Density functional theory and ab initio molecular dynamics study of NO adsorption on Pd(111) and Pt(111) surfaces

The origin of the unique geometry for nitric oxide (NO) adsorption on Pd(111) and Pt(111) surfaces as well as the effect of temperature were studied by density functional theory calculations and ab initio molecular dynamics at finite temperature. We found that at low coverage, the adsorption geometry is determined by electronic interactions, depending sensitively on the adsorption sites and coverages, and the effect of temperature on geometries is significant. At coverage of 0.25 monolayer (ML), adsorbed NO at hollow sites prefer an upright configuration, while NO adsorbed at top sites prefer a tilting configuration. With increase in the coverage up to 0.50 ML, the enhanced steric repulsion lead to the tilting of hollow NO. We found that the tilting was enhanced by the thermal effects. At coverage of 0.75 ML with p(2 x 2)-3NO(fcc+hcp+top) structure, we found that there was no preferential orientation for tilted top NO. The interplay of the orbital hybridization, thermal effects, steric repulsion, and their effects on the adsorption geometries were highlighted at the end.

Full-dimensional analytical ab initio potential energy surface of the ground state of HOI

Extensive ab initio calculations using a complete active space second-order perturbation theory wavefunction, including scalar and spin-orbit relativistic effects with a quadruple-zeta quality basis set were used to construct an analytical potential energy surface (PES) of the ground state of the [H, O, I] system. A total of 5344 points were fit to a three-dimensional function of the internuclear distances, with a global root-mean-square error of 1.26 kcal mol(-1). The resulting PES describes accurately the main features of this system: the HOI and HIO isomers, the transition state between them, and all dissociation asymptotes. After a small adjustment, using a scaling factor on the internal coordinates of HOI, the frequencies calculated in this work agree with the experimental data available within 10 cm(-1). (C) 2011 American Institute of Physics. [doi: 10.1063/1.3615545]

Opposite roles of O-2 in NO- and N2O-carbon reactions: An ab initio study

Previous experimental studies showed that the presence of O-2 greatly enhances NO-carbon reaction while it depresses N2O-carbon reaction on carbon surfaces. A popular explanation for the rate increase is that the addition of O-2 results in a large number of reactive carbon-oxygen complexes, and decomposition of these complexes produces many more active sites. The explanation for the latter is that excess O-2 simply blocks the active sites, thus reducing the rate of N2O-carbon reaction. The contradiction is that O-2 can also occupy active sites in NO-carbon reaction and produce active sites in N2O-carbon reduction. By using ab initio calculation, we find that the opposite roles of O-2 are caused by the different manners of N2O and NO adsorption on the carbon surface. In the presence of excess O-2, most Of the active sites are occupied by oxygen groups. In the competition for the remaining active sites, NO is more likely to chemisorb in the form of NO2 and NO chemisorption is mon thermodynamically favorable than O-2 chemisorption. By contrast, the presence of excess O-2 makes N2O chemisorption much less thermally stable either on the consecutive edge sites or edge sites isolated by semiquinone oxygen. A detailed analysis and discussion of the reaction mechanism of N-2 formation from NO- and N2O-carbon reaction in the presence of O-2 is presented in this paper.

A peptide-binding motif for I-A(g7), the class II major histocompatibility complex (MHC) molecule of NOD and Biozzi AB/H mice

