Thermally induced evolution of phase transformations in gas hydrate sediment

Thermally induced evolution of phase transformations is a basic physical-chemical process in the dissociation of gas hydrate in sediment (GHS). Heat transfer leads to the weakening of the bed soil and the simultaneous establishment of a time varying stress field accompanied by seepage of fluids and deformation of the soil. As a consequence, ground failure could occur causing engineering damage or/and environmental disaster. This paper presents a simplified analysis of the thermal process by assuming that thermal conduction can be decoupled from the flow and deformation process. It is further assumed that phase transformations take place instantaneously. Analytical and numerical results are given for several examples of simplified geometry. Experiments using Tetra-hydro-furan hydrate sediments were carried out in our laboratory to check the theory. By comparison, the theoretical, numerical and experimental results on the evolution of dissociation fronts and temperature in the sediment are found to be in good agreement.

沉积物中导热体周围水合物分解范围研究

沉积物水合物在热源周围的分解范围是水合物热开采以及相关灾害分析的重要基础数据.该文针对平面内边界有恒温热源的水合物热分解范围问题进行了理论分析和四氢呋喃水合物沉积物模型实验,并将两者结果进行了对比.结果表明:沉积物水合物最大分解范围主要取决于热源与环境温度的温差;热源周围水合物热分解最大范围的理论值与实验值接近,误差小于5%

基于连续介质力学的块体单元离散弹簧法研究

提出一种基于连续介质力学的块体单元离散弹簧法,并将其应用于地质体渐进破坏过程的数值模拟研究。该方法以连续介质力学的基本理论为基础,以八节点正六面体单元为离散对象,根据有限元的形函数理论及正六面体单元刚度矩阵的具体表达式,将正六面体单元离散成为12根棱弹簧,并推导各弹簧的弹簧力计算公式,给出各弹簧的弹簧力分量的物理意义、对应的弹簧刚度及相关联的位移。在弹性部分的计算结果与传统的有限元计算结果一致的基础上,在弹簧中引入Mohr-Coulomb准则及拉伸破坏准则,进行弹簧破坏的判断。如果块体内的弹簧全部断裂,便将其视为散体。在判断破坏时采用双重判断模式,块体单元的判断主要用于选取弹簧潜在的破坏面,离散弹簧的判断用于计算弹簧上的真实弹簧力。最后,通过相关算例验证引入破坏准则后所得计算结果的合理性。块体单元离散弹簧法的实质是通过12根离散弹簧将单元转化为结构,因此可以通过分析各弹簧的断裂情况研究块体的内部破坏特征,更可以通过各弹簧的先后断裂过程来研究地质体的渐进破坏过程。

基于连续介质力学的块体单元离散弹簧法研究

提出一种基于连续介质力学的块体单元离散弹簧法,并将其应用于地质体渐进破坏过程的数值模拟研究。该方法以连续介质力学的基本理论为基础,以八节点正六面体单元为离散对象,根据有限元的形函数理论及正六面体单元刚度矩阵的具体表达式,将正六面体单元离散成为12根棱弹簧,并推导各弹簧的弹簧力计算公式,给出各弹簧的弹簧力分量的物理意义、对应的弹簧刚度及相关联的位移。在弹性部分的计算结果与传统的有限元计算结果一致的基础上,在弹簧中引入Mohr-Coulomb准则及拉伸破坏准则,进行弹簧破坏的判断。如果块体内的弹簧全部断裂,便将其视为散体。在判断破坏时采用双重判断模式,块体单元的判断主要用于选取弹簧潜在的破坏面,离散弹簧的判断用于计算弹簧上的真实弹簧力。最后,通过相关算例验证引入破坏准则后所得计算结果的合理性。块体单元离散弹簧法的实质是通过12根离散弹簧将单元转化为结构,因此可以通过分析各弹簧的断裂情况研究块体的内部破坏特征,更可以通过各弹簧的先后断裂过程来研究地质体的渐进破坏过程。

