A simple and effective method for identification of Fraxini Cortex from different sources by multi-mode fingerprint combined with chemometrics

Fraxini Cortex has a long history of being used as a medicinal plant in traditional Chinese medicine. However, it is challenging to differentiate and make quality evaluations for Fraxini Cortex from different origins due to their similarities in morphological features, as well as general chemical composition using traditional chemical analytical methods. In this study, a simple and effective method was developed to identify Fraxini Cortex from different origins by multi-mode fingerprint combined with chemometrics. Digital images of the high-performance thin-layer chromatography profiles were converted to grayscale intensity, and the common patterns of high-performance thin-layer chromatography fingerprints were generated with ChemPattern software. Authentication and quality assessment were analyzed by similarity analysis, hierarchical cluster analysis, principal component analysis, and multivariate analysis of variance. The ultra-high-performance liquid chromatography fingerprints were analyzed by similarity analysis, principal component analysis, and orthogonal partial least square-discriminant analysis. When combined with chemometrics, high-performance thin-layer chromatography and ultra-high-performance liquid chromatography fingerprint provided a simple and effective method to evaluate the comprehensive quality of Fraxini Cortex, and to distinguish its two original medicinal materials (Fraxinus chinensis Roxb. and Fraxinus rhynchophylla Hance.) recorded in the Chinese Pharmacopeia and its three adulterants (Fraxinus mandschurica Rupr., Fraxinus pennsylvanica Marsh., and Juglans mandshurica Maxim.). A similar workflow may be applied to establish a differentiation method for other medicinal and economic plants.     

Antioxidant,anti-lipidemic,hypoglycemic and antiproliferative effects of phenolics from Cortex Mori Radicis

Cortex Mori Radicis (CMR) is enriched in various phenolics, this study aimed to estimate the antioxidant effect, enzyme (lipase, α-amylase, α-glucosidase and acetyl-cholinesterase) inhibition and the anti-proliferative effect of the phenolic compounds in CMR. However, the amount of these compounds obtained from CMR is highly dependent on the processing conditions. In this study, the processing parameters of extracting the phenolics from CMR using ultrasonic technique pooled with high-speed shearing extraction (UTPHSE) were optimized. Subsequently, the phenolics from Cortex Mori Radicis (PCMR) were purified using AB-8 macroporous resin, and their chemical analysis, antioxidant, enzyme inhibition, and antiproliferative activities were studied. Based on our findings, the optimal parameters of UTPHSE were: L/S ratio 25.8:1 (mL/g), voltage 81.0 V, ultrasonic temperature 51.8 ℃ and ultrasonic time 289 s. And under the optimal extraction conditions, the extraction rate of the PCMR was 0.531 ± 0.004%. Compared with PCMR, the contents of “total phenolics, flavonoids, flavonols, flavanols and phenolic acids” increased 2.30, 2.67, 2.59, 3.63 and 2.72 times in the purified phenolics from Cortex Mori Radicis (PPCMR), respectively. In addition, PPCMR depicted significant DPPH, ABTS⁺ and superoxide anion radicals’ scavenging capability, reducing power, ferric ion reducing antioxidant power (FRAP) and remarkable inhibitory activities on “lipase, alpha-amylase, alpha-glucosidase, and the proliferation of HeLa, HepG2 and NCI-H460”. At the same time, the morphological changes of HeLa, HepG2 and NCI-H460 cells suggested that PPCMR could effectively inhibit the proliferation of tumor cells in vitro. Therefore, PPCMR have good potential as natural antioxidants, antilipidemic, hypoglycemic, and antineoplastic agents in functional foods and pharmaceuticals.     

平胃散挥发性成分的研究(Ⅱ)--厚朴挥发油的GC/MS分析

利用色质联用（GC／MS）技术对复方制剂平胃散中的单味药材厚朴的挥发油成分进行测定,基于直观推导式演进特征投影（HELP）法对产生的二维色谱／质谱数据进行分辨,得到各个组分的纯色谱曲线和质谱,根据色谱保留时间和纯质谱在质谱库中进行相似检索以实现对组分的定性,然后采用总休整积分法进行定量,本文分离出98个组分,其中鉴定了44个组分,约占其挥发油总量的58．74％。     

高效液相色谱法测定黄柏中盐酸小檗碱含量的不确定度评估

介绍一种高效液相色谱法测定含量的不确定度计算方法.通过黄柏中盐酸小檗碱含量测定结果,对产生不确定度的各分量进行计算,研究测量不确定度的主要分量,以控制检验环节的质量,保证结果准确度.     

