Effect of quantum nuclear motion on hydrogen bonding

This work considers how the properties of hydrogen bonded complexes, X-H center dot center dot center dot Y, are modified by the quantum motion of the shared proton. Using a simple two-diabatic state model Hamiltonian, the analysis of the symmetric case, where the donor (X) and acceptor (Y) have the same proton affinity, is carried out. For quantitative comparisons, a parametrization specific to the O-H center dot center dot center dot O complexes is used. The vibrational energy levels of the one-dimensional ground state adiabatic potential of the model are used to make quantitative comparisons with a vast body of condensed phase data, spanning a donor-acceptor separation (R) range of about 2.4-3.0 angstrom, i.e., from strong to weak hydrogen bonds. The position of the proton (which determines the X-H bond length) and its longitudinal vibrational frequency, along with the isotope effects in both are described quantitatively. An analysis of the secondary geometric isotope effect, using a simple extension of the two-state model, yields an improved agreement of the predicted variation with R of frequency isotope effects. The role of bending modes is also considered: their quantum effects compete with those of the stretching mode for weak to moderate H-bond strengths. In spite of the economy in the parametrization of the model used, it offers key insights into the defining features of H-bonds, and semi-quantitatively captures several trends. (C) 2014 AIP Publishing LLC.

Revised density of magnetized nuclear matter at the neutron drip line

We study the onset of the neutron drip in high-density matter in the presence of a magnetic field. It has been found that, for systems having only protons and electrons, in the presence of a magnetic field greater than or similar to 10(15) G, neutronization occurs at a density that is at least an order of magnitude higher compared to that in a nonmagnetic system. In a system with heavier ions, the effect of the magnetic field, however, starts arising at a much higher field, greater than or similar to 10(17) G. These results may have important implications for high-magnetic-field neutron stars and white dwarfs and, in general, in nuclear astrophysics when the system is embedded within a strong magnetic field.

The interaction of N-trifluoroacetylgalactosamine and its derivatives with winged bean (Psophocarpus tetragonolobus) basic agglutinin reveals differential mechanism of their recognition: a fluorine-19 nuclear magnetic resonance study

Here, we show the binding results of a leguminosae lectin, winged bean basic agglutinin (WBA I) to N-trifluoroacetylgalactosamine (NTFAGalN), methyl-alpha-N-trifluoroacetylgalactosamine (Me alpha NTFAGalN) and methyl-beta-tifluoroacetylgalactosamine (Me beta NTFAGalN) using (19) F NMR spectroscopy. No chemical shift difference between the free and bound states for NTFAGalN and Me beta NTFAGalN, and 0.01-ppm chemical shift change for Me alpha NTFAGalN, demonstrate that the Me alpha NTFAGalN has a sufficiently long residence time on the protein binding site as compared to Me beta NTFAGalN and the free anomers of NTFAGalN. The sugar anomers were found in slow exchange with the binding site of agglutinin. Consequently, we obtained their binding parameters to the protein using line shape analyses. Aforementioned analyses of the activation parameters for the interactions of these saccharides indicate that the binding of alpha and beta anomers of NTFAGalN and Me alpha NTFAGalN is controlled enthalpically, while that of Me beta NTFAGalN is controlled entropically. This asserts the sterically constrained nature of the interaction of the Me beta NTFAGalN with WBA I. These studies thus highlight a significant role of the conformation of the monosaccharide ligands for their recognition by WBA I.

2-(Phenylazo)pyridineplatinum(II) Catecholates Showing Photocytotoxicity, Nuclear Uptake, and Glutathione-Triggered Ligand Release

Platinum(II) complexes Pt(pap)(an-cat)] (1) and Pt(pap)(py-cat)] (2) with 2-(phenylazo)pyridine (pap), 4-2-(anthracen-9-ylmethylene)amino]ethyl]benzene-1,2-diol (H(2)an-cat), and 4-2-(pyren-1-ylmethylene)amino]ethyl]benzene-1,2-diol (H2py-cat) were prepared, and their photoinduced cytotoxicity was studied. The complexes were found to release catecholate ligand in the presence of excess glutathione (GSH), resulting in cellular toxicity in the cancer cells. The catecholate complex Pt(pap)(cat)] (3) was prepared and used as a control. Complex 3, which is structurally characterized by X-ray crystallography, has platinum(II) in a distorted square-planar geometry. The complexes are redox-active, showing responses near 0.6 and 1.0 V versus SCE in N,N-dimethylformamide/0.1 M tetrabutylammonium perchlorate corresponding to a two-step catechol oxidation process and at -0.3 and -1.3 V for reduction of the pap ligand. Complex 1 showed remarkable light-induced cytotoxicity in HaCaT (human skin keratinocytes) and MCF-7 (human breast cancer) cells, giving IC50 value of similar to 5 mu M in visible light of 400-700 nm and >40 mu M in the dark. The 2',7'-dichlorofluorescein diacetate (DCFDA) assay showed the generation of reactive oxygen species (ROS), which seems to trigger apoptosis, as is evident from the annexin V-fluorescein isothiocyanate (FITC)/propidium iodide (PI) assay. The fluorescence microscopic images showed significant nuclear localization of the complexes and free ligands. A mechanistic study revealed possible reduction of the coordinated azo bond of pap by cellular GSH, releasing the catecholate ligand and resulting in remarkable photochemotherapeutic action of the complexes.

