中药配方颗粒红外指纹图谱研究

采用傅里叶变换红外光谱(FTIR)技术分析鉴别了350种中药配方颗粒红外指纹图谱的结构特征。结果表明，借助于各种药用植物和动物配方颗粒的FTIR指纹图谱的差别可进行快速分类鉴别；根据配方颗粒与中药原药材谱图之间的相关性，以及中药材经过炮制、加热、水提处理后，配方颗粒与原药材之间在谱图上所代表的化学成分上的异同可以进行中药配方颗粒的质量控制；凭借不同炮制方法与未经炮制处理的配方颗粒间FTIR谱图的差别，可以进一步分析炮制后配方颗粒化学成分的变化，不同炮制方法对配方颗粒化学成分的影响；对于不同厂家的配方颗粒及同一厂家不同生产批号的配方颗粒也进行了较系统的分析研究。方法快速，简便，专属性强，不需对样品进行分离提取。     

中药注射剂三维荧光等高线图识别程序的设计与检验

用统计模式识别法设计了中药注射剂三维荧光指纹图谱的识别程序,对刺五加、红花、血栓通和香丹4种注射剂进行了识别,识别结果正确。研究表明:该程序分辨率高,便于自动化,可用于中药注射剂的真伪鉴别和质量监控。     

基于自组织映射神经网络的中药注射剂质量快速鉴别方法

将近红外光谱分析技术与人工神经网络相结合,研究提出一种基于自组织映射神经网络的近红外光谱神经元分类模型,用于对中药注射剂产品的近红外光谱进行计算分析,可实现对注射剂质量的快速鉴别。以3个不同厂家生产的参麦注射剂为研究对象,考察本方法的分类能力,其分类正确率达到96.4%,优于参与比较的判别式偏最小二乘法(90.5%)、反向传播神经网络(88.1%)和支持向量机(90.5%)。     

中药配方颗粒红外光谱法的快速鉴别

采用红外光谱法对中药配方颗粒及其辅料进行了鉴别研究。结果表明：不同生产厂商的配方颗粒中所添加的辅料类型及用量有较大差别；不同种的配方颗粒在辅料含量较低的情况下有较明显的指纹性，而辅料含量较高时，采用差谱技术可以提高谱图的指纹性，达到中药配方颗粒--鉴别的目的。该法简便、快速、可靠，是中药配方颗粒宏观质控的一个强有力的手段。     

红外光谱分析数据特征指纹的可视化表达方法

提出一类红外光谱分析数据特征指纹的可视化表达方法。该方法采用基于贝叶斯准则的多元统计方法对原始数据进行投影变换，再以地维灰度图对变换后数据进行可视化表征，形成基于计算机图像的虚拟化学指纹图谱。将其用于鉴别3种不同产地中药当归样品的结果表明，它能有效提取红外光谱分析数据的特征指纹，实现以虚拟指纹图谱对药材产地的分类鉴别，从而为辨识复杂化学物质体系提供了新的技术手段。     

红外光谱法直接鉴别苦丁茶的研究

本文利用傅立叶变换红外光谱(FTIR)法快速、直接地测定了11种苦丁茶,并对所获得的指纹图谱进行特征峰指认和对比分析。结果表明:各种苦丁茶化学成分相同,而由于各成分间的相对含量的不同,使每种样品都有自己独特的红外谱图,不同产地、不同级别苦丁茶的红外吸收频率、吸收峰的相对强度都存在比较大的差异。同时还运用傅立叶变换红外光谱技术对不同产地、不同级别苦丁茶的混合化学体系进行了全组分快速分析,为苦丁茶的鉴别及质量控制提供了可靠的依据。     

松香及其改性产品的红外光谱法快速鉴别

由于松香、马来松香、聚合松香、歧化松香和氢化松香及其酯等松香深加工产品外观相似,很难凭感官鉴别,给执法部门的监管和企业产品的质量控制造成很大困难。本文通过选用不同松香深加工产品作为研究对象,分类别比较其傅里叶红外光谱和二阶导数红外光谱,对其进行快速鉴别。研究表明:利用红外光谱和二阶导数红外光谱特征吸收峰的位置和吸收强度等差异信息可将它们快速准确鉴别。     

红外三级鉴定法快速鉴别山豆根和北豆根

采用红外光谱三级鉴定法对山豆根和北豆根进行了鉴别研究。结果表明:山豆根和北豆根均含有饱和脂肪酸酯、芳香类化合物、黄酮类化合物和糖苷类化合物等物质。在一维红外光谱中,山豆根1 736、1 249cm-1和1 614、1 514、1 424cm-1峰的相对强度均比北豆根弱,说明山豆根中饱和脂肪酸酯成分、芳香类物质的含量低于北豆根。在高分辨率的二阶导数谱中,根据两者的差异可进一步发现山豆根和北豆根所含的饱和脂肪酸酯类成分存在差异,且北豆根中的芳香类物质含量比山豆根的高,而山豆根中淀粉的相对含量则高于北豆根。而二维相关红外光谱中,根据两者自动峰数目、位置和相对峰强度的差异,可进一步推断山豆根和北豆根所含的黄酮成分、糖苷类化合物是不一致的。因此,红外光谱三级鉴定法可为中药真伪鉴别提供一种快速、无损、整体、客观的方法。     

