Highly proton-ordered water structures on oxygen precovered Ru{0001}

We present helium scattering measurements of a water ad-layer grown on a O(2 1)/Ru(0001) surface. The adsorbed water layer results in a well ordered helium diffraction pattern with systematic extinctions of diffraction spots due to glide line symmetries. The data reflects a well-defined surface structure that maintains proton order even at surprisingly high temperatures of 140 K. The diffraction data we measure is consistent with a structure recently derived from STM measurements performed at 6 K. Comparison with recent DFT calculation is in partial agreement, suggesting that these calculations might be underestimating the contribution of relative water molecule orientations to the binding energy.

Three dimensional picture of the local structure of 1,4-Polybutadiene from a complete atomistic model and neutron scattering data

An efficient method of combining neutron diffraction data over an extended Q range with detailed atomistic models is presented. A quantitative and qualitative mapping of the organization of the chain conformation in both glass and liquid phase has been performed. The proposed structural refinement method is based on the exploitation of the intrachain features of the diffraction pattern by the use of internal coordinates for bond lengths, valence angles and torsion rotations. Models are built stochastically by assignment of these internal coordinates from probability distributions with limited variable parameters. Variation of these parameters is used in the construction of models that minimize the differences between the observed and calculated structure factors. A series of neutron scattering data of 1,4-polybutadiene at the region 20320 K is presented. Analysis of the experimental data yield bond lengths for C-C and C=C of 1.54 and 1.35 Å respectively. Valence angles of the backbone were found to be at 112 and 122.8 for the CCC and CC=C respectively. Three torsion angles corresponding to the double bond and the adjacent R and β bonds were found to occupy cis and trans, s(, trans and g( and trans states, respectively. We compare our results with theoretical predictions, computer simulations, RIS models, and previously reported experimental results.

Self-assembly of palmitoyl lipopeptides used in skin care products

The self-assembly of three cosmetically active peptide amphiphiles C16-GHK, C16-KT, and C16-KTTKS (C16 denotes a hexadecyl, palmitoyl chain) used in commercial skin care products is examined. A range of spectroscopic, microscopic, and X-ray scattering methods is used to probe the secondary structure, aggregate morphology, and the nanostructure. Peptide amphiphile (PA) C16-KTTKS forms flat tapes and extended fibrillar structures with high β-sheet content. In contrast, C16-KT and C16-GHK exhibit crystal-like aggregates with, in the case of the latter PA, lower β-sheet content. All three PA samples show spacings from bilayer structures in small-angle X-ray scattering profiles, and all three have similar critical aggregation concentrations, this being governed by the lipid chain length. However, only C16-KTTKS is stained by Congo red, a diagnostic dye used to detect amyloid formation, and this PA also shows a highly aligned cross-β X-ray diffraction pattern consistent with the high β-sheet content in the self-assembled aggregates. These findings may provide important insights relevant to the role of self-assembled aggregates on the reported collagen-stimulating properties of these PAs.

Experimentally driven atomistic model of 1,2 Polybutadiene

We present an efficient method of combining wide angle neutron scattering data with detailed atomistic models, allowing us to perform a quantitative and qualitative mapping of the organisation of the chain conformation in both glass and liquid phases. The structural refinement method presented in this work is based on the exploitation of the intrachain features of the diffraction pattern and its intimate linkage with atomistic models by the use of internal coordinates for bond lengths, valence angles and torsion rotations. Atomic connectivity is defined through these coordinates that are in turn assigned by pre-defined probability distributions, thus allowing for the models in question to be built stochastically. Incremental variation of these coordinates allows for the construction of models that minimise the differences between the observed and calculated structure factors. We present a series of neutron scattering data of 1,2 polybutadiene at the region 120-400K. Analysis of the experimental data yield bond lengths for C-C and C=C of 1.54Å and 1.35Å respectively. Valence angles of the backbone were found to be at 112° and the torsion distributions are characterised by five rotational states, a three-fold trans-skew± for the backbone and gauche± for the vinyl group. Rotational states of the vinyl group were found to be equally populated, indicating a largely atactic chan. The two backbone torsion angles exhibit different behaviour with respect to temperature of their trans population, with one of them adopting an almost all trans sequence. Consequently the resulting configuration leads to a rather persistent chain, something indicated by the value of the characteristic ratio extrapolated from the model. We compare our results with theoretical predictions, computer simulations, RIS models and previously reported experimental results.

Synthesis, Characterization, Luminescence and Defect Centres in CaYAl(3)O(7):Eu(3+) Red Phosphor

CaYAl(3)O(7):Eu(3+) phosphor was prepared at furnace temperatures as low as 550A degrees C by a solution combustion method. The formation of crystalline CaYAl(3)O(7):Eu(3+) was confirmed by powder X-Ray diffraction pattern. The prepared phosphor was characterized by SEM, FT-IR and photoluminescence techniques. Photoluminescence measurements indicated that emission spectrum is dominated by the red peak located at 618 nm due to the (5)D(0)-(7)F(2) electric dipole transition of Eu(3+) ions. Electron Spin Resonance (ESR) studies were carried out to identify the centres responsible for the thermoluminescence (TL) peaks. Room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0126 is identified as an O(-) ion while centre II with an isotropic g-factor 2.0060 is assigned to an F(+) centre (singly ionized oxygen vacancy). An additional defect centre is observed during thermal annealing experiments and this centre (assigned to F(+) centre) seems to originate from an F centre (oxygen vacancy with two electrons). The F(+) centre appears to correlate with the observed high temperature TL peak in CaYAl(3)O(7):Eu(3+) phosphor.

