268 resultados para HPLC-ESI-MSn


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利用电喷雾串联质谱(ESI-MSn)系统地研究了乌头属植物和中药煎煮液中的乌头碱型生物碱的质谱行为。实验表明,ESI-MSn不仅是一种灵敏的药用植物中乌头生物碱的分析方法,也是研究中药配伍规律和阐释中药复方合理内涵的有效工具。低能诱导碰撞解离肠导下,具有乌头碱骨架类型的生物碱断裂规律相似:丢失C8乙酰基或长链脂肪酰基是它们在MSZ中的特征断裂,在MS3和MS4中丢失1-4CH3OH,1-3H2O,CO,BzOH,CH3(N)或C2H5(N)是其他所有可能的断裂方式,并且结构的微小差别也能在串联质谱中得到反映。利用这些规律分析了生附子、生草乌、生草乌花、生白山草乌和制雪上一支蒿中的生物碱,我们不仅发现所有已知的化合物,还部分表征了50余种新化合物,其中具有15C,17C,19C和ZOC饱和或不饱和脂肪酰基,以10-OH-中乌头碱和10-OH-乌头碱为骨架的脂碱以及三脂型脂碱为首次在乌头属植物中发现。该结果提出了脂类生物碱在乌头属植物中普遍存在的可能性。另一方面,我们发现中药煎煮液具有缓冲溶液的性质,酸性和糖是影响剧毒性双酯型生物碱水解的两个因素。在pH5.0-5.5和糖的存在下,大部分双酯型生物碱水解为苯甲酰单酯型生物碱,少部分被转为脂碱,在pH2.8到3.5之间(半夏等与附子禁用中药煎煮液的pH),双酯型生物碱十分稳定,既不水解,也不转为脂碱。这样,我们不仅解释了传统中医药配伍理论的合理内涵,也表明她可能.存在着不足。此外,脂碱难溶于水,大部分脂碱煎煮后仍残留在药材组织中。最后,为评价脂碱的抗癌效果,我们用在水相下合成了8-棕榈酰-苯甲酰乌头原碱,体外实验表明,0.001mg/ml的8-棕榈酰-苯甲酰乌头原碱对肝癌细胞SMMC-7721和黑色素瘤细胞B16即具有很强的杀伤作用,并且提示它们可能具有不同的作用机制。

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随着软电离技术的发展,特别是基质辅助激光解析(MALDI)和电喷雾(ESI)两种软电离技术的出现,使质谱分析生物大分子成为可能,将质谱的应用范围迅速扩展到生命科学的诸多研究领域,特别是成为了蛋白质组分析,医学诊断,药物分析等领域不可替代的新工具。首先,采用凝胶电泳与傅立叶变换离子回旋共振质谱(FT-ICR MS)的高分辨率和高质量精确度性能相结合的新方法,对不同肺病患者的支气管肺泡灌洗液进行了快速直接的蛋白质组分析,为肺疾病诊断学、肺病相关机理的研究以及高分辨质谱在蛋白质组分析中的应用奠定了基础。一维(1-D)和二维(2-D)凝胶电泳与高分辨FT-ICR MS相结合,对慢性支气管炎(cblonic broncnitis,CB)和囊泡纤维化(cystic fibrosis,CF)患者的支气管肺泡灌洗液(BALF)中表面蛋白A和D进行了鉴定;并对表面蛋白的翻译后修饰(hydroxy-prollne)进行了直接的确定;对来自于不同肺泡蛋白沉积症(PAP)患者的BALF中的特异性蛋白进行了鉴定,鉴定出表面蛋白A的两个降解片段,为研究与肺病相关的SP-A降解产物的可能降解途径提供了初步的信息。证实了FT-ICR MS的高分辨率和高质量精确度在蛋白质的鉴定过程中的突出作用:(i)利用单个多肤的精确质量,可以避免依赖离子的串联质谱数据进行蛋白质鉴定,即无需对谱图中的离子进行串联质谱分析,就可实现蛋白质或蛋白质混合物的快速、确切的鉴定;(ii)在数据库检索中应用很小的误差范围可以大大提高蛋白质鉴定时的选择性;(iii)通过来自于微量蛋白质的少量肤峰就可以进行蛋白质的准确鉴定。通过MALDI/EST FT-ICR MS、园二色谱(CD)和H/D交换实验(hydrogedeuteriuln exchange)对一系列人SP-C及其类似物进行了表征。证实了溶液相中FFI-SP-C和rh-SP-C的非共价二聚体的存在;研究了人SP-C在有机溶剂中的构象变化和聚集行为,为探讨肺病相关机理奠定了基础。其次,以电喷雾多级串联质谱为研究手段,对部分生物类黄酮及其络合物进行系统的质谱研究,发现二氢黄酮及二氢黄酮醇类化合物在电喷雾条件负离子模式下具有不同的特征质谱行为,为质谱区分这两类化合物提供了重要的依据;黄酮金属络合物的研究中,四种二价过渡金属(Cu(II),Zn,Mn(II)和Fe(II))与芸香普均可以形成络合物,探讨了芸香普一铜络合物软电离条件下的碎裂机理,并利用多级串联质谱数据探讨了络合物C和D的结构,为质谱方法探讨金属清除疾病相关自由基的机理以及提高金属的生物利用度奠定了基础。

