Study of the characteristic fragmentation behavior of hydroquinone glycosides by electrospray ionization tandem mass spectrometry with optimization of collision energy.

J Mass Spectrom. 2009 May 7; Liu Y, He J, Zhang R, Shi J, Abliz ZThe fragmentation behavior of hydroquinone glycosides involving one or two sugar groups from Fraxinus sieboldiana and their analogue arbutin was investigated systematically by electrospray ionization tandem mass spectrometry in negative ion mode. The characteristic fragmentation reaction of these compounds was through the homolytic and heterolytic cleavage of the O-glycosidic bond to produce radical aglycone ion ([Y(0) - H](-*)) and aglycone ion (Y(0) (-)), respectively. Unambiguous differentiation between the mono-O-glycoside isomers which differ in glycosylation position was achieved by comparing the relative abundance of [Y(0) - H](-*) and Y(0) (-) ions with the optimized collision energy. In the fragmentation of 1, 4-di-O-glycosides, only the Y(0) (-) ion was produced when the first glucosyl residue was expelled. However, both the [Y(0) - H](-*) and Y(0) (-) ions were present when the second glucosyl residue was eliminated. In addition, an interesting [Y(0)-2H](-) ion was present in the product ion spectra of hydroquinone glycosides with methoxy group(s) substituted at C-3 or/and C-5 positions of the benzene ring. The results of this study can facilitate the rapid determination of hydroquinone glycosides in crude plant extracts and also reveal that the systematic investigation and optimization of collision energy play an important role in the differentiation of isomers which have subtle differences in structures. Copyright (c) 2009 John Wiley & Sons, Ltd.

Discrimination of three medicinal materials from the Citrus genus by HPLC fingerprint coupled with two complementary software.

Phytochem Anal. 2009 May 8; Qin XM, Dai YT, Zhang LZ, Guo XQ, Shao HXINTRODUCTION: Pericarpium Citri Reticulatae, Pericarpium Citri Reticulatae Viride and Fructus Aurantii come from the fruit of Citrus genus and possess analogous pharmacological activities. Either two or three of them are often present in one preparation. However, there is no standard method to differentiate the three herbal medicines for quality control. OBJECTIVE: To develop a fingerprint method for authentication of these three herbal medicines by HPLC. METHODOLOGY: Methanol extracts were analysed by HPLC, with a mobile phase of 0.1% phosphoric acid in water (A) and acetonitrile (B) in a gradient programme. The flow rate was set at 0.8 mL/min and UV detection at 320 nm. Principal component analysis and similarity evaluation were employed to analyse the chromatographic dataset. RESULTS: The chromatograms of 20 Pericarpium Citri Reticulatae, 13 Pericarpium Citri Reticulatae Viride and 15 Fructus Aurantii samples from diverse habitats had 13 peaks in common, and showed one peak characteristic for Pericarpium Citri Reticulatae Viride and two peaks characteristic for Fructus Aurantii. Furthermore, it was possible to differentiate the three medicines by a 'fingerprint region'. The difference between Pericarpium Citri Reticulatae and Fructus Aurantii was much bigger than that between Pericarpium Citri Reticulatae and Pericarpium Citri Reticulatae Viride, as could be shown by calculation of common peak ratio and variation peak ratio. CONCLUSION: A reliable HPLC fingerprint method coupled with principal component analysis and similarity evaluation was developed and showed substantial differentiation power for the three medicines. Copyright (c) 2009 John Wiley & Sons, Ltd.

Inhibitory effects of atractylodis lanceae rhizoma and poria on collagen- or thromboxane a(2)-induced aggregation in rabbit platelets.

Biol Pharm Bull. 2009 May; 32(5): 856-60Nasu Y, Iwashita M, Saito M, Fushiya S, Nakahata NKami-shoyo-san (Jia-Wei-Xiao-Yao-San), Toki-shakuyaku-san (Dang-Gui-Shao-Yao-San) and Toki-shigyaku-ka-goshuyu-shokyo-to (Dang-Gui-Si-Ni-Jia-Wu-Zhu-Yu-Sheng-Jiang-Tang) are Kampo (traditional Chinese) medicines which are traditionally and effectively used for the treatment of chilly sensation (Hiesho) in Japan, but the active components and their detailed mechanisms have not yet been clarified. Etiologies of Hiesho include poor peripheral blood circulation and platelet aggregability contributes to peripheral blood circulation; therefore, we investigated the effect of Kampo medicines on platelet aggregation using rabbit platelets in vitro. Collagen and U46619, a thromboxane A(2) receptor agonist, caused rabbit platelet aggregation, which was potently inhibited by pretreatment of platelets with Kami-shoyo-san and Toki-shakuyaku-san in vitro. Toki-shigyaku-ka-goshuyu-shokyo-to, however, did not significantly inhibit collagen- or U46619-induced platelet aggregation. Therefore, we examined the effect on platelet aggregation of two herbal medicines, Atractylodis Lanceae Rhizoma and Poria, both of which are contained in Kami-shoyo-san and Toki-shakuyaku-san but not in Toki-shigyaku-ka-goshuyu-shokyo-to. As the results indicate, Atractylodis Lanceae Rhizoma inhibited platelet aggregation induced by collagen but not by U46619. Poria effectively inhibited U46619-induced platelet aggregation and it partially inhibited collagen-induced platelet aggregation. On the other hand, Atractylodis Lanceae Rhizoma and Poria did not inhibit adrenaline/adenosine diphosphate- or adrenaline/serotonin-induced platelet aggregation. These results suggest the possibility that the inhibition of platelet aggregation by two Kampo medicines, Kami-shoyo-san and Toki-shakuyaku-san, is one of the mechanisms underlying the improvement of Hiesho. Furthermore, Atractylodis Lanceae Rhizoma and Poria are possible herbal medicines for the inhibition of platelet aggregation.

