原子吸收光谱测定刺五加中金属元素的含量

用原子吸收光谱法测定了刺五加根、茎、叶中Ca、Cu、Mg、Fe、Zn、K、Mn、Na等8种矿物质元素的含量,并对其结果进行了分析比较,以此研究了这8种金属元素在刺五加体内的分布。结果显示：各元素在实验范围内,线性关系良好,加标回收率在99%—109.6%之间,相对标准偏差为0.2%—1.8%。刺五加中不同部位的这8种元素间存在显著差异,根中Ca〉Mg〉K〉Fe〉Na〉Mn〉Zn〉Cu,其叶中的含量以K为高,而且各部位均有较高的Ca、Cu、Mg、Fe、Zn、K、Mn、Na。从微量元素的角度分析,刺五加的根、茎、叶均有一定的应用价值。     

FTIR结合化学计量学对三七地下部位鉴别及皂苷含量预测

当今中药市场上掺假现象屡见不鲜，不良商贩利用三七须根粉末假冒主根和剪口粉末，严重影响三七的质量与药效。通过傅里叶变换红外光谱(FTIR)结合化学计量学建立三七主根、剪口和须根粉末鉴别及四种皂苷含量快速预测模型，为快速三七质量控制提供基础。采集三七主根、剪口和须根红外光谱，超高效液相色谱(UPLC)测量样品中三七皂苷R₁、人参皂苷Rg₁、人参皂苷Rb₁和人参皂苷Rd含量。采用纵坐标归一化及二阶导数对原始红外光谱进行预处理；Kennard-stone算法将60个样本分为2/3训练集与1/3预测集。训练集数据结合支持向量机(SVM)判别建立三七主根、剪口和须根粉末鉴别模型，最佳核函数c和g采用交叉验证进行网格式搜索，预测集数据用于对判别模型进行外部验证。正交信号校正偏最小二乘回归(OSC-PLSR)建立三七中四种皂苷含量预测模型，红外光谱采用一阶、二阶导数及Savitsky-Golay平滑5点、7点、9点、11点预处理。60个样本分为2/3训练集与1/3预测集，训练集数据建立OSC-PLSR模型，预测集数据对OSC-PLSR模型的预测结果进行外部验证。结果显示： (1)二阶导数可有效的分离原始谱图的叠合隐蔽谱峰，并提高谱图的分辨率；(2)交叉验证网格式搜索计算出最佳核函数c=2.828 43，g=4.882 81×10-4，此时训练集判别正确率为100%；(3)SVM判别模型核函数设置为最佳核函数，预测集数据外部验证正确率为100%，所有样本均被正确鉴别；(4)三七皂苷R₁、人参皂苷Rg₁、人参皂苷Rb₁和人参皂苷Rd最优含量预测模型预测值与UPLC检测值接近，预测效果良好。FTIR结合SVM判别能对三七主根、剪口和须根粉末快速鉴别，结合OSC-PLSR能对四种皂苷含量进行准确预测。该方法准确可靠，可为中药材三七提供快速有效的质量控制。     

Cerebrosides from the Rhizomes of Gynura Japonica

Four new cerebrosides, gynuramides I?IV ( 1 ‐ 4 ), together with 37 known compounds were isolated from the rhizome of Gynura japonica. The structures of cerebrosides 1 ‐ 4 were determined by chemical and spectroscopic examination to be: (2S,3S,4R,8E)‐2‐[(R)‐2‐hydroxypentacosanoylamino]‐8‐en‐1,3,4‐octadecanetriol, (2S,3S,4R,8E)‐2‐[(R)‐2‐hydroxytetracosanoylamino]‐8‐en‐1,3,4‐octadecanetriol, (2S,3S,4R,8E)‐2‐[(R)‐2‐hydroxytricosanoylamino]‐8‐en‐1,3,4‐octadecanetriol, and (2S,3S,4R,8E)‐2‐[(R)‐2‐hydroxydocosanoylamino]‐8‐en‐1,3,4‐octadecanetriol.     

