几种中药材的化学成分及其定性定量检测方法研究

本论文由四部分组成。第一部分报道了佛手参提取物的化学成分研究，建立了活性成分含量测定的高效液相测定和指纹图谱研究，采用液质联用技术鉴定了主要色谱峰；第二部分报道了丹参及其复方制剂的特征图谱研究；第三部分探讨了两面针生物碱的电喷雾质谱裂解规律，并采用液质联用技术分离鉴定了提取物中的多种生物碱。第四部分概述了液质联用在药物代谢研究中的运用。 第一部分包括第一、第二和第三章。第一章针对佛手参（Gymnadeniaconopsea）块茎的甲醇提取物，采用大孔树脂和反相硅胶柱层析等各种分离方法，共分离鉴定出4 个化合物，通过波谱分析将它们的结构确定为dactylorhin B (1)、loroglossin (2)、dactylorhin A (3)和militarine (4)。这4 个化合物均是首次从佛手参中分离得到的琥珀酸葡萄糖苷类成分。第二章采用高效液相色谱法对西藏、四川、河北、青海和尼泊尔等不同地区产的十个佛手参样品进行腺嘌呤核苷和对羟基苯甲醇的定量分析，结果表明这2 个成份可视为佛手参的特征成分，但也注意到产地不同该2 个特征成分的含量也有所不同。第三章采用标准中药指纹图谱相似度计算软件，以10 个佛手参样品HPLC 图谱的平均值为相似性评价对照模板，对10 个样品进行了相似度评价，并经液质联用分析指认了7 个共有峰，分别为腺嘌呤核苷(1)、对羟基苯甲醇(2)、对羟基苯甲醛(3) 、dactylorhin B(4) 、loroglossin(5)、dactylorhin A(6)和militarine(7)。 第二部分包括第四、第五、第六和第七章。第四章运用电喷雾质谱检测了对照药材和五个不同产地的丹参药材中脂溶性和水溶性成分，系统地探讨了多种成分的电喷雾质谱规律，并以对照药材为标准建立了特征指纹图谱。五个产地的药II材通过与对照药材相对比，采用聚类分析的方法，得到了定性的鉴别与判断。并采用液质联用技术对丹参药材提取液中的化学成份进行分析，推测了九个特征峰，并对六样品的液相色谱图进行了聚类分析。第五章探讨了三七皂苷的电喷雾质谱电离和裂解规律，并采用电喷雾质谱法对三七标准药材，血通片中的皂苷成分进行了分析。第六章运用电喷雾质谱研究复方丹参片提取液的特征图谱，并和单味药材丹参和三七的特征图谱进行了对比研究。并运用HPLC-ESI MSn 分析鉴定了复方丹参片提取液中的化学成分，推测了12 个色谱峰。第七章总结了电喷雾质谱和液质联用技术在丹参药材，三七药材及复方丹参制剂中的运用的优势和局限性。 第三部分（第八章）研究了两面针生物碱中二氢白屈菜红碱(1)、二氢两面针碱(2)、8-酮基二氢白屈菜红碱(3)、8-丙酮基二氢两面针碱(4)、两面针碱(5)、和1,3-二(8-二氢两面针碱)丙酮(6)等六个苯并菲啶型生物碱的电喷雾质谱裂解规律，其中二氢两面针碱和二氢白屈菜红碱，8-丙酮基二氢两面针碱和8-酮基二氢白屈菜红碱是两对二个甲氧基分别在C-9 和C-10，C-10 和C-11 的同分异构体。实验结果表明，在相同的碰撞能下，这类位置异构体的ESI MS2 质谱二级碎片离子的相对峰度存在很大差异，这可以用于区分该类同分异构体，采用液-质联用可以对两面针的总生物碱提取物中的这些同分异构体加于区分。同时在本实验采用的液相色谱条件下，多种生物碱得到较好的分离，通过和对照品的保留时间，紫外吸收光谱及电喷雾质谱图对照，鉴定了11 个主要色谱峰。 第四部分（第九章）对液质联用技术在药物代谢中的运用进行了综述。 This dissertation consisted of four sections. The first two sections elaborated thephytochemical investigation of the rhizomes Gymnadenia conopsea R. Br., methoddevelopment for rapid identifying and qutifying the chemical condtituent of thistibetant medicine, and the chemical fingerprint analysis of rhizomes of G. conopsea,Salviae miltiorrhiza and P. notoginseng. The third section studied the fragmentationmechanism of six alkaloids from Zanthoxylum nitidium and method development forrapid identifying varieties of alkaloids from the extract of this herbal medicine. Thefourth section reviewed HPLC- MS method in drug metabolism studies. The first section consisted of chapters 1, 2, 3. Chapter 1 elaborated the phytochemicalinvestigation of Gymnadenia conopsea R. Br. Four succinate derivative esters wereisolated from the methanol extract of the rhizomes of G. conopsea through repeatedcolumn chromatography on normal and reversed phase silica gel, their structures weredetermined by ESI-MS, 1D and 2D NMR evidence. They were firstly discoveredfrom this species. In chapter 2, a high-performance liquid chromatography.diodearray detection (HPLC-DAD) method has been firstly developed for quantitation oftwo characteristic constituents, adenosine and 4-hydroxybenzyl alcohol, from theextract of rhizomes of G. conopsea. All 10 samples of G. conopsea contained differentamount of adenosine and 4-hydroxybenzyl alcohol. Adenosine and the4-hydroxybenzyl alcohol can be applied in identification and quality control for theroots of G. conopsea. In chapter 3, a high-performance liquid chromatography.diodearray detection.tandem mass spectrometry (HPLC-DAD-MSn) method has