No description available.

Histamine is metabolized by several enzymes in vitro and in vivo. The relevance of this metabolism in the mammalian heart in vivo is unclear. However, histamine can exert positive inotropic effects (PIE) and positive chronotropic effects (PCE) in humans via H2- histamine receptors. In transgenic mice (H2-TG) that overexpress the human H2 receptor in cardiomyocytes but not in wild-type littermate mice (WT), histamine induced PIE and PCE in isolated left or right atrial preparations. These H2-TG were used to investigate the putative relevance of histamine degrading enzymes in the mammalian heart. Histidine, the precursor of histamine, increased force of contraction (FOC) in human atrial preparations. Moreover, histamine increased the phosphorylation state of phospholamban in human atrium. Here, we could detect histidine decarboxylase (HDC) and histamine itself in cardiomyocytes of mouse hearts. Moreover, our data indicate that histamine is subject to degradation in the mammalian heart. Inhibition of the histamine metabolizing enzymes diamine oxidase (DAO) and monoamine oxidase (MAO) shifted the concentration response curves for the PIE in H2-TG atria to the left. Moreover, activity of histamine metabolizing enzymes was present in mouse cardiac samples as well as in human atrial samples. Thus, drugs used for other indication (e.g. antidepressants) can alter histamine levels in the heart. Our results deepen our understanding of the physiological role of histamine in the mouse and human heart. Our findings might be clinically relevant because we show enzyme targets for drugs to modify the beating rate and force of the human heart.

Size-selected Pd nanoparticles were synthesized by the reverse-micelle encapsulation method and deposited on a ZrO2 support for the catalytic NO reduction by H2. All of our samples were found to be highly selective, but a significant size effect was not seen for Pd nanoparticles of between 1.2 nm and 5.5 nm. Ultra-small Pd clusters of less than 1 nm were found to be much less active, and are assumed to be affected by an encapsulation effect of the support. Catalyst activity was comparable to that of literature, and is applicable to H2-SCR research.

No description available.

L’étude de la dissociation de molécules poly-atomiques en surface est d’une importance à la fois fondamentale et industrielle. La compréhension du mécanisme et la dynamique réactionnelle sous-jacents représente un défi. Comme un système modèle, la dissociation de méthane sur la surface de nickel a fait l’objet de nombreuses études pour élucider les chemins de réaction et le transfert d’énergie parmi les différents degrés de liberté durant la réaction. La mode-spécifique ou liaison-spécifique réactivité pour la dissociation de CH4 sur Ni(111) et Ni(100) ont été mise en évidence récemment par des expériences de pointe du jet moléculaire. Jusqu’à présent, les études théoriques de la dynamique réactionnelle ont été effectuées avec un modèle simplifié dans lequel CH4 est décrit comme une molécule pseudo-diatomique. Le concept d’un groupe méthyle spectateur introduit dans un tel modèle impose des contraintes drastiques. Par exemple, l’indiscernabilité des quatre liaisons C-H de méthane est violée par le fait que la liaison C-H capable de se dissocier se singularise par rapport aux trois autres liaisons inertes. En réalité, n’importe quelle des quatre liaisons est susceptible de se dissocier. Par ailleurs, l’unique mode vibrationnel du modèle pseudo-diatomique ne ressemble à aucun des quatre modes vibrationnels principaux du méthane, qui décrivent tous des mouvements collectifs de plusieurs atomes. Lorsque tous les degrés de liberté sont pris en compte, la dimensionnalité de la surface de l’énergie potentielle pour CH4/Ni(111) est très élevée (15 degrés de liberté pour CH4 et certains degrés de liberté du substrat). Construire une surface de l’énergie potentielle fiable à une telle grande dimension est, en