Mono layer to Interdigitated Partial Bilayer Smectic C Transition in Thiophene-Based Spacer Mesogens: X-ray Diffraction and C-13 Nuclear Magnetic Resonance Studies

Mesophase organization of molecules built with thiophene at the center and linked via flexible spacers to rigid side arm core units and terminal alkoxy chains has been investigated. Thirty homologues realized by varying the span of the spacers as well as the length of the terminal chains have been studied. In addition to the enantiotropic nematic phase observed for all the mesogens, the increase of the spacer as well as the terminal chain lengths resulted in the smectic C phase. The molecular organization in the smectic phase as investigated by temperature dependent X-ray diffraction measurements revealed an interesting behavior that depended on the length of the spacer vis-a-vis the length of the terminal chain. Thus, a tilted interdigitated partial bilayer organization was observed for molecules with a shorter spacer length, while a tilted monolayer arrangement was observed for those with a longer spacer length. High-resolution solid state C-13 NMR studies carried out for representative mesogens indicated a U-shape for all the molecules, indicating that intermolecular interactions and molecular dynamics rather than molecular shape are responsible for the observed behavior. Models for the mesophase organization have been considered and the results understood in terms of segregation of incompatible parts of the mesogens combined with steric frustration leading to the observed lamellar order.

Energia nuclear

v. 1. Legislação -- v. 2. Mensagens presidenciais e outros documentos (notas, ofícios, cópias autênticas de documentação oficial diversa): Acordo de cooperação para usos civis de energia atômica entre o governo dos Estados Unidos do Brasil e o governo dos Estados Unidos da América. Programa Conjunto de Cooperação para o Reconhecimento dos Recursos de Urânio no Brasil. Decisão do Conselho de Segurança Nacional quanto à Política Nacional de Energia Nuclear -- v. 3. Legislação: Projetos. Comissão Parlamentar de Inquérito para Proceder a Investigações sobre o Problema de Energia Atômica no Brasil.

Atuação da Anvisa na fiscalização do setor nuclear brasileiro

Consultoria Legislativa - Área XVI - Saúde Pública, Sanitarismo.

Relatório do grupo de trabalho fiscalização e segurança nuclear

Relatório sobre o setor nuclear no Brasil desenvolvido por meio de ações do grupo de trabalho criado pela Comissão de Meio Ambiente e Desenvolvimento Sustentável.

Two Nuclear Localization Signals in USP1 Mediate Nuclear Import of the USP1/UAF1 Complex

9 p. : il.

Analysis of fish diversion efficiency and survivorship in the fish return system at San Onofre Nuclear Generating Station

This study examined the efficiency of fish diversion and survivorship of diverted fishes in the San Onofre Nuclear Generating Station Fish Return System in 1984 and 1985. Generally, fishes were diverted back to the ocean with high frequency, particularly in 1984. Most species were diverted at rates of 80% or more. Over 90% of the most abundant species, Engraulis mordax, were diverted. The system worked particularly well for strong-swimming forms such as Paralobrax clothratus, Atherinopsis californiensis, and Xenistius californiensis, and did not appreciably divert weaker-swimming species such as Porichthys notatus, Heterostichus rostratus, and Syngnathus sp. Return rates of some species were not as high in 1985 as in 1984. Individuals of most tested species survived both transit through the fish return system and 96 hours in a holding net. Some species, such as E. mordox, X. californiensis, and Umbrina roncador, experienced tittle or no mortality. Survivorship of Seriphus politus was highly variable and no Anchoa delicatissima survived. (PDF file contains 22 pages.)