南北五味子醇提液的荧光光谱鉴别

建立了用荧光光谱法快速鉴别五味子和部分含五味子制剂中五味子药材种属的方法. 研究了五味子中的五味子醇甲、五味子酯甲、五味子甲素、五味子乙素和安五脂素5种活性成分以及南北五味子和护肝片的乙醇提取液的荧光光谱,并用高效液相色谱测定了供试品中5种活性成分的含量. 结果表明,安五脂素和五味子乙素具有强荧光性且峰形差异显著,五味子甲素和五味子醇甲的荧光性较弱,而五味子酯甲不具有荧光性;南北五味子的主要荧光物质分别为安五脂素和五味子乙素,据此可用乙醇提取液的荧光光谱快速鉴别南北五味子.     

南北五味子荧光光谱差异的原因

建立了用荧光法快速鉴别五味子和部分含五味子制剂中五味子是属于北五味子还是南五味子的方法,探明了南北五味子荧光光谱差异的主要原因。研究了五味子的五种活性成分五味子醇甲、五味子酯甲、五味子甲素、五味子乙素和安五脂素的荧光性质和五味子以及护肝片乙醇提取液的荧光光谱,并用高效液相色谱测定了供试品五种活性成分的含量。研究表明：发光效率按安五脂素、五味子乙素、五味子甲素和五味子醇甲依次减弱,五味子酯甲不具有荧光性;北五味子的主要荧光物质为五味子乙素,而南五味子的主要荧光物质是安五脂素,它们是导致南北五味子荧光光谱差异的主要原因。用荧光法鉴别南北五味子具有简单、快速和灵敏的特点     

Tentative fingerprint-efficacy study of Houttuynia cordata injection in quality control of traditional Chinese medicine

To establish potent fingerprint for quality control of traditional Chinese medicine, Houttuynia cordata (Saururaceae) injection (HCI), the attempt on fingerprint-efficacy was developed in this study. HCI from ten different factories were determined by gas chromatography-mass spectrum (GC-MS) and classified by hierarchical clustering. The anti-inflammatory effect of HCI was characterized with the rat pleurisy model induced by carrageenin and the mice ear edema model by xylene. The results showed that anti-inflammatory effect of the injections from most of factories on the two models was significant. There was corresponding relationship between the fingerprint of HCI and efficacy to certain extent. The main common constitutes in injection from the factories that possess anti-inflammatory activity were analysed with GC-MS and identified using the NIST Mass Spectral Database. This common pattern of HCI based on the efficacy was helpful for the purpose of quality control.     

Qualitative and quantitative analysis of cinobufacini injection using rapid separation liquid chromatography coupled with quadrupole‐time‐of‐flight mass spectrometry and HPLC‐photodiode array detection,a feasible strategy for the quality control of Chinese medicine injections

Cinobufacini injection, prepared from the skin of Bufo bufo gargarizans Cantor, has presented its significant effects on the treatment of hepatitis and various cancers in the clinic. However, as an unclear complex chemical system, the optimization of its quality control markers has been a long‐term challenge. In present study, a feasible strategy integrated markers screening, determination, and statistical analysis was efficiently proposed, especially for the undefined Chinese medicine injections. First, rapid separation LC‐quadrupole‐TOF‐MS method was applied in the identification of 19 major compounds in the cinobufacini injection for the first time. Further, nine high‐level contents active compounds were selected as quality control markers for the quantification analysis. An acceptable and validated determination method was established in 17 batches of cinobufacini injection by HPLC‐photodiode array detection method, including linear regression relationship (r², 0.9996–1), precisions (RSD, 0.02–1.35%), repeatability (RSD, 0.05–1.97%), stability (RSD, 0.1–3.85%), and recovery (95.88–104.89%). Each analyte was detected at its maximum ultraviolet spectra wavelength. Finally, based on the quantification results, principal component analysis was performed on the quality assessment of cinobufacini injections. This three‐step strategy provides a newly feasible solution for the quality control of Chinese medicine injections.     