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首先,对虎眼万年青中化学成分进行了分离提取研究,采用柱层析和薄层层析等方法,并利用电喷雾质谱技术跟踪洗脱流分,首次从虎眼万年青氯仿提取物中分离得到两个新化合物。其一为单菇内酷loliolide,通过FT-ICRMS高分辨质谱、IR和NMR等手段对其结构进行了确定,并通过IHNMR和旋光法确定了其绝对构型。此外,还利用电喷雾多级串联质谱(ESI一MSn)技术对其质谱裂解规律进行了系统研究,其分析结果与NMR解析结果完全一致,建立了该类化合物结构解析的简便、快速的质谱新方法;另一化合物为生物碱类化合物,采用电喷雾多级串联质谱技术对其质谱裂解规律进行了详细研究,并对其结构进行了初步推断,进一步的NMR结构确定正在进行中。其次,对虎眼万年青多糖成分进行了分离提取研究,并结合体外抑瘤活性评价实验,确定了两种具有抑瘤生物活性的多糖成分OC一2一1一c和OC一2一卜d。并通过SDS凝胶电泳和糖基组成分析,初步证明了虎眼万年青中的活性多糖成分为阿拉伯半乳糖蛋白(AGPs),为进一步研究虎眼万年青抗肿瘤活性提供了基础数据和理论指导。此外,还对虎眼万年青中的微量元素及其溶出率进行了初步的研究,研究结果表明,其水煎液中Cu/Zn比值明显低于癌症患者血清中的Cu/Zn比值,因此,虎眼万年青可能有助于调节癌症患者体内的Cu、Zn平衡,从而达到抗癌目的;而虎眼万年青中Se、Ge含量很低,不能作为两种微量元素的药用来源。为了进一步研究抗癌药物的作用机理,我们采用电喷雾质谱技术,对三种临床疗效较好的抗癌药物与DNA相互作用进行了系统的研究,确定了复合物的化学计量比及其结合的特异性,并利用竞争实验方法,研究了抗癌药物的相对结合强度。质谱实验结果与液相行为完全一致,其中抗癌药物米托葱醒为首次利用质谱进行研究。最后,采用电喷雾质谱技术,对硝酸盐离子簇合物进行了详细研究,发现了双电荷簇合物离子,并且在离子簇合物中还发现了魔数规律的存在。利用电喷雾多级串联质谱技术,研究了双电荷簇合物离子的质谱裂解规律,并对其稳定性进行了分析。此外,还讨论了溶液浓度和毛细管温度对离子簇合物形成的影响规律。

