目的:通过超高效液相串联质谱(UPLC-MS/MS)方法测定番泻叶中吡咯里西啶生物碱(PA)的含量,为番泻叶的安全评估奠定基础.方法:以95％甲醇水为溶剂对番泻叶药材进行超声提取,阳离子交换固相萃取小柱净化富集.采用Zorbax Eclipse Plus C18(150 mm ×3.0 mm,1.8 μm)色谱柱,流动相为甲醇-水-0.1％甲酸,梯度洗脱,流速为0.4 mL· min-1;电喷雾离子源,正离子多反应监测模式.结果:14个PA化合物具有较好的线性关系(r ＞0.990 5),各化合物回收率为80.60％ ～ 103.22％,精密度和准确度良好,方法检出限和定量限分别为0.1～0.5、0.2～1.0 μg·L一.从12批番泻叶主要检测出5种PA,且PA的总质量分数为7.06 ～ 187.97 μg·kg-1.根据最高日摄入量计算,5批番泻叶药材中的PA摄入量超过0.42 μg·d-1.结论:本研究首次通过UPLC-MS/MS检测到了番泻叶中的PA,通过对其日摄入量的分析,为番泻叶的安全评价提供参考.

AIM To establish the HPLC fingerprints of Kangfuxin Liquid (extract of Periplaneta americana L.) and to determine the contents of six constituents.METHODS The analysis of this drug was performed on a TOSOH TSK-GEL ODS column (250 mm × 4.6 mm,5 μm),with the mobile phase comprising of acetonitrile-water (containing 0.07％ acetic acid) flowing at 1.0 mL/min in a gradient elution manner,and the detection wavelength was set at 280 nm.RESULTS There were twenty-four common peaks in the fingerprints of ten batches of samples (Ⅰ-Ⅹ) with the similarities of 0.932-0.993 (except for sample Ⅰ).Uracil,hypoxanthine,xanthine,inosine,protocatechuic acid and Cyclo (Gly-Tyr) showed good linear relationships within the ranges of 3.460-173.0,3.960-198.0,3.596-179.8,1.338-66.9,3.672-183.6 and 3.552-177.6 μg/mL,whose average recoveries (RSDS) were99.8％ (2.65％),98.0％ (2.55％),99.7％ (1.59％),100.7％ (2.80％),102.0％ (2.09％) and 99.6％ (1.88％),respectively.CONCLUSION This accurate,stable and simple method can be used for the quality control of Kangfuxin Liquid.

Objective:To study the chemical constituents of Kangfuxin Liquid.Methods:The chemical constituents were isolated and purified on silica gel column chromatography,Sephadex LH20 and semi-preparing liquid chromatography,and identified by MS and NMR.Results:Thirteen compounds were obtained and identified as following:uracil(1),hypoxanthine (2),cyclo-(Tyr-Gly) (3),protocatechuic acid (4),inosine (5),glycerol (6),leucine (7),isoleucine (8),phenylalanine (9),tyrosine (10),valine (11),alanine (12),glycine (13).Conclusion:Compounds 3 and 4 are isolated from Periplaneta americana for the first time.

Periplaneta America are the folk traditional medicine derived from southwest area.Until now there have been four related postmarketing drugs on sale-"Kangfuxin Liquid","Xinmailong Injection","Ganlong Capsule" and "Xiaozheng Yigan Tablet".The modem studies show they have obvious effects on inflammation and tumefaction,wound surface,cardio-cerebrovascular diseases,Hepatitis B and liver cancer.But it's very little known about the active ingredients and mechanisms of action,this will significantly limit its usage in future.So,at present,many researchers are engaged in this field and make some progress by extracting secondary metabolites like isoflavones and isocoumarins from the crude materials.Also some of them consider that the mechanism is the result of multiple factors and cytokines.This review outlines recent advances of Periplaneta America in related aspects and is expected to provide a support to the thorough research of Periplaneta America.

