普遍意义 ,但理论推导繁琐 .我们曾完善了推求二维卷积整数的普遍方法 [5] ,并研究和解决了一维和二维卷积中的信息丢失问题 [6 ,7] .本文提出了一种简化的求算二维卷积整数的方法 .理论推导表明 ,二维卷积…     

光谱相关色谱及其在中药色谱指纹图谱分析中的应用

基于相同的化学物质具有相同的光谱，在大多数情况下，同一样本的化学成分在同种类型的色谱柱上虽然保留时间不可能完全相同，但是洗脱的顺序应基本一致，提出光谱相关色谱的新概念。利用联用色谱的光谱信息与色谱信息，判断复杂中药色谱指纹图谱中的组分相关性和表征不同实验条件下所得的中药色谱指纹图谱，从而实现仪器的系统误差的化学计量学校准。     

广义二维相关光谱及其在分析领域中的应用

广义二维相关光谱(generalized two-dimensional correlation spectroscopy)的理论提出至今, 得到了国际学术界的极大关注, 其分析方法已经在分析领域中被广泛应用. 文中在叙说广义二维相关光谱的数学处理过程及其谱图的物理意义的同时, 列举了在化学分析和分子生物学等领域中的有机溶剂成分分析、生物分子在不同pH中的特性分析和蛋白结构分析等应用实例, 并详细地对广义二维相关光谱理论和分析方法进行了评述.     

二维液相色谱接口技术

二维液相色谱具有峰容量大、分辨率高、分析速度快等优点,已经成为复杂样品分离分析的重要工具。两种分离模式的转换通常需要经过一个特殊接口来完成,接口是二维液相色谱系统的核心,也是限制二维液相色谱应用的瓶颈;两种流动相不互溶时,接口尤为重要。本文针对二维液相色谱接口技术近期的发展和应用进行总结。引用文献51篇。     

二维高效液相色谱技术用于分析中药制剂中麻黄类生物碱

构建了一个离线的二维高效液相色谱系统,以解决成分复杂的中药样品的分离和痕量组分的定量问题。该系统在原有的单泵、单检测器高效液相色谱仪的基础上作了相应的改进而构成,样品先在第一维的Zor-bax SB-C18色谱柱中进行分离之后,利用一个六通切换阀将目标组分切换并收集,浓缩后再注入第二维的Ai-chrom Bond-AQ C18色谱柱中进行分离。利用上述方法对3种麻黄类生物碱进行了二维分离和分析,实验结果表明,样品的分离明显改善,并且这个系统可用于中药的直接进样分析。     

Application of two‐dimensional liquid chromatography in the separation of traditional Chinese medicine

Traditional Chinese medicines have been widely used to prevent and cure diseases for thousands of years. For the purpose of better understanding the extremely complicated traditional Chinese medicines, powerful separation techniques are essential. Two‐dimensional liquid chromatography has been proven to be more powerful for the separation of complex traditional Chinese medicines due to its enhanced peak capacity and resolution compared with one‐dimensional liquid chromatography. Enormous efforts have been made on the coupling of independent separation mechanisms to improve the resolving power for complex traditional Chinese medicine samples, including the development and introduction of novel stationary phases. This review aims to give an overview on the applications of two‐dimensional liquid chromatography in traditional Chinese medicine research since 2008, including comprehensive two‐dimensional liquid chromatography, heart‐cutting two‐dimensional liquid chromatography both in on‐line, and off‐line mode. Different couplings of separation modes were respectively discussed based on specific studies, with emphasis on the applications of novel stationary phases in the two‐dimensional liquid chromatography.     

Simultaneous determination of some active ingredients in anti-viral preparations of traditional Chinese medicine by micellar electrokinetic chromatography

A simple and rapid micellar electrokinetic chromatography method was developed for the simultaneous determination of quercetin, gentiopicrin, forsythin, chlorogenic acid and caffeic acid in anti-viral preparations of traditional Chinese medicine (apTCM). In this method, the effects of buffer pH, concentration of the borax and SDS, organic modifiers, applied voltage and temperature on the separation were tested and discussed. The results showed that the fi ve analytes could be well separated within 11 min under conditions of 40 mM borax (pH 9.65) containing 20 mM SDS, 20 kV, at 25 degrees C. In the tested concentration range, regression equations revealed good linear relationships (correlation coefficients 0.9920-0.9991) between the peak areas and corresponding concentrations. In addition, a multiple linear regression QSPR model was constructed to predict the migration times of the analytes and the results were satisfactory. The method was validated by analysis of the five compounds in three representative apTCM samples with recoveries ranging from 89.2 to 106.6%.     

Chemometrics and modernization of traditional Chinese medicine

Development of chromatographic fingerprinting and its related chemometric methods in the research of quality control of traditional Chinese medicines(TCMs) are discussed. The quality control methods for guarantying the authentication and stability of products and semi-products of TCMs are firstly assessed. The technique based on chromatographic fingerprinting is essentially a kind of high-through put and integral tools to explore the complexity of herbal medicines. In order to further control the comprehensive quality of TCMs,confirmation and identification of their important chemical components are necessary. Some new strategies are proposed to trace the chemical changes of chromatographic fingerprints both in product processing and/or after their administration by modern chromatographic techniques and chemometrics. Combined with systems biology and bioinformatics,it seems possible for one to reveal the working mechanism of TCMs and to further control their intrinsic quality comprehensively.     

