苦豆子提取过程中氧化苦参碱与苦参碱、氧化槐果碱与槐果碱的相互转化

目的 研究苦豆子药用植物提取过程中氧化苦参碱与苦参碱、氧化槐果碱与槐果碱的相互转化。方法 采用不同提取溶媒(水及55%乙醇)、不同pH及不同提取时间3个因素,HPLC测定苦豆籽、苦豆草植物中氧化苦参碱与苦参碱,氧化槐果碱与槐果碱的含量。结果 随着提取时间的增加,氧化型生物碱转化为还原型生物碱的量随之增大;提取溶剂对苦豆子中生物碱转化的影响无明显差异;随着提取时间的增加,氧化苦参碱与苦参碱总量呈缓慢下降的趋势,氧化槐果碱与槐果碱总量也呈缓慢下降的趋势。结论 氧化型生物碱与还原型生物碱转化趋势可为苦豆子生物碱质量控制提供依据,也可为工业化提取苦豆子生产工艺提供依据。     

HPLC-DAD法测定商品苦参根茎和根中5个生物碱的含量

目的:测定商品苦参根茎和根中苦参碱、氧化苦参碱、槐果碱、氧化槐果碱、槐定碱的含量,主要了解苦参根茎中苦参碱和氧化苦参碱总量是否达到中国药典2010年版规定的不低于1.0%。方法:采用Welch Materials XtimateTM C18(4.6 mm×150mm,5μm)色谱柱,流动相A为10 mmol.L-1醋酸铵水溶液(0.1%氨水调至pH 9.2),流动相B为乙腈,梯度洗脱,流速1 mL.min-1,检测波长220 nm。结果:苦参碱进样量在0.1575～2.205μg(r=0.9999),氧化苦参碱在0.8985～12.58μg(r=0.9999),槐果碱在0.1360～1.904μg(r=0.9999),氧化槐果碱在0.4398～6.153μg(r=0.9998),槐定碱在0.2092～2.926μg(r=0.9998)范围内呈良好的线性关系;加样平均回收率(n=3)分别为101.0%～102.5%(RSD≤2.1%),100.8%～101.6%(RSD≤2.8%),102.3%～103.6%(RSD≤1.2%),102.2%～103.4%(RSD≤1.1%),102.4%～103.3%(RSD...     

反相离子对色谱法同时测定复方苦参注射液中4个生物碱含量

目的:建立反相离子对色谱同时测定复方苦参注射液中苦参碱、槐果碱、氧化槐果碱和氧化苦参碱含量的方法。方法:色谱条件:Diamonsil C18(250 mm×4.6 mm,5.0μm)色谱柱;流动相为0.04%磷酸-10 mmol·L-1戊烷磺酸钠水溶液(A)和乙腈(B),线性梯度洗脱,流速为1.2 mL·min-1;柱温为30℃;紫外检测波长:210 nm。结果:苦参碱、槐果碱、氧化槐果碱和氧化苦参碱质量浓度分别在18.92～946.0,4.052～202.6,9.293～464.6,34.73～1736 mg·L-1范围内线性关系良好,相关系数均为0.9999;RSD重复性试验中4个生物碱含量均小于2.1%;平均加样回收率分别为98.2%,96.4%,96.9%,97.1%。结论:该方法简便、准确,重复性好,可用于复方苦参注射液的质量控制。     

HPLC、TLC检测砂生槐种子中的生物碱

目的：建立一种快速，有效的方法测定砂生槐种子中生物碱的种类和含量。方法：用TLC快速分离定性总生物碱，并结合HPLC进行精确定量。TLC采用Merck Silica gel 60 F254薄层层析板，氯仿-甲醇-浓氨水（5：0．6：0．1）为展开系统对总碱中主要成份进行定性分析；而后用HPLC法对其中苦参碱，氧化苦参碱和槐果碱的含量进行测定。色谱柱为VP—ODS（5μm，150mm×4．6mm）柱，流动相为乙腈（A），含0．035％三乙胺的0．02mol·L^-1醋酸铵溶液（B）进行梯度洗脱，检测波长210nm，流速1．0mL·min^-1，进样量20μL。结果：TLC分析结果表明生物碱中含有苦参碱，氧化苦参碱，槐果碱，槐定碱和金雀花碱等。HPLC测定时氧化苦参碱，苦参碱，槐果碱分别在3．0—97．0、2．5—80．0和1．6～50．7mg·L^-1范围内呈线性相关，r分别为0．9996，0．9999，0．9999。结论：沙生槐种子中含有苦参碱，氧化苦参碱，槐果碱，槐定碱和金雀花碱，其中氧化苦参碱，苦参碱，槐果碱含量约为21％，9％，0．9％，本文建立的方法能快速准确的测定沙生槐总碱中氧化苦参碱，苦参碱，槐果碱的含量。     