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首先,利用现代软电离质谱技术--一电喷雾质谱技术以及电喷雾源内碰撞诱导解离(CID)技术,对传统中药--一黄连中的生物碱类化合物小聚碱及其同分异构体表小粟碱化合物的质谱碎裂机理进行了详细研究,实验结果表明,随着碰撞能量的变化,两者的质谱碎裂规律具有明显的差异,据此,建立了简便、快速、准确的小巢碱和表小聚碱两种同分异构体化合物区分的质谱新方法,为该类药材及其相应的中药制剂的质控提供了有效的手段和方法。其次,还利用电喷雾多级串联质谱(ESI-MSn)技术,系统地研究了传统中药--一黄连中生物碱类化合物的质谱碎裂规律,我们通过一级质谱的数据,获得了黄连中生物碱类化合物的分子量信息,并对其中五个已知的生物碱进行了初步的确认,同时,通过一级质谱的结果,首次在黄连中发现的分子量为366的未知生物碱类化合物,并通过电喷雾多级串联质谱技术对上述六种化合物的结构进行了详细的研究,结合标准样品的串联质谱数据和文献资料,确认了五个已知的生物碱类化合物分别为小粟碱、巴马汀、药根碱、黄连碱和13-甲基小桨碱,并推断未知生物碱类化合物为13-甲基巴马汀,建立了黄连中生物碱类化合物简便、快速的质谱分析表征新方法,并为其他传统中药中生物碱类化合物的分析与表征积累了重要的理论数据,更重要的是建立了传统中药中未知生物碱类化合物确认和结构分析的质谱方法。此外,还利用量子化学DFT-B3LYP方法,6-31G(d)基组,详细研究了传统中药黄连中小璧碱分子的质谱碎片的相对稳定性。并通过对结合能的理论计算,探讨 质谱碎裂过程中关键基团的相对活性。结合几何参数比较和前线分子轨道分析等方法,从理论上解释了小聚碱化合物的质谱碎裂规律的合理性、分子结构特征及基团活性等,为研究该化合物的药效作用机理,以及药物分子的全合成提供理论依据。同时,还利用电喷雾质谱和薄层层析等方法,对含有黄连的传统复方--一半夏泻心汤进行了初步的考察研究,通过复方中黄连的阴、阳性溶液对比分析,发现在半夏泻心汤中主要的生物碱类化合物,如:小聚碱、巴马汀、药跟碱、黄连碱在复方煎煮过程中在仅仅表现在数量的变化,而没有质的变化,进一步揭示了在半夏泻心汤复方中黄连中的生物碱类化合物的变化规律,为阐明传统复方的药效物质基础提供了科学依据。最后,确定了黄连中生物碱类化合物的毛细管电泳分析的最佳条件,并对黄连中小粟碱化合物进行了定量分析研究,建立了生物碱类化合物毛细管电泳分析的新方法。