soi, un grand défi. A notre connaissance, ce défi n’a jamais été tenté auparavant pour quelconque réaction d’une molécule poly-atomique sur une surface métallique. En utilisant un champ de force réactif, nous avons développé, dans le présent travail, une surface de l’énergie potentielle qui prend en compte tous les 15 degrés de liberté de CH4 ainsi que ceux des 3 premières couches de NI(111). Des simulations de dynamique moléculaire ont été effectuées pour étudier la dynamique réaction de CH4 sur Ni(111) aussi bien dans son état fondamental vibrationnel que dans un état excité. Ces simulations ont permis de révéler des comportements dynamiques inattendus et très intéressants. / In the present work, we undertook a challenging task, i.e., construction a full-dimension potential energy surface (PES) for a benchmark poly-atomic molecular surface reaction, CH4/Ni(111), by using a reactive force field. Careful appraisal of the PES was made in order to establish the validity of the PES. The differences between the results for the transition state (dissociation barriers and structures) given by our PES and those by DFT calculations do not exceed 15%. The molecular dynamics simulation results obtained by using our PES are compared to experimental results for CH4 dissociation probability on Ni(111). For the vibrationally excited state, v3 (v=1, J=0), the agreement between our simulation results and the experimental ones is excellent. For the ground state, the sticking coefficient is somehow over-estimated because of the under-estimation of the dissociation barrier by about 150 meV with our reactive force field. Nevertheless, the overall agreement between simulation and experiment is pretty good. Within the help of the full-dimensional PES, we have extensively studied some important aspects of reaction dynamics, e.g., the effects of surface impact position, surface temperature, vibrationally excited state, rotationally excited states etc. For CH4 in ground state (v=0, J=0), the investigation of the effect of CH4 impact position shows that the top site is the most reactive one. The surface temperature strongly affects the reactivity of methane, especially in the region of the low incident energy near to the dissociation threshold, while in the high incident energy region, the effect is less important. For CH4 v3 (v=1, J=0), an important coupling between rotation and vibration is found. The rotation of CH4 can enhance its reactivity in the following way. In its ground state (v=0, J=0), CH4 does not rotate during its flight to the surface. In this case, only one of the two lowest C-H bonds pointing initially toward the surface can be cleaved while the two other bonds never break. In v3 (v=1, J=0) vibrational state, due to the rotation induced by vibration-rotation coupling, any of the four H atoms can be dissociated even if it forms a C-H bond which has an unfavorable initial orientation (i.e., pointing away from the substrate). The rotation of CH4 induced by vibration-rotation coupling near the substrate allows for bringing an unfavorable initial orientation of C-H bond to the right one required by a transition state (TS) during the adsorbate’s approaching to the substrate. As the enhanced reactivity of vibrationally excited molecules is concerned, the intuitively limpid and overwhelmingly accepted explanation is that the vibration-induced bond stretching helps bond breaking. Our simulation results show clearly that the vibration-induced CH4 rotation contributes an important part to the enhanced reactivity of a v3 (v=1, J=0) vibrationally excited CH4. A series of simulations to determine the sticking curves for CH4 in the vibrational ground state (ν=0) but excited to higher rotational levels (J=0-12) have also been performed. Due to its small level spacing, the lowest rotational excited states (J=1-3) of CH4 do not affect its reactivity on Ni(111) as observed experimentally. We found that rotation enhances significantly CH4 reactivity on