Validación de la cuantificación de la concentración hepática de hierro mediante resonancia magnética nuclear de 1-Tesla

Introducción: La medición de la concentración de hierro hepática (CHH) por RM es una técnica no invasiva de gran utilidad en el diagnóstico de los pacientes con sospecha de sobrecarga férrica en hígado. Objetivo:Validar la eficacia de la RM 1 Tesla en la determinación de la (CHH) en pacientes con sospecha de sobrecarga férrica. Validar su capacidad para diagnosticar o descartar la presencia de una CHH sugestiva de hemocromatosis. Pacientes y métodos:Estudio observacional, transversal, con inclusión prospectiva de pacientes consecutivos. De 2002 a 2010 hemos obtenido la CHH estimada mediante RM 1 Tesla (método Gandon) y de RM 1,5 Tesla (método Alústiza), y mediante BH, en 56 pacientes consecutivos (58RM:35/23). Resultados:Grupo RM 1 Tesla: de acuerdo con CHH en BH, 15 pacientes clasificados como normales (<36µmol/g)-la RM valoró correctamente 7; sobreestimó 8-; 15 grupo hemosiderosis (36-80 µmol/g)-RM valoró correctamente 5, sobreestimó 10-; 5 grupo hemocromatosis (>80 µmol/g)-valoró correctamente las 5-. Existió una correlación entre la determinación de la CHH por BH y RM 1 Tesla con r=0.619. Existieron diferencias estadísticamente significativas (p<0.05) entre CHH media por biopsia (53.43/DE45.67/IC95%37.74 a 69.12) y por RM 1 Tesla (76.14/DE47.31/IC95% 60.46 a 92.97), con sobrevaloración por parte de la RM. Grupo RM 1,5 Tesla: de acuerdo con CHH en BH, normal en 14, hemosiderosis en 6 y hemocromatosis en 3. La RM valoró correctamente 6 y sobreestimó 8 en grupo normal; grupo hemosiderosis, 3 correctamente, 3 sobrevalorados; grupo hemocromatosis, valoró correctamente los 3. La correlación entre CHH por BH y RM 1,5 Tesla fue de r=0.815. La CHH media obtenida por BH (69,34/DE152.1/IC95% 3.57 a 135.1 ) y RM 1,5 Tesla (70.43/DE 57.63/IC95% 45.51 a 95.36) no demostraron diferencias significativas (p>0.05). Conclusiones: La determinación de CHH por RM 1 Tesla (método Gandon) es útil para diagnosticar o descartar hemocromatosis y para diagnosticar CHH normal. Existe una importante tendencia a la sobreestimación en pacientes sin y con sobrecarga férrica en la CHH obtenida por RM 1 Tesla. La determinación de CHH por RM 1,5 Tesla (método Alústiza) es superior a la de RM 1 Tesla, aunque también existe una tendencia a sobreestimar. La CHH media obtenida por BH o RM 1,5 Tesla no tuvieron diferencias significativas. En cambio si existieron entre BH y RM 1 Tesla.

Nuclear Hartree-Fock calculations on parallel computers

Hartree-Fock (HF) calculations have had remarkable success in describing large nuclei at high spin, temperature and deformation. To allow full range of possible deformations, the Skyrme HF equations can be discretized on a three-dimensional mesh. However, such calculations are currently limited by the computational resources provided by traditional supercomputers. To take advantage of recent developments in massively parallel computing technology, we have implemented the LLNL Skyrme-force static and rotational HF codes on Intel's DELTA and GAMMA systems at Caltech.

We decomposed the HF code by assigning a portion of the mesh to each node, with nearest neighbor meshes assigned to nodes connected by communication· channels. This kind of decomposition is well-suited for the DELTA and the GAMMA architecture because the only non-local operations are wave function orthogonalization and the boundary conditions of the Poisson equation for the Coulomb field.

Our first application of the HF code on parallel computers has been the study of identical superdeformed (SD) rotational bands in the Hg region. In the last ten years, many SD rotational bands have been found experimentally. One very surprising feature found in these SD rotational bands is that many pairs of bands in nuclei that differ by one or two mass units have nearly identical deexcitation gamma-ray energies. Our calculations of the five rotational bands in ^(192)Hg and ^(194)Pb show that the filling of specific orbitals can lead to bands with deexcitation gamma-ray energies differing by at most 2 keV in nuclei differing by two mass units and over a range of angular momenta comparable to that observed experimentally. Our calculations of SD rotational bands in the Dy region also show that twinning can be achieved by filling or emptying some specific orbitals.

The interpretation of future precise experiments on atomic parity nonconservation (PNC) in terms of parameters of the Standard Model could be hampered by uncertainties in the atomic and nuclear structure. As a further application of the massively parallel HF calculations, we calculated the proton and neutron densities of the Cesium isotopes from A = 125 to A = 139. Based on our good agreement with experimental charge radii, binding energies, and ground state spins, we conclude that the uncertainties in the ratios of weak charges are less than 10^(-3), comfortably smaller than the anticipated experimental error.