9种人参皂苷同时测定方法及在人参质量鉴别中的应用

建立可同时测定人参皂苷Rg1、Re、Rf、Rg2、Rb1、Re、Rb2、Rb3和Rd含量的反相高效液相色谱（RP—HPLC）方法。采用Agilent Zorbax SB-C18柱,以乙腈-水-0．05％磷酸为流动相,流速1．5mlMmin,柱温35℃,检测波长203nm。在此色谱条件下,各组分在60min内均得到较好分离,回收率符合含量测定要求。运用该方法对不同产地人参进行含量测定,道地药材主根中9种人参皂苷总含量为1．19—1．45％,须根为5．47—6．90％,3个非道地药材主根分别为1．03％、1．04％、1．85％。聚类分析结果表明,根据测定的9种皂苷含量能准确区分人参的主根与须根,并判断其道地性。     

在线二维柱切换高效液相色谱法同时测定牙膏中三七皂苷R1、人参皂苷Rg1、Re和Rb1

使用双梯度液相色谱系统紫外检测器,建立了二维液相色谱法全自动快速同时测定牙膏中三七皂苷R1、人参皂苷Rg1、Re和Rb1的含量。样品经超声提取后,以Syncronis C18为一维分析柱,ODS C18为二维分析柱,利用一维色谱柱完成三七皂苷R1和人参皂苷Rb1分离测定以及人参皂苷Rg1和人参皂苷Re的净化;利用二维色谱柱完成人参皂苷Rg1和人参皂苷Re的分析。一维分析和二维分析均以乙腈-水体系作为流动相,梯度洗脱,检测波长为203 nm,整个分析过程仅需30 min。三七皂苷 R1、人参皂苷 Rg1、Re 和 Rb1在0.5~200 mg/L范围内线性良好,相关系数R2分别为0.9994,0.9996,0.9995和0.9994,平均回收率均在86.4％~95.1％之间。本方法简便快速,测定结果准确可靠,可用于牙膏中三七皂苷R1、人参皂苷Rg1、Re和Rb1含量的测定。     

泡沫浮选-固相提取分离富集三七提取液中的人参皂苷

采用泡沫浮选-固相提取联用法,分离富集三七中的R1,Rg1,Re,Rc,Rb2,Rb3,Rd和Rb1,并用液相色谱法测定其含量,检测灵敏度和选择性都有所提高.对泡沫浮选过程的载气流量、浮选时间、样品溶液pH值和固相提取柱的洗脱条件进行了优化.原人参二醉型皂苷R1,Rc,Rb2,Rb3,Rd和Rb1的回收率在85.0%9...     

改性松香键合二氧化硅高效液相色谱固定相的制备及其对三七总皂苷的分离

三七中发挥药效的主要成分为三七皂苷R1、人参皂苷Rg1、人参皂苷Re、人参皂苷Rb1和人参皂苷Rd,用于贫血、冠心病、高血压、脑卒中后遗症等疾病的治疗,但其化学成分多且难分离.将氢化松香丙烯酸羟乙酯(HRHA)通过巯基-烯点击化学反应键合到烷基化硅胶表面,制备出一种新型的改性松香键合二氧化硅高效液相色谱固定相(SiO2...     

HPLC-ELSD测定茜芷胶囊中三七皂苷R1、人参皂苷Rg1及Rb1的含量

利用HPLC-ELSD对茜芷胶囊中的活性成分三七皂苷R1、人参皂苷Rg1和Rb1的含量进行测定.三七皂苷R1、人参皂苷Rg1及Rb1分别在0.13~2.60、0.30~6.00、0.38~7.60μg范围内呈现良好的线性关系,平均回收率分别为98.0%(RSD1.7%),97.1%(RSD1.8%),97.0%(RSD1.5%).该方法简便、准确、重现性好,可用于茜芷胶囊的质量控制.     

