Identification and determination of active anthraquinones in Chinese teas by micellar electrokinetic capillary chromatography

The simultaneous determination of emodin, aloe-emodin and rhein, in Semen Cassiae, Qinghai Wild Dahuang tea, Ningxia Juemingzi tea, Lanzhou Juemingzi tea and Surong Juemingzi tea, has been investigated by micellar electrokinetic capillary chromatography for the fi rst time. With an electrolyte containing 15 mm borax, 30 mm SDS, 10% (v/v) ethanol, at pH 9.60 and 20 kV applied voltage, the three analytes were completely separated within 12 min. The effects of the concentration of borax, electrolyte pH, the concentrations of SDS and organic modifier and the applied voltage on electropheoretic behavior and separation were studied. The linear calibration range was 4-120 micro g/mL (r = 0.9921) for emodin, 10-200 micro g/mL (r = 0.9970) for aloe-emodin and 2-100 micro g/mL (r = 0.9971) for rhein, respectively. Under the optimum conditions, the relative standard deviation (RSD) values (n = 6) of the migration time and the peak area of each peak was 0.59-0.80% and 1.30-3.22%, respectively. The contents of the analytes in Rheum, Qinghai Wild Dahuang tea, Semen Cassiae and three other kinds of teas were easily determined with recoveries ranging from 95.3 to 104.4%.     

大黄素/Mg-Al-LDHs纳米杂化物的制备及缓释性能研究

以Mg-Al型层状双金属氢氧化物(Mg-Al-LDHs)为载体,将大黄素分子通过二次组装法成功插入其层间,得到大黄素/Mg-Al-LDHs纳米杂化物。XRD结果显示,Mg-Al-LDHs粒子层间距由0.48 nm增大到3.35 nm。差热曲线(DTA曲线)分析结果表明,该纳米杂化物分子中大黄素的分解温度比纯大黄素的分解温度高50℃。分别在pH 4.8和pH 7.5的缓冲溶液中测定了大黄素/LDHs的缓释性能,结果表明大黄素/LDHs的药品释放速率明显低于二者的物理混合物,并探讨了释放机理。     

Bioguided Isolation of Active Compounds from Rhamnus alaternus against Methicillin-Resistant Staphylococcus aureus (MRSA) and Panton-Valentine Leucocidin Positive Strains (MSSA-PVL)

Despite intensified efforts to develop an effective antibiotic, S. aureus is still a major cause of mortality and morbidity worldwide. The multidrug resistance of bacteria has considerably increased the difficulties of scientific research and the concomitant emergence of resistance is to be expected. In this study we have investigated the in vitro activity of 15 ethanol extracts prepared from Moroccan medicinal plants traditionally used for treatment of skin infections. Among the tested species I. viscosa, C. oxyacantha, R. tinctorum, A. herba alba, and B. hispanica showed moderate anti-staphylococcal activity. However, R. alaternus showed promising growth-inhibitory effects against specific pathogenic bacteria especially methicillin-susceptible Staphylococcus aureus Panton-Valentine leucocidin positive (MSSA-PVL) and methicillin-resistant S. aureus (MRSA). The bioguided fractionation of this plant using successive chromatographic separations followed by nuclear magnetic resonance (NMR) and mass spectrometry (MS) including EIMS and HREIMS analysis yielded the emodin (1) and kaempferol (2). Emodin being the most active with MICs ranging between 15.62 and 1.95 µg/mL and showing higher activity against the tested strains in comparison with the crude extract, its mechanism of action and the structure-activity relationship were interestingly discussed. The active compound has not displayed toxicity toward murine macrophage cells. The results obtained in the current study support the traditional uses of R. alaternus and suggest that this species could be a good source for the development of new anti-staphylococcal agents.     

大黄素的电化学氧化还原机理研究

本文利用循环伏安法(CV)、红外光谱循环伏吸法(CVA)和导数循环伏吸法(DCVA)研究大黄素(Q)在乙腈溶剂中的电子转移机理.Q的还原过程中阴离子自由基Q^?-会结合中性分子Q生成二聚物Q₂^?-.Q₂^?-在更负的电位下进一步还原为Q₂^2-.当扫描范围为-0.2 ~ -2.0 V时,经过一个循环伏安过程,在扫描结束物质并没有回到反应物Q,而是Q₂^2-. Q₂^2-会继续发生电化学反应,经历两步一电子过程,分别生成Q₂^3-. 和Q₂^4-.,对应CV图中峰C₃和C₄.当扫描范围扩大至1.0~-2.0 V时,在更正的电位下,观察到两个新的氧化峰A₁和A₂,该范围内的三圈扫描结果表明,在扫描结束物质重新氧化回到Q.当扫描范围缩小至0.3 ~ -1.4 V,A2峰随着扫描圈数的增加而增大,与A2峰对应的氧化产物Q₂^?-在溶液中不断积累.A1峰对应于Q₂^?-氧化回到Q.     