有机质谱裂解规律及智能解析方法研究

本学位论文分为四个部分，第一部分报道了用串联质谱快速分析合成药物中的微量杂质成分以及分析中药材中的化学成分。第二部分报道了通过质谱和串联质谱发现并合成新型的PdPincer 催化剂，同时对其活性进行测试。第三部分为串联质谱自动解析软件的设计及应用。第四部分概述了应用在质谱中的各种碎裂方式。 第一部分首先总结了5-溴粉防己碱及其类似物的裂解规律，并以此为根据推测出2 个微量杂质的结构。随后针对无患子（Sapindus mukurossi Gatren.）中的皂苷成分，由ESI-QTOF 得到各个皂苷成份的高分辨质量数据进而得到其分子式，然后利用ESI-IT 电喷雾串联质谱对无患子总皂苷中各皂苷成分的结构进行进一步的鉴定。进而以同样的方式，先通过ESI-QTOF 得到黄山药（Dioscoreapanthaica）总皂苷中各个组分化合物的分子式，然后对已有的薯蓣皂苷标准品做串联质谱分析，以得到该类化合物的裂解规律并给出解析该类化合物的流程图。在此利用计算化学的方法讨论了离子的丰度与裂解活化能之间的关系。然后应用APCI-MS/MS 方法探讨了四对同分异构体和几个已知的化合物，并最后用液质联用对其进行确认，同时还给出了4 个未知化合物的可能结构。 第二部分报道通过质谱和串联质谱发现并合成新型的PdPincer 催化剂，同时对其活性进行测试。钯催化的交联反应是有机合成中C-C 键形成的最有效的方法，且硫脲是一类对空气和水都稳定的化合物，因此我们设计并合成了一系列的硫脲钯催化剂并得到了很好的催化活性。我们在对其中一类环状双硫脲化合物进行质谱实验的时候，在正离子模式下发现了反常的[M.H]+，通过串联质谱进一步确定了它是一种新型的PdPincer 结构。我们将其合成出来并通过X-ray 衍射实验确定了它的结构。同时测定其催化活性并与未形成pincer 的类似物进行比较发现该类化合物具有较宽的底物适用性。 第三部分为串联质谱自动解析软件的设计及应用。通过前面两部分的启示，独立设计开发了AuMass（1.0）。其算法是：先通过查找特殊的碎片离子，中性丢失或碎片离子质量差来确定某类化合物的骨架结构，然后利用该类化合物的自动解析流程来对其周边取代基进行确认。通过它快速地对白芍中的化学成分进行解析，并对未知的化合物进行了推测。为了增加它的解析能力，我又对其它类型的化合物裂解规律进行总结，并给出了自动解析流程。实践证明该软件具有相当好的应用价值。 第四部分综述了应用在质谱上的各类母离子的碎裂技术。这里包括了碰撞诱导裂解（CID）、光诱导碎裂（LID）、电子捕获裂解/电子转移裂解（ECD/ETD）、红外多光子解离（IRMPD）、黑体辐射解离（BIRD）和PQD 裂解技术。 This dissertation consists of four chapters. The first chapter reports the rapidanalysis of trace impurities from synthetical medicine and analysis of the chemicalconstitutents from Chinese herb medicines. The second chapter elaborates the studieson the discorvery and synthesis of new type of Pd Pincer catalyst by using MS andtandem MS together with the testing of its catalyst activity. The third chapter dwellson the designation and development of automatic tandem mass spectrometry analysissoftware. The last chapter presents a review on the dissociation technique of massspectrometry. The first chapter reports the rapid analysis of trace impurities from synthesismedicine and analysis of the chemical constitutents from Chinese herb medicines. The fission mechanism of 5-bromotetrandrine was obtained by analysis of the dissociationpathways of major product, by using which the possible structure of the two traceimpurties was assumed. There are lots of saponins in Sapindus mukurossi. Except forthe good spumescence and decontamination，it possesses the bioactivity of antigenand antitch. First of all, the high resolution mass information was obtained by ESI-QTOF. Hence the possible molecular formulars were acquired too. Then weconducted the further detection of the structures of its saponins by using ESI-ITtechnology. In the same manner, first the molecular formulars of every constituentfrom Dioscorea panthaica in total saponins were obtained by ESI-QTOF, and thenacquired the fission mechanism of this type of compounds by tandem massexperiment on a series of known and available saponins. In the same time, theanalysis flowchart was concluded. Here the relationship between the ion intensity andthe corresponding dissiociation activation energy was studied by computer chemistry.Then the four pairs of isomers were differentiated by APCI-MS/MS, as well as thecharacterization of known and unknown compounds. The assumption was confirmed by HPLC-MS/MS. Among them the possible structures of four unknown saponinswas presented. The second part was discovery and synthesis of a new type of Pd pincer catalystby MS and tandem MS. The coupling reaction catalyzed by Pd is the most effectivemethod in C-C formation in organic synthesis. Apart from that, thiourea is type ofcompounds that are stable to atmosphere and moisture. Hence we designed a series ofPd thiourea catalysts. Some of them show the excellent catalyst activity. The abnormalparent ion [M.H]+ was founded in positive ESI mode when we conduct some massspectrometry experiments on the bicyclical thiourea Pd complex. The structure wasproposed by mass and tandem mass spectrometry. Because it was a new type of pincer,we want to test its catalyst activity. So the Pd pincer was synthesized and the detailstructure was obtained by x-ray experiment. It shows the more fitness in catalysis ofSuzuki reaction by comparison with the analogue. The third chapter dwells on the design and development of automatic tandemmass spectrometry analysis software. Inspired by the former two chapters, theAuMass (version 1.0) was developed. Its algorithm is: first check the diagnostic ion,diagnostic neutral loss or diagnostic ions mass intervals in database to find out whatthe analyst’s skeleton belongs to, then identify the peripheral functional group by thecorresponding analysis flowchart. The chemical constituents of Paeonia lactiflorawere identified rapidly by using AuMass. To increase the analysis ability, the othertypes of compounds from Chinese herbs was concluded. Actually, the software isproven to have the much valuable application. The last chapter presented the review on the some kinds of fission technique ofmass spectrometry. It involves the collision induced dissociation (CID), laser induceddissociation (LID), electron capture dissociation/electron transfer dissociation(ECD/ETD), infrared multiple photons dissiociation, black body irraditiondissociation and PQD fission technique from Finnigan.

