土茯苓及其混淆品的薄层色谱鉴别

土茯苓为常用中药,商品为百合科植物土茯苓的根茎,具有解毒、除湿的功效。在我国南方大部分省份皆有生长,其伪品多为菝葜类植物。采用薄层色谱法对土茯苓及其混淆品进行鉴别已有报道[1,2],但由于所涉及的混淆品品种较少,难以满足实际工作的需要。在我们前面的工作中[3～5],已对土茯苓及其混淆品进行了性状、显微及紫外光谱的系统鉴别研究。本文对产地不同、外表颜色深(淡棕色)浅(类白色)不同的正品土茯苓商品及其多种混淆品进一步加以研究,建立了真伪土茯苓鉴别的薄层色谱方法。1　实验部分1.1　实验材料　　实验材料来源及植物学名见文…     

HSGC-MSD及HSGC法鉴别草豆蔻真伪品

草豆蔻为姜科(Zingiberaceae)植物草豆蔻Alpinia katsumadai Hayata干燥成熟种子团.同属植物草豆蔻伪品长柄山姜Alpinia kwangsiensis T.L.Wu et Senjen的干燥种子团(民间代山姜).两者外形极易混淆,本文根据二者气味差异,试用顶空气相色谱(HSGC)及其顶空气相色谱-质谱(HSGC-MS)法对其进行了鉴别.     

用电化学方法研究红景天和丹参清除超氧阴离子自由基和羟基自由基的作用

利用单扫示波极谱法研究了红景天和丹参对活性氧自由基(O_2~-,OH)的清除作用.超氧阴离子自由基(O_2~-)通过邻苯三酚自氧化体系产生.羟基自由基由Fenton反应生成,用自旋捕集剂苯基叔丁基氮酮(PBN)捕捉生成的OH,以单扫示波极谱法检测自旋加合物.红景天和丹参样品对O_2~-和OH均有一定的清除作用,丹参对活性氧自由基的清除作用强于红景天.对O_2~-的清除能力为:红景天甙>吉林长白山红景天>西藏红景天;丹参对照品>安国丹参(Ⅰ)>安国丹参(Ⅱ).对OH的清除能力为:红景天甙>吉林长白山红景天>西藏红景天;安国丹参(Ⅱ)>安国丹参(Ⅰ)>丹参对照品.分别计算了各样品对自由基清除作用的IC_(50)值.     

基于核磁共振氢谱及偏最小二乘判别分析法的红木快速识别模型的建立与应用

以核磁共振技术为基础,采用核磁共振氢谱(1H NMR)对奥氏黄檀、巴里黄檀、交趾黄檀、刺猬紫檀、大果紫檀和檀香紫檀6类国标红木及胶漆树、染料紫檀2类混淆品的甲醇超声提取液进行检测分析,并结合聚类分析法、主成分分析法(PCA)和偏最小二乘判别分析法(PLS-DA)等模式识别方法对其进行快速鉴别。结果显示,利用PLS-DA法建立的模型前3个主成分累积贡献率达79%,能将国标红木与混淆品进行有效区分,且能大致区分不同种类的国标红木。该方法快速、高效,在红木快速鉴别分析中具有较大的潜力。     

对于原子轨道和电子云图形的常见误解的辨析

目前,原子轨道和电子云的各种图形在化学教科书和有关书刊中出现得日益普遍,亦有不少文章作过介绍和讨论,但初学者仍不免有难以区分之感,甚至一些书刊中也出现某些混淆和谬误。要澄清这些混乱,看来仅从正面介绍还不够,因此,本文试图从各种图形的分类人手,专门列举几种常见的误解和混淆现象,逐一加以辨析。     

复方丹参配伍比例对丹参化学成分溶出的影响

采用高效液相色谱峰比值法比较了由丹参和三七组成的复方丹参中丹参与三七的比例(以质量比计)从10∶0变化到1∶10的过程中丹参化学成分的变化。结果表明：所有合煎样品中丹参的主要成分含量均比单味药丹参中丹参主要成分的含量高,并且经典方(m(丹参)∶m(三七)＝5∶3)中丹参主要成分的含量最高。因此,丹参与三七以一定的比例(5∶3)配伍并且采用合煎的方法能够增加丹参成分的溶出率, 由此看来中医药中讲究的配伍规律是有其内在的科学道理的。     