Ni(111) with a deposited rotational energy amounting only to 12% of the dissociation barrier. Moreover, in a hypothetic simulation, we found also very striking evidences that rotation can even promote better dissociation of CH4 on Ni(111) than vibration. In a vibrationally excited CH4, its C-H bonds undergo alternate stretching and compressing and the latter hinders dissociation. In this case, the reactivity is inevitably modulated by vibration phase. However, the centrifugal force due to rotation tends always to stretch the C-H bonds for CH4 in rotationally excited states. / 多原子气相分子的分解，不仅在物理，化学及相关学科有着基本的重要性，而且可以促进工业进程，如工业制氢气。对其涉及的反应，即化学键的断裂与形成，在理解其反应机制和动力学上更是一项挑战。作为多原子气相-固相化学反应中最为典型的反应，甲烷分子在金属镍表面的分解，已经被广泛地研究从而理解其在动力学过程中的能量转化和反应路径。最近，选态分子束实验报道了有关甲烷在镍表面分解反应的重要特征，即模式选择性和化学键选择性。从理论角度来看，以前大多数理论研究都是基于一个简化模型，即将甲烷分子看成是一个赝双原子分子(CH4=RH,其中R=CH3)。在该简化模型中，将甲基团当做一个“spectator”会导致严重的限制性，如四个碳氢键的不可分辨性就被破坏。因为在简化模型中，只有一个可分解的碳氢键而其他三个碳氢键则被保护起来；而在实际的分解反应过程中，甲烷分子的任何一个碳氢化学键应该都有概率被分解掉。此外，在该赝双原子分子模型中，单键伸长振动模式不能类比于甲烷的四个基本振动模式，因为其每种基本振动模式都涉及多个原子的复合运动。如果不将甲烷处理成赝双原子分子，那么该体系（CH4/Ni(111)）的势能面的维度会很高，即甲烷的15 个自由度加上部分基地原子的自由度。欲建立一个如此高维度而且又可靠的势能面，本身就是一个值得挑战的研究任务。据我们所知，目前对多原子分子在金属表面反应的高维度势能面的报道几乎没有。在本论文中，我们运用键序反应力场（REBO），为体系CH4/Ni(111)，首次建立起一个全维度的势能面。该势能面的维度包含甲烷的15 个自由度和3 层基地原子的自由度。在经典分子动力学（和准经典分子动力学）模拟下，我们研究了甲烷处于基态和激发态时在金属表面的分解活性，并发现了一些非常有趣的结果。本论文包含以下六章：第一章：简单介绍了甲烷在过渡金属表面分解的最新进展。在选态分子束试验报道中，我们介绍了一些有关该反应的重要特征，如模式选择性，化学键选择性，表面温度效应，空间效应，旋转激发效应等。在理论工作方面，主要介绍了两个理论研究小组近期在简化模型下的一些量子动力学结果。第二章：对本文所运用的理论方法和近似做了基本的介绍。这些方法主要归纳于两类：i)电子结构计算；ii) 分子动力学模拟。我们重点介绍了这些方法和近似的特征。第三章：我们运用二阶矩近似力场(SMA)和键序反应力场(REBO)模拟了氢分子在金属钯表面的分解反应, 从而验证反应力场在模拟表面化学反应的适用性。该章讨论了在参数化反应力场时的一些影响因素，如有效数据库大小，不同排斥势以及长程作用项等，为对复杂体系的研究提供了有效的帮助。第四章：基于键序反应力场(REBO)，我们首次为CH4/Ni(111) 体系建立起一个全维度势能面(PES)。同时我们对该势能面(REBO(PES))做了全面评估，如比较势能面(REBO(PES))与DFT计算得到的过渡状态结构和与之对应的分解势垒，比较两者对于不同形式相互作用给出的势能变化等。此外，我们还直接模拟了甲烷在基态时的活性，其模拟结果与实验有着很好的符合度，从而进一步地说明了该势能面(REBO(PES))的可靠性。第五章：在全维度势能面下，我们深入地研究了甲烷处于不同状态时在镍表面分解的反应活性，即基态(v=0,J=0)，反对称振动态v3 (v=1,J=0)和旋转激发态(v=0,J=1-12)。对于基态的甲烷，我们定性并定量地分析了表面碰撞位置，表面温度对其分解概率的影响。对于反对称振动态的甲烷，我们观察到振动激发态的甲烷分子反应活性比基态甲烷的反应活性要大大地增强。究其根源在于，平动能量不易转换至旋转自由度，而振动能量则非常容易转入到旋转自由度。我们利用三个定量参数详细地阐述了这种振动耦合转动的重要性。此外，对于甲烷处于旋转激发态时，我们发现其激发状态非常有利于甲烷的分解，尽管其旋转能量只有分解势垒的12%。更为惊奇的是，对于甲烷分子而言，其旋转激发态比振动激发态更有利于其分解。其相应的物理解释是，对于振动激发的甲烷，它的碳氢键处于伸长与收缩的交替中，而后者却阻止其分解。对于旋转激发中的甲烷，其离心力一直促使碳氢键的伸长。第六章：总结和展望。我们总结了本文的主要结论以及给出一些将来需要进行的工作，如同位素效应等。

This paper responds to the development policy debate involving the World Bank and the IMF on the use of fiscal policy not only for economic stabilization but also to promote economic growth and increase per capita income. A key issue in this debate relates to the effect of the composition of public expenditure on economic growth. Policy makers and some researchers have argued that expenditure on growth-enhancing functions could enhance future revenue and justify the provision of "fiscal space" in the budget. But there are no simple ways to identify the growth-maximizing composition of public expenditure. The current paper lays out a research strategy to explore the effects of fiscal policy, including the composition of public expenditure, on economic growth, using a time series approach. Based on the modeling strategy of Greiner, Semmler and Gong (2005) we develop a general model that features a government that undertakes public expenditure on (a) education and health facilities which enhance human capital, (b) public infrastructure such as roads and bridges necessary for market activity, (c) public administration to support government functions, (d) transfers and public consumption facilities, and (e) debt service. The proposed model is numerically solved, calibrated and the impact of the composition of public expenditure on the long-run per capita income explored for low-, lower-middle- and uppermiddle-income countries. Policy implications and practical policy rules are spelled out, the extension to an estimable model indicated, a debt sustainability test proposed, and the out-of-steady-state dynamics studied.