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本论文由四章组成,第一、二、三章为实验论文,分别报道了中药羌活、菊花、全缘叶绿绒蒿的化学成分的高效液相色谱(HPLC)和液相色谱-质谱(LC-MS)联用分析以及挥发油的气相色谱-质谱(GC-MS)联用分析。第四章概述了重要藏药材化学成分的研究进展。 第一章首先对28批不同产地的羌活药材进行了HPLC分析,建立了羌活的指纹图谱。结果表明,不同产地羌活的化学成分基本相似,但是各组分在含量上存在较大差异。其次,对羌活的主要化学组分包括紫花前胡苷、紫花前胡素、6'-O-反式阿魏酸紫花前胡苷、茴香酸对羟基苯乙酯、羌活醇和异欧前胡素进行了定量分析。此外,针对同一产地不同采集时间的羌活挥发油进行系统分析,结果表明它们的化学成分基本相似,主要含有a-蒎烯、b-蒎烯、柠檬烯和龙脑乙酸酯等,只是各组分含量有所变化,这说明采集药材时要注意采集时间。 第二章分别报道了不同产地不同品种菊花非挥发性成分的液相色谱-二极管阵列检测-串联质谱(LC-PDA-MSn)分析和挥发性成分的气相色谱-质谱(GC-MS)联用分析比较。首先通过液相色谱-质谱-串联质谱对各色谱峰进行定性分析,通过与标准品对照,以及UV和MSn提供的结构信息,结合文献报道共鉴定了11个化学成分,包括绿原酸和10个黄酮化合物,并比较了不同品种菊花的化学成分相同之处和不同之处。另外,对七种不同品种不同产地的菊花挥发性成分通过GC-MS分析表明其主要挥发性成分为单萜类、倍半萜类化合物,共有成分樟脑、龙脑和龙脑乙酸酯等,各成分在不同挥发油中的含量变化明显。 第三章为藏药全缘叶绿绒蒿不同部位挥发油成分的气相色谱-质谱(GC-MS)联用分析,比较其挥发油化学成分及其含量变化的异同点。研究结果表明,全缘叶绿绒蒿花精油的化学成分明显多于全草部位,且两者主要成分有较大的差别。 第四章综述了青藏高原重要藏药材化学成分的研究进展。分别对藏药的资源特色和110多种常用重要藏药材的化学成分的研究情况以及藏药未来发展思路进行了阐述,以期对相关的研究提供一些信息。 This dissertation consists of four parts. The first part reports studies on the fingerprint of Notopterygium incisum and N. forbesii by HPLC-PDA-MSn, and on the constitutents of essential oil by GC-MS. The second part elaborates the chemical constitutents of Chrysanthemum L. by LC-MS and GC-MS analysis. The third part reports the chemical compositions of the essential oil from the different parts of Meconopsis integrifolia. The fourth part reviews on the progress of the studies on the chemical constitutents in Tibetan medicines. The first chapter is about HPLC analysis of a traditional Chinese herbal medicine Qiang-huo (Notopterygium incisum and N. forbesii ). Firstly, based on analyzing and contrasting the relative retention time and relative paek area in chromatographic fingerprint, the HPLC chromatographic fingerprint of Notopterygium incisum was established, which can used as a scientific basement for the quality evalution of this herb. Secondly, quantitative analysis were performed on the main chemical constitutents of Notopterygium incisum and N. forbesii including nodakenin, nodakenetin, 6’-O-trans-feruloylnodakenin, p-hydroxypenethylanisate, notopterol and isoimperatorin. The results indicated that the contents were variable related to different growth regions. Lastly, the essential oil of Notopterygium incisum collected in different harvest times is analyzed by GC-MS. The second chapter is about HPLC-MS and GC-MS analysis of several species of Chrysanthemum L. Firstly, eleven compounds including chlorogenic acid and ten flavone compounds were identified in the methanol extract of Chrysanthemum morifolium Ramat. from different regions by HPLC-MS analysis. Secondly, the essential oil of seven different species of Chrysanthemum L.were extracted by steam distillation, and its compositions were isolated and identified by GC-MS. The main active constitutents such as camphor, borneol and bornyl acetate were detected, but the relative content varied notably. The third chapter is about GC-MS analysis of the essential oil from different parts of Meconopsis integrifolia. It indicated great difference of the chemical compositions of their oil in the flowers and residual overground part. The last chapter is a review of the research progress of the Tibetan medicines, which includes their features and their main chemical constitutents.