两种银莲花属植物的化学成分研究

本学位论文由5 章组成。第1 章报道了两头尖中三萜皂苷类化合物的全扫描电喷雾多级质谱分析及银莲花素A 的电喷雾质谱裂解规律；第2 和3 章报道了两种银莲花属药用植物化学成分的研究结果；第4 章报道了银莲花素A 的化学结构修饰及其对一种蛋白酪氨酸磷酸酯酶（PTP-1B）的抑制活性；第5 章综述了电喷雾质谱在皂苷类化合物结构鉴定中的应用进展。 第1 章报道了运用全扫描电喷雾多级质谱对两头尖中三萜皂苷类化合物的快速定性检测，共检测出18 个准分子离子峰，根据多级质谱数据并结合文献报道，对其中的15 个准分子离子峰进行了归属，并区分了一些同分异构体；更有意思的是，发现了3 个未见文献报道的三萜皂苷类化合物。根据它们的多级质谱数据，对其结构分别进行了初步解析。本章同时对银莲花素A 特殊的质谱裂解途径通过衍生物制备及其质谱分析进行了确认。 第2 和3 章，分别报道了两头尖和打破碗花花中水溶性多糖苷的分离纯化和结构鉴定。采用D101 大孔树脂和反复硅胶柱层析等分离手段，从两头尖水溶性部分分离得到8 个三萜皂苷类化合物，通过红外、电喷雾质谱和核磁共振等现代谱学方法，并结合传统的化学手段鉴定了它们的结构，其中4 个化合物为新化合物，分别命名为多被银莲花皂苷19、多被银莲花皂苷20、多被银莲花皂苷21和多被银莲花皂苷22。从打破碗花花水溶性部位分离得到6 个三萜皂苷类化合物，通过现代谱学手段，并结合传统的化学方法对它们进行了鉴定，其中1 个为新化合物，命名为打破碗花花苷H。 第4 章报道了以银莲花素A 及其同系物为先导化合物，进行化学结构修饰并对修饰产物进行广泛的生物活性筛选，发现在银莲花素A 及其同系物的结构中引入一些酸性基团后，其生物活性发生了变化，一些修饰产物显示出很强的PTP-1B 抑制作用，提示这些化合物有可能用于治疗II 型糖尿病。 第5 章综述了电喷雾多级质谱用于皂苷类化合物结构鉴定的研究进展。 This dissertation composes of five chapters. The first chapter elaborates the detection and qualification of the triterpenoidal saponins in Anemone raddeana by positive and negative full scan ESI-MSn. This part also reports the special fragmentation pathway of Raddeanin A by ESI-MS/MS. The second and third chapters present the phytochemical investigation of two medicinal plants from Anemone. The fourth part dwells on the structure modification of Raddeanin A and their inhibitory activity against PTP-1B. The last part is a review on the progress in the application of ESI-MSn in the structure identification of saponins. The first chapter reports the application of full scan ESI-MSn for fast analysis of triterpenoid saponins in Anemone raddeana. Eighteen quasi- molecular ion peaks were detected in the positive full scan ESI-MS and fifteen of them were identified by analysis of their tandem mass spectral data in the negative ion mode. Several isomers were differentiated. More interesting, three unreported triterpenoid saponins in this medicinal plant were detected and their structures were deduced according to the dissociation pathway of the known triterpenoidal saponins. This chapter also confirms the special fragmentation pathway of Raddeanin A by its derivative and the mass spectral analysis. The second and third chapters expatiate on the isolation and identification of the chemical constituents from A. raddeana and A. hupehensis. Eight compounds were isolated from the roots and stems of A. raddeana by methanol extraction and repeated column chromatography (including D101 and silica gel), and their structures were determined on the basis of IR, ESI-MS, NMR and chemical methods (including acid hydrolysis and alkaline saponification). Among them, four are new triterpenoid saponins and named as Raddeanoside R19, Raddeanoside R20, Raddeanoside R21 and Raddeanoside R22. Six compounds were isolated from the whole plants of A. hupehensis by the same methods as