麦角生物硷的层离研究 Ⅱ.麦角生药的柱层离定量

麦角中生物硷的含量测定,一般均按中国药典及 N.F.方法.但这两个方法只能测出总生物硷和水溶性生物硷的含量,对最有效成份——水溶性生物硷中的麦角新硷无法单独测定.Grove 曾用提取方法分离麦角新硷和麦角异新硷,进行个别定量,但手续麻烦,而且提取液体积较大,含量少时测定困难.Carless 用纸纤维柱层离法分别测定麦角中各种生物硷含量,样品用量很少,全部过程需两天.根据作者之一用硅藻土柱层离法自麦角生药中提取麦角新硷的结果,我们认为有可能达到定量目的,因此进行了以下试     

麦角生物硷的层离研究 Ⅰ.我国野生麦角的成分鉴定及麦角新硷的定量

近年来国内发现几种野生麦角,本院药用植物系进行了调查研究,从分怖地区及麦角外部形态方面作了初步报导,为进一步了解和探讨其中生物硷成分及麦角新硷含量,我们用纸屑离法进行研究。一般化学测定法只能测定麦角总硷含量及水溶性生物硷含量,对于个别生物硷无法测定,自1949年Foster应用纸屑离法后,就大大方便了从事研究麦角复杂成分的方法。 Foster用正丁醇、醋酸、及水的混合液作扩展溶剂,把水溶性及水不溶性生物硷在     

麦角菌发酵物中生物碱的化学研究

利用麦角菌生物合成制取麦角新碱的方法已推广应用于生产。该菌种在小麦种子培养基上培养以后,除麦角新碱外,根据薄层层离鉴定结果证明还产生三种麦角生物碱。为了利用麦角新碱生产过程中母液里的其他麦角生物碱,并为进一步研究生物合成机制提供资料,必须先对母液中所含麦角生物碱进行分离和鉴定。曾采用无粘合剂的氧化鋁薄层层离法,从母液中分离出了四种生物碱。除麦角新碱外,其余三种生物碱通过薄层层离鉴定;熔点、比旋度测定;紫外吸收光谱、红外吸收光谱和元素分析等分别鉴定,证明为麦角异新碱、麦角生碱和麦角异生碱。     

麦角菌发酵物中生物碱的化学研究

利用麦角菌生物合成制取麦角新碱的方法已推广应用于生产。该菌种在小麦种子培养基上培养以后,除麦角新碱外,根据薄层层离鉴定结果证明还产生三种麦角生物碱。为了利用麦角新碱生产过程中母液里的其他麦角生物碱,并为进一步研究生物合成机制提供资料,必须先对母液中所含麦角生物碱进行分离和鉴定。曾采用无粘合剂的氧化鋁薄层层离法,从母液中分离出了四种生物碱。除麦角新碱外,其余三种生物碱通过薄层层离鉴定;熔点、比旋度测定;紫外吸收光谱、红外吸收光谱和元素分析等分别鉴定,证明为麦角异新碱、麦角生碱和麦角异生碱。     

嘌呤族生物鹼的非水溶液光度滴定法

嘌呤族生物鹼类中常见的三种生物酸包括咖啡鹼、可可鹼及茶鹼等,这兰种生物鹼在各国药典中尚没有规定含量测定方法。有关它们的原料及制品的分析,文献上规定的方法大都手续繁、费时多,尚难令人满意。近年来非水溶液滴定法有了很大的发展,Pifer氏等曾提出以水醋酸为溶剂,用HClO_4的水醋酸溶液行电位滴定来测定咖啡鹼等的有机鹼类。同年Poulous报告用     

非挥发性毒物的纸层析

毒物的系统分析中,同一类或同一族的各种毒物,不能加以分离,要靠专一反应来检出与鉴别.若有两种以上同族的毒物同时存在,就不易各别检出.因此,我们应用纸析法来分离并检出各族中的各种毒物.C.Romano曾以盐酸丁醇作溶剂,用纸析法作九种有毒生物鹼的毒物定性分析;但所报告的比移值(R_f value)都很大,而且彼此很接近,因此不能分离与分别检出.A.S.Curry等曾用枸櫞酸二氢钠浸过的滤纸,以丁醇枸櫞酸作溶剂,升渗法纸层析鹼     

