电致化学发光生物检测技术的新进展

电致化学发光作为一种分析技术,不仅可用于化学分析,而且正在被越来越多地用于生物检测和传感技术中。随着该分析技术与免疫检测技术生化固定化技术和微细加工技术等的相互融合,电致化学发光生物检测技术具有了更高的精度、分辨率和更广的应用范围。     

地质分析的历史发展及当今热点

简要回顾了地质分析技术的历史与发展,分析了当代地学研究对地质分析提出的新要求和当前分析科学所能提供的基础条件,评价和展望了现代地质分析的重要领域和热点技术：整体分析,显微分析技术的发展及对气体地球化学分析、现场分析、地质标准物质和“绿色”分析技术的需求。“地质分析”从“岩析分析”走来,并将向涉及更广领域的“天然材料分析”扩展。整体分析、显微分析、有机和无机生化分析将是其3个重要发展方向。     

现代中药分析新进展

近年来中药分析领域取得了非常大的进展,主要特点有:中药分析的对象更集中于针对中医药现代化研究中的关键科学问题,提出切合实际的系统的解决方案;中药分析不再局限于提供化学分析的工具,而是将各种新方法、新技术整合使之成为解决关键科学问题的新体系;中药分析已经不再局限于分析中药的物质组成,更注重解决的是物质的组成及其功能的相关性.本文从中药信息表达模式的改变、成分研究策略的改变、分析对象的改变和药物效应分析模式的改变等四个方面对中药现代分析的进展和发展趋势进行了综述和讨论.     

高效液相色谱-质谱联用技术的应用进展

高效液相色谱-质谱联用技术具有高分离能力、高灵敏度、应用范围广和极强的专属性等特点。对高效液相色谱-质谱联用技术在药物分析、食品分析和环境分析等领域的应用,特别是在中草药成分分析、中药指纹图谱研究、药物代谢研究、体内药代动力学研究、西药及中成药成分分析、药物筛选研究等方面的应用进行了综述。     

炔雌醇在玻碳电极上的电化学行为研究

炔雌醇,又名乙炔雌二醇(Ethinylestradiol,EE),是一种雌激素.本文采用了现代电化学分析方法系统研究了炔雌醇在玻碳电极上的电化学行为.实验表明炔雌醇在玻碳电极上的氧化是不可逆过程,在不同pH值介质中,在玻碳电极上都有一定的吸附性.实验研究了在不同pH值条件下炔雌醇的各种电化学性质,并寻找到在不同条件下的定量方法,对实际样品进行了测定.     

毛细管电泳用于药物分析的研究进展

药物分析是毛细管电泳（CE）的重要应用领域,所有CE分离模式与检测方法都在各种药物及其不同形式样品的分离分析中显示出特色和应用能力。该文从药品分析领域中的小分子药物（包括手性药物）及其有关物质、中药与天然产物、体内药物分析、生物制品药物分析等几个方面,综述了近几年CE在这些传统药物分析领域应用的研究进展。限于篇幅,未包括现代药物分析研究比较活跃的理化常数测定、亲和毛细管电泳与结合常数研究（药物与受体间的相互作用等）、临床生物标志物分析、代谢组学和微流控芯片CE分析等方面的内容。根据目前传统药物分析领域的发展,该文关注到近期CE在顺应药物分析的法规需求、电容耦合非接触电导检测（CE-C⁴ D）、改进检测灵敏度与精密度、CE-十二烷基硫酸钠（SDS）毛细管电泳、全柱成像毛细管等电聚焦（icIEF）、抗体分析等方面的新进展。该文结合文献,讨论了目前传统药物分析领域的需求,以及CE在其中的地位、挑战和机遇。对目前CE主要作为互补分析方法在化学药和中药分析中的应用研究提出了一些针对性的建议,期待CE在生物制品分析中的特色和能力得到进一步的发挥,同时提出CE-MS和对CE分析重复性改进等新进展可能对未来CE应用领域的大幅度扩展。该综述主要涉及近3年（2017年1月到2020年2月）及部分2016年的相关文献。     