磷钼钨酸-干酪素法测定丹参药材中鞣质的含量

建立了磷钼钨酸/干酪素法测定丹参药材中鞣质含量的方法。采用室温浸提过夜提取鞣质,在磷钼钨酸与多酚类物质的显色反应进行到90~120min时,于760nm波长处,分别测定供试品溶液中的总酚和不被吸附的多酚的吸光度,以吸光度之差用标准曲线法求得鞣质含量,线性范围为2.00~8.00mg/L,线性关系良好(r=0.9997)。方法具有较高的灵敏度与选择性,精密度和重复性均较好,其RSD分别为0.4%和6.9%,标准加入回收率在80.2%~106%之间,RSD为11.8%。该方法简单、准确,并应用于不同来源的丹参药材的检测,获得了满意的结果。可用于监测丹参药材以及丹参注射液生产过程中鞣质含量的变化。     

高效液相色谱-电喷雾离子阱质谱法鉴定复方丹参方化学及代谢成分

应用高效液相色谱-电喷雾离子阱质谱法鉴定了复方丹参方和其在家兔血浆、尿及粪便中的代谢产物。实验采用ZorbaxC18色谱柱,二元线性梯度洗脱进行色谱分离,并与电喷雾质谱联用,根据正离子和负离子模式下的分子离子峰获得化合物分子量信息,通过与文献数据或部分对照品对照,确定化合物的可能结构。     

真伪大黄的二维相关红外光谱

采用红外光谱法并结合二维相关光谱(two-dimensional correlation spectroscopy)分析技术，对药用西宁大黄和伪品华北大黄进行了无损快速鉴别研究。西宁大黄和华北大黄在一维谱图上差别不显著，而在二维谱图上显示出较大的差别。在1200-1700cm-1波段范围内，西宁大黄在同步图上有两个较强的自动峰，分别在1460和1560cm^-1附近，而华北大黄只有一个较强的自动峰，在1460cm^-1附近；同样在1030-1170cm-1波段范围内西宁大黄有两个较强的自动峰，分别在1060和1080cm^-1附近，而伪品大黄也只有一个较强的自动峰，在1080cm^-1附近。两个波段的异步谱也显示出较大的差别。结果表明：二维相关谱可以提高谱图的分辨率，增加谱图的识别能力，可用于药材真伪品的鉴别。该法快速、准确，为客观评价中药材的来源提供了一种新的方法。     

同步荧光光谱法研究丹参素-牛血清白蛋白体系的光增强效应

采用紫外光谱法和同步荧光光谱法研究了丹参素与牛血清白蛋白的结合特性.体系的紫外光谱显示,丹参素与牛血清白蛋白(BSA)之间发生了相互作用并生成新的复合物,同步荧光光谱则表明,丹参素对BSA存在荧光增强效应.随着丹参素浓度的增加,Δλ=15 nm时体系荧光强度明显增强,最大发射波长为285 nm,且不随浓度增加而发生变化...     

Identification of Salvia species using high‐performance liquid chromatography combined with chemical pattern recognition analysis

Salvia miltiorrhiza, also known as Danshen, is a widely used traditional Chinese medicine for the treatment of cardiovascular diseases and hematological abnormalities. The root and rhizome of Salvia przewalskii and Salvia yunnanensis have been found as substitutes for Salvia miltiorrhiza in the market. In this study, the chemical information of 14 major compounds in Salvia miltiorrhiza and its substitutes were determined using a high‐performance liquid chromatography method. Stepwise discriminant analysis was adopted to select the characteristic variables. Partial least squares discriminant and hierarchical cluster analysis were performed to classify Salvia miltiorrhiza and its substitutes. The results showed that all of the samples were correctly classified both in partial least squares discriminant analysis and hierarchical cluster analysis based on the four compounds (caffeic acid, rosmarinic acid, salvianolic acid B, and salvianolic acid A). This method can not only distinguish Salvia miltiorrhiza and its substitutes, but also classify Salvia przewalskii and Salvia yunnanensis. The method can be applied for the quality assessment of Salvia miltiorrhiza and identification of unknown samples.     

Thermal degradation products derived from the smoke of Salvia divinorum leaves

Smoking of Salvia divinorum leaves is the most common method for its psychotropic effects. Eleven thermal degradation products, including a new neoclerodane diterpene derivative, were isolated from the smoke of S. divinorum leaves, and their structures were identified by spectroscopic methods. The isolated compounds were evaluated for their binding affinities at the opioid receptors, and salvinorin A is still the most potent kappa opioid receptor agonist.     

