Comparative evaluation of chemical profiles of three representative 'snow lotus' herbs by UPLC‐DAD‐QTOF‐MS combined with principal component and hierarchical cluster analyses

Herbal healthcare products are used worldwide as relatively safe and effective alternatives to allopathic drugs. Saussurea laniceps Hand.‐Mazz. (SL), S . medusa Maxim. (SM) and S . involucrata (Kar. et Kir.) Sch.Bip. (SI) are three sources of the renowned 'snow lotus', Chinese materia medica for treating inflammatory diseases. The three species have different therapeutic effects, among which SL has been proved to be the most potent, but they are frequently confused on the market and in the academic community. An ultra‐high performance liquid chromatography‐diode array detector‐quadrupole time of flight‐mass spectrometry (UPLC‐DAD‐QTOF‐MS) method was developed and used to analyze 49 herbal samples for species analysis and overall quality evaluation. With 25 simultaneously identified constituents, of which 12 were quantified, the three herbs showed different chemical profiles. Four‐dimensional principle component analysis (4D‐PCA) and orthogonal hierarchical cluster analysis (2D‐HCA) results illustrated that SL should be grouped away from SM and SI, contradicting the botanical record in Flora of China . The present chemical determination and pattern recognition results directly explain the therapeutic potency of SL and distinguish the three confused snow lotus herbs. Furthermore, the findings suggest a possible extensive quality evaluation model for multi‐origin medicinal plants and help monitor falsification of snow lotus herbal products on the market, contributing to a more regulated pharmaceutical industry. Copyright © 2016 John Wiley & Sons, Ltd.     

青蒿挥发油成分的GC-MS分析与化学计量学解析法

目的:分析青蒿挥发油的化学成分.方法:用水蒸气蒸馏法从青蒿中提取挥发油成分,采用气相色谱-质谱(GC-MS)联用技术,结合化学计量学解析法(CRM)对重叠色谱峰进行分辨解析,并利用程序升温保留指数辅助定性.结果:共分辨出73个色谱峰,鉴定了其中66个组分,占青蒿挥发油总含量的95.25%,其主要化学成分为:丁子香烯、丁子香烯环氧化物、稚槛蓝(树)油烯、α-甜没药萜醇等.结论:使用CRM解析色谱峰,比单独使用GC-MS法能更真实、全面地反映其挥发油化学成分.     

基于HPLC指纹图谱及多指标成分定量分析的不同产地当归质量特征研究

目的 建立不同产地当归Angelicae sinensis的HPLC指纹图谱并测定其主要成分的含量,结合化学计量学分析,建立各产地当归的“识别标志”。方法 采用HPLC-DAD方法建立甘肃、四川和云南等地当归的指纹图谱,并对指标成分进行含量测定。进行相似度评价结合主成分分析（principal component analysis,PCA）、偏最小二乘法判别分析（partial leastsquares discrimination analysis,PLS-DA）、Fisher线性判别（fisher linear discrimination analysis,FLDA）等模式识别技术进行分析。结果 HPLC指纹图谱共标定了不同产地当归中的13个共有峰,指认出绿原酸、阿魏酸、洋川芎内酯I、洋川芎内酯H、阿魏酸松柏酯、E-藁本内酯、E-丁烯基苯酞、Z-藁本内酯8个色谱峰,样品相似度均在0.90以上。绿原酸、洋川芎内酯I、E-丁烯基苯酞、总阿魏酸（阿魏酸与阿魏酸松柏酯换算后总量）、Z-藁本内酯6个指标成分含量测定变化范围分别为0.10～0.52 mg/g、0.10～0.24 mg/g、0.19～0.54 mg/g、1.42～2.66 mg/g、21.75～29.15 mg/g。PCA、PLS-DA分析结果表明,Z-藁本内酯、E-藁本内酯、阿魏酸松柏酯、阿魏酸在不同产地当归的中变化显著,Z-藁本内酯、E-丁烯基苯酞、总阿魏酸分别可作为甘肃当归、四川当归、云南剑川当归的成分识别标志。逐步线性判别验证当归产地其中自身判别正确率为96.3%,交叉验证正确率为92.3%。结论 建立的HPLC指纹图谱结合含量测定、PCA、PLS-DA客观、全面、有效地对不同产区当归质量特征进行探究,确认各产地当归的标志性成分,为当归的产地溯源及质量控制提供科技支撑。     