高效液相色谱-飞行时间质谱联用法分析人参及人参皂苷与山楂配伍过程中的水解行为

利用高效液相色谱-飞行时间质谱联用的方法,分别对人参配伍山楂前后人参皂苷的变化进行分析,同时对人参皂苷Re、Rg1、Rb1、Rd与山楂配伍的水解规律进行系统研究,并与单独煎煮液、仿山楂配伍pH值煎煮液的水解产物进行比较,结果发现人参与山楂配伍后人参皂苷Rg1、Rb1含量明显减少,而人参皂苷Re、Rd、Rg2、Rg3、F2、Rh1含量明显增加,其中人参皂苷Re与山楂配伍后水解产物为人参皂苷20(R)-Rg2、20(S)-Rg2,仿山楂配伍pH值水解产物为人参皂苷20(R)-Rg2、20(S)-Rg2、Rg4、Rg6;人参皂苷Rg1与山楂配伍后水解产物为20(S)-Rh1、20(R)-Rh1,仿山楂pH值水解产物为20(S)-Rh1、20(R)-Rh1、Rh4、Rk3;人参皂苷Rb1与山楂配伍后水解产物为Rd、20(S)-Rg3,仿山楂pH值水解产物为F2、20(S)-Rg3;人参皂苷Rd与山楂配伍后水解产物为F2、20(S)-Rg3、20(R)-Rg3,仿山楂pH值水解产物为20(S)-Rg3、20(R)-Rg3。研究表明,不同人参皂苷和山楂配伍后与仿山楂pH值的水解产物并不相同,人参与山楂配伍改变了人参皂苷成分的种类及含量。本研究为临床方剂中人参与山楂配伍后成分的变化提供物质基础数据。     

中药材三七中皂苷类成分的近红外光谱快速无损分析新方法

提出了用近红外漫反射光谱快速无损测定三七中皂苷类成分的新方法采用 HPLC分析了中药材三七固皂昔R_1,人参皂苷Hg_1,Rb_1和Rd的含量,用吸附树脂 比色法测定了三七总皂苷（PNS）的含量,共获得R_1,Bg_1,Rb_1,Rd,PNS的含 量范围分别为1,58-5．08,21,68-46.13,11.46-40.41粉．在3500-1100cm~(-1) 扫描样品,以交叉验证误差均方根（RMsECV）为指标,通过筛选,近红外波段和光 谱预处理方法．采用偏最小二乘算法建立了近红外光谱与5个组分PHLC分析值之间 的校正模型,预测了8个未知样本．R_1,Rg_1,Rb_1,Rd及PNS校正模型的RMSECV 分别为0．40,1.47,1.94,0RMSEP分别为0．53,3．15,2．14,0．70,9．03． 该方法快速无损,结果可靠,为中药材复杂体系中化学组分的测定提供了新的绿色 分析手段．     

高效液相色谱法测定竹节参中多种人参皂苷含量

建立了高效液相色谱法(HPLC)测定竹节参中人参皂苷Rg1、Re、Rb1、Rb2、Rg2、Rd含量的方法.运用二极管阵列检测器(DAD)峰纯度和光谱检索功能,结合保留时间定性,外标峰面积法定量.采用C18反相柱,以乙腈-水梯度洗脱测定了同一批竹节参总皂苷中人参皂苷Rg1、Re、Rd的含量分别为0.81%、0.15%、2.99%,回收率为93.46%~94.02%,含量及回收率的RSD均小于5%,该方法简便、灵敏,精密度及准确度在允许范围内,可作为竹节参皂苷提取物中多种人参皂苷的同时测定方法.     