Structure of salvioccidentalin, a diterpenoid with a rearranged neo-clerodane skeleton from Salvia occidentalis

From the aerial parts of Salvia occidentalis (Labiatae) a new diterpenoid with a rearranged neo-clerodane skeleton was isolated. This new compound was named salvioccidentalin and its structure was established by spectroscopic means. A probable biogenetic relationship with salvigenolide from S. fulgens and salvileucalin A and spiroleucantholide from Salvia leucantha is proposed.     

Sugar Profiling of Honeys for Authentication and Detection of Adulterants Using High-Performance Thin Layer Chromatography

Honey adulteration, where a range of sugar syrups is used to increase bulk volume, is a common problem that has significant negative impacts on the honey industry, both economically and from a consumer confidence perspective. This paper investigates High-Performance Thin Layer Chromatography (HPTLC) for the authentication and detection of sugar adulterants in honey. The sugar composition of various Australian honeys (Manuka, Jarrah, Marri, Karri, Peppermint and White Gum) was first determined to illustrate the variance depending on the floral origin. Two of the honeys (Manuka and Jarrah) were then artificially adulterated with six different sugar syrups (rice, corn, golden, treacle, glucose and maple syrup). The findings demonstrate that HPTLC sugar profiles, in combination with organic extract profiles, can easily detect the sugar adulterants. As major sugars found in honey, the quantification of fructose and glucose, and their concentration ratio can be used to authenticate the honeys. Quantifications of sucrose and maltose can be used to identify the type of syrup adulterant, in particular when used in combination with HPTLC fingerprinting of the organic honey extracts.     

TLC-MS versus TLC-LC-MS fingerprints of herbal extracts. Part III. Application of the reversed-phase liquid chromatography systems with C18 stationary phase

In the previous paper from this series, we proposed mass spectrometric fingerprinting of complex botanical samples upon the examples of the pharmacologically important phenolic acids and flavonoids selectively extracted from Salvia lavandulifolia. In this study, we explore fingerprinting efficiency with a novel two-dimensional analytical system composed of the reversed-phase thin-layer chromatography and the reversed-phase high performance liquid chromatography with mass spectrometric detection (2D RP-TLC-RP-LC-MS). We also compare its efficiency with that of the one-dimensional analytical system (the reversed-phase thin-layer chromatography with mass spectrometric detection; 1D RP-TLC-MS). As our present study is basically focused on the method development, we considered it as justified to carry out our comparison with the phenolic acid extracts selectively derived from the Salvia lavandulifolia species, similar as it was done in Part II from this series. Upon the results obtained, it was established that the 1D RP-TLC-MS mode and the 2D RP-TLC-RP-LC-MS mode can be applied to fingerprinting of herbal extracts, and that the 2D RP-TLC-RP-LC mode can provide a more abundant information than that originating from the 1D RP-TLC mode.     

消费品中限用化学物质的法规要求及相关检测技术

近期国内外市场相继发生多起消费品因含有重金属、邻苯二甲酸酯增塑剂、致癌芳香胺等有害化学物质而大规模召回的质量安全事件,引致各国陆续发布涉及消费品化学物质的技术性法规和标准,对其中含有的化学物质提出越来越高的要求.该文研究了欧盟、美国和中国等国家涉及玩具、纺织品服装、电子电气产品、家具和食品接触材料等重要消费品的质量安全技术法规的状况及相关的禁(限)用化学物质的要求,并针对检测这些化学物质所涉及的多种最新样品前处理技术和先进仪器分析检测技术进行了综述,以满足其在生产和外贸通关的检验需求.     

Determination of Three Tanshinones from Radix Salvia Miltiorrhiza by Molecularly Imprinted Solid-phase Extraction

A selective molecularly imprinted solid‐phase extraction procedure was developed for the selective separation of tanshinone I, tanshinone IIA, and cryptotanshinone from Radix Salvia Miltiorrhiza samples. Tanshinone IIA imprinted polymers (MIP) synthesized in ethanol‐dodecanol system show high affinity to tanshinone IIA and its structure analogs in aqueous environment and the affinity can be controlled by adjusting the intensity of the eluents. By using 60% water‐40% methanol (volume ratio) and 99.5% methanol‐0.5% trifluoroacetic acid (volume ratio) as washing and eluting solvents, most interferences originating from the salvia matrix were eliminated. The extracts were sufficiently clean enough to be directly injected into HPLC for further chromatographic analysis. Good linearity was obtained from 0.4 to 500.0 mg·L^?1 (r²=0.999) with the relative standard deviations less than 4.2%. The mean recoveries of tanshinone IIA in Radix Salvia Miltiorrhiza were more than 85.6% at three different concentrations and the limits of detection were 0.06–0.09 mg·L^?1. This method is a viable alternative tool to the existing HPLC methods for analyzing the content of the three tanshinones in Radix Salvia Miltiorrhiza samples.     