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本学位论文由5 章组成。第1 章报道了两头尖中三萜皂苷类化合物的全扫描电喷雾多级质谱分析及银莲花素A 的电喷雾质谱裂解规律;第2 和3 章报道了两种银莲花属药用植物化学成分的研究结果;第4 章报道了银莲花素A 的化学结构修饰及其对一种蛋白酪氨酸磷酸酯酶(PTP-1B)的抑制活性;第5 章综述了电喷雾质谱在皂苷类化合物结构鉴定中的应用进展。 第1 章报道了运用全扫描电喷雾多级质谱对两头尖中三萜皂苷类化合物的快速定性检测,共检测出18 个准分子离子峰,根据多级质谱数据并结合文献报道,对其中的15 个准分子离子峰进行了归属,并区分了一些同分异构体;更有意思的是,发现了3 个未见文献报道的三萜皂苷类化合物。根据它们的多级质谱数据,对其结构分别进行了初步解析。本章同时对银莲花素A 特殊的质谱裂解途径通过衍生物制备及其质谱分析进行了确认。 第2 和3 章,分别报道了两头尖和打破碗花花中水溶性多糖苷的分离纯化和结构鉴定。采用D101 大孔树脂和反复硅胶柱层析等分离手段,从两头尖水溶性部分分离得到8 个三萜皂苷类化合物,通过红外、电喷雾质谱和核磁共振等现代谱学方法,并结合传统的化学手段鉴定了它们的结构,其中4 个化合物为新化合物,分别命名为多被银莲花皂苷19、多被银莲花皂苷20、多被银莲花皂苷21和多被银莲花皂苷22。从打破碗花花水溶性部位分离得到6 个三萜皂苷类化合物,通过现代谱学手段,并结合传统的化学方法对它们进行了鉴定,其中1 个为新化合物,命名为打破碗花花苷H。 第4 章报道了以银莲花素A 及其同系物为先导化合物,进行化学结构修饰并对修饰产物进行广泛的生物活性筛选,发现在银莲花素A 及其同系物的结构中引入一些酸性基团后,其生物活性发生了变化,一些修饰产物显示出很强的PTP-1B 抑制作用,提示这些化合物有可能用于治疗II 型糖尿病。 第5 章综述了电喷雾多级质谱用于皂苷类化合物结构鉴定的研究进展。 This dissertation composes of five chapters. The first chapter elaborates the detection and qualification of the triterpenoidal saponins in Anemone raddeana by positive and negative full scan ESI-MSn. This part also reports the special fragmentation pathway of Raddeanin A by ESI-MS/MS. The second and third chapters present the phytochemical investigation of two medicinal plants from Anemone. The fourth part dwells on the structure modification of Raddeanin A and their inhibitory activity against PTP-1B. The last part is a review on the progress in the application of ESI-MSn in the structure identification of saponins. The first chapter reports the application of full scan ESI-MSn for fast analysis of triterpenoid saponins in Anemone raddeana. Eighteen quasi- molecular ion peaks were detected in the positive full scan ESI-MS and fifteen of them were identified by analysis of their tandem mass spectral data in the negative ion mode. Several isomers were differentiated. More interesting, three unreported triterpenoid saponins in this medicinal plant were detected and their structures were deduced according to the dissociation pathway of the known triterpenoidal saponins. This chapter also confirms the special fragmentation pathway of Raddeanin A by its derivative and the mass spectral analysis. The second and third chapters expatiate on the isolation and identification of the chemical constituents from A. raddeana and A. hupehensis. Eight compounds were isolated from the roots and stems of A. raddeana by methanol extraction and repeated column chromatography (including D101 and silica gel), and their structures were determined on the basis of IR, ESI-MS, NMR and chemical methods (including acid hydrolysis and alkaline saponification). Among them, four are new triterpenoid saponins and named as Raddeanoside R19, Raddeanoside R20, Raddeanoside R21 and Raddeanoside R22. Six compounds were isolated from the whole plants of A. hupehensis by the same methods as above, and their structures were also determined with the same way. One of them was confirmed to be new triterpenoid saponins and named as hupehensis saponin H. In the fourth chapter, in order to look for new active compounds, the structure of Raddeanin A and its analogs were modified. It was found that the modified products exhibited obvious inhibitory activity against PTP-1B when several acid groups were introduced. The fifth chapter summarizes the progress on the application of ESI-MSn in the structure identification of saponins.