流动注射分析

溶液化学分析的自动化是现代分析化学发展的一个重要方向,从60年代开始在临床化学分析等领域应用日益广泛。Skeggs提出的连续流动比色分析系统曾是发展最为迅速、应用最为广泛的技术之一。1974年Ruzicka采用注射进样并废除了Skeggs系统在管道中引入气泡的做法,创造了流动注射分析(Flow Injection Analysis,简称FIA),使连续流动分析发展到一个新水平,这一新技术的基本特点是分析速度快、精度高、适应性广,并能大幅度节省试样和试剂。一般分析速度可达100—200样次/小时,分析精度达到1％,相对标准偏差     

示波滴定

本文综述南京大学化学系电化学分析小组几年来在示波滴定方面的研究工作。文中提出了一系列新的电滴定方法,这些方法兼有指示剂法和物理化学滴定法的优点,即终点直观、仪器便宜,操作简便、快速准确,适用于药物分析及冶金分析,受到国内分析工作者的重视。文中提出了示波滴定的定义、分类和每一方法的特点及发展前途的预测。     

扁桃酸在玻碳电极上的电化学行为研究

扁桃酸(mandelicacid)具有较强的抑菌作用,可用于治疗泌尿系统疾病,同时也是合成许多抗生素药物的中间体.因此,它在医药合成中具有广泛的用途.对扁桃酸的测定,已有紫外、HPLC、气相色谱、毛细管电泳等方法报道;电化学法测定还未见报道.本文采用现代电化学分析方法系统研究了扁桃酸在玻碳电极上的电化学行为.实验表明扁桃酸在玻碳电极上的氧化是不可逆过程,在pH 2.0介质中,在玻碳电极上都有一定的吸附性.实验研究了在pH 2.0条件下扁桃酸的各种电化学性质,并分别寻找到在不同条件下的定量方法,对实际样品进行了测定,方法简便、快速.     

毛细管电泳安培检测法在中草药分析中的应用

由于毛细管电泳安培检测法(CE-AD)具有高的分离效率和低的检测限的优势,现已在分析科学的各个领域,特别是在药物行业中得到广泛应用。中草药的研究在我国医药事业中占有重要的地位,采用CE-AD分离并检测中草药中有效成分对于促进中草药的药理药效研究及中草药的定量分析和质量监测等有重要意义。本文综述了CE-AD在中草药及中药复方制剂中有效成分分析中的应用,评述了该法与其他分离分析方法相比在中草药分析中的优越性,并对CE-AD在中草药分析中的发展进行了展望。     

中药材提取物的混批勾兑研究

采用非线性最小二乘拟合计算中药材提取物的勾兑系数,不同批的中药材提取物经过勾兑后与参照样品的差异减小,各成分含量稳定。采用数据预处理的方法,并对数据预处理方法进行改进,使峰面积较小的色谱峰可以实现较小的相对差异。引入误差控制系数,可实现对特定色谱峰的控制要求。实验结果表明,非线性最小二乘拟合可以用于计算中药材提取物的勾兑系数。     

Characterization of in Vitro Metabolism of Loganin by Human Intestinal Microflora Using Ultra-High Performance Liquid Chromatography–Quadrupole Time-of-Flight Mass Spectrometry

Human intestinal microbiota comprise a complex biological system with considerable metabolic activity. Various studies have focused on the bioconversion of flavonoids. However, in addition to flavonoids, bioactive components such as iridoids also exist in many natural and traditional Chinese medicines. Little is known about the interactions of the iridoids with bacteria. Loganin, one of the main effective iridoids in the valuable traditional Chinese herbal medicine Cornus officinalis, exhibits various pharmacological activities and biological effects. Human intestinal bacteria were isolated and the conversion capability of loganin was investigated. The metabolites were determined by ultra-high performance liquid chromatography–quadrupole time-of-flight mass spectrometry. Loganin was metabolized to hydrogenated and hydroxylated loganin sulfate, acetylated loganin, loganetin, methylated loganetin, hydrogenated, and hydroxylated loganetin. The metabolic routes and metabolites of loganin were reported for the first time. These metabolites may influence the biological activities of loganin in vivo. Thus, this study provides fundamental information about a traditional Chinese medicine.     

