小檗碱的药物代谢动力学

小檗碱是中药三棵针的主要有效成分之一，为了研究小檗碱的药物代谢动力学，本文采用胶束增敏荧光法对小檗碱在兔体内的血药浓度进行２４ｈ监测，求出毓药物代谢动力学参数，结果表明小檗碱在动物体内的Ｋａ为１．６３７ｈ＾－１，ｔ１／２（α） ０．３８６９ｈ，ｔ１／２（β）为６．７６ｈ，Ｋ２１为０．１５５３ｈ＾－１，Ｋ１２ｏ ０．０３８４ｈ＾－１，ＡＵＣ为２１１。９４μｇ．ｈ／ｍｌ。     

Small molecule-biopolymer interactions: Ultraviolet-visible and fluorescence spectroscopy and chemometrics

Interactions between small molecules with biopolymers e.g. the bovine serum albumin (BSA protein), are important, and significant information is recorded in the UV-vis and fluorescence spectra of their reaction mixtures. The extraction of this information is difficult conventionally and principally because there is significant overlapping of the spectra of the three analytes in the mixture. The interaction of berberine chloride (BC) and the BSA protein provides an interesting example of such complex systems. UV-vis and fluorescence spectra of BC and BSA mixtures were investigated in pH 7.4 Tris-HCl buffer at 37 °C. Two sample series were measured by each technique: (1) [BSA] was kept constant and the [BC] was varied and (2) [BC] was kept constant and the [BSA] was varied. This produced four spectral data matrices, which were combined into one expanded spectral matrix. This was processed by the multivariate curve resolution-alternating least squares method (MCR-ALS). The results produced: (1) the extracted pure BC, BSA and the BC-BSA complex spectra from the measured heavily overlapping composite responses, (2) the concentration profiles of BC, BSA and the BC-BSA complex, which are difficult to obtain by conventional means, and (3) estimates of the number of binding sites of BC.     

Quantitative Analysis of Berberine in Processed Coptis by Near-Infrared Diffuse Reflectance Spectroscopy

The near-infrared（NIR） diffuse reflectance spectroscopy was used to study the content of Berberine in the processed Coptis. The allocated proportions of Coptis to ginger, yellow liquor or Evodia rutaecarpa changed according to the results of orthogonal design as well as the temperature. For as withdrawing the full and effective information from the spectral data as possible, the spectral data was preprocessed through first derivative and multiplicative scatter correetion（MSC） according to the optimization results of different preprocessing methods. Firstly, the model was established by partial least squares（PLS）; the coefficient of determination（R2） of the prediction was 0.839, the root mean squared error of prediction（RMSEP） was 0.1422, and the mean relative error（RME） was 0.0276. Secondly, for reducing the dimension and removing noise, the spectral variables were highly effectively compressed via the wavelet transformation（WT） technology and the Haar wavelet was selected to decompose the spectral signals. After the wavelet coefficients from WT were input into the artificial neural network（ANN） instead of the spectra signal, the quantitative analysis model of Berberine in processed Coptis was established. The R^2 of the model was 0.9153, the RMSEP was 0.0444, and the RME was 0.0091. The values of appraisal index, namely R^2, RMSECV, and RME, indicate that the generalization ability and prediction precision of ANN are superior to those of PLS. The overall results show that NIR spectroscopy combined with ANN can be efficiently utilized for the rapid and accurate analysis of routine chemical compositions in Coptis. Accordingly, the result can provide technical support for the further analysis of Berberine and other components in processed Coptis. Simultaneously, the research can also offer the foundation of quantitative analysis of other NIR application.     

纳米金光度法测定药物中盐酸小檗碱

氯金酸用葡萄糖还原制得纳米金,最终获得浓度为2.4×10-4mol.L-1且呈酒红色的纳米金悬浮溶液。试验证实纳米金颗粒被均匀地分散在悬浮溶液中,其吸收光谱中在525 nm波长处出现一吸收峰。当在纳米金悬浮溶液中加入盐酸小檗碱,由于两者间的静电结合导致溶液在525 nm波长处的吸光度降低,且其降低的幅度与盐酸小檗碱浓度在2.0×10-7～3.0×10-6mol.L-1范围内呈线性关系,其检出限(3S/N)为1.7×10-8mol.L-1。应用此方法分析了3个批号的药物盐酸小檗碱或片剂样品,所测得的结果与按药典方法测得结果相符。     

Electrochemical Oxidation of Berberine and of Its Oxidation Products at a Glassy Carbon Electrode

The electrochemical behavior of berberine, an isoquinoline plant alkaloid with a wide spectrum of physiological effects, was studied at a glassy carbon electrode using cyclic, differential pulse and square‐wave voltammetry. The oxidation of berberine is a quasireversible, diffusion‐controlled process and occurred in a cascade mechanism with the formation of several oxidation products. The diffusion coefficient of berberine was calculated from cyclic voltammetry studies to be D=1.69×10^?6 cm² s^?1. The oxidation process of berberine is also pH dependent and the number of electrons and protons transferred was determined using differential pulse voltammetry. The formation of several oxidation products that adsorbed at the glassy carbon electrode surface was observed and their electrochemical behavior characterized. A mechanism for the oxidation of berberine at a glassy carbon electrode was proposed.     