Development and validation of an LC-MS-MS method for determination of methyl kulonate in rat plasma

A sensitive, rapid and specific LC‐MS‐MS method was established and validated for determination of methyl kulonate, a major bioactive constituent isolated from Meliae Cortex, in rat plasma. Plasma samples were treated by precipitating protein with methanol and were chromatographed using a Capcell Pak C₁₈ column (100 × 4.6 mm, 5 µm) with the mobile phase comprising a mixture of methanol, 10 m m ammonium formate and formic acid (95:5:0.1, v/v/v). Detection and quantification were performed by mass spectrometry in the multiple reaction monitoring mode with positive atmospheric ionization at m/z 467 → 311 for methyl kulonate, and m/z 469 → 451 for dubione B (internal standard), respectively. A good linear response was observed over the concentration range 1.00–500 ng/mL with the lower limit of quantification 1.00 ng/mL in rat plasma. The method also afforded satisfactory results base on sensitivity, specificity, precision, accuracy, recovery, freeze–thaw and long‐time stability. The validated method was successfully applied to determine the pharmacokinetic properties of methyl kulonate in rats after oral administration at dose of 100 mg/kg. This pharmacokinetic study of methyl kulonate is reported here for the first time. Copyright © 2011 John Wiley & Sons, Ltd.     

Preparation of a stationary phase with quaternary ammonium embedded group for selective separation of alkaloids based on ion‐exclusion interaction

A stationary phase (named QA C10) with quaternary ammonium embedded between a propyl and a decyl chain was synthesized by immobilization of N,N‐dimethyldecylamine on chloropropyl–silica surface. A set of representative neutral, basic, and acidic compounds was employed to evaluate its chromatographic properties. The results illustrated that QA C10 was a mixed‐mode stationary phase possessing both hydrophobic and ionic characteristics. The QA C10 stationary phase was further used for selective separation of alkaloids from Cortex phellodendri. Under acidic condition, alkaloids could be eluted in first 8 min, while other neutral and acidic fractions were retained better on QA C10 column. Then, obtained alkaloid fraction was analyzed by LC‐MS/MS and 22 alkaloids were identified. Our study confirmed the advantages and application potential of the QA C10 stationary phase for alkaloids separation.     

不同产地杜仲的紫外光谱鉴别研究

利用不同溶剂在微波条件下对于3种不同产地杜仲进行提取,应用紫外分光光度计对相同溶剂的提取物进行研究,发现其紫外光谱有差异,可用于不同产地杜仲的鉴别.     

A convenient semisynthetic route to hypericin

Summary A semisynthetic route to produce hypericin was established usingCortex frangulae as the starting point. The emodin isolated from it easily and in good yield was reduced to emodin anthrone by means of SnCl₂. The latter was reacted via a known oxidative dimerization and photocyclization reaction into hypericin.

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Ein bequemer semisynthetischer Zugang zu Hypericin

Zusammenfassung Eine semisynthetische Route zur Darstellung von Hypericin unter Verwendung vonCortex frangulae als Ausgangsmaterial wurde erarbeitet. Das daraus einfach und in guten Ausbeuten isolierte Emodin wurde mit Hilfe von SnCl₂ zu Emodinanthron reduziert. Letzteres wurde dann über eine bekannte oxidative Dimerisierung und Photocyclisierung zu Hypericin umgesetzt.

     

加压毛细管电色谱在建立中药黄柏指纹图谱中的方法学研究

以加压毛细管电色谱（pCEC）为技术平台,对其在建立中药黄柏指纹图谱中的方法学进行了研究．通过对提取溶剂、流动相中有机相种类、盐溶液等条件的优化,发现1％盐酸的甲醇溶液为提取溶液,20mmol／LNH4C1溶液．乙腈为流动相梯度洗脱,紫外检测波长为230nm时对其分离效果最好．并通过在色谱柱上施加不同的电压,详细地阐明了pCEC的双重分离机制对分离选择性的影响,发现黄柏中的主要成分药根碱、巴马汀和小檗碱在pCEC模式中随电压的不同,有不同的出峰顺序．当电压为0—4kV时出峰顺序为药根碱、巴马汀和小檗碱,当电压为8—14kV时出峰顺序为药根碱、小檗碱和巴马汀．对此原因进行了详细讨论,同时与微径液相色谱模式进行了比较,说明pCEC可以为复杂样品的分离提供更多更好的分离途径．     

Comparison of the volatile constituents of different parts of Cortex magnolia officinalis by GC‐MS combined with chemometric resolution method

Volatile compositions of different parts (stem, branch and root barks) of Cortex magnolia officinalis, cultivated in China, were investigated for the first time by GC‐MS with the help of heuristic evolving latent projection (HELP). Identification of components was conducted by similarity matching to NIST mass library but also assisted by comparison of temperature‐programmed retention indices (PTRIs) with the data web available. A total of 90, 82 and 76 volatile compounds in the essential oils of the three samples taken from the same batch aforementioned were qualitatively and quantitatively determined, representing 84.03, 83.68 and 83.10% of the total content, respectively. Among the constituents determined, there were 50 components coexisting. Eudesmol and its isomers were shown to be the principal compounds in the studied samples, accounting for 47.66, 36.74 and 36.31%, respectively. The three kinds of isomers (α‐, β‐ and γ‐eudesmol) in houpo volatile oils have been tentatively qualified and quantified simultaneously for the first time. By comparative analysis, significant qualitative and semi‐quantitative differences and similarities were observed among the three samples. The results achieved provide a scientific evidence for further exploitation of Magnolia bark and clinical medication.