苦参生物碱的分析方法和药动学研究进展

<正>苦参是传统中药,系豆科槐属植物苦参Sophora flavescens Ait.的干燥根,素有清热利湿、祛风杀虫之功,其主要化学成分是生物碱。苦参生物碱主要为喹诺西啶类生物碱,其中主要有苦参碱(Matrine)、氧化苦参碱(Oxymatrine)、槐果碱(Sophocarp- ine)、氧化槐果碱(Oxysophocarpine)、槐定碱(Sophoridine)等,具有广泛的生理活性。近年来大量的药理和临床研究发现,苦     

高效液相色谱法测定藏药砂生槐子中4种生物碱含量

目的:运用高效液相色谱法分析砂生槐子中氧化苦参碱、槐果碱、槐定碱和苦参碱的含量。方法:改良砂生槐子中生物碱提取工艺,采用Diamonsil C18(2)(4.6 mm×250 mm,3μm)色谱柱,以0.02 mol·L-1磷酸缓冲盐(p H 8)-甲醇(55∶45),流速1.0 m L·min-1,检测波长220 nm,柱温35℃。结果:氧化苦参碱、槐果碱、槐定碱和苦参碱质量浓度在0.46~59.00、0.40~51.60、0.55~70.00、0.59~75.00μg·m L-1的范围内线性良好,相关系数分别为0.999 9、0.999 9、0.999 9、0.999 8;加样回收率分别为99.98%、100.3%、99.69%、100.2%。氧化苦参碱、槐果碱、槐定碱和苦参碱4种生物碱的含量分别为59.37、0.99、0.26、15.35μg·g-1。结论:该方法经方法学验证可用于砂生槐子中生物碱的含量测定。     

HPLC-DAD法测定自采苦参根茎和根中5个生物碱的含量

目的:测定自采苦参根茎和根中苦参碱、氧化苦参碱、槐果碱、氧化槐果碱、槐定碱的含量,以便了解采自同一株植物的苦参根茎和根中苦参碱和氧化苦参碱的总量。方法:采用Welch Materials XtimateTMC18(4.6 mm×150 mm,5μm)色谱柱,流动相A为10 mmol.L-1醋酸铵水溶液(0.1%氨水调至pH 9.2),流动相B为乙腈,梯度洗脱,流速1 mL.min-1,检测波长220nm。结果:自采苦参根茎中苦参碱和氧化苦参碱的总量为四川资阳2.17%、北京怀柔2.53%、山西原平3.21%,根中二者总量为四川资阳2.86%、北京怀柔2.26%、山西原平3.34%。结论:采自不同产地或同一株植物的苦参根茎和根中,苦参碱和氧化苦参碱的总量各有高低。     

大孔吸附树脂分离苦参中三种生物碱的研究进展

大孔树脂在吸附苦参总碱及分离苦参中苦参碱、氧化苦参碱、氧化槐果碱的研究中有显著的特点,本文就近lO年文献作一概述,以期对今后的工艺研究中有所帮助。     

苦参总碱注射液中苦参碱、氧化苦参碱、氧化槐果碱含量及其在制剂中的均一性

采用薄层扫描法测定苦参总碱中苦参碱、氧化苦参碱、氧化槐果碱３种主要成分在注射液中的含量．     

高效液相色谱法同时分离测定氧化苦参碱、槐定碱、槐胺碱、苦参碱、槐果碱

目的：建立高效液相色谱法同时分离测定氧化苦参碱、槐定碱、槐胺碱、苦参碱、槐果碱5种生物碱。方法：色谱柱为Waters XTerra^TM RP C18（3．9mm&#215;150mm，5μm），流动相为0．01mol&#183;L^-1磷酸盐缓冲液（pH8．5）～甲醇（78：22），流速1．0mL&#183;min^-1，检测波长为220nm。结果：5种生物碱在上述色谱条件下达到完全的基线分离。氧化苦参碱在2．1～207．0μg&#183;mL^-1（r=0．9999）、槐定碱在10．2—204．1μg&#183;mL^-1（r：0．9999）、槐胺碱在10．1—201．3μg&#183;mL^-1（r=0．9999）、苦参碱在5．0～201．8μg&#183;mL^-1（r=0．9999）、槐果碱在5．0～201．5μg&#183;mL^-1（r=0．9999）的浓度范围内线性良好。结论：本方法简便易行，可用于含该类生物碱的生药与制剂的分析。     

