基于化学计量学结合ICP-MS的党参道地性的研究及安全评价

微量元素与中药的功效和安全性密切相关,也是药材道地性研究的一部分,为探讨党参中重金属元素的安全性、风险性及道地性的相关性。本文采用电感耦合等离子体质谱法（ICP-MS）及原子荧光光谱法(AFS)测定来源于甘肃、山西、湖北、四川等产区的39批党参药材中的20种元素的含量,结果结合化学计量学分析对党参产区进行差异判别。通过单因子污染指数法和内梅罗综合污染指数法对其进行安全性评价,通过健康风险基于暴露量、危害指数法和暴露限值法对其进行风险评估。结果表明,重金属在各自范围内线性关系良好,加样回收率,仪器精密度和重复性良好,其中 Ba、Sr、Mn的含量最高。主成分分析显示39批药材分为三类,同一产区的党参能较好的聚在一起,元素含量差异与产区分布有一定规律,其中Cs、Ga、As、Co、Li、Pb、Hg、Se、V、Mn为关键的差异标志物,为产地元素特征分析鉴别提供依据。安全评价结果为39批党参药材污染等级为安全,但风险评估后DS-31、DS-32、DS-34、DS-36及 DS-37在人体长期蓄积中具有健康风险。结论：本研究方法高效、准确、简便,结合化学计量学可以对党参进行有效的产地判别,评价党参中元素的安全性及风险性,为党参道地性及健康评价提供了科学依据。     

滋补药材川明参的化学成分分析

综合报道我国特有滋补药材川明参的化学成分分析.川明参含有大量线性呋喃香豆素和少量简单香豆素、三萜、黄酮和甾体等化合物.分析表明不同产地和不同部位川明参的化学成分结构类型相似,但所含化合物的具体结构存在较大差别,在开发和应用时应引起注意.     

白芍中芍药甙及元素含量的测定

用薄层扫描法和等离子体发射光谱法分别测定了不同产地白芍中芍药甙及元素的含量。     

南雄银杏叶中内酯的高效液相色谱法测定

用高效液相法分析了广东省南雄市不同采收时间，不同树龄的银杏叶中的银杏内酯含量；采用Kromasil C18柱、甲醇－水－四氢呋喃流动相、流速1mL/min、差示折光检测器、柱温35℃、外标法定量，样品用聚酰胺柱纯化，获得了满意的分离效果；结果表明银杏内酯含量随树龄不同，采收时间不同而不同，南雄银杏叶内酯平均含量为0．23％（w）。     

不同产地金银花药材的HPCE指纹图谱分析

以40mmoL/L硼砂溶液为缓冲液,利用高效毛细管电泳(HPCE)法,建立不同产地金银花的HPCE指纹图谱并测定其中绿原酸的含量。工作电压为17kV,温度为25℃,压力进样时间为6s。不同产地金银花药材中绿原酸的含量为3.2%4.4%。通过对HPCE指纹图谱共有峰数据进行判别分析和聚类分析,可以将不同产地的金银花进行判别分类。HPCE指纹图谱可以用于较全面地考察金银花药材的质量。     

不同产地黄芩中黄芩甙及元素的含量比较

用高效液相色谱法和原子吸收光谱法分别对１０个不同产地正品黄芩中黄芩甙及元素的含量进行了分析比较。     

纹党参与白条党参红外光谱的SIMCA聚类鉴别方法研究

以纹党参和白条党参的红外光谱为聚类分析的对象,研究了红外光谱结合SIMCA聚类分析法对纹党参和白条党参进行识别与分类的可行性.选取400 ～2 000 cm~(-1)范围内的光谱,通过基线补偿(Offset)和散射校正(MSC)等预处理后,采用SIMCA聚类分析法建立识别模型.结果表明,所建模型对纹党参和白条党参的识别率分别达92%和96%,拒绝率均为100%.用盲样对所建模型进行了测试,测试结果全部正确.该法可实现对纹党参和白条党参的快速鉴别.     

豫产桔梗的土壤与药材中部分微量元素含量与分析

为了解桔梗中微量元素含量特征,研究土壤中微量元素对桔梗药材道地性的影响,采用原子吸收光谱法、冷原子荧光法、双道原子荧光法对不同产地的桔梗药材及生境土壤中8种微量元素含量进行了测定,所得数据用SPSS 11.0软件进行分析比较。结果表明,不同产地的桔梗微量元素含量有差异;药材与土壤中微量元素之间具有相关性。桔梗对土壤中微量元素是主动与被动相结合的有选择吸收。     

