Chapter 17: X-Ray rheology of liquid crystal polymers

X-ray Rheology is an experimental technique which uses time-ressolved x-ray scattering as probe of the molecular level structural reorganisation which accompanies flow. It provides quantitative information on the direction alignment and on the level of global orientation. This information is very helpful in interpreting the classic rheological data on liquid crystal polymers. In this research we use data obtained from a cellulose derivate which exhibits a thermotropic liquid crystal phase. We show how increased shear rates lead to a rapid rise in the global orientation and we related this to therories of flow in liquid crystal polymers from the literature. We show that the relaxation time is independent of the prior shear rate.

CONSTRAINING THE NONEXTENSIVE MASS FUNCTION OF HALOS FROM BAO, CMB AND X-RAY DATA

Clusters of galaxies are the most impressive gravitationally-bound systems in the universe, and their abundance (the cluster mass function) is an important statistic to probe the matter density parameter (Omega(m)) and the amplitude of density fluctuations (sigma(8)). The cluster mass function is usually described in terms of the Press-Schecther (PS) formalism where the primordial density fluctuations are assumed to be a Gaussian random field. In previous works we have proposed a non-Gaussian analytical extension of the PS approach with basis on the q-power law distribution (PL) of the nonextensive kinetic theory. In this paper, by applying the PL distribution to fit the observational mass function data from X-ray highest flux-limited sample (HIFLUGCS), we find a strong degeneracy among the cosmic parameters, sigma(8), Omega(m) and the q parameter from the PL distribution. A joint analysis involving recent observations from baryon acoustic oscillation (BAO) peak and Cosmic Microwave Background (CMB) shift parameter is carried out in order to break these degeneracy and better constrain the physically relevant parameters. The present results suggest that the next generation of cluster surveys will be able to probe the quantities of cosmological interest (sigma(8), Omega(m)) and the underlying cluster physics quantified by the q-parameter.

Influence of quantum-dots density on average in-plane strain of optoelectronic devices investigated by high-resolution X-ray diffraction

High-resolution X-ray diffractometry is used to probe the nature of a diffraction-peak broadening previously noticed in quantum dots (QDs) systems with freestanding InAs islands on top of GaAs (001) substrates [Freitas et al., Phys. Status Solidi (A) 204, 2548 (2007)]. The procedure is hence extended to further investigate the capping process of InAs/GaAs QDs. A direct correlation is established between QDs growth rates and misorientation of lattice-planes at the samples surfaces. This effect provides an alternative too] for studying average strain fields on QDs systems in standard triple axis diffractometers running on X-ray tube sources, which are much more common than synchrotron facilities. (C) 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

X-ray spectrometry: a powerful tool for the measurement of complete fusion of weakly bound nuclei

We describe how the method of detection of delayed K x-rays produced by the electron capture decay of the residual nuclei can be a powerful tool in the investigation of the effect of the breakup process on the complete fusion (CF) cross-section of weakly bound nuclei at energies close to the Coulomb barrier. This is presently one of the most interesting subjects under investigation in the field of low-energy nuclear reactions, and the difficult experimental task of separating CF from the incomplete fusion (ICF) of one of the breakup fragments can be achieved by the x-ray spectrometry method. We present results for the fusion of the (9)Be + (144)Sm system. Copyright (c) 2008 John Wiley & Sons, Ltd.

Study of the phenanthroline-Mn-imidazole bonding in Mn(I) triscarbonyl complex: A X-ray and DFT computational analysis