免疫分析技术在农药残留分析中的研究进展及在中药中的应用展望

中药材的农药残留问题一直是人们关注的重点,免疫分析技术作为一项特异性强、灵敏度高的快速分析检测技术,在实现中药材农药残留快速筛查方面发挥着重要作用。该文结合近年免疫分析相关研究进展,对不同的免疫分析技术在中药农药残留分析方面的应用、技术优势以及局限性进行总结分析,并对免疫分析技术的发展前景进行了展望,对免疫分析技术在农残分析领域的发展以及保障中药材的安全方面具有指导意义。     

中草药微量元素数据的数据库管理

中草药微量元素数据库收集有四百多种常用中草药六十多种元素的测定数据，具有检索、打印、统计等多种功能，对逐步建立中草药微量元素背景值，促进中草药微量元素的研究具有重要的作用。     

基于g-C3N4/P25复合光电敏感体系的中草药抗氧化容量测定

采用粒径为25 nm的锐钛矿和金红石型混合相二氧化钛(TiO₂)材料(P25)替代常规锐钛矿型TiO₂, 制备了基于石墨氮化碳(g-C₃N₄)/混合相TiO₂(g-C₃N₄/P25)的可见光激发光电敏感体系. 研究结果表明, 石墨氮化碳(g-C₃N₄)大的平面结构不仅能够成为TiO₂纳米材料合适的高分散载体, 其高效载流子传输能力还赋予了复合体系优异的光电性能. 当g-C₃N₄掺杂质量分数仅为0.5%时, 复合体系的光电流响应信号可提高至原来的4.5倍, 增敏效果最好. 该光敏体系的研制显著简化了制备工艺并降低了成本, 同时有效提高了体系的可见光利用效率. 基于该g-C₃N₄/P25光电敏感复合体系, 首次采用光电化学方法实现了中草药抗氧化容量的测定, 为量化中药体系抗氧化性能评估提供了新的思路.     

Rapid identification and comparative analysis of the chemical constituents and metabolites of Phellodendri amurensis cortex and Zhibai dihuang pill by ultra‐performance liquid chromatography with quadrupole TOF‐MS

Zhibai dihuang pill is a famous traditional Chinese medicine formula containing the herbal medicine Phellodendri amurensis cortex. In this work, an integrative pattern recognition approach including principal component analysis and orthogonal partial least squared discriminant analysis based on ultra‐performance liquid chromatography coupled to MS was successfully applied for the rapid discovery of natural compounds from herbal medicines. In a 24 min analysis, 93 compounds were identified or tentatively characterized from Zhibai dihuang pill based on their fragmentation behaviors, 23 of which were from Phellodendri amurensis cortex. A total of 26 metabolites in plasma were identified from Phellodendri amurensis cortex in Zhibai dihuang pill formula, among them, 12 prototypes and 14 metabolites through metabolic pathways of demethylation, methylation, hydrolysis, sulfate conjugation, and glucuronide conjugation, which were seven metabolites more than that of the single drug, suggesting the importance of the compatibility of traditional Chinese medicine. The present study provided important structural information on the metabolism of Zhibai dihuang pill. Furthermore, the results of this work have demonstrated the feasibility of ultra‐performance liquid chromatography coupled to MS for the rapid and reliable characterization of metabolites from herbal medicines. Based on these results, this method could be a novel approach for identifying potentially bioactive components in other traditional Chinese medicines.     

