中国的中药微量元素研究Ⅴ.微量元素:中药质量控制不可或缺的特征参数

从中药鉴定、分类、组方解析、疗效相似药物筛选、质量控制5个方面综述了中国的中药微量元素质控研究概况.     

半夏中微量元素的测定及半夏模糊聚类分析

采用原子吸收分光光度法测定了20个不同产地半夏样品中Fe,Mn,Cu,Zn,Cr,Ca,Mg,Ni,Pb等9种元素的含量。由于不同产地的半夏中微量元素含量数据离散,根据一种或几种微量元素的含量难以评价药物的相似性,故以9种元素含量并结合Zn/Cu值和Ca/Mg值为指标,运用模糊聚类分析方法研究半夏药物的质量分类。结果显示,当阈值λ=0.55时,20个半夏样品聚为4类;当λ=0.65时,20个半夏样品聚为6类;当λ=0.70时,20个半夏样品聚为10类。半夏中微量元素含量丰富,微量元素的种类及含量与药物疗效密切相关。在高阈值λ上截取聚为一类的药物其组成与质量相似性较大,该研究为中药质量评价提供了一种新的方法。     

治疗小儿厌食症中药强壮灵冲剂微量元素测定及其与疗效关系探讨

已证明小儿厌食症除与缺乏微量元素锌关系密切外,还与其他多种微量元素和宏量元素的缺乏或低下也有关。本院以自行研制的中药强壮灵冲剂治疗小儿厌食症疗效显著。其于浸膏粉经２０余种微量元素测定表明含有锌、铁、钴、铜、镍、锰、铬、锗、锶、铝、钡、硒、硅、钛等多种人体必需且品种齐全,含量适度的微量元素。上述元素又恰是患儿体内所缺乏和低下的品种,无疑对患儿全面适度的补充大有裨益．中药强壮灵与西药硫酸锌临床对比研究表明,无论比发锌回升数值以及从厌食等全面疗效统计,中药组均明显优于西药组,并且发现疗效与药物的补锌量不成正相关。说明中药的调理脾胃功能及综合整体治疗作用是其突出优点,值得推广．     

相似系统理论用于中药色谱指纹图谱的相似度评价

研究了中药色谱指纹图谱相似度的评价方法,提出了改良的程度相似度的计算方法。以模拟数据和实验数据研究了相关系数、夹角余弦和改良程度相似度的优劣,发现相关系数和夹角余弦对数据的差异不够敏感,经预处理之后仍然不灵敏;采用改良的程度相似度可以反映数据的差异,因此可以将其用于评价中药色谱指纹图谱共有峰的相似度。     

甘肃干沙鄂博稀土矿床萤石成因研究

通过晚期与稀土元素矿化相关的萤石中流体包裹体岩相学、显微测温分析,以及萤石、矿石及碱性岩体的稀土及微量元素分析,系统地探讨了沙鄂博稀土矿床成矿流体的特征、成矿物质来源及萤石成因。与稀土矿化相关的晚期萤石中发育大量的熔体包裹体及流体-熔体包裹体,表明萤石归属于岩浆成因,同时表明成矿与岩浆作用有关。碱性斑岩体、晚期萤石和矿石的稀土元素具相似的配分模式,表现为向右陡倾的分配曲线。微量元素分析结果表明:含矿碱性岩体、晚期萤石和矿石均富集大离子亲石元素,并具明显的Ba, Th, Ce, Sr和Hf等负异常,微量元素蛛网图相似。含矿碱性岩体、矿石及与稀土矿化相关的萤石的稀土元素及微量元素的相似特征,表明成矿物质来自碱性岩体。通过包裹体、稀土与微量元素研究认为,干沙鄂博稀土矿床中萤石成因类型为岩浆成因非热液成因。     

微量元素与儿童健康

论述了常见微量元素与儿童健康的关系，并简要地介绍了部分常见微量元素对人体的作用。提出了一些微量元素缺少或过量的药物治疗方法。     

人参、当归中微量氟的离子色谱分析

近年来,对中药研究的报道大多数侧重于有机成份的分析,而对其中无机成份研究较少。文献报道了126种中药中微量元素的系统分析,但未对人体必需的十四种微量元素之一——氟进行测定。氟是人体必需的微量元素,对牙齿及骨骼的形成和结构,以及钙和磷的代谢均有重要的作用。维持人体内部微量元素平衡的主要来源是食物和药物,为此本文选用人参和当归二种中药,用离子色谱法测定其煎剂中的微量氟,对探讨中药中微量成份的分布与疗效之问的关系有着一定的意义,人参和当归中微量氟的离子色谱分析尚未见文献报道,本文提出了一种简便、快速、准确地测定中药煎剂中微量元素氟的可靠的分析方法。     