The photocatalytic water splitting reaction showed to be a promising process to obtain renewable and clean energy, but the efficiency reached in this process is still low and must be improved to be viable. Considering this, the research on improving the efficiency of photocatalysts has attracted a strong interest in the past last years. Cerium oxide (CeO2−, 0 < x < 0.5) is a material recently investigated as a possible photocatalyst to obtain H2 from H2O. In this work, cerium oxide nanoparticles with high surface area (104 < S < 201 m2/g), high pore volume (32 < V < 132 mm3/g) values, wide range of diameter (2 < d < 90 nm) and O vacancies population (0.05 < x < 0.46) were applied to the H2 production photocatalytic reaction. The nanoparticles presented activity of up to 10 times higher than the commercial cerium oxide standard. UV-Vis, X-ray Diffraction, X-ray Absorption Spectroscopy, X-ray Photoelectron Spectroscopy, Ultraviolet Photoelectron Spectroscopy and Fourier Transform Infrared measurements were performed aiming to elucidate these results and to determine the main structural and electronic properties that can improve the H2 production photocatalytic reaction. It was obtained that the band gap energy depends on the nanoparticle synthesized and can be as low as 2.73 eV. The Ce 4f orbital occupation and the structural disorder presented by the nanoparticles is directly related with the band gap energies obtained. Density Functional Theory (DFT) calculations were performed to obtain the relation between the band structure (DOS) and the O vacancy population in order to explain the dependence of the band gap energy with the Ce 4f orbital occupation. Moreover, the O vacancies population at the surface have a very different effect depending on the presence or absence of mesopores, where a lower O vacancy population at the surface is better (worse) to the photocatalytic activity in the presence (absence) of mesopores. Furthermore O vacancies population at the surface plays a more fundamental role on the photocatalytic activity than the band gap energies for the samples presenting mesopores. The results allowed shedding light on the improvement of the properties of cerium oxide nanoparticles applied to optimize the H2 production photocatalytic activity.