above, and their structures were also determined with the same way. One of them was confirmed to be new triterpenoid saponins and named as hupehensis saponin H. In the fourth chapter, in order to look for new active compounds, the structure of Raddeanin A and its analogs were modified. It was found that the modified products exhibited obvious inhibitory activity against PTP-1B when several acid groups were introduced. The fifth chapter summarizes the progress on the application of ESI-MSn in the structure identification of saponins.

Pion Production in Heavy-ion Collisions in the 1 A GeV region

Within the framework of the improved isospin dependent quantum molecular dynamics (ImIQMD) model, the pion emission in heavy-ion collisions in the region 1AGeV is investigated systematically, in which the pion is considered to be mainly produced by the decay of resonances ∆(1232) and N∗(1440). The in-medium dependence and Coulomb effects of the pion production are included in the calculation. Total pion multiplicity and π−/π+ yields are calculated for the reaction 197Au+197Au in central collisions for selected Skyrme parameters SkP, SLy6,Ska, SIII and compared them with the measured data by the FOPI collaboration.

Fusion dynamics of symmetric systems near barrier energies

Within the framework of the improved isospin-dependent quantum molecular dynamics (ImIQMD) model,he fusion dynamics of symmetric reaction systems are investigated systematically. Calculations show that the number of nucleon transfer in the neck region is appreciably dependent on the incident energies, but strongly on he reaction systems. A comparison of the neck dynamics is performed for the symmetric reactions 58Ni+58Niand 64Ni+64Ni at energies in the vicinity of the Coulomb barrier. An increase of the ratios of the neutron to proton in the neck region at initial collision stage is observed and obvious for the latter system, which reduces the fusion barrier of two colliding nuclei. The distribution of the dynamical fusion barriers and the fusion excitation functions are calculated and compared with the available experimental data.

Pion Production in Heavy-Ion Collisions in the 1 A GeV Region

Within the framework of the improved isospin dependent quantum molecular dynamics (ImIQMD) model, pion emission in heavy-ion collisions in the region 1 A GeV is investigated systematically, in which the pion is considered to be mainly produced by the decay of resonances Delta(1232) and N*(1440). The in-medium dependence and Coulomb effects of pion production are included in the calculation. Total pion multiplicity and pi(-)/pi(+) yields are calculated for the reaction Au-197+(197) Au in central collisions for selected Skyrme parameters SkP, SLy6, Ska, SIII and compared with the measured data of the FOPI collaboration.