New drimane-type sesquiterpene cryptoporol A (1), cryptoporic acid derivative 6′-cryptoporic acid E methyl ester (2), and pseudouridine derivative cryptoporine A (3), as well as a known ergosterol 5α,8α-epidioxy-22E-ergosta-6,22-dien-3β-ol (4), were isolated from a 90 % alcohol extract of the fruiting bodies of Cryptoporus volvatus. The structures of these compounds were established by spectroscopic analysis and circular dichroism. 5α,8α-epidioxy-22E-ergosta-6,22-dien-3β-ol (4) exhibited antiviral activity against porcine reproductive and respiratory syndrome virus, and all compounds showed weak antioxidant activities.

A new drimane-type sesquiterpene with an isocitric acid moiety, cryptoporic acid S (1), together with six known compounds, cryptoporic acid D (2), β-sitosterol (3), β-daucosterol (4), stigmast-4-en-3-one (5), ergosterol (6), and (22E,24R)-ergosta-7,22-diene-3β,5α,6β-triol (7), was isolated from the fruiting bodies of Cryptoporus volvatus. The structures of these compounds were established on the basis of UV, IR, MS, 1D and 2D NMR analysis. In the meanwhile, compounds 1 and 2 were evaluated for antioxidant activity using the methods of 2,2-diphenyl-1-picrylhydrazyl free radical scavenging activity (DPPH-RSA) and ferric reducing antioxidant power (FRAP) assay, and they exhibited moderate antioxidant activities.

目的:优化新疆阿魏种子中总倍半萜香豆素的提取工艺.方法:以乙醇体积分数、料液比、提取时间为自变量,在单因素试验的基础上,应用Box-Behnken中心组合设计建立数学模型,以总倍半萜香豆素提取率为响应值,进行响应面分析.结果:最佳提取工艺条件为80％乙醇加热回流提取40 min,料液比为1∶40.总倍半萜香豆素提取率预测值为6.60％,实际值为6.62％,相对误差为0.3％.结论:该优选工艺稳定可靠,为新疆阿魏资源的合理利用提供参考.

A new sesquiterpene coumarin with a novel sesquiterpene carbon framework, Sinkiangenorin D, and ten known sesquiterpene coumarins were isolated from the seeds of Ferula sinkiangensis. The structures of these compounds, including the relative stereochemistry, were elucidated on the basis of spectroscopic data. All of the isolated compounds were tested against the AGS, HeLa, and K562 human cancer cell lines and showed cytotoxic activities with 50% inhibitory concentration values between 12.7 and 226.6 μM.

Two new cryptoporic acid derivatives, cryptoporic acid R (1) and 6',6 '''-cryptoporic acid G dimethyl ester (2), together with two known compounds, cryptoporic acid E (3) and cryptoporic acid E pentamethyl ester (4), were isolated from a 90% alcohol extract of the fruiting bodies of Cryptoporus volvatus. Their structures were established on the basis of NMR spectroscopic and mass spectrometry data. Cryptoporic acid E (3) and cryptoporic acid E pentamethyl ester (4) exhibited antiviral activity against porcine reproductive and respiratory syndrome virus. (C) 2015 Phytochemical Society of Europe. Published by Elsevier B.V. All rights reserved.

Objective: To analyze the caffeoylquinic acids and to develop an HPLC method for simultaneous determination of neochlorogenic acid,chlorogenic acid and cryptochlorogenin acid in Huahong capsules. Methods: A UPLC / Q- TOF- MS / MS method was developed to rapidly identify the caffeoylquinic acids in Huahong capsules. And the UPLC separation was performed on a Thermo BEH C 18 column( 2. 1 mm × 100 mm,1. 7 μm) with 0. 1% formic acid acetonitrile- 0. 1% formic acid as the mobile phase in gradient elution at a flow rate of 0. 4 μL · min- 1. The column temperature was set at 40 °C. The MS spectrometry detection was performed with electrospray ionization in negative ion mode,and using the following operating parameters: scan range,100- 1500 m / z; capillary voltage,2. 5 kV; skimmer voltage,40 kV; ion source temperature,120 °C; drying gas temperature,450 °C and sample collision energy,15- 40 eV. Besides,HPLC was performed on a Phenomenex C18( 250 mm ×4. 6 mm,4 μm)column with 0. 1% formic acid acetonitrile- 0. 1% formic acid as the mobile phase in gradient elution( 0- 7 min,5% →8% A; 7- 17 min,8% →15% A; 17- 45 min,15% →30% A; 45- 55 min,30% →50% A; 55- 60 min,50% →100% A) at a flow rate of 1. 0 mL·min- 1. The detect wavelength was set at 326 nm,and the column temperature was set at 30 °C. Results: Based on the UPLC / Q- TOF- MS / MS analysis,four caffeoylquinic acids,neochlorogenic acid,chlorogenic acid and cryptochlorogenin acid and isochlorogenic acid A,were identified from Huahong capsules. In addition,by using HPLC method,the correlation between the concentration and the chromatographic peak area of neochlorogenic acid,chlorogenic acid and cryptochlorogenin acid was linear in ranges of 3. 54-176. 80 μg·mL- 1( r = 0. 9999),6. 98- 348. 80 μg·mL- 1( r= 0. 9999),4. 06- 202. 80 μg·mL- 1( r =0. 9999),respectively. The average recoveries of the three caffeoylquinic acids were in the range of 101. 5%-102. 2%,and the relative standard deviations( RSD) were in the range of 1. 9%- 2. 4%. Conclusion: The UPLC /Q- TOF- MS / MS and HPLC methods do not only pave a way for further understanding of the chemical constituents in Huahong capsules,but also provide scientific evidences for the quality control of Huahong capsules.