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本学位论文报道了西藏产三种藏族传统植物药材的化学成分研究。论文由四章组成,前三章是实验部分,分别报道了尼泊尔黄堇(Corydalis hendersonii Hemsl.)、藏波罗花(Incarvillea younghusbandii Sprague)和全缘叶绿绒蒿(Meconopsis interifolia Franch.)的化学成分研究结果。从这三种青藏高原药用植物中共分离鉴定出33 个化合物,其中1 个是新化合物。第四章概述了罂粟科紫堇属植物的化学和药理研究进展。 第一章为尼泊尔黄堇的化学成分研究。通过正、反相硅胶柱色谱等分离方法从药用植物尼泊尔黄堇的地上部分共分离纯化得到12 个化合物。运用MS、1H-NMR、13C-NMR、DEPT、HMBC、NOESY 等现代波谱学方法将它们的结构鉴定为:刺罂粟碱(1) , 普托品(2) , 新那亭(3) , 斯可任(4) , tetrahydrothalifendine (5) ,9-methyl-decumbenine C (6),tetrahydroberberrubine (7),隐品碱(8),α-别隐品碱(9),6,7-methylenedioxy-1(2H)-oxoisoquinolinone (10),6-丙酮基-5,6 -二氢血根碱(11)和β-谷甾醇(12)。其中化合物6 为新化合物,为首次发现的分子骨架上C-9 位连有甲基的苯肽异喹啉类型生物碱。另外,除化合物1 和2 外,其它9 个生物碱(3~11)均为首次从该种植物中分离得到。同时,我们还对对尼泊尔黄堇中的总生物碱进行了串联质谱分析。 第二章为藏波罗花的化学成分研究。从该药用植物的地上部分共分离得到16个化合物,通过理化常数和波谱数据鉴定为:异佛手柑内酯(1),6-甲氧基当归素(2),欧前胡素(3),花椒毒内酯(4),珊瑚菜素(5),水合氧化前胡素(6),rivulobirin A (7),齐墩果酸甲酯(8),咖啡酸甲酯(9),银桦酸(10),(D)-boschniakinic acid (11),对羟基苯甲酸(12) , tert-O-β-D-glucopyranosyl-(R)-heraclenol (13) , 5-methoxy-8-O-β-D-glucopyranosyloxypsoralen (14),前胡苷V(15)和苯乙醇-O-β-D-吡喃葡萄糖-(1→2)-O-β-D-吡喃葡萄糖苷(16)。所有以上化合物均为首次从该种植物中分离得到。另外我们还首次对藏波罗花挥发油的化学成分进行了气相色谱-质谱(GC-MS)联用分析,共鉴定出39 个挥发性成分。 第三章为全缘叶绿绒蒿化学成分的分离鉴定。从传统藏药材全缘叶绿绒蒿地上部分共分离纯化出8 个化合物。通过理化常数和波谱数据将他们的结构分别鉴定为:去甲血根碱(1),β-谷甾醇(2),3-羟基-齐墩果烷-12(13)-烯-30-酸(3),6-丙酮基-5,6-二氢血根碱(4),木犀草素(5),胡萝卜苷(6),quercetin 3-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranoside (7)和普托品(8)。其中化合物1,4 和7 为首次从该种药用植物中分离得到。 第四章为综述,总结和归纳了近年来罂粟科紫堇属植物的化学和药理研究进展。 This dissertation consists of four parts. The first, second and third parts report the studies on the chemical constituents from the medicinal plants of Corydalis hendersonii, Incarvillea younghusbandii and Meconopsis interifolia. The forth part reviews the progress of the studies on Corydalis species. The first chapter is about the isolations and identifications of alkalids from the aerial parts of C. hendersonii which is a traditional Tibetan medicine to treat febrifuge, high blood pressure and hepatitis. A new isoquinoline alkaloid, 9-methyl-decumbenine C (6), together with ten known alkaloids, stylopine (1), protopine (2), canadine (3), scoulerine (4), tetrahydrothalifendine (5), tetrahydroberberrubine (7), cryptopine (8), α-allocryptopine (9), 6,7-methylenedioxy-1(2H)-isoquinolinone (10) and 6-acetonyl-5,6-dihydrosanguinarine (11), and β-sitosterol (12) were isolated. Their structures were elucidated by spectroscopic methods. Furthermore, the total alkaloids were analyzed by ESI-MSn. The second chapter is about the isolations and identifications of chemical constituents from the aerial parts of I. younghusbandii. Sixteen compounds were isolated and purified by normal and reversed phase silica gel column chromatography. By spectral analysis, there structures were identified as isobergapten (1), sphondin (2), imperatorin (3), xanthotoxin (4), phellopterin (5), heraclenol (6), rivulobirin A (7), methyl oleanolate (8), methyl caffeate (9), grevillic acid (10), (D)-boschniakinic acid (11), 4-hydroxybenzoic acid (12), tert-O-β-D-glucopyranosyl-(R)-heraclenol (13), 5-methoxy-8-O-β-D-glucopyranosyloxypsoralen (14), decuroside Ⅴ(15), and phenylethyl-O-β-Dglucopyranosyl-(1→2)-β-D-glucopyranoside (16). All of these compounds were isolated from this plant for the first time.By the way, the chemical components of the essential oil from I. younghusbandii were analyzed by GC-MS for the first time. The third chapter is about the the isolations and identifications of the chemical constituents of M. interifolia. Eight compounds were isolated and identified as norsanguinarine (1), β-sitosterol (2), 3-hydroxyolean-12(13)-en-30-oic acid (3), 6-acetonyl-5,6-dihydrosanguinarine (4), luteolin (5), daucosterol (6), quercetin 3-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranoside (7) and protopine (8). The compounds 1, 4 and 7 were isolated from this herb for the first time. The last chapter is a review of the research progress of the studies on Corydalis species, which includes the chemical constituents in this genus and their pharmacology.