Sputtering induced by highly charged Pb-208(q+) bombardment on Al surface

Highly charged ions (HCls) carrying high Coulomb potential energy (E-p) could cause great changes in the physical and chemical properties of material surface when they bombard on the solid surface. In our work, the secondary ion yield dependence on highly charged Pbq+ (q = 4-36) bombardment on Al surface has been investigated. Aluminum films (99.99%) covered with a natural oxide film was chosen as our target and the kinetic energy (E-k) was varied between 80 keV and 400 keV. The yield with different incident angles could be described well by the equation developed by us. The equation consists of two parts due to the kinetic sputtering and potential sputtering. The physical interpretations of the coefficients in the said equation are discussed. Also the results on the kinetic sputtering produced by the nuclear energy loss on target Surface are presented.

An introduction to the trapping of clusters with ion traps and electrostatic storage devices

This paper presents an introduction to the application of ion traps and storage devices for cluster physics. Some experiments involving cluster ions in trapping devices such as Penning traps, Paul traps, quadrupole or multipole linear traps are briefly discussed. Electrostatic ion storage rings and traps which allow for the storage of fast ion beams without mass limitation are presented as well. We also report on the recently developed mini-ring, a compact electrostatic ion storage ring for cluster, molecular and biomolecular ion studies.

Shell effect and capture cross sections in the synthesis of superheavy nuclei

The shell effect is included in the improved isospin dependent quantum molecular dynamics model in which the shell correction energy of the system is calculated by using the deformed two-center shell model. A switch function is introduced to connect the shell correction energy of the projectile and the target with that of the compound nucleus during the dynamical fusion process. It is found that the calculated capture cross sections reproduce the experimental data quantitatively at the energy near the Coulomb barrier. The capture cross sections for reaction (35) (80) Br + (82) (208) Pb -> (117) (288) X are also calculated and discussed.

Emission characteristics of three final continuum electrons produced in low-energy double ionization of helium

The double ionization of helium by electron impact for 106 eV incident energy was studied in a kinematically complete experiment by using a reaction microscope. The pattern of the angular correlation of the three emitted electrons was analyzed by selecting different values of the recoil ion longitudinal momentum. The Wannier predicted geometry appears when the recoil ion carries the full initial projectile momentum. It was found that at this low impact energy, the outgoing electrons still remember the initial-state collision information.

Flux-dependent shot noise through an Aharonov-Bohm interferometer with an embedded quantum dot

Shot noise through a closed Aharonov-Bohm interferometer carrying a quantum dot in one of its two current paths is investigated. It is found that the shot noise can be modulated by the magnetic flux Phi, the dot level, and the direct tunneling. Due to the interference between the two transmission channels, the Kondo correlation manifests itself in the flux dependence of the shot noise, which exhibits oscillation behavior with a period of Phi(0)/2 (Phi(0) is the flux quantum) for small voltages below the Kondo temperature T-K. At voltages well above T-K or outside the Kondo regime, the shot noise is determined by high-energy Coulomb and hybridization processes, and its Aharonov-Bohm oscillations restore the fundamental period of Phi(0). As a result of its two-particle nature, the shot noise contains higher-order harmonics absent in the current, demonstrating the fact that the noise is more sensitive to the effects of quantum interference than the current.

A ionization theory based on united and separated atom model

The direct Coulomb ionization process can be generally well described by the ECPSSR theory, which bases on the perturbed-stationary- state(PSS) and accounts for the energy-loss, Coulomb-deflection, and relativistic effects. But the ECPSSR calculation has significant deviations for heavy projectile at low impinging energies. In this paper we propose a new modified ECPSSR theory, i.e. MECUSAR, in which PSS is replaced by an united and separated atom model, and molecule-orbit effect is considered. The MECUSAR calculations give better agreement with the experimental data at lower impinging energies, and agree with the ECPSSR calculations at high energies. By using OBKN (Oppenheimer-Brinkman-Kramers formulas of Nikolaev) theory to describe the contribution of the electron capture, we further modified the proposed MECUSAR theory, and calculated the target ionization cross sections for different charge states of the projectile.