A capsule review of recent studies on the application of mass spectrometry in the analysis of Chinese medicinal herbs

Chinese herbal medicine is gaining increasing popularity worldwide as an alternative approach to the development of pharmaceuticals in therapeutic applications. Chemical characterization and compositional analysis of Chinese medicines provide the necessary scientific basis for the discovery and development of new drugs of natural origin. Applications of mass spectrometry in the analysis of Chinese herbal medicines have been growing rapidly in recent years owing to the rapid technical advances and increasing availability of the instrumentation. This paper reviews the current status of how different mass spectrometric techniques are being used to support research studies of Chinese medicines. The focus is on crude herbal medicines and their derived products. The review is not meant to be exhaustive, but rather to provide a general overview of the various research activities in this rapidly expanding field. In the discussion of specific herbs, the emphasis is placed on ginseng and Danshen, two of the herbs for which active experimental work is on-going in the authors' laboratories. Other selected herbs will be discussed only briefly, aiming primarily to illustrate the current status of research in the area.     

A metabolomic strategy to screen the prototype components and metabolites of Qingkailing injection in rat urine by high‐performance liquid chromatography with tandem mass spectrometry

Xenobiotic metabolome identification of Chinese herbal formula in biological systems is a very challenging task. Qingkailing injection is a typical Chinese herbal injection, which is wildly used clinically in China. However, the holistic metabolic fate of the ingredient from Qingkailing injection remains unclear. In this work, a metabolomic strategy for comprehensively elucidating Qingkailing injection derived prototype components and metabolites in rat urine conducted by hybrid linear ion trap high‐resolution mass spectrometry was developed. High‐performance liquid chromatography coupled with hybrid linear ion trap high‐resolution mass spectrometry was developed to obtain the urine profiling between the control group and Qingkailing injection treated group. Orthogonal partial least squares discriminate analysis was applied to distinguish the exogenous and the endogenous. In the S‐plot, 37 xenobiotics derived from Qingkailing injection were found in urine, including 18 prototype compounds and 19 metabolites. The characterization of the prototype components and metabolites in rat's urine provided essential data for further pharmacological studies of Qingkailing injection. Our results indicated that the metabolomic approach was an effective tool to discover, screen, and analyze the multiple prototype components and their metabolites from complicated traditional Chinese preparations in vivo.     

Determination of Sulfite in Botanical Medicine Using Headspace Thin-Film Microextraction and Surface Enhanced Raman Spectrometry

A facile method using headspace thin-film microextraction (HS-TFME) coupled with surface enhanced Raman spectrometry (SERS) has been developed for the determination of sulfite in traditional Chinese herbal medicine. The extraction substrate was synthesized by depositing urchin-like ZnO micron particles on glass sheets using chemical liquid phase deposition. Under the optimal conditions, the intensity of the SERS signal at 630–640?cm^?1 provided a good linear relationship with the concentration of sulfite from 25 to 400?mg/kg, and the linear correlation coefficient (R) was 0.996 with a detection limit of 6?mg/kg. The method was employed for the determination of sulfite in herbal medicines, and the results were confirmed by a traditional distillation-titration method. Therefore, this developed HS-TFME-SERS method may play an important role in the rapid, simple, and selective determination of sulfite residues in Chinese herbal medicine and become a potentially universal method for this analyte in various solid samples.     

Newly Generated Atractylon Derivatives in Processed Rhizomes of Atractylodes macrocephala Koidz

Thermally processed rhizomes of Atractylodes macrocephala (RAM) have a long history of use in traditional Chinese medicine (TCM) for treating various disorders, and have been an integral part of various traditional drugs and healthcare products. In TCM, herbal medicines are, in most cases, uniquely processed. Although it is thought that processing can alter the properties of herbal medicines so as to achieve desired functions, increase potency, and/or reduce side effects, the underlying chemical changes remain unclear for most thermally processed Chinese herbal medicines. In an attempt to shed some light on the scientific rationale behind the processes involved in traditional medicine, the RAM processed by stir-frying with wheat bran was investigated for the change of chemical composition. As a result, for the first time, five new chemical entities, along with ten known compounds, were isolated. Their chemical structures were determined by spectroscopic and spectrometric analyses. The possible synthetic pathway for the generation of such thermally-induced chemical entities was also proposed. Furthermore, biological activity evaluation showed that none of the compounds possessed cytotoxic effects against the tested mammalian cancer and noncancer cell lines. In addition, all compounds were ineffective at inhibiting the growth of the pathogenic microorganisms.