355 nm light irradiation of fac-[Mn(CO)(3)(phen)(imH)](+) (fac-1) produces the mer-1 isomer and a long lived radical which can be efficiently trapped by electron acceptor molecules. EPR experiments shows that when excited, the manganese(I) complex can be readily oxidized by one-electron process to produce Mn(II) and phen(.-). In the present study, DFT calculations have been used to investigated the photochemical isomerization of the parent Mn(I) complex and to characterize the electronic structures of the long lived radical. The theoretical calculations have been performed on both the fac-1 and mer-1 species as well as on their one electron oxidized species fac-1+ and mer-1+ for the lowest spin configurations (S = 1/2) and fac-6 and mer-6 (S = 5/2) for the highest one to characterize these complexes. In particular, we used a charge decomposition analysis (CDA) and a natural bonding orbital (NBO) to have a better understanding of the chemical bonding in terms of the nature of electronic interactions. The observed variations in geometry and bond energies with an increasing oxidation state in the central metal ion are interpreted in terms of changes in the nature of metal-ligand bonding interactions. The X-ray structure of fac-1 is also described. (C) 2011 Elsevier B.V. All rights reserved.

A combined X-ray and theoretical study of flavonoid compounds with anti-inflammatory activity

The structure of 7,4`-dimethoxy-3`-acetylflavone (tithonin-Ac) has been determined by X-ray diffraction and its geometry is compared with optimized geometrical parameters obtained by means of density functional theory at the B3LYP/6-311++G(d,p) level of calculation. in addition, vertical ionization potential (IPv) and acidity for tithonin-Ac and two derivatives have been also calculated. Calculations of spin densities were also performed for the radical formed by the electron abstraction of other flavones. The unpaired electron is located on C3 carbon atom (21-25%). (C) 2008 Elsevier B.V. All rights reserved.

Synthesis, spectroscopic characterization and X-ray structures of five-coordinate diorganotin(IV) complexes containing 5-hydroxypyrazoline derivatives as ligands

Four new diorganotin(IV) complexes have been prepared from R(2)SnCl(2) (R = Me, Ph) with the ligands 5-hydroxy-3-metyl-5-phenyl-1-(S-benzildithiocarbazate)-pyrazoline (H(2)L(1)) and 5-hydroxy-3-methyl-5-phenyl-1-(2-thiophenecarboxylic)-pyrazoline (H(2)L(2)). The complexes were characterized by elemental analysis, IR. (1)H (13)C, (119)Sn NMR and Mossbauer spectroscopes The complexes [Me(2)SnL(1)], [Ph(2)SnL(1)] and [Me(2)SnL(2)] were also studied by single crystal X-ray diffraction and the results showed that the Sn(IV) central atom of the complexes adopts a distorted trigonal bipyramidal (TBP) geometry with the N atom of the ONX-tridentate (X = O and S) ligand and two organic groups occupying equatorial sites. The C-Sn-C angles for [Me(2)Sn(L(1))] and [Ph(2)Sn(L(1))] were calculated using a correlation between (119)Sn Mossbauer and X-ray crystallographic data based on the point-charge model Theoretical calculations were performed with the B3LYP density functional employing 3-21G(*) and DZVP all electron basis sets showing good agreement with experimental findings General and Sn(IV) specific IR harmonic frequency scale factors for both basis sets were obtained from comparison with selected experimental frequencies (C) 2010 Elsevier B V All rights reserved

Structural Characterization of Nanocrystalline Sb-Doped SnO2 Xerogels by Multiedge X-ray Absorption Spectroscopy

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Crystallization and preliminary X-ray diffraction analysis of importin-alpha acomplexed with NLS peptidomimetics

Importin-alpha is the nuclear import receptor that recognizes cargo proteins with nuclear localization sequences (NLSs). Tile study of NLS peptidomimetics can provide a better understanding of the requirements for the molecular recognition of cargo proteins by importin-alpha, and potentially engender a large number of applications in medicine. Importin-a was crystallized with a set of six NLS peptidomimetics, and X-ray diffraction data were collected in the range 2.1-2.5 angstrom resolution. Preliminary electron density calculations show that the ligands are present in the crystals. (c) 2005 Elsevier B.V All rights reserved.