基于化学计量学的酒萸肉特征性成分识别及定量测定

目的识别酒萸肉特征性成分并检测其含量。方法应用UPLC-Q-TOF/MS检测酒萸肉及其生品化学成分谱,并基于化学计量学方法识别酒萸肉的特征成分。建立基于超高效液相色谱-光电二极管矩阵检测器(UPLC-PDA)的酒萸肉特征成分含量测定方法,对12批次酒萸肉及其生品的特征成分含量进行检测。结果酒萸肉及其生品的化学成分谱不尽相同,共获得10个可表征酒萸肉的特征成分,包括5-羟甲基糠醛、没食子酸、原儿茶酸、莫诺苷、马钱苷酸、獐芽菜苷、山茱萸苷、二氢槲皮素、马钱苷、山茱萸新苷。建立了基于UPLC-PDA的多成分含量测定方法,方法学考察结果显示10个特征成分线性关系良好(r≥0.999 7)。与同批次生品比较,酒萸肉中的5-羟甲基糠醛、二氢槲皮素、没食子酸、马钱苷、莫诺苷、山茱萸苷和獐芽菜苷7个成分含量显著升高,原儿茶酸、马钱苷酸和山茱萸新苷3个成分含量显著降低。结论基于化学计量学筛选获得的特征成分可以区分酒萸肉及其生品,建立的酒萸肉多成分含量测定方法,线性关系良好、快速简便、稳定可靠,可为酒萸肉质量控制提供参考。     

气相色谱-质谱和化学计量学解析法分析药对麻黄-桂枝挥发油成分

利用气相色谱-质谱对药对麻黄-桂枝及单味药麻黄和桂枝的挥发油成分进行检测，通过化学计量学解析法对产生的二维色谱-质谱数据进行解析，得到各组分的纯色谱和质谱，根据其保留时间和质谱，在质谱库中进行相似检索，实现对组分的定性，再用总体积积分法进行定量。麻黄-桂枝、麻黄和桂枝挥发油分别定性了97，72和68个色谱峰，占总含量的89.76%，90.08%和91.62%。药对挥发油成分的数目大致为麻黄和桂枝挥发油成分的加和，但相对含量有变化。     

基于指纹图谱通便灵胶囊的化学计量学分析

目的 通过HPLC建立通便灵胶囊指纹图谱，并借助化学计量学分析，对其进行系统、科学的质量评价。方法 采用JADE-PAK ODS柱（250 mm×4.6 mm，5 μm），以流动相为甲醇（A）-0.1%甲酸溶液（B），进行梯度洗脱，流速1.0 mL·min^–1，柱温30℃，检测波长340 nm，建立通便灵胶囊的指纹图谱，通过ChemPattern软件确立共有峰，利用UPLC-Q/TOF-MS对共有峰进行成分确认，并进行化学计量学分析。结果 通过建立的通便灵胶囊指纹图谱确定14个共有峰，主成分分析得分图显示4个厂家的样品能够明显区分开，偏最小二乘判别分析载荷图显示化学成分松果菊苷、山柰酚-3-O-β-D-槐糖苷和异鼠李素-3-O-龙胆二糖苷对4个厂家样品的区分有较大贡献。结论 不同厂家样品存在较大差异，有可能会造成药效的不一致，此方法可为通便灵胶囊的质量控制提供参考依据。     

化学模式识别技术在药物分析中的应用与研究进展

介绍化学模式识别技术的一些基本概念和原理,以及在药物分析中的应用与研究进展。化学模式识别技术在色谱和光谱数据处理、药物成分分析、定性定量、药物质量评价和控制,中药材真伪优劣评价等方面有独特的优势。常见的化学模式识别技术,如主成分分析法、因子分析、聚类分析和判别法等越来越成为药物分析中不可或缺的工具之一。     

Micromechanical and physical stability analysis of an irradiated poly (lactic-co-glycolic acid) donut-shaped minitablet device for intraocular implantation