Two new steroidal esters with an unusual framework, Sinkiangenorin A and B, a new organic acid glycoside, Sinkiangenorin C, and four known lignin compounds were isolated from the seeds of Ferula sinkiangensis. The structures of these compounds were established by spectroscopic analysis and single-crystal X-ray diffraction. All of the isolated compounds were tested against Hela, K562 and AGS human cancer cell lines. Sinkiangenorin C showed cytotoxic activity against AGS cells with an IC50 of 36.9 mu M. (C) 2014 Elsevier B.V. All rights reserved.

目的:研究一点红的HPLC指纹图谱,并测定该药材中新绿原酸①、绿原酸②、隐绿原酸③这3个咖啡酰奎宁酸类的含量,为其质量控制提供参考.方法:采用Phenomenex C18色谱柱(250mm×4.6mm,4μm),0.1％甲酸乙腈-0.1％甲酸水为流动相,梯度洗脱,流速1.0mL/min,检测波长326nm,柱温为30℃.对10批不同产地的一点红药材的HPLC图谱进行相似度评价.采用外标法,利用①-③的混合对照品测定其在10批药材中的含量.结果:确定该10批不同产地的一点红药材具有18个共有峰,10批药材的相似度范围为0.851-0.992;测定了10批一点红中的3个咖啡酰奎宁酸类成分的含量,结果显示,不同产地一点红中3个成分的含量差异明显.结论:HPLC指纹图谱方法与3个成分的含量测定方法准确、稳定、简单,可为一点红质量控制提供参考.

Objective To study the chemical constituents from the roots and rhizomes of Acorus tatarinowii. Methods Using different chromatographic methods to isolate and purify the constituents of A. tatarinowii, and their structures were identified by physicochemical properties and spectroscopic technology. Results Thirteen compounds were isolated and identified as fumaric acid (1), nicotinic acid (2), p-hydroxybenzonic acid (3), uracil (4), N-trans-feruloyltyramine (5), thymine (6), variecolorquinone A (7), butanedioic acid (8), tatarol (9), tataroside-12-β-D-glucoside (10), β-sitosterol (11), 2, 5-dimethoxy benzoquinone (12), and 5-hydroxymethyl-2-furaldehyde (13). Conclusion Compounds 1—7 are isolated from the plants in Acorus L. for the first time.

A new pyrrolidine alkaloid, Emiline (1), was isolated from the 90% EtOH extract of the aerial parts of Emilia sonchifolia. Its structure was established by various spectroscopic methods, including NMR, IR, HR-ESI-MS and X-ray crystallography. It was characterized by its skeleton derived from a bicyclo-[2.2.2]-oct-5-one ring and a pyrrolidine unit. The racemic mixture, (+/-)-Emiline, displayed good neuroprotective effect against the corticosterone-induced apoptosis in PC12 cells. (C) 2013 Phytochemical Society of Europe. Published by Elsevier B.V. All rights reserved.