Study on the inclusion interactions of berberine hydrochloride and cucurbit[7] by spectrofluorimetry

The inclusion interaction between berberine hydrochloride(BRH) and cucurbit[7](CB[7]) has been studied by spectro-fluorimetry. The result showed that CB[7]interaction with BRH to form a stable inclusion complex with an association constant of 9.57×10~4 L/mol and the fluorescence intensity of the complex was enhanced in 17 times higher than that of the studied drug itself. Based on the significant enhancement of fluorescence intensity of B RH in inclusion complex,a spetrofluorimetric method with high sens...     

小檗碱-[AuI4]-缔合纳米微粒体系的吸收光谱研究及分析应用

在0.008 mol·L-1HCl介质中, Au(Ⅲ)与I-形成[AuI4]-; [AuI4]-和小檗碱(BB)通过静电引力作用形成疏水性的(AuI4-BB)缔合物分子. 由于(AuI4-BB)缔合物分子间存在较强的分子间作用力和疏水作用力而生成橙黄色(AuI4-BB)n缔合纳米微粒, 在520 nm处产生一个共振散射峰; 其吸收峰仍位于[AuI4]-的吸收峰350 nm处, 但在可见光范围内的吸光度增大. 在选定条件下, BB浓度在0.8×10-6～20×10-6 mol·L-1范围内与A450 nm呈线性关系. 实验结果表明, (AuI4-BB)n缔合纳米微粒的形成是产生共振散射的根本原因.     

Optical sensor for berberine utilizing its intrinsic fluorescence enhanced by the formation of inclusion complex with butylated-β-cyclodextrin

An optical sensor for berberine, the basic ingredient of the widely used traditional Chinese medicine Coptis Chinensis, based on its intrinsic fluorescence enhanced by butylated-β-cyclodextrin (HDB-β-CD) immobilized in plasticized poly(vinyl chloride) (PVC) membrane has been developed. The drastic enhancement of fluorescence intensity of berberine was attributed to the formation of an inclusion complex between HDB-β-CD and berberine, which has been utilized as the basis of the fabrication of a berberine-sensitive fluorescence sensor. The proposed sensor was quite distinct from those fluorescent sensors for berberine reported so far which relied upon quenching the fluorescence of the sensing reagent immobilized on membrane by berberine. The response mechanism of optode membrane was discussed in detail from the view of molecular dynamics and the optimum steric configuration of the inclusion complex was presented by molecular dynamics simulation. The analytical performance characteristics of the proposed berberine-sensitive sensor were investigated. The sensor can be applied to the quantification of berberine with a linear range covering from 4.0×10⁻⁷ to 2.0×10⁻⁵ mol l⁻¹ with a detection limit of 8.0×10⁻⁸ mol l⁻¹. The sensor exhibits excellent reproducibility, reversibility and selectivity. The recommended method was successfully used for the determination of berberine in pharmaceutical preparations.     

Capillary zone electrophoresis as a tool for the quality control of goldenseal extracts

The root extracts of goldenseal (Hydrastis canadensis L.) are popular phytomedicines for the treatment of gastrointestinal disorders and upper respiratory tract infections. Here we describe a simple and fast capillary zone electrophoresis (CZE) method with ultraviolet detection at 225 nm for the quantification of the major goldenseal constituents, berberine and hydrastine, in herbal remedies containing goldenseal root extracts. Tritoqualine, an antihistaminic drug with a hydrastine-like phthalidisoquinoline structure, was applied as an internal standard. The running buffer was a 1:5 mixture of 500 mM ammonium acetate (adjusted to pH 3.4 with acetic acid) and methanol. Our newly developed CZE method was validated regarding limit of detection (LOD), limit of quantification, linearity, accuracy and precision. For both berberine and hydrastine, the LOD was 1.0 microg/mL and the linearity was obtained between 2.5 and 500 microg/mL. Using our newly developed method, both the alkaloids could be analysed in herbal remedies containing goldenseal root extracts within 8 min.     

表面增强拉曼光谱研究小檗碱与DNA的相互作用

用表面增强拉曼光谱研究了小檗碱（BER）与小牛胸腺DNA（ct DNA)的相互作用,并对重要谱峰进行了归属。在Ag胶体系中,小檗碱分子的拉曼信号增强显著,表明小檗碱阳离子键合到银胶粒子的表面。加入ct NA之后,小檗碱分子的大部分SERS带的强度进一步增加,而仅有少数几个带的信号强度趋于消失,可能是小檗碱分子的异喹啉部分键合到DNA的小沟槽,小檗碱与DNA的相互作用模式主要是通过静电力及疏水相互作用,吸收光谱表明,Ag胶体系的存在并未改变小檗碱分子与DNA的相互作用模式。