反相离子对高效液相色谱分析厚朴类原植物中季铵生物碱

本文建立了厚朴类原植物中三种主要生物碱(厚朴碱、柳叶木兰花碱、武当木兰碱)的反相离子对高效液相色谱法。用Nucleosil C₁₈固定相,0.003 mol/L辛烷磺酸钠—乙腈(74:26)为流动相。方法简便、灵敏,并用此法分析比较了木兰属、木莲属16种36个样品,为指导临床用药、资源开发利用提供了一定科学依据。     

乌头中主要生物碱的高效液相色谱测定

用高效液相色谱分离、测定乌头及附子中一些主要生物碱。生药的乙醚提取物在十八烷基键合相柱上,用甲醇—水—氯仿—三乙胺(70:30:2:0.1)作流动相,中乌头碱、乌头碱及次乌头碱与其它杂质能很好分离。以β-甲基萘作内标化合物,用峰高比测定各生物碱含量。曾测定了不同品种、不同产地及不同加工炮制方法的一些样品,其生物碱组成及比例相差较大。     

Study on the aconitine‐type alkaloids of Radix Aconiti Lateralis and its processed products using HPLC‐ESI‐MSn

The type and content change of alkaloids of Radix Aconiti Lateralis (Lateral root of Aconitum carmichaeli Debx, an important and popular medicinal herb in Traditional Chinese Medicine) in processing were studied using high performance liquid chromatography‐electrospray ionization‐multi‐stage mass spectrometry (HPLC‐ESI‐MSⁿ). Extract containing alkaloids, which were known to be the main bioactive components of the herb, was prepared by 1% (v/v) hydrochloric acid solution. An HPLC method which can simultaneously separate these alkaloids was established with gradient elution mode. Forty‐eight compounds were structurally identified by employing LC‐MSⁿ techniques; the MSⁿ spectra of most alkaloids displayed a characteristic behaviour of loss of CH₃COOH (60 u), CH₃OH (32 u), C₆H₅COOH (122 u), CO (28 u) and H₂O (18 u). Among them, the fragmentation ion C6H5COOH (122 u) was reported for the first time. By comparison, 22 compounds were found both in the crude materials and the processed products; 17 alkaloids were only found in the processed products and 9 alkaloids,which existed in crude material, could not be detected after processing. In the process of identification, we found new kinds of alkaloids, with protonated molecules at m/z 452, 468, and 482. We called these compounds dehydra‐hypaconine, dehydra‐mesaconine, and dehydra‐aconine, respectively. Copyright © 2012 John Wiley & Sons, Ltd.     

吲(口朶)生物碱的高效液相色谱研究

在μ-Bondapak C₁₈柱上以不同比例的磷酸盐缓冲液和甲醇为流动相,在不同pH下研究了16个吲哚生物碱的保留行为以及结构和保留时间的关系。研究结果表明,大部分样品的容量因子(k′)随pH增加而增加,当pH为6左右时k′达到最大值,pH继续增加则k′下降。logk′和甲醇含量之间没有简单线性关系。磷酸盐和柠檬酸盐缓冲液的洗脱能力相近,醋酸盐缓冲液洗脱能力较弱。随磷酸盐缓冲液浓度增加k′缓慢下降。所研究的12个吲哚生物碱在μ-Bondapak C₁₈柱上以pH 7.5的磷酸盐缓冲液—甲醇(30:70)为流动相可得到最佳分离。     

超临界流体萃取法及高效液相色谱法分析延胡索中延胡索乙素的含量

采用超临界流体萃取法提取延胡索及其成方制剂中的延胡索乙素,以苯作改性剂,于40℃,42 MPa压力下,二氧化碳静态萃取5 min,动态萃取3 ml。该法操作简便快速,提取完全,也为其它中药及其制剂中有效成分的定量分析建立了一种简便、快速、有效的提取方法。应用硅胶柱─反相洗脱系统的高效液相色谱法测定延胡索及其成方制剂中延胡索乙素的含量,方法简便、快速、精密度高。此色谱系统同样适于其它中药及其制剂中生物碱的定量分析。     

Cadmium Mobilization in Vivo by Intraperitoneal or Oral Administration of Monoalkyl Esters of meso–2, 3–Dmercaptosuccinic Acid in the Mouse