Ho, Kwok Wa. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references (leaves 60-65). / Abstracts in English and Chinese. / Chapter Chapter I / Chapter 1.1. --- Thromboxane A2 (TP) Receptors --- p.1 / Chapter 1.1.1. --- Gene structure of human TP receptors --- p.1 / Chapter 1.1.2. --- Isoforms of TP receptor --- p.1 / Chapter 1.1.3. --- Distribution and expression of TP receptors in human --- p.2 / Chapter 1.1.4. --- Signal transduction of TP receptors --- p.4 / Chapter 1.1.5. --- Major agonists of TP receptor in animals and humans --- p.7 / Chapter 1.1.5.1. --- Thromboxane A2 --- p.7 / Chapter 1.1.5.2. --- Prostaglandin H2 --- p.7 / Chapter 1.1.6. --- Functional studies: effect of TP receptor activation and blockade on vascular tone and atherosclerosis --- p.8 / Chapter 1.1.6.1. --- Effect of TP receptor activation --- p.8 / Chapter 1.1.6.1.1. --- On vaso-contraction --- p.8 / Chapter 1.1.6.1.2. --- On vaso-relaxation --- p.9 / Chapter 1.1.6.2. --- Effect of TP receptor blockade --- p.9 / Chapter 1.1.6.2.1. --- On endothelium dependent vaso-contraction --- p.9 / Chapter 1.1.6.2.2. --- On animal models related to atherosclerosis --- p.10 / Chapter 1.1.7. --- Objectives of current study --- p.10 / Chapter 1.2. --- Periadventitial Adipose (Fat) Tissue --- p.12 / Chapter 1.2.1. --- "General function, distribution and classification of fat" --- p.12 / Chapter 1.2.2. --- Representative endocrine/paracrine role of adipose tissues --- p.13 / Chapter 1.2.2.1. --- Leptin --- p.13 / Chapter 1.2.2.2. --- Angiotensinogen --- p.14 / Chapter 1.2.3. --- Functional studies on vessels with periadventital fat attached -The beginning of the story of adipcyte-derived relaxing factor (ADRF) --- p.15 / Chapter 1.2.3. --- Mechanisms behind the action of ADRF --- p.17 / Chapter 1.2.3.1. --- Nature of ADRF --- p.17 / Chapter 1.2.3.2. --- The mechanisms controlling the release of ADRF --- p.17 / Chapter 1.2.3.3. --- Proposed mechanisms explaining the anti-contractile effect mediated by ADRF --- p.17 / Chapter 1.2.4. --- Objectives of current study --- p.20 / Chapter Chapter II / Chapter 2.1. --- Tissue Preparation --- p.21 / Chapter 2.1.1. --- Preparation of blood vessels --- p.21 / Chapter 2.1.2. --- Procedures to remove the endothelium --- p.21 / Chapter 2.2. --- The Organ Bath Setups --- p.22 / Chapter 2.3. --- Calculation of Results --- p.24 / Chapter 2.3.1. --- Calculation of active tension --- p.24 / Chapter 2.3.2. --- Measurement of dry weight of arterial rings --- p.24 / Chapter 2.3.3. --- Measurement of the weight for periadventitial fat --- p.24 / Chapter 2.3.4. --- Statistic analysis --- p.24 / Chapter 2.4. --- Chemicals and Solutions --- p.25 / Chapter 2.4.1. --- Chemicals --- p.25 / Chapter 2.4.2. --- Solutions --- p.26 / Chapter Chapter III --- Stimulation of TP receptors by U46619 inhibits cGMP dependent vaso-relaxation --- p.27 / Chapter 3.1. --- Detail methods and materials --- p.27 / Chapter 3.1.1. --- "Safety announcement, tissue preparation and materials" --- p.27 / Chapter 3.1.1. --- Protocol --- p.27 / Chapter 3.1.1.1. --- PartI --- p.27 / Chapter 3.1.1.2. --- Part II --- p.28 / Chapter 3.1.1.3. --- Part III --- p.28 / Chapter 3.2. --- Results --- p.29 / Chapter 3.2.1. --- Effect of U46619 on vaso-relaxation --- p.29 / Chapter 3.2.2. --- Effect of Rho kinase and phosphodiesterase inhibitor on the inhibitory effect of U46619 --- p.29 / Chapter 3.2.3. --- The effect of low concentration of U46619 on vaso-relaxation --- p.29 / Chapter 3.3. --- Discussion --- p.37 / Chapter 3.3.1. --- Implication of the current study --- p.37 / Chapter 3.3.2. --- Formulated Theory --- p.41 / Chapter Chapter IV --- Effect of periadventitial fat on anti-relaxation effect induced by U46619 - A preliminary test --- p.43 / Chapter 4.1. --- Detail methods and materials --- p.43 / Chapter 4.1.1. --- "Safety announcement, tissue preparation and materials" --- p.43 / Chapter 4.1.2. --- Protocol --- p.43 / Chapter 4.1.2.1. --- Part I --- p.43 / Chapter 