人体微量元素补充的最佳形式

论述了人体补充微量元素的几种主要方式,其中包括天然食物、无机化合物、有机化合物、复合微量元素药物和微量元素载体酵母等。     

小儿支气管哮喘与微量元素临床研究

为探讨微量元素与小儿支气管哮喘的发病关系,以及观察用微量元素治疗小儿支气管哮喘的效果,随机选择支气管哮喘患儿病例72例,进行了全血微量元素Zn、Cu、Fe、Ca的检测,同时使用Zn及Ca制剂治疗,观察其疗效。结果表明,小儿支气管哮喘与Zn、Ca缺乏及免疫功能低下有密切关系,补充上述两种元素对提高其免疫功能进而提高本病疗效有重要价值。     

青少年头发中六种微量元素含量随年龄增大的变化差异研究

研究了东北辽源地区5－20风不同年龄段的青少年,1147例头发中六种微量元素含量随着年龄增大的变化规律;既从单因素角度,又从多元素群体、多元统计分析方面研究了不同年龄段青少年头发元素含量的性别差异,相关系数差异及其群体微量元素谱图的差异。     

ICP-AES中乙醇作用机理的定量研究Ⅰ.乙醇干扰函数和各种干扰因素的相对贡献

本文应用Einstein-Boltzmann-Saha方程和Raoult-Clausius-Clapeyron方程,定量地考察了乙醇对电感耦合等离子体(ICP)中各种干扰因素的影响及各干扰因素对乙醇干扰效应(用干扰因子表示)的相对贡献。实验结果表明,Boltzman因子项和活度系数项的变化是乙醇增敏效应的主要来源。由实验结果分别提出了提升量、校正提升量变化后的干扰因子和活度系数项与乙醇浓度的关系方程。     

A simple radioisotope X-ray fluorescence method for provenance studies of archaeological ceramics employing principal component analysis

A simple radioisotope X-ray fluorescence method of 1000 s irradiation of the samples by a ¹⁰⁹Cd source combined with principal component analysis is described for determining the relative mass fractions of trace elements in majolica ceramics for provenance classification. Six provenances from Europe using 29 samples as standards and 12 unknown samples were investigated and characterized using selected trace elements as the variables. The unknown samples were previously assigned, but not definitively, by stylistic analysis and/or thermoluminescence measurements to the provenances of Teruel (Spain) and Holland. Because of a moderate fluorescence time, only the four net peak intensities of Pb, Rb, Sr and Zr could be used as variables. We have also studied the effect of not including the Pb variable, since the clay matrixes could have been contaminated in the glazing process or when the Pb-Sn enamel was removed. It is shown in both cases that the results were more consistent with the stylistic analysis and thermoluminescence measurements when the Pb concentration variable was not considered. A comparison of principal component analysis employing the three elements was similar to plotting of the relative mass fractions on a triangle graph.     

Determination of rare earth elements in fern leaves using instrumental neutron activation analysis

The lanthanides (REE) in 142 fern leaves collected from several sampling sites in Japan have been determined by neutron activation analysis, and the correlations between any two REEs in the logarithmic scattering diagram were examined. The relationship was expressed by the general formula, Y=aX+b with a correlation coefficient R. A strong positive correlation was seen between any two REEs in the diagram with a regression coefficient and a correlation coefficient close to unity. However, between Eu or Tb and other REEs the relationship was split into two lines with the same correlation coefficient. From the intercept b, the relative abundance of the two elements was determined for each REE and compared with those in hickory and tobacco leaves. These findings indicated that the abundance pattern of fern leaves is quite different from those of hickory and tobacco leaves. Namely, the relative abundance of La and Ce was quite similar in the three plants, but the abundance of the other REEs (Nd, Sm, Gd, Dy and Lu) was considerably lower in ferns than in hickory and tobacco leaves. For Eu and Tb the higher values obtained in fern leaves coincided with those of the two plants.     

X-射线荧光光谱法测定锆矿石中锆硅铁钛铝钙

采用熔片法制样,建立了X-射线荧光测定锆矿石中锆、硅、铁、钛、铝、钙的分析方法。使用国家一级标准物质与二氧化锆混合配制的混合标准物质,解决了锆矿石标准物质不足的问题。试样:硼酸锂混合熔剂为1:20,在熔样机中熔成玻璃片,采用经验系数法和散射线内标法校正元素间的谱线重叠效应和基体效应,对标准物质和混配的标准样品进行了分析,标准物质测定结果与推荐值一致,相对标准偏差（RSD%）均小于3.6%。方法能满足高含量锆矿石中主、次量元素的测定。     

EFFECT OF TISSUE ABSORPTION AND MICROSCOPE OPTICAL PARAMETERS ON THE DEPTH OF PENETRATION FOR FLUORESCENCE AND REFLECTANCE MEASUREMENTS OF TISSUE SAMPLES

Abstract— An equation has been derived that is concerned with the measurements of fluorescence or reflectance intensities in reflectance or incident light microscopy. A theoretical basis for the linear relationship between relative fluorescence and reflectance changes is given. This equation predicts both the contributions of different volume elements below the surface of a tissue sample to the total intensity and the depth of penetration of the measured intensities. The relationship requires knowledge of the effective focal points of the excitation beam and the apparent absorption coefficient of the sample. Two procedures are given to provide the empirical values of the effective focal point. The absorption coefficient of mouse liver tissue at 420 nm was determined to be 3.3/mm. The fluorescence intensities of liver slices of differing thickness containing pyrene butyric acid were measured and were found to compare favorably with the calculated values for tissue absorption of 3/mm.     