Abstract: The relative activities of a series of nine monoalkyl esters of meso-2, 3–dimercaptosuccinic acid have been examined as agents for the mobilization of cadmium from mice one week after intraperitoneal administration of cadmium chloride. Eight of these are newly synthetized; all are of the type ROOCCH(SH)CH(SH)COOH, were R=Me, MMDMS; R = C₂H₅, MEDMS; R = (CH₂)₂CH₃, Mn-PDMS; R = CHMe₂) Mi-PDMS; R = (CH₂)₃CH₃, Mn-BDMS; R = CH₂CHMe₂, Mi-BDMS; R = (CH₂)₄CH₃, Mn-ADMS; R=(CH₂)₂CHMe₂, Mi-ADMS; and R = (CH₂)₅CH₃, Mn-HDMS. All are soluble in dilute sodium bicarbonate solutions and can be administered as aqueous solutions. Cadmium mobilization data were collected on each compound using mice previously loaded with cadmium; the monoesters were administered at a level of 0.40 mmol/kg intraperitoneally daily for five days. Data on whole body cadmium mobilization indicated that the monoester with the isoamyl group was the most effective under the conditions used. The relative whole body cadmium mobilization increased with the number of carbon atoms in the alkyl group of the monoester up to C₅ and then decreased for the C₆ compound. Cadmium removal from the kidneys and liver was also measured. It was found that the monoisoamyl ester was the most effective in removing cadmium from both the liver and the kidneys. The monoisoamyl ester also proved to be very effective in mobilizing cadmium from both the liver and the kidneys when given orally. This is the first compound which is reported capable of mobilizing cadmium in vivo from aged deposits after oral administration.     

A SOLID PHASE-FRAGMENT APPROACH TO PEPTIDE SYNTHESIS.

The t-alkyloxycarbonylhydrazide-resin, H₂NNHCOOC(CH₃)₂CH₂CH₂-copolystyrene-divinylbenzene, was applied to the solid phase synthesis of a protected decapeptide hydrazide, Z-Ala-Val-Ser(Bzl)-Ile-GIn-Phe-Met(O)-Asn-Leu-NHNH₂, and the t-alkyl alcohol-resin, HO-C(CH₃)₂CH₂CH₂-copolystyrene-divinylbenzene, was applied to the synthesis of Z-Lys(Z)-Phe-Phe-Gly-OH. The protected tetrapeptide was coupled to H-Leu-Met-OCH₃ by a fragment condensation in solution to give the protected hexapeptide, which was converted by ammonolysis and deprotection with hot trifluoroacetic acid to the active analog of eledoisin, H-Lys-Phe-Phe-Gly-Leu-Met-NH₂     

钩枝藤中生物碱的分离和鉴定

钩枝藤(Ancistrocladus tectorius)的总生物碱对大白鼠W-256有一定的抑制作用,从中分得三种带有萘环的四氢异喹啉生物碱结晶,晶1和晶2分别鉴定为ancistrocladine(Ⅰ)和hamatine(Ⅱ),晶3为新生物碱,命名为钩枝藤碱(ancistrocline),并推定其平面结构和部分立体关系如(Ⅲ)所示,总生物碱,晶1和晶2对小鼠肿瘤S-180和艾氏腹水瘤的抑制作用不明显,其他抗肿瘤试验还在进行中。     

Peptide N-alkylamides by solid phase synthesis*

Three new resins have been developed that allow for the solid phase synthesis of C-terminal peptide N-alkylamides using Boc amino acids, usual side chain protecting groups and hydrogen fluoride cleavage and deprotection. These resins were prepared by reacting the appropriate alkylamine (NH₂ CH₃, NH₂ CH₂ CH₃, NH₂ CH₂ CF₃) to Merrifield's 1% divinylbenzene cross-linked chloromethylated polystyrene resin. The application of these resins to the synthesis of C-terminal GnRH N-alkylamides illustrates the versatility of this approach. GnRH analogs were tested for their ability to release LH from cultured rat anterior pituitary cells. [D Glu⁶, Pro⁹-NHCH₂ CH₃]-GnRH was synthesized for the first time using the solid phase approach and found to be three times more potent than [D Glu⁶]-GnRH. Other analogs including [D Trp⁶, Pro⁹-NHCH₂ CH₃]-GnRH, [D Ala⁶, Pro⁹-NHCH₂ CF₃]-GnRH and related peptides were found to be equipotent and to have the same properties (HPLC retention times, amino acid analysis and specific rotation) as the corresponding peptides synthesized using less amenable strategies; yields were equivalent or better than those reported earlier.     

AN AB INITIO INVESTIGATION OF MOLECULES WITH A DISULFIDE BOND: (HS)2, (CH3S)2 AND CYSTINE

ab initio Calculations at the Gaussian-70 STO-3G and 4-31G basis levels have been carried out for (HS)₂ and (CH₃S)₂. Cystine was investigated at the STO-3G level. The STO-3G energy minimized geometry agrees well with experiments for (HS)₂ and (CH₃S)₂. The barriers to internal rotation are predicted to be (at the 4.31G level): (HS)₂, cis 8.5 kcal, trans 3.03 kcal; (CH₃S)₂, cis 18.47 kcal, trans 6.04 kcal.