Headspace solid-phase microextraction combined with GC×GC-TOFMS for the analysis of volatile compounds of Coptis species rhizomes

In this study, the investigation of the volatile compounds of dried rhizomes of Coptis chinensis Franch, C. deltoidea C. Y. Cheng et Hsiao, and C. teeta Wall was carried out to complete the chemical composition of these valuable natural products. Volatile profiles were established and compared after headspace solid-phase microextraction (HS-SPME) using a polydimethylsiloxane/divinylbenzene (PDMS/DVB, 65 μm) fibre coupled to comprehensive 2D gas chromatography time-of-flight mass spectrometry (GC×GC-TOFMS). Analyses were performed and compared on two column-phase combinations (non-polar/polar and polar/non-polar). The majority of the identified compounds eluted as well-separated (pure) components as a result of high-resolution capability of the GC×GC method, which significantly reduces co-elution. Therefore, this increases the likelihood that pure mass spectra can be obtained. More than 290 volatile and semi-volatile organic compounds were tentatively characterized by means of GC×GC in tandem with TOFMS detection. Improved result interpretations were obtained in terms of compound classification based on the organized structure of the peaks of structurally related compounds in the GC×GC contour plot. These compounds are distributed over the chemical groups of hydrocarbons, acids, alkenes, alkynes, aldehydes, ketones, alcohols, esters, furans, and terpenoids. Among all the chemical groups, terpenoids present the higher number of identified compounds (44), alkenes (41), and aldehydes and ketones (28). This study completed the volatile phytochemical analysis of the headspace composition of various Coptis species rhizomes, and should serve as a means to identify the difference between the rhizomes and may also be useful to confirm individual species based on their volatile chemical profile.     

Relative tissue distribution and excretion studies of gastrodin and parishin from powder and extract of Gastrodiae Rhizoma in rat by UHPLC‐ESI‐MS/MS

New research has indicated that Gastrodiae Rhizome (GR) has potential anti‐diabetic and anti‐asthmatic effects in mouse models. On the basis of our previous study of the relative bioavailability of gastrodin (GAS) and parishin (PA) from extract and powder of GR, we performed further research on the tissue distribution and excretion of the two analytes. A reliable bioanalytical method for the quantification of GAS and PA in rat tissues and excretion is required. Chromatographic separation was carried out on a gradient mobile phase of acetonitrile–water with 0.1% formic acid. Calibration curves (1/x ² weighted) offered satisfactory linearity (r ² > 0.9835) within 100–3000 ng mL⁻¹ for GAS and (r ² > 0.9862) within 10–1000 ng mL⁻¹ for PA. The relative standard deviations of the intra‐day and inter‐day precision were all <14.98%, whilst the relative errors of the intra‐day and inter‐day accuracy were all within ±14.71%. The matrix effect and recovery values were satisfactory in all of the biological matrices examination. The data of relative differences in tissue distribution and excretion of GAS and PA from powder and extract of GR indicated that higher bioavailabilities for GAS and PA were obtained when a dosage of 4 g kg⁻¹ GR powder was used.     

Determination of Pesticides in the Rhizome of Traditional Chinese Medicines by Gas Chromatography with Electron Capture Detection

A simple and efficient gas chromatography method for the determination of 27 organochlorine and pyrethroid pesticides in traditional Chinese medicine was developed. Pesticide residues were extracted from the samples by oscillation and ultrasound, and purified by gel permeation chromatography and florisil solid phase extraction. The analysis was performed by gas chromatography with micro-electron capture detection. The purification conditions, such as the extraction and elution solvents, extraction methodology, and gel permeation chromatography conditions, were optimized. Traditional Chinese medicines were purified by different methods based on their composition. Under optimized conditions, the calibration graph was linear from 10 to 500 µg/L and the correlation coefficients varied from 0.9958 to 0.9997. The detection limits of these pesticides were between 0.09 and 1.82 µg/kg. The recovery of the pesticides spiked in various samples at four concentrations ranged from 73.2% to 106.4%, with relative standard deviations between 1.0% and 14.0%. This study indicates that the method is useful for determining pesticides in rhizome traditional Chinese medicines.     