been firstly developed for chemical fingerprint analysis of rhizomes of G. conopsea andrapid identification of major compounds in the fingerprints. Comparing the UV andMS spectra with those of authentic compounds, seven main peaks in the fingerprintswere identified as adenosine, 4-hydroxybenzyl alcohol, 4-hydroxybenzyl aldehyde,dactylorhin B, loroglossin, dactylorhin A and militarine. The Computer AidedSimilarity Evaluation System for Chromatographic Fingerprint of TraditionalChinese Medicine (CASES) was employed to evaluate the similarities of 10 samplesof the rhizomes of G. conopsea collected from Sichuan, Qinghai and Hebei provincesand Tibet autonomous region of China, and Nepal. These samples from differentsources had similar chemical fingerprints to each other. The second section consisted of chapters 4, 5, 6 and 7. In chapter 4，both thecharacteristic spectra of liposoluble tanshinones and aqueous-soluble salvianolic acidswere established by the electrospray ionization mass spectrometry (ESI MS)technique and the differences between standard and crude rhizomes of Salviaemiltiorrhiza Bge. from 5 sources were analyzed. The law of electrospray ion trap mass(ESI ITMS) of typical tanshinones and salvianolic acids is studied.The analysis of the chemical constituent of rhizomes of Salviae miltiorrhiza Bge. byliquid chromatography coupled with mass spectrum (LC/MS) technique wasestablished，and the distances among standard herb and crude herb from 5 sourceswere calculated by clustering analysis. According the DAD spectra and MS2 data，9tanshinones could be speculated. In chapter 5, the character spectra of total saponinsin P. notoginseng extracts were established by ESI ITMS and selective ion monitoring(SIM) technology. The law of notoginsenosides by ESI MS2 was studied. In chapter 6,the characteristic spectra of Compound Danshen Tablet established and compared byESI-MS and HPLC/DAD/MS, 6 known tanshinones and 3 saponins were speculated.In chapter 7, the advantage and disadvantage of the strategy, using the ESI ITMS andLC/MS techniques for study of characteristic spetra of danshen and Compound Danshen Tablet, were summerized. The third section (chapter 8) studied the fragmentation mechanism of six alkaloids,dihydronitidine, dihydrochelerythrine, 8-acetonyl dihydronitidine,8-acetonyldrochelerythrine, nitidine and 1,3-bis (8-dihydronitidinyl)-acetone, by ESIMSn. Tandem mass spectrometry experiments indicated that different substitutionsites of the methoxyl groups at C-9 and C-10 or at C-10 and C-11 determined thedifferent abundances of the MS2 fragmentation ions using the same collision energy.According to the different abundances of MS2 product ions, positional isomericbenzo[c] phenanthridine alkaloids can be differentiated. Moreover, ten constituents inthe crude alkaloids extract from the roots of Zanthoxylum nitidium were rapidlyidentified by high-performance liquid chromatography coupled with tandem massspectrometry (HPLC-MSn), through comparing the retention times and ESI MSn spectra with the authentic standards. The fourth section (chapter 9) is a review on HPLC-MS method development in drug metabolism studies.

