半制备色谱柱的装填及其在中草药分离中的应用

对填料颗粒的尺寸和不同装填方法,即干法和匀浆法填充的半制备柱的柱效和分离效果进行了研究,并应用于中草药的分离。实验结果表明,粒径小的填料装填的柱效及其分离效果要远远优于粒径大的,匀浆法装填的分离结果好于干法且重现性好;对于芍药和银杏提取物使用自装填半制备色谱柱进行分离,可以得到满意的分离结果。     

International comparison of the determination of cadmium and lead in herb: the Comité Consultatif pour la Quantité de Matière (CCQM) pilot study CCQM-P97

A Comité Consultatif pour la Quantité de Matière (CCQM) inter-laboratory comparison program, CCQM-P97, for the analysis of cadmium and lead in Herba Demodii Styracifolii was organized by the Hong Kong Government Laboratory. The objective of the program was to establish comparability of trace metals analysis in herbal matrices amongst the participating national metrology institutes. The arithmetic mean values of the 13 participants were 0.3186 mg kg⁻¹ (RSD = 11.3%) and 1.650 mg kg⁻¹ (RSD = 11.0%) for cadmium and lead, respectively. The participants using double-isotope dilution mass spectrometry technique for their quantification were found to provide similar mean values to those of non-isotope dilution mass spectrometry users. The observation indicated that trace metal analysis in herbal matrices was not method-dependent, but the use of the highest metrological IDMS approach gave a better precision than other routine calibration methods.     

X射线荧光光谱法测定花草茶中22种元素

采用粉末压片法制样,应用X射线荧光光谱法对花草茶中N,Na,Mg,Al,Si,P,S,Cl,K,Ca,Ti,Cr,Mn,Fe,Ni,Cu,Zn,Br,Rb,Sr,Ba,Pb共22种元素进行了分析。讨论了测量条件的选择,对于22种目标元素的分析线,除Ba,Pb采用L线外,其余都选择K_α线,在对Rh靶K_α线的康普顿散射进行测量时,应适当降低管电压,选择合适的管电流。采用经验系数法和3条散射谱线(Rh靶L_α线的瑞利散射、0.1876nm处的散射线、Rh靶K_α线的康普顿散射)作内标进行基体效应校正,并对N,Na,Ca,Ti,Mn,Sr,Ba等部分元素进行了谱线重叠干扰校正。实验结果表明,该方法对N,Na,Mg,Al,Si,P,S,Cl,K,Ca,Ti,Cr,Mn,Fe,Ni,Cu,Zn,Br,Rb,Sr,Ba,Pb各目标元素的检出限较低,且准确度较好,精密度较高。采用该方法对花草茶中元素的种类和含量信息进行分析发现,花草茶元素组成较为丰富,不同种类花草茶元素种类和含量有差异,且同一种类不同来源花草茶略有差异,但元素组成含量特征大体相似。综上可知,该方法操作简单,能够实现花草茶的低成本、快速、准确、多元素测定。     

Quality assessment of traditional Chinese medicine herb couple by high‐performance liquid chromatography and mass spectrometry combined with chemometrics

This study was designed to develop a simple, specific and reliable method to overall analyze the chemical constituents in clematidis radix et rhizome/notopterygii rhizome et radix herb couple using high‐performance liquid chromatography coupled with tandem mass spectrometry and multiple chemometric analysis. First, the separation and qualitative analysis of herb couple was achieved on an Agilent Zorbax Eclipse Plus C₁₈ column (250 mm × 4.6 mm, 5 μm), and 69 compounds were unambiguously or tentatively identified. Moreover, in quantitative analysis, eight ingredients including six coumarins and two triterpenoid sapogenins were quantified by high‐performance liquid chromatography coupled with tandem mass spectrometry. In terms of good linearity (r² ≥ 0.9995) with a relatively wide concentration range, recovery (85.40–102.50%) and repeatability (0.99–4.45%), the validation results suggested the proposed method was reliable, and successfully used to analyze ten batches of herb couple samples. Then, hierarchical cluster analysis and principal component analysis were used to classify samples and search significant ingredients. The results showed that ten batches of herb couple samples were classified into three groups, and six compounds were found for its better quality control.     

