The reaction route and active site of catalytic decomposition of hydrazine over molybdenum nitride catalyst

The catalytic properties of the passivated, reduced passivated, and fresh bulk molybdenum nitride for hydrazine decomposition were evaluated in a microreactor. The reaction route of hydrazine decomposition over molybdenum nitride catalysts seems to be the same as that of Ir/gamma-Al2O3 catalysts. Below 673 K, the hydrazine decomposes into N-2 and NH3. Above 673 K, the hydrazine decomposes into N-2 and NH3 first, and then the produced NH3 further dissociates into N-2 and H-2. From the in situ FT-IR spectroscopy, hydrazine is adsorbed and decomposes mainly on the Mo site of the Mo2N/gamma-Al2O3 catalyst. (C) 2004 Elsevier Inc. All rights reserved.

THE ISOLATION, CHARACTERIZATION AND OXIDATION REACTION OF ACTIVE INTERMEDIATES OF CYTOCHROME-P-450 MODEL SYSTEM OXOCHROMIUM(V) TETRAPHENYLPORPHYRIN COMPLEXES

Oxochromium (V) tetraphenylporphyrin complexes, O = Cr (V) TPP (Cl) PhI. O = Cr-(V) TPP (N3) PhI and O = Cr (V)TPP (p-CH3OC6H4O)1/2PhI were isolated from the reaction of Cr (III) TPP (Cl). Cr (III) TPP (N3) Py or Cr (III) TPP (p-CH3OC6H4O) THF with iodosy

STUDY ON THE ACTIVE-CENTERS OF METHANE COUPLING CATALYSTS BY MEANS OF FLUORESCENCE EMISSION OF EU3+

Eu3+ ion was adopted as a probe to detect the probability of entrance of alkali elements into the crystal lattice of MgO, CaO and La2O3 by means of its characteristic emission. Based on the experimental data it is concluded that Li+ and Na+ ions can substitute Mg2+ and Ca2+ ions and only a small amount of K+ ion can enter into the lattice of CaO. Whilst Li+ ion can not enter into the lattice of lanthana. The conclusion of this investigation is in good agreement with that obtained by Lunsford by ESR studies.

Variation of active constituents of an important Tibet folk medicine Swertia mussotii Franch. (Gentianaceae) between artificially cultivated and naturally distributed

Concentrations of seven phytochemical constituents (swertiamarin, mangiferin, swertisin, oleanolic acid, 1,5,8-trihydroxy-3methoxyxanthone, 1,8-dihydroxy-3,7-dimethoxyxanthone and 1,8-dihydroxy-3,5-dimethoxyxanthone) of "ZangYinChen" (Swertia mussotii, a herb used in Tibetan folk medicine) were determined and compared in plants collected from naturally distributed high-altitude populations and counterparts that had been artificially cultivated at low altitudes. Levels of mangiferin, the most abundant active compound in this herb, were significantly lower in cultivated samples and showed a negative correlation with altitude. The other constituents were neither positively nor negatively correlated with cultivation at low altitude. Concentrations of all of the constituents varied substantially with growth stage and were highest at the bud stage in the cultivars, but there were no distinct differences between flowering and fruiting stages in this respect. (c) 2005 Elsevier Ireland Ltd. All rights reserved.

Towards Intelligent Structures: Active Control of Buckling

The buckling of compressively-loaded members is one of the most important factors limiting the overall strength and stability of a structure. I have developed novel techniques for using active control to wiggle a structural element in such a way that buckling is prevented. I present the results of analysis, simulation, and experimentation to show that buckling can be prevented through computer-controlled adjustment of dynamical behavior.sI have constructed a small-scale railroad-style truss bridge that contains compressive members that actively resist buckling through the use of piezo-electric actuators. I have also constructed a prototype actively controlled column in which the control forces are applied by tendons, as well as a composite steel column that incorporates piezo-ceramic actuators that are used to counteract buckling. Active control of buckling allows this composite column to support 5.6 times more load than would otherwise be possible.sThese techniques promise to lead to intelligent physical structures that are both stronger and lighter than would otherwise be possible.

Political participation of non-national residents in Portugal

Em Portugal, novas medidas de participação política têm vindo a ser introduzidas tanto por força da transição para uma sociedade multicultural como pela sua participação na integração política europeia que se direcciona para um novo nível de cidadania. O presente artigo pretende mostrar até que ponto os residentes não-nacionais, de países terceiros e da União Europeia, efectivamente usam os seus novos direitos políticos e participam nos actos eleitorais em Portugal, conferindo-lhes a oportunidade de uma maior integração política no seu Estado de residência. In Portugal, new rules of political participation have been imposed by the transition to a multicultural society, in addition to the European political integration that is currently developing towards a new level of citizenship. This paper intends to show to what extent non-national residents, both from EU and non-EU countries, effectively use their new political rights and participate in the Portuguese electoral acts that give them the opportunity for a wider political integration in their state of residence.