加压毛细管电色谱-微流蒸发光散射检测器联用系统的构建及其应用

构建微流蒸发光散射检测器(μELSD)与加压毛细管电色谱(pCEC)联用系统,测定中药提取物注射用血塞通(冻干)中三七皂苷R1、人参皂苷Rg1,Re,Rb1、Rd考察系统的实用性和稳定性。用C18毛细管色谱柱,通过对流动相体系、梯度洗脱条件、雾化载气流速、蒸发温度、施加电压等参数的优化,确定了注射用血塞通(冻干)5种成分含量测定的最佳测定参数。最佳测定参数如下,流动相A为15 mmol/L甲酸-三乙胺乙腈溶液(pH=7.0),流动相B为15 mmol/L甲酸-三乙胺溶液(pH=7.0);梯度洗脱条件:0~10 min,19%A;10~30 min,22%A;30~35 min,36%A;35~45 min,40%A。雾化载气流速2 L/min;蒸发温度120℃;施加电压+8 kV。5种成分线性范围为8.6~146.9 ng(三七皂苷R1)、6.9~189.7 ng(人参皂苷Rg1)、6.8~171.4 ng(人参皂苷Re)、9.4~156.1 ng(人参皂苷Rb1)、7.5~180.5 ng(人参皂苷Rd),5种成分回收率都在95%~105%之间。实验表明,构建的pCEC-μELSD联用系统能用于药物中有效成分的含量测定。μELSD的构建为毛细管液相色谱、毛细管电色谱和毛细管电泳分离技术提供了一种全新的检测手段。     

人参中人参皂苷的直接高压微波辅助降解

采用高效液相色谱-电喷雾质谱联用法测定了人参提取液中的人参皂苷. 考察了天然人参皂苷发生降解的条件, 同时研究了单体人参皂苷Rg1, Re, Rb1, Rc, Rb2和Rd的降解, 并对降解产物进行了分析. 结果表明, 随着提取压力的升高, 提取液中天然人参皂苷的含量逐渐减少, 同时产生多种次级人参皂苷. 当微波提取压力达到600 kPa, 提取时间为10 min时, 提取液中的主要天然人参皂苷达到完全降解, 次级人参皂苷Rg3含量达到最高. 在单体人参皂苷Rb1, Rc, Rb2和Rd的降解产物中均得到人参皂苷Rg3.     

1, 1, 1-Trichloropropanone: A Mild,Selective Acetylating Agent

The use of the title compound in the acetylation of primary and secondary amines i s described.     

Studies on 1, 2, 4-Benzothiadiazine 1, 1-Dioxide IX.1 Synthesis and Pharmacological Evaluation of 1, 2, 4-Benzothiadiazine 1, 1-Dioxide Biphenyl Tetrazoles as Angiotensin II Antagonists

In the course of our investigations on the development of cardiovascular agents, 3-butyl-2-[2′-(2H-tetrazol-5-yl)bipheny]-4-yl]methyl-2H-1, 2, 4-benzothiadiazine 1, 1-dioxide ( 2 ) was considered as a potential angiotensin II antagonist on the basis of bioisosteric replacement of the quinazoline ring of compound 1 with a 1, 2, 4-benzothiadiazine 1, 1-dioxide ring system. Alkylation of 6 with 4 afforded 7 and 8 in 24% and 28% yields, respectively. An attempt to remove the trityl group of compounds 7 and 8 under acidic condition gave the ring opened products 9 and 11 in 28% and 36% yields, respectively. However, compounds 2 and 10 were obtained in 46% and 85% yields when compounds 7 and 8 were refluxed in methanol. Preliminary assays of compounds 9 and 11 against angiotensin II receptors revealed weak activity with IC₅₀ values of 3.6 μM and 5.4 μM, respectively. Compound 10 (IC₅₀ = 87 nM) exhibited stronger binding affinity than compound 2 (IC₅₀ = 750 nM).     