相溶解度法研究芦荟大黄素和环糊精及其衍生物的包结作用

本文用相溶解度法研究了芦荟大黄素与β－环糊精（ＣＤ）衍生物的包结作用,测定了包结物的包结常数,表明β－ＣＤ衍生物对芦蔡大黄素有较好的增溶作用,有应用价值。     

芦荟大黄素与血清白蛋白的相互作用

利用荧光光度法研究了中药有效成分芦荟大黄素与血清白蛋白的相互作用机制 ,求得两者的形成常数 ,讨论了某些金属离子对其形成常数的影响 ,并根据热力学常数确定了它们之间的作用力类型 ,利用F rster非辐射能量转移技术求出了两者的结合位置。     

Optimized protocol for multigram preparation of emodin anthrone,a precursor in the hypericin synthesis

Emodin reduction to emodin anthrone comprise one of three process steps involved in the hypericin synthesis, a powerful natural photosensitiser found in plants of the genus Hypericum. In this communication, an optimized protocol was established for emodin reduction enabling an efficient multigram preparation of emodin anthrone. A screening of reducing agent (SnCl₂·2H₂O and HCl_conc) under different reaction times was employed in micro-scale and monitored by electronic absorption spectroscopy technique. Data showed lower yields of emodin anthrone when some experimental conditions previously described in the literature were reproduce. However, using the optimized protocol for the emodin reduction these yields were overcoming, and a gram-scale supply experiment was reproducible for the preparation of 10 grams of emodin anthrone with excellent yield.     

反相胶束增稳室温荧光法测定血浆中的大黄素

利用高灵敏度的气溶胶ＯＴ／环己烷／水反相胶束增稳定温荧光法，研究了中草药有效成分大黄素的荧光性质。并在最佳的实验条件下，将该法应用于血浆中痕量大黄素含量的测定。     

Use of liquid chromatography hybrid triple‐quadrupole mass spectrometry for the detection of emodin metabolites in rat bile and urine

Emodin is the representative form of rhubarb, which is widely used in traditional Chinese medicine for the treatment of purgative, anti‐inflammatory, antioxidative and antiviral, etc. Previous reports demonstrated that emodin glucuronide was the major metabolite in plasma. Owing to the extensive conjugation reactions of polyphenols, the aim of this study was to identify the metabolites of emodin in rat bile and urine. Neutral loss and precursor ion scan methods of triple‐quadrupole mass spectrometer revealed 13 conjugated metabolites in rat bile and 22 metabolites in rat urine, which included four phase I and 18 phase II metabolites. The major metabolites in rat biosamples were emodin glucuronoconjugates. Moreover, rhein monoglucuronide, chrysophanol monoglucuronide and rhein sulfate were proposed for the first time after oral administration of emodin. Overall, liquid chromatography hybrid triple‐quadrupole mass spectrometry analysis leads to the discovery of several novel emodin metabolites in rat bile and urine and underscores that conjugated with glucuronic acid is the main metabolic pathway.     

On the synthesis of ω-appended hypericin derivatives

Summary A method for the preparation ofbis--appended hypericin derivatives bearingn-octyl,n-hexadecyl, and 2-(2-(2-hydroxyethoxy)-ethoxy)-ethoxymethyl substituents was developed. The key step — the synthesis of appropriately -substituted emodin derivatives — was achieved by solvolyzing 3-bromomethyl-1,6,8-triacetyloxy-anthracene-9,10-dione (-bromo triacetylemodin) in an appropriate alcohol in the presence of silver perchlorate. The correspondingbis--substituted hypericins were then prepared conventionally by dimerizing the -substituted emodin anthrones. The latter were prepared by reduction of the -appended emodins.

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Zur Synthese von -substituierten Hypericinderivaten

Zusammenfassung Eine Methode zur Darstellung vonbis--substituierten Hypericinderivaten wurde entwickelt. Der Schlüsselschritt — die Synthese der entsprechenden Emodinderivate — wurde durch die Solvolyse von 3-Bromomethyl-1,6,8-triacetyloxyanthracen-9,10-dion (-Bromtriacetylemodin) im entsprechenden Alkohol in Gegenwart von Silberperchlorat ermöglicht. Die entsprechendenbis--substituierten Hypericinderivate wurden auf konventionelle Weise durch Dimerisierung der -substituierten Emodinanthrone dargestellt. Letztere erhielt man durch Reduktion der -substituierten Emodine.