麦角生物碱的层离研究——Ⅲ.麦角生药的纸层离定量

在以前的紙层离工作基础上,拟定出麦角新碱、麦角胺与麦角毒碱的紙层离定量方法。紙用緩冲液、甲酰胺、丙酮的混合液(2:1:1)处理,点上样品后以氯仿扩展。然后根据生物碱位置,或收集氯仿洗胱液,或用稀硫酸浸泡洗下,用对二甲氨基苯甲醛显色后定量。緩冲液之pH值对生物碱移动距离有影响,可改变之以达到不同測定目的。麦角胺与麦角毒碱的回收率分别为93.7%与94.4%。曾用此法分析麦角样品,結果与柱层离法相符合。     

薄层层离法在研究天然化合物中的应用 Ⅰ.麦角新碱、麦角胺、麦角毒碱的鉴定

本文研究了影响麦角新碱、麦角胺和麦角毒碱的氧化铝薄层层离的各种因素.实验结果表明,酸性、中性和弱碱性氧化铝均能使三种麦角生物碱分离.氧化铝细度以小于200号筛的层离效果最好,莹光点圆而集中.苯-无水乙醇(10:0.5)是较为理想的推进剂,不仅分离效果好,而且其组成简单,容易处理和回收.层离板的斜度对层离效果影响不大,但以8—16°角较合适.层离槽放入溶剂后,必须先密闭放置10分钟,才能进行层离,否则容易产生边缘效应.根据以上研究桔果,制订了鉴定麦角中三种主要生物碱的方法.     

中药研究中色层分离法的应用(四)麻黄生物鹼的分离和提取

关于离子交换作用在生物鹼类的提取和分离上,曾有过许多报告。例如Apple-zweig 应用离子交换剂自金鸡纳树皮的酸浸出液中直接分离出生物鹼,而建议用于工业生产上;Kingsbury等利用氢离子型交换剂以回收烟厂中因干操烟叶时挥发损失的烟鹼;Grant和Hilty二氏则应用阴离子交换剂分离了吗啡和可待因,并自混合物中,测定了它们的含量;著者等亦应用氢离子型的磺化煤测定了常山中生物鹼的含     

药物中铜与铅杂质的纸层离检验法

在有机药物内检验重金属杂志时,必须先破坏有机物,然后分别检验,手续烦杂,耗费时间。苏联试用氧化铝吸附层离法进行一些药物中铅与铜杂质的检验,这个工作启发了我们试用纸层离法进行药物中重金属的检验。近年来,纸层离法检验金属已被广泛应用于无机分析方面,但应用在药物鉴定上尚不多,我们用纸层离法进行了葡萄糖、磺胺药、缬草酊中铅与铜杂质的测定,结果尚称完满。     

Effect of ergot alkaloids on sulfonylurea-stimulated insulin secretion in dogs.

The insulinogenic response to a standard i.v. dose of a sulfonylurea can be markedly augmented in normal, conscious dogs if they are given 30 min earlier a single i.v. dose of dihydroergotamine (DHE). Since the parent substance ergotamine posssed no such amplifying properties, further experiments were conducted to clarify the essential structural requirements that have to be fulfilled for an ergot alkaloid to act as an amplifier of sulfonylurea-stimulated insulin secretion. Amine alkaloids ergonovine, dihydroergonovone and dihydromethylergonovine had no amplifying potency, but the hydrogenated amino acid alkaloids dihydroergocornine, dihydroergocristine and dihydroergokryptine (Hydergine) were almost as potent amplifiers as was DHE. The data indicate that (a) DHE, Hydergine and by inference all hydrogenated amino acid alkaloids are potent amplifiers of sulfonylurea-stimulated insulin secretion; (b) saturation of the double bond at C9 and C10 of the lysergic acid moiety and the pressence of an amino acid side chain are essential structual requirements for an ergot alkaloid to function as an amplifier of the action of sulfonylureas; and (c) it appears that these compounds are acting chiefly by mechanisms other than alpha-adrenergic and serotonergic receptor blockade, perhaps as regulatory molecules inducing positive cooperative changes in integral proteins of the plasma membrane of beta cells.     