One-step separation and purification of 3,4-dihydroxyphenyllactic acid, salvianolic acid B and protocatechualdehyde from Salvia miltiorrhiza Bunge by high-speed counter-current chromatography

Three kinds of polyphenols of Salvia miltiorrhiza Bunge, 3,4-dihydroxyphenyllactic acid, salvianolic acid B and protocatechualdehyde, were separated and purified in one step with solvent system n-hexane-ethyl acetate-methanol-acetic acid-water (1:6:1.5:1.5:8) by high-speed counter-current chromatography. Acetic acid was successfully used to increase the partition of high polar target compounds in organic phase to modify partition coefficient value. 3,4-Dihydroxyphenyllactic acid, salvianolic acid B and protocatechualdehyde were purified from 100mg water extracted crude sample of Salvia miltiorrhiza Bunge at purity of 97.6%, 94.2% and 98.2% and at yield of 98.6%, 73.6% and 90.2%. High-speed counter-current chromatography together with organic/aqueous solvent system supplied an efficient method to purify water-soluble compounds directly from crude samples of traditional Chinese medicines.     

Forensic analysis of <Emphasis Type="Italic">Salvia divinorum</Emphasis> using multivariate statistical procedures. Part I: discrimination from related <Emphasis Type="Italic">Salvia</Emphasis> species

Salvia divinorum is a hallucinogenic herb that is internationally regulated. In this study, salvinorin A, the active compound in S. divinorum, was extracted from S. divinorum plant leaves using a 5-min extraction with dichloromethane. Four additional Salvia species (Salvia officinalis, Salvia guaranitica, Salvia splendens, and Salvia nemorosa) were extracted using this procedure, and all extracts were analyzed by gas chromatography–mass spectrometry. Differentiation of S. divinorum from other Salvia species was successful based on visual assessment of the resulting chromatograms. To provide a more objective comparison, the total ion chromatograms (TICs) were subjected to principal components analysis (PCA). Prior to PCA, the TICs were subjected to a series of data pretreatment procedures to minimize non-chemical sources of variance in the data set. Successful discrimination of S. divinorum from the other four Salvia species was possible based on visual assessment of the PCA scores plot. To provide a numerical assessment of the discrimination, a series of statistical procedures such as Euclidean distance measurement, hierarchical cluster analysis, Student’s t tests, Wilcoxon rank-sum tests, and Pearson product moment correlation were also applied to the PCA scores. The statistical procedures were then compared to determine the advantages and disadvantages for forensic applications.     

Quality evaluation of Salvia miltiorrhiza Bge. by ultra high performance liquid chromatography with photodiode array detection and chemical fingerprinting coupled with chemometric analysis

An ultra high performance liquid chromatography with photodiode array detection method is developed for the simultaneous quantitative determination of five water‐soluble compounds including danshensu, protocatechualdehyde, rosmarinic acid, salvianolic acid B, and salvianolic acid A in Salvia miltiorrhiza Bge. samples. Through method optimization, the five compounds all expressed good linearity (R² > 0.9990) in a wide concentration range together with satisfactory accuracy, precision, and stability. Moreover, through qualitative analysis of the chemical fingerprint combined with similarity analysis, hierarchical cluster analysis, principle component analysis, and partial least‐squares discriminate analysis, we determined that the 13 batches of Salvia miltiorrhiza Bge. were similar in internal quality and the differences resulted from various cultivation environments, recovery elements, and others. Seen from the results of hierarchical cluster analysis and principle component analysis, the classification of 13 batches was in accordance, and partial least‐squares discriminate analysis technique was more suitable than the principle component analysis model to provide a distinct classification of test samples on the basis of their different components. Moreover, a permutation test verified the rationality of partial least‐squares discriminate analysis and variable importance plot showed that peaks 37 and 38 were the most significant variables in distinguishing the Salvia miltiorrhiza Bge. samples. The idea of the quantitative and qualitative analysis of Salvia miltiorrhiza Bge. was convenient, sensitive, and comprehensive, which could be applied to evaluate the quality of more traditional Chinese medicines.