固相萃取-超高效液相色谱法测定人参中5种原人参二醇型人参皂苷的含量

建立了固相萃取-超高效液相色谱测定人参中5种原人参二醇型人参皂苷的方法。人参药材经粉碎后通过水饱和正丁醇溶液进行超声提取,经过亲水作用固相萃取柱净化后,在ACQUITY UPLC BEH Shield RP18色谱柱（100 mm×2.1 mm,1.7 μm）上分离,利用乙腈/水作为流动相进行梯度洗脱,采用光电二极管阵列检测器检测。结果表明,5种原人参二醇型人参皂苷在5~500 μg/mL范围内具有很好的线性关系,相关系数均大于0.999。方法精密度的RSD值在0.95%~2.62%（n=6）之间,22 h内样品稳定性的RSD值在0.90%~2.15%（n=8）之间,日内和日间重复性的RSD值分别为5.35%~6.47%（n=6）和5.56%~6.34%（n=8）。方法的加标回收率在87.16%~101.92%之间,相对标准偏差在1.54%~4.01%（n=6）之间。所建立的方法采用亲水作用色谱模式的固相萃取材料,药材的提取液可直接作为固相萃取的上样溶液进行人参皂苷的富集和净化,并且超高效液相色谱大大缩短了分析时间。该方法简单快速、通量高、重现性好,适用于人参中5种原人参二醇型人参皂苷的定量分析。     

动态泡沫浮选法分离富集人参提取液中的二醇型人参皂苷

采用动态泡沫浮选法分离富集人参提取液中的二醇型人参皂苷, 用高效液相色谱法测定6种人参皂苷Rg₁, Re, Rb₁, Rc, Rb₂和Rd的含量. 考察了浮选液pH值、电解质NaCl浓度、载气流量、料液浓度及料液流速对人参皂苷浮选率的影响, 确定了动态泡沫浮选的最佳条件, 并与溶剂提取法、溶剂浮选法以及静态泡沫浮选法进行了比较. 结果表明, 动态泡沫浮选法对二醇型人参皂苷Rb₁, Rc, Rb₂和Rd具有高富集效率, 回收率分别为93.3%, 98.6%, 96.9%和98.3%, 而对三醇型人参皂苷Rg1和Re的富集效率却很低, 回收率分别为4.8%和4.2%. 该法是分离纯化二醇型人参皂苷的一种简便有效的方法.     

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.     

LC-MS/MS法测定大鼠血浆中人参皂苷Rb1的含量及其药代动力学研究

采用液相色谱-串联质谱法快速、灵敏地测定大鼠血浆中人参皂苷Rb1(GRb1)的含量,并将该方法应用于大鼠口服GRb1后的代谢动力学研究。血浆样品采用96孔板进行液-液萃取后,应用Agilent SB-C18色谱柱(100 mm×2.1 mm,3.5μm)进行分离,以甲醇-0.1%甲酸溶液(体积比为75∶25)为流动相进行洗脱,在正离子模式下对GRb1和内标人参皂苷Rg1(GRg1)进行检测,用于定量的离子反应分别为1131.5→365.1(GRb1),823.3→643.4(GRg1)。人参皂苷Rb1血浆样品测定方法的定量线性范围为1~500 ng/mL,线性相关系数大于0.999,定量下限为1 ng/mL,批内和批间精密度(RSD)小于9.05%,回收率为79.7%~81.0%,基质效应为96.6%~99.3%。大鼠灌胃给予Rb15 mg/kg后,大鼠体内血药浓度到达高峰时间tmax为1.53 h,半衰期t1/2为13.54 h,药时曲线面积AUC0~72为16237.76(ng·h)/mL。该方法快速、高效、灵敏,适用于人参皂苷Rb1的代谢动力学研究。     

固相萃取结合高效液相色谱-三重四极杆质谱快速分离检测益气养血口服液中人参皂苷的新方法

以无机多孔材料作为固相萃取吸附剂,结合高效液相色谱-三重四极杆质谱(HPLC-QqQ/MS)建立了一种快速分离检测中药复方益气养血口服液中人参皂苷的新方法。考察了SAPO-34、SAPO-11、ZSM-5、Y型分子筛、SBA-15、多壁碳纳米管(MWCNTs) 6种无机多孔材料对4种主要人参皂苷Re、Rg1、Rb1、Ro的吸附活性。在优化条件下,MWCNTs的分离效果最好,可在2 min内分别达到吸附和脱附平衡,吸附率和脱附回收率分别达98.6%和96.8%以上。方法的检出限为0.01～0.05μg/mL,平均回收率为90.5%～99.7%,相对标准偏差为2.2%～4.9%。益气养血口服液中4种人参皂苷含量的分析结果显示,建立的方法对口服液中除皂苷外的其他成分吸附作用不明显,可以有效降低基质干扰并准确分析微量的人参皂苷。该方法在快速检测人参皂苷方面具有潜在的应用价值。     