4.1.2.2. --- Part II --- p.44 / Chapter 4.1.2.3. --- Part III --- p.44 / Chapter 4.1.2.4. --- Part IV --- p.44 / Chapter 4.2. --- Results --- p.45 / Chapter 4.2.1. --- Effect of periadventitial fat on vaso-relaxation of rings contracted by phenylephrine --- p.45 / Chapter 4.2.2. --- Effect of periadventitial fat on vaso-relaxation of rings contracted by U46619 plus phenylephrine --- p.45 / Chapter 4.2.3. --- Effect of S18886 on vaso-relaxation in endothelium removed rings --- p.45 / Chapter 4.2.4. --- Effect of elevated extracellular potassium ions on vaso-relaxation --- p.46 / Chapter 4.3. --- Discussion --- p.56 / Chapter 4.3.1. --- Implication of current study --- p.56 / Chapter 4.3.2. --- Improvements and future perspectives of current study --- p.58 / Summary --- p.59 / References --- p.60

L'hydrogène moléculaire est la molécule la plus simple et la plus répandue dans l'Univers. Elle se présente sous deux formes, ortho- et para- H$_2$, correspondant aux différents alignements des spins de ses deux noyaux. Le rapport ortho/para de H$_2$ est un paramètre essentiel pour comprendre les processus collisionnels inélastiques et réactifs dans les milieux astrophysiques moléculaires. Dans cette thèse, nous nous sommes intéressés à la détermination de ce rapport dans les nuages sombres, régions où H$_2$ ne peut pas être observée directement. Dans ce but, nous avons utilisé la molécule de formaldéhyde (H$_2$CO) dont l'excitation rotationnelle dans ces sources est dominée par les collisions avec H$_2$. Une transition particulière a été choisie pour cette étude : la raie à 6 cm (4,8 GHz) de ortho-H$_2$CO observée en absorption devant le fond diffus cosmologique. Si des études précédentes ont montré que cette absorption (antimaser) peut être expliquée par des effets collisionnels, aucune n'a étudié jusqu'à présent l'impact des formes ortho- et para-H$_2$ sur l'absorption. Nous présentons, dans un premier temps, nos calculs haute-précision des taux d'excitation rotationnelle entre (ortho-,para-)H$_2$CO et (ortho-,para-)H$_2$. Nous montrons qu'il existe des différences significatives sur les taux de collisions selon le type de projectiles, et en particulier qu'il existe des différences entre ortho- et para-H$_2$. Nous présentons ensuite l'utilisation de ces taux dans un modèle de transfert radiatif afin de reproduire les observations que nous avons menées au Green Bank Telescope sur la transition a 6 cm de ortho-H$_2$CO en direction de 3 nuages sombres (B68, L134N et TMC-1). Nous montrons que les différences dans les taux de collisions calculés avec ortho- et para-H$_2$ ont un impact significatif sur les simulations, nous permettant ainsi d'apporter des contraintes sur la valeur du rapport ortho/para de H$_2$ dans ces milieux. Nous traitons en particulier l'exemple de B68, prototype de c\oe ur pre-stellaire.

Nous étudions dans cette thèse les problèmes liés à la Commande Globale de Châssis (CGC) automobile. L'objectif est de développer des méthodes pour piloter différents actionneurs du véhicule (suspensions, freinage et direction) afin de les faire collaborer, dans le but d'améliorer le confort et la sécurité, et, de maitriser la dynamique du véhicule. Ce problème est complexe car il implique des dynamiques variées, non linéaires et de fortes contraintes au niveau des actionneurs. Les méthodes et outils utilisés sont issus des récents développements de l'automatique dans le domaine de la commande robuste pour les systèmes linéaires à paramètres variant (LPV). Dans ce contexte, les principaux thèmes développés concernent la modélisation, l'analyse et le contrôle des véhicules automobiles, ainsi que le contrôle robuste des systèmes LPV, utilisant les outils des inégalités linéaires matricielles (LMIs). Les principaux résultats traitent du développement de méthodes LPV pour la synthèse de commande robuste de suspension semi-active et de la synthèse de contrôle global de châssis (CGC) garantissant sécurité et agrément de conduite.