纸基质室温磷光法快速测定中药材中西维因的研究

以快速定量滤纸为基质,用KI作为重原子微扰剂,建立了快速测定中药材中西维因的固体基质室温磷光(SS-RTP)分析法。其最大激发和发射波长分别为284nm与520nm。在优化的实验条件下,西维因在4×10-6~2×10-4mol/L浓度范围内呈现良好的线性关系。在样品体积为10μL时,方法的检出限为0.89ng/斑点。所建立的方法用于中草药中西维因残留量的测定。     

中药川芎和赤芍配伍规律的方法研究

提出应用HPLC-PAD-MS研究中药配伍多种化学成分的基本思路,指出应用色谱保留时间、紫外光谱及质谱等多信息、综合对照的方法确定合煎液中各峰的归属,从而进一步研究了中药的配伍规律.首先建立了一套稳定、重复而可靠的液相色谱分析方法进行分离,再用统一的分析方法对分离的色谱图进行数据处理.在HPLC-PAD-MS分析中可得到各成分的保留时间、紫外光谱和分子量信息.通过比较合煎液和单煎液中各成分的保留时间及分子量信息可确定合煎液各峰的归属,最后比较了单煎液和合煎液的化学成分变化.结果表明,川芎和赤芍配伍后有一新峰产生,同时有两个成分含量发生变化.     

动力学荧光法测定溴离子的研究

利用溴离子对溴酸钾氧化荧光素的催化作用，建立了动力学荧光法测定微量Ｂｒ＾－的新方法，方法的检出限为１．９４×１０＾－２μｇ／ｍＬ，线性范围为６．０～１２．０μｇ／２５ｍＬ，将方法用于溴吡斯的明药片中Ｂｒ＾－含量的测定，结果满意。     

Theoretical investigation on the interaction between Metformin and Ferulic acid - A DFT approach

We have theoretically studied the interaction of a commonly used drug, Metformin, with the herb, Ferulic acid, applying density functional theory (DFT). The complex was optimized at various positions and confirmed to be in their local minima through vibrational analysis at B3LYP/6–311++G7 level. Study on the molecular geometry along with the interaction energy of the complexes confirmed the presence of interaction between the hydroxyl and amine group of the herb and drug respectively. The calculation of Gibbs free energy and entropy exhibited the stability of the interacting structures along with the vibrational assignment which showed significant red and blue shifts in the complexes. Additionally, NBO analysis and molecular electrostatic potential (MEP) revealed the charge transfer between the complexes identifying an electrostatic interaction prevailing between the herb and drug.     

利用拉曼光谱技术检测中蒙药中朱砂的研究

朱砂有凉性、解热、收敛作用,一般以粉末状入药于中药或蒙药中。然而朱砂具有一定的毒性,因此有必要对药品中朱砂的含量进行检测分析。利用便携式拉曼光谱仪对朱砂进行了鉴别分析,获得了朱砂较为全面的分子结构振动信息。实验结果显示朱砂的拉曼光谱在253,290和343 cm-1等处出现了较强的拉曼特征峰,文中确定以此三处特征峰作为研究对象。同时,检测了蒙药八味止血红花散、朝伦-雄胡-5、外用溃疡散以及中药口腔溃疡散的拉曼光谱。结果在含有朱砂的几种蒙药八味止血红花散、朝伦-雄胡-5和外用溃疡散均检测到了朱砂的特征峰,而在不含有朱砂的中药口腔溃疡散中未检测到拉曼特征峰。此外,对口腔溃疡散中的朱砂进行半定量分析,检测极限可达到质量分数的10%左右。拟合得到了中药口腔溃疡散的拉曼光谱特征峰强度与其中朱砂的掺杂量之间的关系,获得曲线的相关系数r=0.995 9,验证了拟合结果的准确性。该拉曼光谱检测方法具有快速、简便、准确等优点,值得在中蒙药成分鉴定方面得到广泛的应用。     

HPLC法同时测定石蒜中加兰他敏和石蒜碱

建立了高效液相色谱同时测定石蒜中加兰他敏和石蒜碱含量的方法。 采用phenomenex-C18色谱柱,以乙腈(A)-0.1%TFA水溶液(B)为流动相梯度洗脱,检测波长289 nm。 结果表明,加兰他敏和石蒜碱均在0.5～10 mg/L(r=0.9999)呈现良好的线性关系,最低检测限(S/N=3)分别为0.09和0.15 mg/L,平均加样回收率分别为99.53%和96.82%。 该方法简单、快速、准确,适合于石蒜中加兰他敏和石蒜碱的测定。