Densities and viscosities for binary mixtures of phenetole with 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol,and 1-decanol at different temperatures

Density (ρ) and viscosity (η) values of the binary mixtures of phenetole+1-pentanol, + 1-hexanol, + 1-heptanol, + 1-octanol, + 1-nonanol, and + 1-decanol over the entire range of mole fraction at 293.15, 298.15, 308.15, and 318.15 K have been measured at atmospheric pressure. The excess molar volume (V^E), viscosity deviations (Δη), and excess Gibbs energy of activation (G*^E) have been calculated from the experimental measurements. These results were fitted to Redlich and Kister polynomial equation to estimate the binary interaction parameters. The viscosity data were correlated with equations of Grunberg and Nissan, Hind et al., Frenkel, and McAllister. While the excess molar volumes of phenetole+1-pentanol, + 1-hexanol are positive, the remaining binary mixtures are negative. The viscosity deviations and excess Gibbs energy of activation are negative for all investigated systems. As the chain length of 1-alkanols increases, both viscosity deviations and excess molar volume values decrease while excess Gibbs energy of activation value increase. The temperature has no effect on excess molar volume, slight effect on excess Gibbs energy of activation, and significant effect on viscosity deviations. The calculated functions have been used to explain the intermolecular interaction between the mixing components.     

Synthese von 1, 2-annelierten 1, 4-Benzodiazepinen und 4, 1-Benzoxazepinen

The syntheses of 1, 2-annelated 1, 4-benzodiazepines (IV, Y = N) and 4, 1-benzoxazepines (IV, Y = 0) are described (Scheme 1). The key step is a nucleophilic aromatic substitution of 2-substituted piperazines (II, Z = N? CH₃), piperidines (II, Z = CH₂) or pyrrolidines (II, Z= (CH₂)₀) with activated aryl halides (I).     

Reaction of 1, 1-dichloro-1-nitrosobutane with N,N-dimethylamidodichlorophosphite

Conclusions 1,1-Dichloro-1-nitrosobutane reacts exothermally with N, N-dimethylamidodichlorophosphite to give N,N-dimethylamidotetrachlorophosphorane and a nitrile oxide. In the presence of SO₂,this reaction gives O-propylchloroformimino-N, N-dimethylamidochlorophosphate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1416–1418, June, 1989.     

3-甲基-1a-(4-甲氧基苯基)-1, 1-二氯-1, 1a, 2, 3-四氢-吖丙 啶并[1, 2-d] [1, 5]苯并硫氮杂卓的合成和晶体结构

通过2-甲基-4-(4-甲氧基苯基)-2,3-二氢-1,5-苯并硫氮杂卓与二氯卡宾的[2+1]环加成反应制备了标题化合物,用X射线单晶衍射测定了其晶体结构。分子式C~1~8H~1~7Cl~2NOS,分子量366.30,晶体属正交晶系,空间群P~b~c~a,晶胞参数:a=1.2246(3)nm,b=1.5219(4)nm,c=1.9272(9)nm,V=3.592(2)nm^3,Z=8,D~c=1.355g.cm^-^3。位于中心的1,5-硫氮杂卓环为扭曲的类船式构象,船头与苯环并合,船底与吖丙啶环并合。     

Chemistry and polymerization of 1, 1, 3, 3-tetramethyl-1, 3-disila-2-oxaindane

Reaction of o-dichlorobenzene with dimethylmethoxychlorosilane and sodium leads to the isolation of dimethyl(o-chlorophenyl) methoxysilane, o-bis(bimethylmethoxysilyl)benzene, 1,1,3,3-tetramethyl-1,3-disila-2-oxaindane, and 1, 1-dimethyl-1-silarribenzocycloheptatriene. When I is polymerized with H₂SO₄, the phenyl group is observed to split off.     

One-pot carbanionic synthesis of P1,P2-diglycosyl, P1,P1,P2-triglycosyl, and P1,P1,P2,P2-tetraribosyl methylenediphosphonates

Novel lithiated carbanions derived from ethyl glycosyl- and diglycosyl methylphosphonates were used in a direct and convenient synthesis of P1,P2-diglycosyl, P1,P1,P2-triglycosyl, and P1,P1,P2,P2-tetraribosyl methylenediphosphonates involving a one-pot methylidenediphosphonylation of sugars.