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The electrospray ionization ion trap multiple-stage tandem mass spectrometry (ESI-MSn) and electrospray ionization Fourier transform ion cyclotron resonance multiple-stage tandem mass spectrometry (ESI-FT-ICR-MSn) have been applied successfully to the direct investigation of a number of dibenzocyclooctadiene lignan constituents from the methanol extracts of the Fructus Schisandrae in the positive ion mode. The detailed structural characterization of the same skeleton and different peripheral substituents had been studied and the precise elemental compositions of ions at high mass resolution had been obtained. So the fragmentation mechanisms could be clarified.

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利用电喷雾串联质谱(ESI-MSn)技术研究马钱苷的质谱碎裂机理,探讨其碎裂方式,并利用傅立叶变换离子回旋共振质谱(FTICR-MS)及SORI-CID高分辨率、高质量准确度对其碎裂机理进行验证研究。采用H/D交换和串联质谱的方法,发现马钱苷羟基上的活泼氢在质谱中性碎片丢失过程中较易被转移,表现出较大的化学活性。通过加入特定的Na+和Li+等碱金属离子,极大地提高了马钱苷化合物质谱分析的灵敏度,获得了更多的结构信息,建立了马钱苷化合物质谱鉴定和分析的新方法。

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In vitro α-glycosidase inhibition assays and Ultrafiltration LC-DAD-ESI-MSn were combined to screening α-glucosidase inhibitors from hawthorn leaves flavonoids extract. As a result, hawthorn leaves flavonoids extract showed strong α-glucosidase inhibitory activity, four compounds presented α-glucosidase inhibitory effects were observed and identified by LC-DAD-MSn, and further confirmed by high resolution SORI-CID FT ICR MS data.

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Four saponins were isolated from the leaves of Aralia elata, and established using NMR and other spectroscopic methods, as well as data reported in the literature. Three Aralia saponins from the leaves of Aralia elata sharing the same structures as those isolated from the root bark suggested that the leaves would be a good substitute for the root bark of Aralia elata. These four Aralia saponins were then extensively investigated using complementarily positive and negative electrospray ionization multistage tandem mass spectrometry (ESI-MSn). Two isomers of saponins with different sugar linkages were then successfully differentiated by positive ESI-MSn and verified with different retention times and the collision-induced dissociation (CID) spectra by LC-MS. A simple and effective LC-MS method was thus developed for the rapid identification and screening of these saponins in plant extracts from leaves of Aralia elata.