基于多壁碳纳米管的人参皂苷快速分离

将多壁碳纳米管(MWCNTs)作为选择性吸附材料,用于快速分离人参提取物中的人参皂苷.人参经甲醇溶液超声提取后,提取物中主要为人参皂苷和糖类.人参中的糖类与人参皂苷的极性相近,是提取分离人参皂苷时的主要干扰物. MWCNTs可以快速吸附和脱附人参皂苷,但是对糖类无吸附作用.利用其选择性吸附性能,建立了MWCNTs快速分离人参提取物中人参皂苷和糖类的方法.在优化的分离条件下,MWCNTs对人参提取物中糖类的分离度高于90%,对8种主要人参皂苷[Rb1,Rb2,Rc,Rd,Re,Rg1,20(S)-Rf和Ro]的吸附容量为15. 0~24. 0μg/mg,回收率高于90%.进一步研究表明,人参皂苷在3 min内即可达到吸附和脱附平衡,并且人参皂苷的回收率受脱附溶剂极性的影响.相比于常规材料大孔树脂,MWCNTs可以更快速、简便地分离人参皂苷.     

高效液相色谱法快速测定七叶神安片中的人参皂苷Rb3

建立了高效液相色谱法快速测定七叶神安片中的人参皂苷Rb3含量的方法。采用核壳型色谱柱分离,按照等度分离条件,流动相为32%乙腈的0.2%磷酸溶液,流量为0.85 mL/min,人参皂苷Rb3的质量浓度在6～120μg/m L的范围内与色谱峰面积线性关系良好,线性相关系数为0.999 0,检出限为0.23μg/mL,平均回收率为95.6%～98.3%,相对标准偏差为0.6%～1.2%。在保持常规全多孔型分离填料梯度淋洗的分离度的前提下,人参皂苷Rb3的峰保留时间缩短至四分之一,检出限提高4倍。该方法可有效节约仪器配置、节省溶剂的使用和处理成本,提高工作效率,可为七叶神安片的质量监控提供新的检测方法参考。     

固相萃取/超高效液相色谱-三重四极杆质谱法测定人参、人参叶与人参花中10种人参皂苷含量

该文建立了超高效液相色谱－三重四极杆质谱测定人参、人参叶和人参花中10种主要人参皂苷的方法。采用Alumina－N/XAD-2 SPE Cartridge复合固相萃取柱净化样品,通过Hypersil Gold C18色谱柱（100 mm × 2.1 mm,1.9 μm）,以5 mmol/L乙酸铵溶液（含0.1%甲酸）和乙腈为流动相进行分离,在电喷雾离子源负离子模式下,以多反应监测方式（MRM）检测。结果表明,10 种人参皂苷在5 ~ 2 500 ng/mL质量浓度范围内具有很好的线性关系,相关系数（r）均不小于0.998 0,检出限和定量下限分别为0.25 ~ 2.5 mg/kg和0.75 ~ 7.5 mg/kg。以人参叶为典型样品,在不同浓度加标水平下的平均回收率为87.3% ~ 110%,相对标准偏差（RSD）为1.4% ~ 9.3%。对不同批次的人参、人参叶和人参花检测结果表明,人参叶、人参花含有与人参相似的人参皂苷成分,且部分人参皂苷单体和10种主要人参皂苷总量远大于人参根部。该方法净化效果好,灵敏度高,重复性好,为人参资源的综合评价和全面控制提供了可靠的检测方法,同时为人参资源的开发和利用提供了基础资料。     

高效液相色谱法快速测定参芪降糖胶囊中人参皂苷的含量

建立了高效液相色谱法快速测定参芪降糖胶囊中人参皂苷Rg1、人参皂苷Re、人参皂苷Rd含量的方法.采用3.5μm Coreshell C18核壳型分离填料(3.0 mm×150 mm)为色谱柱,分别以纯乙腈、纯水为流动相进行梯度淋洗,流量为0.43 mL/min,柱箱温度为25℃,检测波长为203 nm.人参皂苷Rg1、...     

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.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。