Separation of aqueous electrolyte solutions with asymmetric membranes containing one charged layer

The Nernst-Planck equation and fine-pore membrane model are applied to describe the ultra- and nanofiltration of electrolyte solutions through a inhomogeneous membrane containing one charged layer. Concentration and electric potential distributions, as well as dependences of electrolyte rejection coefficient (selectivity) and streaming potential on system parameters are determined. Asymmetry effect is revealed with respect to the rejection coefficient and streaming potential at different orientations of the selective charged layer relative to the direction of the filtration flow. The cases of 1: 1 and 1: 2 electrolytes are investigated in detail. Theoretical calculations demonstrate that the rejection coefficient of a bi-layer membrane rises in the following series of binary electrolytes: 1: 2 < 1: 1 < 2: 1, when the first layer is positively charged, and in the opposite series of these electrolytes, when the first layer is negatively charged.     

激光诱导击穿光谱(LIBS)法微损快速检测党参中Pb

中药材重金属元素快速检测对污染监控及人们健康具有重要意义。激光诱导击穿光谱技术(Laser Induced Breakdown Spectroscopy, LIBS)属于一种快速检测方法,研磨压片等预处理方法相对样品消解已有所简化,但破坏了样品的物理性质,且不能满足中药材大宗品种、大批量检测需求。若进一步简化样品预处理,将更加凸显LIBS快速检测的优势。本文建立了激光诱导击穿光谱技术(LIBS)快速微损检测中药材样品重金属元素定标方法。线性相关系数R2为0.7764,建立的微损定标曲线线性可用于切片党参LIBS快速检测,对待测党参切片样品检测平均相对误差为3.74%,与电感耦合等离子体质谱法(ICP-MS)对比,相关系数R2为0.7957,验证了LIBS技术微损检测的可行性。制备的党参参考定标样品可多次重复用于待测样定标和仪器标定等。实验对待测党参样品仅进行切片处理,避免了研磨、压片等预处理,更加充分地体现LIBS快速检测的优势,为LIBS技术应用于中药材重金属元素快检等领域提供了一种新方法。     

ICP-AES法测定方铅矿中多元素的方法研究

采用电感耦合等离子体原子发射光谱法(ICP-AES)进行方铅矿中多元素同时测定.通过对方铅矿样品化学处理试验建立了HCl-NH4Cl-HNO3的溶矿体系.本体系采用基体匹配、背景系数和元素干扰系数校正及元素内标法确定了最佳综合实验测试条件.本实验建立的ICP-AES法同时测定方铅矿中镉、钴、铜、铁、铟、铅、锌7种元素的方法,本方法测量相对误差RE (n=8)为1.50%～7.50%,相对标准偏差RSD (n=8)为1.7%～5.7%.经国家一级标准物质GBW 07269分析验证可以满足方铅矿单矿物样品的分析要求.     

Pair diffusion in quasi-one- and quasi-two-dimensional binary colloid suspensions

The authors report the results of measurements of the center of mass and relative pair diffusion coefficients in quasi-one-dimensional (q1D) and quasi-two-dimensional (q2D) binary colloid suspensions. The new results extend the findings of similar studies of one-component quasi-one-dimensional and quasi-two-dimensional colloid suspensions. Our principal new finding is that the presence of the smaller diameter component can destroy the oscillatory structure of the separation dependence of the q2D relative pair diffusion coefficient of the large particles even though the oscillatory character of the large particle equilibrium pair correlation function remains prominent, and that no such effect occurs with the q1D suspension. An interpretation of these results is proposed.     

Quantitative elemental analysis of nutritional,hazardous and pharmacologically active elements in medicinal Rhatany root using laser induced breakdown spectroscopy

Rhatany roots (RRs) have been used in indigenous systems of medicines to treat many common illnesses due to the presence of highly active astringent and antiviral biochemical constituents that possess strong therapeutic and pharmacological properties. Due to its widespread use, the accurate knowledge on the elemental composition of this medicinal plant can set a pharmacological research platform to investigate the effect of certain elements, and their ions in mediating the human metabolism and therapy. In this work calibration-free laser-induced breakdown spectroscopy (CF-LIBS) is used to detect the elements present in RRs sample, by analyzing the characteristic emission wavelengths and their respective intensities in the laser induced plasma, without the need for using any calibration standards or methods. Many nutritional elements, which are of human health significance and instrumental in mediating the established biological activities of RRs, were identified in a relative abundance. In addition to this, our analysis identified the trace level of a few toxic elements, whose overdose due to reckless intake wreaks havoc to human health and wellbeing. The reliability of qualitative and quantitative detection of the elements in RR by LIBS were validated by the standard inductively coupled plasma optical emission spectroscopy (ICP OES), the results of which are in good agreement with LIBS data with better relative accuracy. Also, in order to discriminate, and single out any two elements with the overlapping emission wavelength in LIBS, X-ray photoelectron spectroscopy was also carried out, which in its own right is in good agreement with the elemental analysis of LIBS in general.