Crystallization and preliminary X-ray diffraction analysis of a myotoxic Lys49-PLA(2) from Bothrops jararacussu venom complexed with p-bromophenacyl bromide

For the first time, a non-catalytic and myotoxic Lys49-PLA(2) (BthTX-I from Bothrops jararacussu venom) has been crystallized with BPB inhibitor. X-ray diffraction data were collected and electron-density calculations showed that the ligand is bound to the His48 residue. BthTX-I with His48 chemically modified by BPB shows strongly reduced myotoxic and cytotoxic activities. This suggests a biological correlation between the modification of His48, which is associated with catalytic activity of PLA(2)s, and other toxicological activities of Lys49-PLA(2)s.

Crystallization and preliminary X-ray crystallographic studies of a Lys49-phospholipase A(2) homologue from Bothrops pirajai venom complexed with rosmarinic acid

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Crystallization and preliminary X-ray diffraction analysis of a Lys49-phospholipase A(2) complexed with caffeic acid, a molecule with inhibitory properties against snake venoms

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Microbiological or Chemical Models of Enamel Secondary Caries Compared by Polarized-Light Microscopy and Energy Dispersive X-ray Spectroscopy

Different secondary caries models may present different results. The purpose of this study was to compare different in vitro secondary caries models, evaluating the obtained results by polarized-light microscopy (PLM), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). Standardized human enamel specimens (n = 12) restored with different materials (Z250 conventional composite resin-CRZ, Freedom polyacid-modified composite resin-CRF, Vitremer resin-modified glass-ionomer-GIV, and Fuji IX conventional glass-ionomer cement-GIF) were submitted to microbiological (MM) or chemical caries models (CM). The control group was not submitted to any caries model. For MM, specimens were immersed firstly in sucrose broth inoculated with Streptococcus mutans ATCC 35688, incubated at 37 degrees C/5% CO(2) for 14 days and then in remineralizing solution for 14 days. For CM, specimens were submitted to chemical pH-cycling. Specimens were ground, submitted to PLM and then were dehydrated, gold-sputtered and submitted to SEM and EDS. Results were statistically analyzed by Kruskall-Wallis and Student-Newman-Keuls tests (alpha = 0.05). No differences between in vitro caries models were found. Morphological differences in enamel demineralization were found between composite resin and polyacid-modified composite resin (CRZ and CRF) and between the resin-modified glass-ionomer and the glass-ionomer cement (GIF and GIV). GIF showed higher calcium concentration and less demineralization, differing from the other materials. In conclusion, the glass-ionomer cement showed less caries formation under both in vitro caries models evaluated. (C) 2009 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 90B: 635-640, 2009

Ability of different restorative materials to prevent in situ secondary caries: analysis by polarized light-microscopy and energy-dispersive X-ray

Secondary caries is the main cause of direct restoration replacement. The purpose of this study was to analyze enamel adjacent to different restorative materials after in situ cariogenic challenge using polarized-light microscopy (PLM), scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDS). Twelve volunteers, with a low level of dental plaque, a low level of mutans streptococci, and normal salivary flow, wore removable palatal acrylic appliances containing enamel specimens restored with Z250 composite, Freedom composite, Fuji IX glass-ionomer cement, or Vitremer resin-modified glass-ionomer for 14 days. Volunteers dripped one drop of 20% sucrose solution (n = 10) or distilled water (control group) onto each specimen 8 times per day. Specimens were removed from the appliances and submitted to PLM for examination of the lesion area (in mm(2)), followed by dehydration, gold-sputtering, and submission to SEM and EDS. The calcium (Ca) and phosphorus (P) contents were evaluated in weight per cent (%wt). Differences were found between Z250 and Vitremer, and between Z250 and FujiIX, when analyzed using PLM. Energy-dispersive X-ray analysis results showed differences between the studied materials regarding Ca %wt. In conclusion, enamel adjacent to glass-ionomer cement presented a higher Ca %wt, but this material did not completely prevent enamel secondary caries under in situ cariogenic challenge.

Retention Characteristics of CBTi144 Thin Films Explained by Means of X-Ray Photoemission Spectroscopy

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