铅锌矿区毛竹林土壤重金属的分布特征

铅锌矿开采对周边林地及农田土壤造成了较为严重的重金属污染。以我国分布面积广、经济效益高的毛竹林为对象,研究了铅锌矿区周边林分土壤中Cu,Zn,Pb和Cd四种重金属的分布特征,结果表明,毛竹根围土壤Cu,Zn,Pb和Cd含量分别为38.10～50.87,92.24～137.75,32.04～46.22和0.03～0.35mg.kg-1,明显低于非根围土壤,说明竹子发达的鞭根系统和频繁的人为抚育管理对土壤重金属浓度和分布有较大影响;从距离和坡位两个因素的影响来看,随距污染源距离增大,土壤中重金属含量呈下降趋势,且多以中坡位含量较高,上坡位较低。     

中药三七不同部位和组织的红外光谱分析

采用溴化钾压片法及傅里叶变换红外光谱技术对中药三七(Panax notoginseng)的剪口、主根、筋条、绒根等不同部位以及表皮、韧皮部、形成层和木部等不同组织的红外光谱及其二阶导数谱进行了研究。三七不同部位及组织红外光谱的整体峰形相似;在3 400,2 930,1 645,1 155,1 080和1 020cm-1附近有淀粉的特征吸收峰,其主体成分均为淀粉。但各部位和组织的红外光谱及其特征性化学成分有差异。剪口在1 077和1 152cm-1处峰的强度比大于其他部位,皂苷的含量最高。剪口及其表皮在1 317和780cm-1特征峰明显,含草酸钙;并且剪口表皮中草酸钙的含量比剪口中的含量高。绒根在1 384和825cm-1处有硝酸盐的特征峰,说明绒根富含硝酸盐类成分。主根表皮在2 926,2 854和1 740cm-1处的吸收峰较强,酯类成分的含量较高。形成层的红外光谱中酰胺Ⅰ带和酰胺Ⅱ带峰明显,富含蛋白质。由此可见,三七不同部位和组织的红外光谱及其二阶导数谱各有特征,不仅揭示了整体化学成分,还能提供有机大分子、无机小分子等特征性成分信息。红外光谱可用于三七及其不同部位和组织的准确、快速鉴别及质量评价。     

Studies on Triterpenoid Glycosides from Rhizomes of Panacis majoris and Their Antiplatelet Aggregation Activity

A new triterpenoid glycoside(1) and seven known triterpenoid glycosides, pseudoginsenoside RT2(2), yesanchinoside R2(3), vinaginsenoside R13(4), vinaginsenoside R8(5), notoginsenoside E(6), 6'-O-acetylginsenoside Re(7), 6"-O-acetylginsenoside Rb₁(8), were isolated from the rhizomes of Panacis majoris. The new triterpenoid glycoside was elucidated as 3-O-[β-D-glucopyranosyl-(1→2)-β-D-(6'-O-ethyl)-glucuronopyranosyl]-oleanolic acid-28-O-β-D-glucopyranoside by extensive spectroscopic and phytochemical methods. Compounds 2-8 were obtained from the plant for the first time. Compounds 3 and 4 displayed good activities against adenosine diphosphate (ADP)-induced platelet aggregation, and compounds 1, 5, 6 and 8 showed moderate activities. Compound 6 exhibited moderate antiplatelet aggregation activity induced by arachidonic acid(AA).     

半夏及其伪品天南星的近红外漫反射快速无损鉴别

利用近红外漫反射光谱法,结合聚类分析和相似度计算,对不同产地半夏药材及其伪品天南星进行了快速无损鉴别研究。近红外光谱图的聚类分析和相似度计算结果一致,为中药的产地、真伪鉴别分析提供了一种新的方法,具有较好的应用价值。