大城市内部商业环境满意度评价与消费区位决策研究-以北京市西城区和海淀区为例

Since 1990s, commercial conditions in China including commercial environment, retail types, scale of retail enterprises, spatial structure of retail and shopping decision making factors have changed. In order to keep up with these changes, commercial geography should set up new perspectives, theories and methods to analyze its internal mechanism and changing rules, and thus provide reasonable and practical scientific basis to commercial planning, location decision of retail enterprises and commercial environment construction. Taking Xicheng and Haidian District of Beijing as research case, which is a sector region from city center to rural region, this paper selects 12 commercial centers as most important study objects of this sector. This paper mainly makes use of the methods of Modeling, Pearson Bivaiiate Correlations Analysis, Factor Analysis and Logit model. Based on 1300 questionnaires and fieldwork, this paper focuses on modeling of Consumer Satisfaction of Commercial Environment (CSCE), evaluation of commercial environment and driving factors of consumers' shopping location decision. Firstly, this paper discusses the development of commercial geography and commercial environment evaluation, the new characteristics and trends of commercial development in Beijing and physical commercial environment of Xicheng and Haidian District of Beijing from chapter 1 to chapter 4. Secondly, this paper summarizes characteristics of residents' shopping behavior in chapter 5. Thirdly, this paper sets up an evaluative model of CSCE, and analyzes consumer satisfaction indexes of commercial environment and their spatial features in chapter 6. Fourthly, this paper infers how residents' attributes and shopping behaviors affect their preferences of shopping location and what are residents' shopping location decisions and their influencing factors in chapter 7. Fifthly, this paper constructs a significant index model and a pyramidal framework of CSCE, and further analyzes the diversity and competitive advantage of commercial environment in chapter 8. Finally, some conclusions are drawn as follows: 1. Characteristics of residents' shopping behavior mostly embody residents' time distance preference, commodity consumption preference, shopping time distribution and shopping activity characteristics. The important factors that influence shopping location choice of residents are distance, transportation, commodity price, commodity types and commodity quality. However, the important factors, which influence shopping location re-choice of residents, are commodity price, commodity quality, commodity types and transportation. 2. CSCE indexes of 12 commercial centers show us significant spatial characteristics, such as spatial differences of "Center-fringe region", spatial characteristics of axes, spatial diversity of ring roads and so on. 3. Influencing factors including factor endowments, relative establishment factor and location and transportation factor of commercial environment are of importance for CSCE. 4. Logit model 1 indicates that shopping behavior of residents is significantly and positively related to working in high-tech companies, high income and by car and positively related to high school diploma, by bus and subway. 5. Logit model 2 indicates that residents' shopping location decision is significantly and positively related to leisure establishment and relative restaurant and entertainment establishment and negatively related to commercial location, commodity price, service quality, parking site. 6. The significant index model and the pyramidal framework of CSCE indicate competitive advantages are crucial to attractive capability of commercial center, and competitive weakness limits development of commercial centers, in particular the weakness of service quality and parking site now is the chief factors restricting development of commercial centers

地幔对流理论及其在解释地球物理观测的应用

With the improving of mantle convection theory, the developing of computing method and increasing of the measurement data, we can numerically simulate more clearly about the effects on some geophysical observed phenomenons such as the global heat flow and global lithospheric stress field in the Earth's surface caused by mantle convection, which is the primary mechanism for the transport of heat from the Earth's deep interior to its surface and the underlying force mechanism of dynamics in the Earth.Chapter 1 reviews the historical background and present research state of mantle convection theory.In Chapter 2, the basic conception of thermal convection and the basic theory about mantle flow.The effects on generation and distribution of global lithospheric stres s field induced by mantle flow are the subject of Chapter 3. Mantle convection causes normal stress and tangential stresses at the bottom of the lithosphere, and then the sublithospheric stress field induces the lithospheric deformation as sixrface force and results in the stress field within the lithosphere. The simulation shows that the agreement between predictions and observations is good in most regions. Most of subduction zones and continental collisions are under compressive. While ocean ridges, such as the east Pacific ridge, the Atlantic ridge and the east African rift valley, are under tensile. And most of the hotspots preferentially occur in regions where calculated stress is tensile. The calculated directions of the most compressive principal horizontal stress are largely in accord with that of the observation except for some regions such as the NW-Pacifie subduction zone and Qinghai-Tibet Plateau, in which the directions of the most compressive principal horizontal stress are different. It shows that the mantel flow plays an important role in causing or affecting the large-scale stress field within the lithosphere.The global heat flow simulation based on a kinematic model of mantle convection is given in Chapter 4. Mantle convection velocities are calculated based on the internal loading theory at first, the velocity field is used as the input to solve the thermal problem. Results show that calculated depth derivatives of the near surface temperature are closely correlated to the observed surface heat flow pattern. Higher heat flow values around midocean ridge systems can be reproduced very well. The predicted average temperature as a function of function of depth reveals that there are two thermal boundary layers, one is close to the surface and another is close to the core-mantle boundary, the rest of the mantle is nearly isothermal. Although, in most of the mantle, advection dominates the heat transfer, the conductive heat transfer is still locally important in the boundary layers and plays an important role for the surface heat flow pattern. The existence of surface plates is responsible for the long wavelength surface heat flow pattern.In Chapter 5, the effects on present-day crustal movement in the China Mainland resulted from the mantle convection are introduced. Using a dynamic method, we present a quantitative model for the present-day crustal movement in China. We consider not only the effect of the India-Eurasia collision, the gravitational potential energy difference of the Tibet Plateau, but also the contribution of the shear traction on the bottom of the lithosphere induced by the global mantle convection. The comparison between our results and the velocity field obtained from the GPS observation shows that our model satisfactorily reproduces the general picture of crustal deformation in China. Numerical modeling results reveal that the stress field on the base of the lithosphere induced by the mantle flow is probably a considerable factor that causes the movement and deformation of the lithosphere in continental China with its eflfcet focuing on the Eastern China A numerical research on the small-scale convection with variable viscosity in the upper mantle is introduced in Chapter 6. Based on a two-dimensional model, small-scale convection in the mantle-lithosphere system with variable viscosity is researched by using of finite element method. Variation of viscosity in exponential form with temperature is considered in this paper The results show that if viscosity is strongly temperature-dependent, the upper part of the system does not take a share in the convection and a stagnant lid, which is identified as lithosphere, is formed on the top of system because of low temperature and high viscosity. The calculated surface heat flow, topography and gravity anomaly are associated well with the convection pattern, namely, the regions with high heat flow and uplift correspond to the upwelling flow, and vice versa.In Chapter 7, we give a brief of future research subject: The inversion of lateral density heterogeneity in the mantle by minimizing the viscous dissipation.