This study pragmatically characterized the micromechanical and physical stability of a poly(lactic-co-glycolic acid) (PLGA)-based ganciclovir (GCV)-loaded donut-shaped minitablet (DSMT) device for intraocular implantation. Thermal and spectroscopic analysis was performed on various drug-polymer permutations. Porositometric profiles were quantitatively analyzed coupled with qualitatively SEM imaging. The tensile strength (TS) and fracture energy (FE) of the device was also determined pre- and post-γ-sterilization. Inimitably, chemometric and molecular modeling provided a supportive confirmatory tool for establishing fundamental correlative suppositions between the transitioned surface morphology and the micromechanical stability after γ-irradiation. Isotherm plot volumes ranged between ?0.028?±?0.022 and 0.110?±?0.005 m²/g for pre- and post-sterilized devices, respectively, revealing a microporous alteration in porosity. Pre-sterilized devices had larger pores (BJH_a?=?286.22 vs. 192.49 Å) and lower FE (151.301?±?6.089 N/m) and TS (26.396?±?1.062 N) values while sterilized devices had crystalline matrices that facilitated the superiorly controlled drug release kinetcs obtained. DSC thermograms displayed the characteristic disordered crystallization of GCV and hydration exotherms resulting from ionization during γ-irradiation. FTIR spectrograms showed fingerprint molecular imprints of GCV and axial stretching of hybridized carbons of PLGA with no subversive drug-polymer interactions after γ-irradiation. Integration of the results inveterately revealed that compression and subsequent γ-irradiation of the device affected desirable micromechanical and solid-state stability behavior.     

Physical Properties,Spectroscopic, Microscopic,X-ray,and Chemometric Analysis of Starch Films Enriched with Selected Functional Additives

Biodegradable materials are used in the manufacture of packaging and compostable films and various types of medical products. They have demonstrated a large number of potential practical applications in medicine and particularly in the treatment of various cardiac, vascular, and orthopedic conditions in adults as well in children. In our research, the extrusion-cooking technique was applied to prepare thermoplastic starch (TPS), which was then utilized to obtain environmentally friendly starch-based films. Potato starch was the basic raw material exploited. Polyvinyl alcohol and keratin were used as functional additives in amounts from 0.5 to 3%, while 20% of glycerol was harnessed as a plasticizer. The processing of the thermoplastic starch employed a single screw extruder-cooker with an L/D ratio of 16. The film blowing process was carried out using a film-blowing laboratory line with L/D = 36. FTIR Spectroscopy was applied for the assignment of the prominent functional groups. The results showed that the processing efficiency of thermoplastic starch with functional additives varied depending on the level of polyvinyl alcohol and keratin addition. Moreover, the FTIR data correlated with the changes in the physical properties of the tested films. The analysis of FTIR spectra revealed several changes in the intensity of bands originating from stretching vibrations characteristic of the –OH substituent. The changes observed depended on the presence/lack of the hydrogen bonding occurring upon interactions between the starch molecules and the various additives used. In addition, notable changes were observed in bands assigned to glycoside bonds in the starch.     

Comprehensive analysis of Polygoni Multiflori Radix of different geographical origins using ultra-high-performance liquid chromatography fingerprints and multivariate chemometric methods

Polygoni Multiflori Radix (PMR) is increasingly being used not just as a traditional herbal medicine but also as a popular functional food. In this study, multivariate chemometric methods and mass spectrometry were combined to analyze the ultra-high-performance liquid chromatograph (UPLC) fingerprints of PMR from six different geographical origins. A chemometric strategy based on multivariate curve resolution–alternating least squares (MCR–ALS) and three classification methods is proposed to analyze the UPLC fingerprints obtained. Common chromatographic problems, including the background contribution, baseline contribution, and peak overlap, were handled by the established MCR–ALS model. A total of 22 components were resolved. Moreover, relative species concentrations were obtained from the MCR–ALS model, which was used for multivariate classification analysis. Principal component analysis (PCA) and Ward's method have been applied to classify 72 PMR samples from six different geographical regions. The PCA score plot showed that the PMR samples fell into four clusters, which related to the geographical location and climate of the source areas. The results were then corroborated by Ward's method. In addition, according to the variance-weighted distance between cluster centers obtained from Ward's method, five components were identified as the most significant variables (chemical markers) for cluster discrimination. A counter-propagation artificial neural network has been applied to confirm and predict the effects of chemical markers on different samples. Finally, the five chemical markers were identified by UPLC–quadrupole time-of-flight mass spectrometer. Components 3, 12, 16, 18, and 19 were identified as 2,3,5,4′-tetrahydroxy-stilbene-2-O-β-d-glucoside, emodin-8-O-β-d-glucopyranoside, emodin-8-O-(6′-O-acetyl)-β-d-glucopyranoside, emodin, and physcion, respectively. In conclusion, the proposed method can be applied for the comprehensive analysis of natural samples.