The class II major histocompatibility complex molecule I-A(g7) is strongly linked to the development of spontaneous insulin-dependent diabetes mellitus (IDDM) in non obese diabetic mice and to the induction of experimental allergic encephalomyelitis in Biozzi AB/H mice. Structurally, it resembles the HLA-DQ molecules associated with human IDDM, in having a non-Asp residue at position 57 in its beta chain. To identify the requirements for peptide binding to I-A(g7) and thereby potentially pathogenic T cell epitopes, we analyzed a known I-A(g7)-restricted T cell epitope, hen egg white lysozyme (HEL) amino acids 9-27. NH2- and COOH-terminal truncations demonstrated that the minimal epitope for activation of the T cell hybridoma 2D12.1 was M12-R21 and the minimum sequence for direct binding to purified I-A(g7) M12-Y20/K13-R21. Alanine (A) scanning revealed two primary anchors for binding at relative positions (p) 6 (L) and 9 (Y) in the HEL epitope. The critical role of both anchors was demonstrated by incorporating L and Y in poly(A) backbones at the same relative positions as in the HEL epitope. Well-tolerated, weakly tolerated, and nontolerated residues were identified by analyzing the binding of peptides containing multiple substitutions at individual positions. Optimally, p6 was a large, hydrophobic residue (L, I, V, M), whereas p9 was aromatic and hydrophobic (Y or F) or positively charged (K, R). Specific residues were not tolerated at these and some other positions. A motif for binding to I-A(g7) deduced from analysis of the model HEL epitope was present in 27/30 (90%) of peptides reported to be I-A(g7)-restricted T cell epitopes or eluted from I-A(g7). Scanning a set of overlapping peptides encompassing human proinsulin revealed the motif in 6/6 good binders (sensitivity = 100%) and 4/13 weak or non-binders (specificity = 70%). This motif should facilitate identification of autoantigenic epitopes relevant to the pathogenesis and immunotherapy of IDDM.

Ab initio modelling of basal plane oxidation of graphenes and implications for modelling char combustion

Ab initio calculations have been performed to determine the energetics of oxygen atoms adsorbed onto graphene planes and the possible reaction path extracting carbon atorns in the form of carbon monoxide. Front the energetics it is confirmed that this reaction path will not significantly contribute to the gasification of well ordered carbonaceous chars. Modelling results which explore this limit Lire presented. (C) 2002 Elsevier Science Ltd, All rights reserved.

A presença meso-assíria no Médio Eufrates: o contributo da cerâmica de Tall Qabr Abū al-'Atīq (Deir ez-Zor, Síria)

Dissertação apresentada para cumprimento dos requisitos necessários à obtenção do grau de Mestre em Arqueologia.

Nota sobre antígeno relacionado à hepatite (HB Ag) e anticorpo (HB Ab) em população do território Federal do Amapá

53 amostras de soro, provenientes de Ferreira Gomes, no Amapá, foram testados para antígeno HB Ag e anticorpo HB Ab, com uma positividade de 3,7% para HB Ag, sub-tipo D. Os autores acentuam a necessidade de inquéritos em populações brasileiras a fim de estabelecer os sub-tipos associados à hepatite.

Martini Vahlii, profess. botan. Haun. membr. societ. lit. plur. Enumeratio plantarum :vel ab aliis, vel, ab ipso observatum, cum earum differentiis specificis, synonymis selectis et descriptionibus succinctis.

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Martini Vahlii, profess. botan. Haun. membr. societ. lit. plur. Enumeratio plantarum :vel ab aliis, vel, ab ipso observatum, cum earum differentiis specificis, synonymis selectis et descriptionibus succinctis.

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Plantae Preissianae sive Enumeratio plantarum quas in Australasia occidentali et meridionali-occidentali annis 1838-1841 :collegit Ludovicus Preiss /Partim ab aliis partim a se ipso determinatas descriptas illustratas edidit Christianus Lehmann.

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Plantae Preissianae sive Enumeratio plantarum quas in Australasia occidentali et meridionali-occidentali annis 1838-1841 :collegit Ludovicus Preiss /Partim ab aliis partim a se ipso determinatas descriptas illustratas edidit Christianus Lehmann.

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Index filicum,sive, Enumeratio omnium generum specierumque filicum et Hydropteridum ab anno 1753 ad finem anni 1905 descriptorium : adjectis synonymis principalibus, area geographica, etc. /Carl Christensen.

Fascicles 1-12, 1753-1906

Index filicum,sive, Enumeratio omnium generum specierumque filicum et Hydropteridum ab anno 1753 ad finem anni 1905 descriptorium : adjectis synonymis principalibus, area geographica, etc. /Carl Christensen.

Suppl. 1906-12