Magnetron Sputtering Growth of InAs0.3Sb0.7 Films on (100) GaAs Substrates: Strong Effect of Growth Conditions on Film Structure

The growth of highly lattice-mismatched InAs0.3Sb0.7 films on (100) GaAs Substrates by magnetron Sputtering has been investigated and even epitaxial lnAs(0.3)Sb(0.7) films have been successfully obtained. A strong effect of the growth conditions on the film structure was observed, revealing that there was a growth mechanism transition from three-dimensional nucleation growth to epitaxial layer-by-layer growth mode when increasing the substrate temperature. A qualitative explanation for that transition was proposed and the critical conditions for the epitaxial layer-by-layer growth mode were also discussed.

对童氏"7.5B"计算及乙型水驱法的改进

研究了童宪章院士"7.5B"的准确性和适应性,指出了"7.5B"方法只适用于多个油田的统计计算,而不完全适应于单一油藏.从理论上推导了"7.5B"的数学表达式,给出了一条准确计算该值的有效途径.对童氏水油比与采出程度关系乙型水驱法及采出程度与含水关系图版作了改进.

Coherent Structures in Transition of a Flat-Plate Boundary Layer at Ma=0.7

Direct numerical simulation (DNS) of a spatially evolving flat-plate boundary layer transition process at free stream Mach number 0.7 is performed. Tollmien-Schlichting (T-S) waves are added on the inlet boundary as the disturbances before transition. Typical coherent structures in the transition process are investigated based on the second invariant of velocity gradient tensor. The instantaneous shear stress and the mean velocity profile in the transition region are studied. In our view, the fact that the peak value of shear stress in the stress concentration area increases and exceeds a threshold value during the later stage of the transition process plays an important role in the laminar breakdown process.

Comparative Study Of The Influence Of Natural Convection On Directional Solidification Of Al-3.5 Wt% Ni And Al-7 Wt% Si Alloys

We present numerical simulations of thermosolutal convection for directional solidification of Al-3.5 wt% Ni and Al-7 wt% Si. Numerical results predict that fragmentation of dendrite arms resulting from dissolution could be favored in Al-7 wt% Si, but not in Al-3.5 wt% Ni. Corresponding experiments are in qualitative agreement with the numerical predictions. Distinguishing the two fragmentation mechanisms, namely dissolution and remelting, is critical during experiments on earth, when fluid flow is dominant. (C) 2007 COSPAR. Published by Elsevier Ltd. All rights reserved.