色谱数据可视化及天然植物药指纹特征发现方法

提出一类色谱分析数据可视化方法,并用于发现天然植物药的化学指纹特征。选取中药材川芎作为典型研究对象,采用核主成分分析和空间投影变换法对色谱分析数据进行预处理,提取特征信息,再利用二维灰度映像对变换后的数据进行可视化表达,发现其化学指纹特征,从而直接反映出药材质量类别间的化学模式差异。将该方法用于辨识34个不同产地及等级的川芎样品,结果令人满意,证明其具有视觉模式分辨优点,是表达隐含特征指纹和辨识复杂化学物质体系的有力工具。     

UV–化学模式识别不同产地的丹参

建立由UV–化学模式识别法评价丹参质量的方法。分别用正己烷、乙酸乙酯、水、乙醇提取不同产地的丹参,并测绘其紫外光谱。取紫外光谱各波长的吸光度为特征数据,进行主成分分析、聚类分析,对不同产地丹参质量的差异进行了评价。不同溶剂提取液的光谱聚类结果有所差异,可将不同产地丹参聚为3类。UV–化学模式识别技术可以从整体上反应丹参所含成分的差异,可为丹参质量控制与评价提供依据。     

Use of capillary electrophoresis to monitor wheat maturation

Summary The maturation of wheat varieties with different harvest times has been examined by high-performance capillary electrophoresis. The unique proteins of the albumin, gliadin and glutenin fractions of Hungarian winter wheat cultivars Bánkúti 1201 (early harvest time), Martonvásári 23 (medium harvest time), and Martonvásári 15 (semi-late harvest time) were analysed. An acidic phosphate buffer containing a polymeric additive and organic modifiers was used in capillary zone electrophoresis mode. Formation of albumin followed the same time scale, and the patterns were quite similar, for all three cultivars. For gliadins and glutenins the time scale and patterns were different and some correlation was observed between harvest time and gliadin formation. Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001     

烟草及香烟中锌的溶出特性及其形态探讨

为探讨烟草和香烟中微量元素锌的存在形态，采用不同极性溶剂做萃取剂，分别萃取了白肋烟叶和两种品牌香烟中的锌，并用火焰原子吸收分光光度法（FAAS）测定了萃取液中的锌含量。结果表明，烟草和香烟丝中锌主要是以水溶态的无机Zn^2＋或水溶态的低相对分子质量有机态结合锌形式存在；烟草对锌的利用率高。     

Analytical Assessment of Bioelements in Various Types of Black Teas from Different Geographical Origins in View of Chemometric Approach

A comprehensive approach to the mineral composition of black teas of different origins was studied using the Flame Atomic Absorption Spectrometry (FAAS) method, supported by chemometric tools including Principal Component Analysis PCA) and Classification and Regression Trees (CART). Significant differences between the teas from seven countries (Japan, Nepal, Kenya, Iran, Sri Lanka, India, and China) were shown. K was the main element determined in all teas, with an average concentration of 11,649 mg/kg, followed by Ca, Mg and Mn. In general, regarding all investigated black teas, the element content was ranked in the following order: K > Ca > Mg > Mn > Fe > Na > Zn > Cu. The applied chemometric methods allowed us to recognize black tea clusters based on their mineral composition and place of cultivation, and allowed us to find correlations between particular elements in black teas. The performed analyses revealed interesting correlations between the concentration of various elements in black teas: K was negatively correlated with Na, Fe, Mn and Cu; K was positively correlated with the content of Ca and Mg. Significant positive correlations between Mn and Fe and Mn and Zn in the studied black tea samples were also revealed. It was shown that mineral composition may be a significant factor regarding the origin of the black tea, not only considering the country, but also the region or province.     

FAAS法测定鸡血藤中的微量元素

为研究金属元素在鸡血藤中的含量与药用功能采用标准曲线法,用空气-乙炔火焰原子吸收光谱法测定了鸡血藤中多种微量元素的含量。结果表明,方法的加标回收率在97．50％～99．60％范围内,RSD（n=6）在0．36％～0．57％之间。测定方法简单易行,方便快捷。     

Application of silica gel organofunctionalized with 3(1-imidazolyl)propyl in an on-line preconcentration system for the determination of copper by FAAS

This study presents a new procedure for the determination of trace levels of copper(II) in an aqueous matrix, through flow injection (FI) on-line preconcentration with a minicolumn packed with silica gel modified with 3(1-imidazolyl)propyl groups. After the preconcentration stage, the analyte was eluted with a HNO₃ solution and determined by flame atomic absorption spectrometry (FAAS). The measurements of the analytical signals were carried out as peak area and peak height with the objective of evaluating the most appropriate absorption measurement for the proposed method. Four procedures to calculate the experimental enrichment factor (EF) were also studied. For a preconcentration time of 90 s the enrichment factors found in this study varied between 19.5-25.8 and 36.2-42.2 for peak area and peak height, respectively. The precision of the proposed method was calculated for a solution containing 20 μg l⁻¹ of Cu(II), when 11.2 ml of solution was preconcentrated (n=7), and their respective relative standard deviation (R.S.D.) values were 1.2 and 1.4% for peak area and peak height, respectively. The detection limits obtained were 0.4 and 0.2 μg l⁻¹ of Cu(II) for peak area and peak height, respectively, with a preconcentration time of 90 s. The on-line preconcentration system accuracy was evaluated through a recovery test on the aqueous samples and analysis of a certified material.     