The mechanism of the inhibition by carbonic acid of the smooth muscle contraction produced by histamine and oxytocin

Carbonic acid inhibited the stimulating action of histamine on guinea-pig intestine and of oxytocin on the uterus of many animal species. This effect was relatively specific. Under the same conditions the actions of acetylcholine, KCl, adrenaline (on rabbit uterus), and ergot alkaloids were not inhibited. The electrical excitability of smooth muscle was similarly not affected. The inhibitory action of carbonic acid is directly proportional to its concentration in the medium in which the isolated organ is maintained. The study of the activity of histamine and oxytocin at different pH in a medium free of NaHCO₃ and buffered with a mixture of sodium maleate and maleic acid suggested that the inhibitory action exerted by carbonic acid was specific and independent of the simultaneous modifications of the hydrogen ion concentration. The mechanism of these phenomena is discussed.     

Cleaving Ergot Alkaloids by Hydrazinolysis—A Promising Approach for a Sum Parameter Screening Method

Ergot alkaloids are mycotoxins formed by fungi of the Claviceps genus, which are some of the most common contaminants of food and feed worldwide. These toxins are a structurally heterogeneous group of compounds, sharing an ergoline backbone. Six structures and their corresponding stereoisomers are typically quantified by either HPLC-FLD or HPLC-MS/MS and the values subsequently summed up to determine the total ergot alkaloid content. For the development of a screening method targeting all ergot alkaloids simultaneously, the alkaloids need to be transferred to one homogeneous structure: a lysergic acid derivative. In this study, two promising cleaving methods—acidic esterification and hydrazinolysis—are compared, using dihydroergocristine as a model compound. While the acidic esterification proved to be unsuitable, due to long reaction times and oxidation sensitivity, hydrazinolysis reached a quantitative yield in 40‒60 min. Parallel workup of several samples is possible. An increasing effect on the reaction rate by the addition of ammonium iodide was demonstrated. Application of hydrazinolysis to a major ergot alkaloid mix solution showed that all ergopeptines were cleaved, but ergometrine/-inine was barely affected. Still, hydrazinolysis is a suitable tool for the development of a sum parameter screening method for ergot alkaloids in food and feed.     

几种制剂中生物碱的离子交换分离测定法

制剂中生物碱的含量測定,各国药典經典方法均采用有机溶剂提取,分离杂貭后再测定含量。近几年来,采用离子交换法分离制剂中生物碱的方法已有不少报导。由于离子交換剂能够比較簡单的定量交換生物碱,并可以用一定溶剂洗脫,这样可以避免一般較复杂费时的提取手續,因而采用离子交换法分离生物碱具有一定的优点。Kamp等报告了用IMAC-22強酸树脂,从顛茄、番木鱉等数种生药及其制剂中分离生物碱,对于用交換柱操作方法、洗脫条件等都进行一定工作。Brochmann-Hanssen連續报导了快速分离测     

Biosynthetic Pathways of Ergot Alkaloids

Ergot alkaloids are nitrogen-containing natural products belonging to indole alkaloids. The best known producers are fungi of the phylum Ascomycota, e.g., Claviceps, Epichloë, Penicillium and Aspergillus species. According to their structures, ergot alkaloids can be divided into three groups: clavines, lysergic acid amides and peptides (ergopeptines). All of them share the first biosynthetic steps, which lead to the formation of the tetracyclic ergoline ring system (except the simplest, tricyclic compound: chanoclavine). Different modifications on the ergoline ring by specific enzymes result in an abundance of bioactive natural products, which are used as pharmaceutical drugs or precursors thereof. From the 1950s through to recent years, most of the biosynthetic pathways have been elucidated. Gene clusters from several ergot alkaloid producers have been identified by genome mining and the functions of many of those genes have been demonstrated by knock-out experiments or biochemical investigations of the overproduced enzymes.     

决明子中大黄素的提取、分离和纯化方法的研究

目的寻求获得高纯度大黄素的可行性。方法先用稀硫酸溶液将蒽醌苷水解成苷元，再用热氯仿将苷元提取出来，然后用PH8．0缓冲液将大黄酸从氯仿液中除去，再用0．2％NaOH反复萃取将大黄素从氯仿液中提取出来，用层析柱法将大黄素分离纯化，经用丙酮反复多次重结晶可得纯度较高的大黄素。结果本方法提纯得到的大黄素的纯度达到98．1％以上。结论该方法操作简单、实用性强、成本低、可以推广应用。