InAs0.3Sb0.7 films grown on (100) GaSb substrates with a buffer layer by liquid-phase epitaxy

The growth of InAsxSb1-x films on (100) GaSb substrates by liquid-phase epitaxy (LPE) has been investigated and epitaxial InAs0.3Sb0.7 films with InAs0.9Sb0.09 buffer layers have been successfully obtained. The low X-ray rocking curve FHWM values of InAs0.3Sb0.7 layer shows the high quality of crystal-orientation structure. Hall measurements show that the highest electron mobility in the samples obtained is 2.9 x 10(4) cm(2) V-1 s(-1) and the carrier density is 2.78 x 10(16)cm(-3) at room temperature (RT). The In As0.3Sb0.7 films grown on (10 0) GaSb substrates exhibit excellent optical performance with a cut-off wavelength of 12 mu m. (c) 2007 Elsevier B.V. All rights reserved.

第7届国际等离子体化学会议(ISPC-7)

<正> Ⅰ.概况 国际等离子体化学会议(ISPC)每两年举行一次,主要交流等离子体化学如下几方面的研究和发展情况:合成,诊断,等离子体刻蚀,等离子体沉积和聚合,模型,表面作用以及熔化、气化、等离子体喷涂等。ISPC-7由荷兰Ejndhoven技术大学负责组织,Philips公司支持,在Philips会议中心举行。会议期1985年7月1—5日。第一天样品展览,

万家寨引黄工程7~#土质引水隧洞变形的有限元分析

在山西省万家寨引黄入晋工程总干线 7#隧洞的开挖和衬砌的应力应变分析中 ,为确定土体c、Φ值和邓肯 -张模型参数 ,分别进行了加载试验和卸载试验 ,本文对用两种试验获得的模型参数进行有限元变形分析的结果进行比较。

ANSYS 7.0分析实例与工程应用

Effects of wall temperature on boundary layer stability over a blunt cone at Mach 7.99

Effects of wall temperature on stabilities of hypersonic boundary layer over a 7-degree half-cone-angle blunt cone are studied by using both direct numerical simulation (DNS) and linear stability theory (LST) analysis. Four isothermal wall cases with Tw/T0= 0.5, 0.7, 0.8 and 0.9, as well as an adiabatic wall case are considered. Results of both DNS and LST indicate that wall temperature has significant effects on the growth of disturbance waves. Cooling the surface accelerates unstable Mack II mode waves and decelerates the first mode (Tollmien–Schlichting mode) waves. LST results show that growth rate of the most unstable Mack II mode waves for the cases of cold wall Tw/T0=0.5 and 0.7 are about 45% and 25% larger than that for the adiabatic wall, respectively. Numerical results show that surface cooling modifies the profiles of rdut/dyn and temperature in the boundary layers, and thus changes the stability haracteristic of the boundary layers, and then effects on the growth of unstable waves. The results of DNS indicate that the disturbances with the frequency range from about 119.4 to 179.1 kHz, including the most unstable Mack modes, produce strong mode competition in the downstream region from about 11 to 100 nose radii. And adiabatic wall enhances the amplitudes of disturbance according to the results of DNS, although the LST indicates that the growth rate of the disturbance of cold wall is larger. That because the growth of the disturbance does not only depend on the development of the second unstable mode.

Laser action from 1,3,5,7-tetramethyl-2,6-diethyl-8-n-propyl pyrromethene-BF2

We measured spectroscopic and laser action properties of a novel 8-position substituted pyrromethene-BF2, namely 1,3,5,7-tetramethyl-2,6-diethyl-8-n-propyl pyrromethene-BF2 complex. The laser action was performed with the corresponding dye solution in ethanol, which was placed in a Littman-type laser cavity pumped by the second harmonic of a Q-switched Nd:YAG laser. The spectroscopic measurements clearly indicated that the corresponding dye solution in ethanol exhibited intense absorption in the visible spectral region with large fluorescence quantum yield. It possesses rather low triplet-triplet absorption in the spectral region 460-550 nm and almost negligible triplet-triplet absorption in the lasing spectral region. As a consequence, it lases nearly as efficiently as commercially available benchmark laser dyes such as Rhodamine-6G and outperformed them in wavelength tunability in our laser cavity and pump geometry. (C) 2002 Optical Society of America.

7 fs超快强激光驱动Ar原子产生支持单个阿秒脉冲的高次谐波连续谱

采用脉冲宽度为7 fs，脉冲能量为0．4mJ的超快强激光脉冲与气体盒子中Ar原子作用获得了高次谐波截止区连续谱，并发现当驱动激光稳定在不同的载波包络相位时，高次谐波的谱结构、谱调制深度和连续谱的带宽都有很大区别。在某些载波包络相位时获得了平滑的连续谱，调制深度小于17％，连续带宽达10eV，从而支持时域上获得变换极限500as的单个阿秒脉冲。