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首次采用LC/ESI-MSn方法对乌头碱灌胃给药后不同时间内家兔尿液中的乌头碱代谢产物进对比研究。经与空白尿样对照发现,在0~4h和4~8h两个时间段,家兔尿液中除乌头碱(AC)原形外,均含有相同的代谢产物,但相对含量差别很大。通过总离子流色谱图(TIC)可以发现3个主要代谢产物(M1,M2,M4)。分别测定了各代谢产物的准分子离子及其各级碎片离子,与AC在ESI-MSn条件下的质谱碎裂规律相比较,并参考AC体内代谢文献,推断尿液中的主要代谢产物M1为16-O-去甲基乌头碱;M2和M4的m/z均为616,为同分异构体,结构还需要进一步的确认。

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The hydrolysis of ginsenoside standards and the crude extracts of ginseng has been investigated at different pH values (2.4 - 11.2) using high performance liquid chromatography-electrospray ionization mass spectrometry (HPLC-ESI-MS). The experimental results indicated that the pH value of aqueous solutions is an important factor in changing the composition of ginsenosides. For (20S)-protopanaxadiol ginsenosides, ginsenosides with a large mass hydrolyzed to form hydrolysates (20S)-Rg(3) and (20R)-Rg(3) at pH 4.3. There were more hydrolyzed products observed at pH 3.3: (20S)-F-2, C-25,26 hydrated ginsenoside "C-Y-1" and "C-Y-2" (MW = 802 Da) accompanied with (20S)-Rg(3), (20R)-Rg(3). At pH 2.4, only (20R)-Rg(3), (20S)-F-2, a small quantity of (20S)-Rg(3) and three C-25,26 hydrated ginsenosides were obtained. For (20S)protopanaxatriol Re, no hydrolysates were observed at pH 4.3; it was hydrolyzed at pH 3.3 to form hydrolysates (20S)-Rg, (20R)Rg(2) and hydrated C-25,26 (MW = 802 Da) and at pH 2.4 only C-25,26 hydrated ginsenosides "C-Y-1" and "C-Y-2" (MW = 802 Da) were left in the solution. Similar hydrolysis reactions could be also observed for the crude extracts of ginseng. It showed that HPLC/ESI-MS is a fast and convenient method to study the hydrolysis of ginseng.

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Paeoniflorin standard was first investigated by electrospray ionization Fourier transform ion cyclotron resonance tandem mass spectrometry (ESI-FTICR-MS/MS) using a sustained off-resonance irradiation (SORI) collision-induced dissociation (CID) method at high mass resolution. The experimental results demonstrated that the unambiguous elemental composition of product ions can be obtained at high mass resolution. Comparing MS/MS spectra and the experimental methods of hydrogen and deuterium exchange, the logical fragmentation pathways of paeoniflorin have been proposed. Then, the extracts of the traditional Chinese medicine Paeonia lactiflora Pall. were analyzed by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry (HPLC/ESI-MS/MS). By comparison with the ESI-FTICR-MS/MS data of paeoniflorin, the isomers paeoniflorin and albiflorin in Paeonia lactiflora Pall. have been identified using HPLC/MS with CID in an ion trap and in-source CID. Furthermore, using the characteristic fragmentation pathways, the retention times (t(R)) in HPLC and MS/MS spectra, the structures of three other kinds of monoterpene glycoside compounds have been identified on-line without time-consuming isolation.

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According to their molecular mass and ESI-MSn data, the trace alkaloid isomers pseudostrychnine and strychnine N-oxide in extracts of the total alkaloids from Strychnos nux-vomical were qualitatively analyzed by electrospray ionization tandem mass spectrometry (ESI-MSn) method after rough silica gel-column chromatographic separation. We also investigated the relationship between their fragmentation mechanism and structures of the two alkaloid isomers. A new method for quickly and highly sensitively analyzing the two alkaloid isomers was proposed.