Diagnóstico do meio escolar

Dissertação apresentada à Universidade Fernando Pessoa, como parte dos requisitos para a obtenção do grau de mestre em Psicologia, ramo de Psicologia da Educação e Intervenção Comunitária

The Right to Participation of Minorities and Irish Travellers

The idea of participation is becoming increasingly important in international human rights law and recent political and constitutional theory. There is an emerging international law right of minorities to participate in public life. There are many problems though with putting this right into practice. It is not enough to offer formal opportunities for representation or even to facilitate more participatory processes. This article explores how participation is more easily proclaimed than practised by examining the position of one ethnic minority, Travellers, in a liberal democracy, Ireland. While there are many formal opportunities for participation, these do not necessarily result in effective participation on a basis of equality, and may still result in decisions which fail to consider the Traveller culture and identity. Travellers still suffer from an imbalance of power in these arrangements. There are hopeful avenues to pursue in improving participation, the role of civil society and the use of a dialogue between non-governmental organisations and international organisations to put pressure on a national government, including special representation to offset the disadvantages of traditional representative democracy and emphasising the role of special parliamentary bodies; and the need to address the politics of recognition so as to strengthen the hand of disadvantaged groups such as Travellers.

A Density Functional Theory Study on the Active Center of Fe-Only Hydrogenase: Characterization and Electronic Structure of the Redox States

We have carried out extensive density functional theory (DFT) calculations for possible redox states of the active center in Fe-only hydrogenases. The active center is modeled by [(H(CH(3))S)(CO)(CN(-))Fe(p)(mu-DTN)(mu-CO)Fe(d)(CO)(CN(-))(L)](z) (z is the net charge in the complex; Fe(p)= the proximal Fe, Fe(d) = the distal Fe, DTN = (-SCH(2)NHCH(2)S-), L is the ligand that bonds with the Fed at the trans position to the bridging CO). Structures of possible redox states are optimized, and CO stretching frequencies are calculated. By a detailed comparison of all the calculated structures and the vibrational frequencies with the available experimental data, we find that (i) the fully oxidized, inactive state is an Fe(II)-Fe(II) state with a hydroxyl (OH(-)) group bonded at the Fe(d), (ii) the oxidized, active state is an Fe(II)-Fe(l) complex which is consistent with the assignment of Cao and Hall (J. Am. Chem. Soc. 2001, 123, 3734), and (iii) the fully reduced state is a mixture with the major component being a protonated Fe(l)-Fe(l) complex and the other component being its self-arranged form, Fe(II)-Fe(II) hydride, Our calculations also show that the exogenous CO can strongly bond with the Fe(II)-Fe(l) species, but cannot bond with the Fe(l)-Fe(l) complex. This result is consistent with experiments that CO tends to inhibit the oxidized, active state, but not the fully reduced state. The electronic structures of all the redox states have been analyzed. It is found that a frontier orbital which is a mixing state between the e(g) of Fe and the 2pi of the bridging CO plays a key role concerning the reactivity of Fe-only hydrogenases: (1) it is unoccupied in the fully oxidized, inactive state, half-occupied in the oxidized, active state, and fully occupied in the fully reduced state; (ii) the e(g)-2pi orbital is a bonding state, and this is the key reason for stability of the low oxidation states, such as Fe(l)-Fe(l) complexes; and (iii) in the e(g)-2pi orbital more charge accumulates between the bridging CO and the Fe(d) than between the bridging CO and the Fe(p), and the occupation increase in this orbital will enhance the bonding between the bridging CO and the Fe(d), leading to the bridging-CO shift toward the Fe(d).

DFT and in situ EXAFS investigation of gold/ceria-zirconia low-temperature water gas shift catalysts: Identification of the nature of the active form of gold

A combined experimental and theoretical investigation of the nature of the active form of gold in oxide-supported gold catalysts for the water gas shift reaction has been performed. In situ extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) experiments have shown that in the fresh catalysts the gold is in the form of highly dispersed gold ions. However, under water gas shift reaction conditions, even at temperatures as low as 100 degrees C, the evidence from EXAFS and XANES is only 14 consistent with rapid, and essentially complete, reduction of the gold to form metallic clusters containing about 50 atoms. The presence of Au-Ce distances in the EXAFS spectra, and the fact that about 15% of the gold atoms can be reoxidized after exposure to air at 150 degrees C, is indicative of a close interaction between a fraction (ca. 15%) of the gold atoms and the oxide support. Density functional theory (DFT) calculations are entirely consistent with this model and suggest that an important aspect of the active and stable form of gold under water gas shift reaction conditions is the location of a partially oxidized gold (Audelta+) species at a cerium cation vacancy in the surface of the oxide support. It is found that even with a low loading gold catalysts (0.2%) the fraction of ionic gold under water gas shift conditions is below the limit of detection by XANES (<5%). It is concluded that under water gas shift reaction conditions the active form of gold comprises small metallic gold clusters in intimate contact with the oxide support.