中药材提取物的混批勾兑研究

采用非线性最小二乘拟合计算中药材提取物的勾兑系数,不同批的中药材提取物经过勾兑后与参照样品的差异减小,各成分含量稳定。采用数据预处理的方法,并对数据预处理方法进行改进,使峰面积较小的色谱峰可以实现较小的相对差异。引入误差控制系数,可实现对特定色谱峰的控制要求。实验结果表明,非线性最小二乘拟合可以用于计算中药材提取物的勾兑系数。     

The quality assessment of compound liquorice tablets by capillary electrophoresis fingerprints.

Capillary electrophoresis (CE) is a powerful separation technique that is peculiarly able to determine the fingerprints of traditional Chinese medicine. The Capillary Electrophoresis Fingerprints (CEFP) of compound liquorice tablets (CLTs) was established to evaluate the quality of CLTs. The background electrolyte was a 50 mM sodium borate solution. The detection wavelength was 228 nm and a 14 kV voltage was applied. Hydrochlorothiazide served as an internal standard and temperature was 24-25 degrees C. The CLTs were extracted by a 50 mM borate solution containing 10% (v/v) methanol. The results showed that CE was a powerful tool for detecting of the fingerprints of traditional Chinese medicine and their constituents. The quality assessments were performed to compare the correlation coefficients (R) and cos theta (C) between each batch vector of CLTs and the total standard profile vector (TSPV), which was the mean vector of all the batch vectors of CLTs with 1.0. The nearer to 1.0 was the R or C, the higher was the similarity. The values of R and C between the TSPV and each batch vector of CLTs produced at different factories were all above 0.9150. The values of R and C between every two standard profile vectors (SPV) from different factories were all above 0.9420. A good stability and reproducibility of the CEFP of CLTs were obtained in the study. Further, we first put forward a new parameter Q to evaluate both the quantification accuracy and the qualitative accuracy for a CEFP, which was verified by determinations of GHIA, GHEA, MP and SB in CLTs. The CEFP was successfully employed to assess the quality of CLTs produced at Kunming Pharmaceutical Factory to be good.     

指纹图谱法在参麦注射液质控中的应用

 中医药理论和实践要求综合评价中药的质量 ,指纹图谱法是对中药制剂进行综合宏观分析的可行手段之一 ,因此采用反相高效液相建立了参麦注射液的特征指纹图谱。条件 :Hypersil C18(4 6mmi d × 2 5 0mm ,5 μm)反相柱 ,流动相由水 (A)和乙腈 (B)组成 ,B的体积分数在 5 0min内由 5 %线性增长到 95 % ,流速为1 0mL/min ;紫外检测 ,波长为 2 0 2nm。 2 3个特征指纹峰与内标 (联苯 )的峰面积比作为指标 ,结合主成分分析 投影判别法比较了同一厂家不同批次产品和不同厂家同类产品的化学指纹差异。     

A pseudotargeted method based on sequential window acquisition of all theoretical spectra mass spectrometry acquisition and its application in quality assessment of traditional Chinese medicine preparation-Yuanhu Zhitong tablet

Quality control plays a key role in the application of Chinese materia medica, especially in the preparation of traditional Chinese medicine. A pseudotargeted analysis method using an ultra-high-performance liquid chromatography-quadrupole-time-of-flight-mass spectrometry that was operated in the sequential window acquisition of all theoretical spectra mode was proposed to explore the chemical markers of traditional Chinese medicine preparation. Full-scan-based untargeted analysis was applied to extract the target ions. After data preprocessing, 302 target ions were extracted and used for the subsequent sequential window acquisition of all theoretical spectra analyses. The established sequential window acquisition of all theoretical spectra-based pseudotargeted approaches exhibited good repeatability and a wide linear range. The established method was successfully applied to discover analytical markers for the Yuanhu Zhitong tablet. After multivariate statistical analysis, 94 potential markers were identified. Ten markers were annotated by matching accurate m/z and product ion information obtained from previous reports. It is clearly indicated that the pseudotargeted analysis could make a great contribution to the quality assessment of traditional Chinese medicine preparation as a newly emerging technique.     

基于三波长融合谱的系统指纹定量法鉴定龙胆泻肝丸的真实质量

建立了龙胆泻肝丸(Longdanxiegan pill,LDXGP)三波长融合高效液相色谱(HPLC)指纹图谱,以系统指纹定量法全面鉴定LDXGP的质量。采用反相高效液相色谱法(RP-HPLC),运用多波长融合指纹图谱技术对色谱图进行处理,以黄芩苷为参照物峰,确立了63个共有指纹峰,以宏定性相似度为参量对12个厂家的12批LDXGP进行聚类分析,确定用其中10批生成对照指纹图谱(RFP),以此RFP为标准用系统指纹定量法评价12批LDXGP的质量。结果鉴别出9批质量完全合格,1批含量明显偏高,2批化学成分数量和分布比例不合格。基于多波长融合技术的系统指纹定量法是评价中药真实质量的可靠方法。