Metabolomics analysis of Ligustri Lucidi Fructus at different harvest times during the whole growing period based on ultra-high-performance liquid chromatography with mass spectrometry

After medicinal market research, it was found that the harvest time of Ligustri Lucidi Fructus (LLF) was chaotic in practice. In order to determine the optimal harvest period of LLF to ensure its pharmacological activity, metabolomics analysis of LLF at different harvest times based on ultra-high-performance liquid chromatography-triple quadrupole-(linear ion trap)-tandem mass spectrometry was established. In this study, 166 differential metabolites (DMs) in 448 metabolites at different harvest times were screened out based on variable importance in projection value, and among them, 94 DMs with regular trends of change in relative content (59 increased and 35 decreased with the growth period) were chosen to further research. The result of the multivariate statistical analysis showed that November was the optimal harvest period of LLF. Additionally, 10-hydroxyligustroside, oleoside 11-methyl ester, and salidroside were screened out to be used as the evaluation indicators of immature LLF, while specnuezhenide, nuezhenoside G13, and neonuezhenide were the evaluation indicators of mature LLF. This study provides fundamental insight for metabolite identification and proposes the best harvest period of LLF to avoid confusion in the medicinal market.     

浊点萃取-火焰原子吸收光谱法测定矿渣中痕量金

研究了以双硫腙为络合剂,以非离子型表面活性剂Triton X-100为萃取剂的浊点萃取-火焰原子吸收光谱法(CPE-FAAS)测定痕量金(Ⅲ)的新方法。详细考察了溶液的pH值、络合剂和表面活性剂浓度、平衡温度和时间等条件对浊点萃取效果的影响。该方法的线性范围为0.05~0.8μg/mL,检出限为7.9 ng/mL,相对标准偏差为4.12%(n=11),回收率在98.0%~102.0%之间,用于矿渣中金的测定,结果满意。     

Enantiodivergent synthesis of cyclobutyl-(Z)-α,β-dehydro-α-amino acid derivatives from (−)-cis-pinononic acid

The two enantiomers of the title dehydroamino acids (DHAAs) have been synthesized through respective Wadsworth–Emmons condensations of a suitable phosphonate with enantiomeric cyclobutyl aldehydes. These compounds, in turn, were prepared by selective manipulation of the functional groups starting from (−)-cis-pinononic acid as the common chiral precursor. The CD spectra of the prepared DHAAs are described. These products are suitable for the stereocontrolled synthesis of diferent types of saturated cyclobutyl amino acids and their derivatives.     

电渗泵—流动注射在线稀释法在火焰原子吸收光谱分析高浓度样品中？…

采用电渗泵流动注射－火焰原子吸收法（ＦＩ－ＦＡＡＳ）,研究了高浓度镁样品的在线稀释和分析。电渗泵在低流量时有很好的稳定性。利用控制采样时间的办法,可以准确采集微量样品,在线稀释。同时使用Ｔ型客对雾化量进行补偿,在线稀释倍数可达１０００以上,相对标准偏差〈１．５％（ｎ＝６）。通过改变采样电压（速度）,载流速度和采样时间可以方便地得到不同的稀释倍数,测定速度可达１００个／ｈ样品以上。     

SYNTHESIS AND CHARACTERIZATION OF SOME THERMOTROPIC LIQUID CRYSTALLINE POLYAMIDES

A series of novel mesogenic polyamides containing a flexible pendent side group wassynthesized by solution condensation polymerization. The new monomers, diacids and di-amines containing flexible elements of diferent lengths, were also synthesized and character-ized by ~1HNMR, mass spectroscopy and elemental analysis. The polymers were character-ized by viscosity measurements, differential scanning calorimetry (DSC), X-ray diffiactionand polarizing optical microscopy These studies revealed that polyamides containingflexible elements of a sufficient length exhibited thermotropic liquid crystalline(LC) pro-perties. The melting temperatures of this series of polymers were particularly sensitive tothe length of the flexible segment on the main chain and that of the flexible pendent esterside chain. Lyotropic LC behaviours were also observed in solution.