A new cyclohexylacetic acid derivative, named 2-{4-hydroxy-7-oxabicyclo [2.2.1] heptanyl}-acetic acid (1), was isolated from Emilia sonchifolia, together with a known analogue, 2-(1,4-dihydroxy cyclohexanyl)-acetic acid (2). Their structures were determined on the basis of spectroscopic techniques including IR, NMR, HR-ESI-MS and X-ray diffraction.

OBJECTIVE:To study the chemical constituents contained in ethanol extracts from aerial parts of Emilia sonchifolia. METHOD:The compounds were separated and purified with various chromatographic techniques, and their structures were identified on the basis of physicochemical properties and spectral data. RESULT:Fifteen compounds were separated from ethyl acetate fraction of 90% ethanolic extract and identified as rhamnetin (1), isorhamnetin (2), quercetin (3), luteolin (4), tricin-7-O-beta-D-glucopyranoside (5), 8-(2"-pyrrolidinone-5"-yl) -quercetin (6), 5, -2', 6'-trihydroxy-7, 8-dimethoxyflavone-2'-O-beta-D-glucopyranoside (7), succinic acid (8), fumaric acid (9), p-hydroxybenzoic acid (10), 4-hydroxy isophthalic acid (11), 3, 4-dihydroxycinnamic acid (12), esculetin (13), isowedelolactone (14) and uracil (15), respectively. CONCLUSION:All compounds except compound 3 were separated from this genus for the first time.

To review the research progress on chemical constituents and pharmacological activities of plants belonging to genus Emilia and provide useful references for the further research.The literatures and monographs about genus Emilia over the past decades were referred,and the progress of the chemical constituents and pharmacological activities were summarized.Alkaloids,flavonoids,volatile oils are the main chemical constituents of genus Emilia.Many extracts prepared from the plants of the discussed genus show various biological activities,such as anti-tumor,anti-inflammatory,anti-nociceptive,anti-oxidant,etc.Because they have wide application prospects in anti-tumor,anti-inflammatory and other aspects,the study of the substance basis of the plants of genus Emilia should be enhanced.And it is important to strengthen the research in toxicity,due to poisonous pyrrolizidine alkaloids,in order to provide references for safty.

Objective: The chemical constituents from the seeds of Ferula sinkiangensis were studied.Methods: The constituents were isolated and purified by column chromatographies and their structures were identified by physico-chemical properties as well as spectral data.Results: Six compounds were isolated from the seeds of F.sinkiangensis and their structures were elucidated as stigmasterol(1),stigmasterol-3-O-glucoside(2),colladonin(3),siknianone(4),ferulic acid(5),7-hydroxycoumarin(6).Conclusion:Compounds 1,2,3,5,6 were isolated from the seeds of F.sinkiangensis for the first time.

Fourteen compounds were isolated from Amomum villosum Lour.Their structures were identified by physical-chemical and spectral analysis as Quercetin(1),Quercitroside(2),Isoquercitroside(3),Vanillic acid (4),3,4-Dihydroxy-benzoic acid(5),β-Sitosterol(6),Daucosterol(7),Stigmasterol(8),Ergosterol(9),ergosta-7,22dien-3β,5α,6β-triol(10),Stearic acid(11),Palmitic acid(12),Typhonoside B(13),Polygonin(14).Among them,Compounds 1,9,10,13,and 14 were isolated from Amomum villosum Lour.for the first time.

Objective To study the phloroglucinol derivatives of dryopteris crassirhizoma Nakai,and determine them anti-virus material basis.Methods The quantitative tests on three main factors which affect separation on the basis of buffered-silica-gel-column-chromatography method were applied to find a rapid method for separation and purification of the phloroglucinol derivatives at last.Results 5compounds including 4phloroglucinol derivatives were separated from the rhizome of Dryopteris Crassirhizoma.On the basis of NMR and MS spectroscopic analyses,these compounds were identified as filixic acid ABA(1),filixic acid ABB(2),filixic acid ABP(3),dryocrassin ABBA(4)and pentacosanol(5).Compounds(3)were isolated from Dryopteris crassirhizoma Nakai for the first time.Conclusion The optimized buffered-silica-gel-column-chromatography method has a good separation effect and a high sample recovery,which is suitable to study the phloroglucinol derivatives of Dryopteris crassirhizoma Nakai.