Associations of Herbal and Specialty Supplements with Lung and Colorectal Cancer Risk in the VITamins And Lifestyle Study.

Cancer Epidemiol Biomarkers Prev. 2009 May; 18(5): 1419-28Satia JA, Littman A, Slatore CG, Galanko JA, White EMillions of Americans use dietary supplements with little knowledge about their benefits or risks. We examined associations of various herbal/specialty supplements with lung and colorectal cancer risk. Men and women, 50 to 76 years, in the VITamins And Lifestyle cohort completed a 24-page baseline questionnaire that captured duration (years) and frequency (days per week) of use of commonly used herbal/specialty supplements. Dose was not assessed due to the lack of accurate potency information. Supplement exposure was categorized as "no use" or "any use" over the previous 10 years. Hazard ratios (HR) were estimated by multivariate Cox regression models. Incident lung (n = 665) and colorectal cancers (n = 428) were obtained from the Surveillance, Epidemiology, and End Results cancer registry. Any use of glucosamine and chondroitin, which have anti-inflammatory properties, over the previous 10 years, was associated with significantly lower lung cancer risk: HR 0.74 [95% confidence interval (95% CI), 0.58-0.94] and HR 0.72 (95% CI, 0.54-0.96) and colorectal cancer risk: HR 0.73 (95% CI, 0.54-0.98) and HR 0.65 (95% CI, 0.45-0.93), respectively. There were also statistically significantly inverse associations of fish oil: HR 0.65 (95% CI, 0.42-0.99), methylsulfonylmethane: HR 0.46 (95% CI, 0.23-0.93), and St. John's wort: HR 0.35 (95% CI, 0.14-0.85) with colorectal cancer risk. In contrast, garlic pills were associated with a statistically significant 35% elevated colorectal cancer risk. These results suggest that some herbal/specialty supplements may be associated with lung and colorectal cancer risk; however, these products should be used with caution. Additional studies examining the effects of herbal/specialty supplements on risk for cancer and other diseases are needed. (Cancer Epidemiol Biomarkers Prev 2009;18(5):1419-28).

Estrogenic effects of herbal medicines from Costa Rica used for the management of menopausal symptoms.

Menopause. 2009 May 6; Doyle BJ, Frasor J, Bellows LE, Locklear TD, Perez A, Gomez-Laurito J, Mahady GBOBJECTIVE:: Outcomes from the Women's Health Initiative have demonstrated adverse effects associated with hormone therapy and have prioritized the need to develop new alternative treatments for the management of menopause and osteoporosis. To this end, we have been investigating natural herbal medicines used by Costa Rican women to manage menopausal symptoms. METHODS:: Seventeen plant species were collected and extracted in Costa Rica. To establish possible mechanisms of action and to determine their potential future use for menopause or osteoporosis, we investigated the estrogenic activities of the herbal extracts in an estrogen-reporter gene estrogen receptor (ER) beta-Chemically Activated Luciferase Expression assay in U2-OS cells and in reporter and endogenous gene assays in MCF-7 cells. RESULTS:: Six of the plant extracts bound to the ERs. Four of the six extracts stimulated reporter gene expression in the ER-beta-Chemically Activated Luciferase Expression assay. All six extracts modulated expression of endogenous genes in MCF-7 cells, with four extracts acting as estrogen agonists and two extracts, Pimenta dioica and Smilax domingensis, acting as partial agonist/antagonists by enhancing estradiol-stimulated pS2 mRNA expression but reducing estradiol-stimulated PR and PTGES mRNA expression. Both P. dioica and S. domingensis induced a 2ERE-luciferase reporter gene in transient transfected MCF-7 cells, which was inhibited by the ER antagonist ICI 182,780. CONCLUSIONS:: This work presents a plausible mechanism of action for many of the herbal medicines used by Costa Rican women to treat menopausal symptoms. However, it further suggests that studies of safety and efficacy are needed before these herbs should be used as alternative therapies to hormone therapy.