Computer-aided target optimization for traditional Chinese medicine by ultra-performance liquid chromatography

A new strategy of target optimization was developed for resolving the separation problems of complex samples. Computer-aided target optimization for separation of complex samples by ultra-performance liquid chromatography (UPLC) was studied. Taking traditional Chinese medicine (TCM) (Rhizoma Coptidis) as an example, separation conditions of target compounds - overlapping peaks and all components - were optimized based on moved overlapping separation ranging map (OSRM) and artificially intervention. After calculating retention parameters and peak shape parameters of the target peaks, the optimization was operated in an emulational picture through the computer without further experiments. The emulational chromatogram was proved to be authentic by the estimated values, which were almost identical to experimental results. The method was very helpful for obtaining the satisfied separation conditions of target compounds rapidly and efficiently.     

荧光光谱法对中药注射液热稳定性的研究

采用荧光光谱法对中药注射液热稳定性进行了初步探讨。发现在恒温（40℃、80℃）条件下、不同中药注射液随时间变化的荧光强度和荧光谱图，呈现出类似规律性的变化，但又有各自的特点。通过对其谱图和荧光强度的分析，能够反映出中药注射液在受热条件下，随时间变化的荧光谱的差异，不同温度对谱峰强度的差异性影响及不同注射剂热稳定性变化曲线的差异，从而提示中药注射液受热变质中组分变化的一些特点。找出了不同温度下不同中药注射液荧光强度减弱10％的时间。     

超声波和微波对中药提取的促进和影响

本文主要讨论超声波、微波在中药有效成分提取中的作用机理,探讨频率、强度、时间、占空比对提取率的影响,介绍现代检测技术与超声波、微波相结合的方法。证明超声波、微波作用于药物提取具有提取率高、可靠性强、操作简便、大大缩短提取时间等优点。     

The metabolomic study on atherosclerosis mice and its application in a traditional Chinese medicine Sishen granule

Although an atherosclerosis (AS) model using low‐density lipoprotein receptor deletion mice has been widely applied, its pathological pathway in metabolite level is still not clear. To further reveal the metabolite profile and identify the potential biomarkers in AS development, a serum metabolomic approach was developed based on reversed‐phase liquid chromatography/quadrupole time‐of‐flight mass spectrometry (LC‐Q‐TOF‐MS). The established metabolomic platform was also used for elucidating the therapeutic mechanism of a traditional Chinese medicine named Sishen granule (SSKL). Twenty‐one potential biomarkers in AS mouse serum were identified. Through functional analysis of these biomarkers, inflammation, proliferation, dysfunction of energy metabolism and amino acid metabolism were considered the most relevant pathological changes in AS. DNA damage products were found for the first time in the metabolomic study of AS. The network established by 20 biomarkers revealed that pyruvate metabolism, citrate cycle, fatty acid metabolism and urea metabolism were seriously disturbed. This metabolomic study not only supplied a systematic view of the progression of AS but also provided a theoretical basis for the treatment of AS. This metabolomic study also demonstrated that SSKL had therapeutic effectiveness for AS through partly reversing the inflammation reaction and amino acid metabolism dysfunction. Copyright © 2015 John Wiley & Sons, Ltd.     

Application of gas chromatography-mass spectrometry in research of traditional Chinese medicine

It is well known that traditional Chinese medicine (TCM) plays a more and more important role in modern pharmaceutical industry. It has been used in the therapy of many diseases for several thousand years because of its high pharmacological activity, low toxicity and rare side effects. In TCM, as an important group of secondary metabolites, essential oils have attracted a great deal of attention in recent years. Gas chromatography-mass spectrometry (GC-MS) is the most commonly used technique for the analysis of liposoluble constituents, especially volatile/semi-volatile compounds, and their metabolites in biological fluids due to its high resolution, selectivity and sensitivity. This review briefly describes the applications of GC-MS for the isolation and characterization of volatile compounds from TCM. In addition, GC-MS methods adopted in the metabolic profiling of volatile compounds in biological matrices are also described.     

Salt‐assisted dispersive liquid–liquid microextraction for enhancing the concentration of matrine alkaloids in traditional Chinese medicine and its preparations

A fast, simple, and efficient salt‐assisted dispersive liquid–liquid microextraction coupled with high‐performance liquid chromatography was developed and introduced for the simultaneous enrichment, extraction, and determination of the trace levels of matrine alkaloids (sophoridine, matrine, and sophocarpine) in Sophorae Flavescentis Radix and Composite Kushen injection. Compared with conventional dispersive liquid–liquid microextraction, the proposed method, with added salt but without dispersant and centrifuging, makes the operation simpler, greener, and leads to a higher enrichment factor. The crucial parameters affecting the enrichment factors of target analytes, such as type and volume of extraction solvent, pH of sample phase, salt concentration, volume of sample phase, and extraction time, were investigated and optimized, meanwhile, the extraction mechanism of the method was analyzed and described. Under the optimized conditions, the enrichment factors of the three matrine alkaloids were 150, 178, and 227, respectively. Good linearities (r² ≥ 0.9992) for all analytes, low limits of detection (less than 0.08 ng/mL), satisfactory precisions (2.1–12.3%), and accuracies (recoveries, 99.3–103.9%) were achieved. The experimental results showed that the approach is a simple, fast, green, eco‐friendly, and sensitive method and can be used for the preconcentration and determination of matrine alkaloids in traditional Chinese medicines and their preparations.