Footemineite, the Mn-analog of atencioite, from the Foote mine, Kings Mountain, Cleveland County, North Carolina, USA, and its relationship with other roscherite-group minerals

Footemineite, ideally Ca2Mn2+square Mn22+Be4(PO4)(6)(OH)(4)-6H(2)O, triclinic, is a new member of the roscherite group. It occurs on thin fractures crossing quartz-microcline-spodumene pegmatite at the Foote mine, Kings Mountain, Cleveland County, North Carolina, U.S.A. Associated minerals are albite, analcime, eosphorite, siderite/rhodochrosite, fairfieldite, fluorapatite, quartz, milarite, and pyrite. Footemineite forms prismatic to bladed generally rough to barrel-shaped crystals up to about 1.5 mm long and I mm in diameter. Its color is yellow, the streak is white, and the luster is vitreous to slightly pearly. Footemineite is transparent and non-fluorescent. Twinning is simple, by reflection, with twin boundaries across the length of the crystals. Cleavage is good on {0 (1) over bar1}) and {100}. Density (calc.) is 2.873 g/cm(3). Footemineite is biaxial (-), n(alpha) = 1.620(2), n(beta) = 1.627(2), n(gamma) = 1.634(2) (white light). 2V(obs) = 80 degrees, 2V(calc) = 89.6 degrees. Orientation: X boolean AND b similar to 12 degrees, Y boolean AND c similar to 15 degrees, Z boolean AND a similar to 15 degrees. Elongation direction is c, dispersion: r > v or r < v, weak. Pleochroism: beta (brownish yellow) > alpha = gamma (yellow). Mossbauer and IR spectra are given. The chemical composition is (EDS mode electron microprobe, Li and Be by ICP-OES, Fe3+:Fe2+ y Mossbauer, H2O by TG data, wt%): Li2O 0.23, BeO 9.54, CaO 9.43, SrO 0.23, BaO 0.24, MgO 0.18, MnO 26.16, FeO 2.77, Fe2O3 0.62, Al2O3 0.14, P2O5 36.58, SiO2 0.42, H2O 13.1, total 99.64. The empirical formula is (Ca1.89Sr0.03Ba0.02)Sigma(1.94)(Mn-0.90(2+)square(0.10))Sigma(1.00)(square 0.78Li0.17Mg0.05) Sigma(1.00)(Mn3.252+Fe0.432+ Fe0.093+Al0.03)Sigma(3.80) Be-4.30(P5.81Si0.08O24)[(OH)3.64(H2O)0.36]Sigma(4.00)center dot 6.00H(2)O . The strongest reflection peaks of the powder diffraction pattern [d, angstrom (1, %) (hkl)] are 9.575 (53) (010), 5.998 (100) (0 (1) over bar1), 4.848 (26) (021), 3.192 (44) (210), 3.003 (14) (0 (2) over bar2), 2.803 (38) ((1) over bar 03), 2.650 (29) ((2) over bar 02), 2.424 (14) (231). Single-crystal unit-cell parameters are a = 6.788(2), b = 9.972(3), c = 10.014(2) A, (x = 73.84(2), beta = 85.34(2), gamma = 87.44(2)degrees,V = 648.74 angstrom(3), Z = 1. The space group is P (1) over bar. Crystal structure was refined to R = 0.0347 with 1273 independent reflections (F > 2(5). Footemineite is dimorphous with roscherite, and isostructural with atencioite. It is identical with the mineral from Foote mine described as ""triclinic roscherite."" The name is for the Foote mine, type locality for this and several other minerals.

Unusual phase behaviour of the organic ionic plastic crystal N,N-dimethylpyrrolidinium tetrafluoroborate

Analysis of N,N-dimethylpyrrolidinium tetrafluoroborate by ¹H and ¹¹B NMR, Raman spectroscopy and powder XRD shows that this organic ionic plastic crystal material exhibits unusual phase behaviour. ¹H NMR analysis indicates that the mobility of the pyrrolidinium cation decreases when the material is heated into phase I, while the X-ray diffraction pattern changes from a simple, one peak structure in phase II to a more complex pattern in phase I. The possible origins of these unusual transitions are discussed.

Understanding physicochemical changes in pretreated and enzyme hydrolysed hemp (Cannabis sativa) biomass for biorefinery development

The physicochemical properties of hemp biomass structure to pretreatment and enzymatic hydrolysis were investigated to improve upon reducing sugar production for biofuel development. Sodium hydroxide pretreated biomass (SHPB) yielded maximum conversion of holocellulose into reducing sugar (72 %). Scanning electron microscopy (SEM) revealed that enzymatic hydrolysis generated regular micropores in the fragmented biomass structure. The thermogravimetric analysis (TGA) curve suggested the degradation of hemicellulose and cellulose, which conformed well to the subsequent nuclear magnetic resonance (NMR) studies indicating the presence of α- and β-glucose (28.4 %) and α- and β-xylose (10.7 %), the major carbohydrate components commonly found in hydrolysis products of hemicellulose and cellulose. Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectra showed stretching modes of the lignin acetyl group, suggesting the loosening of the polymer matrix and thus the exposure of the cellulose polymorphs. X-ray diffraction pattern indicated that enzymatic hydrolysis caused a higher crystallinity index (36.71), due to the fragmentation of amorphous cellulose leading to the reducing sugar production suitable for biofuel development.

Efeito da moagem de alta energia na microestrutura e nas propriedades magnéticas do compósito wc-10%p.Co

This work a studied the high energy milling effect in microstructure and magnetic properties of the WC-10wt.%Co composite. The composite powders were prepared by mechanical mixed and milled at 2 hours, 100 hours, 200 hours and 300 hours in planetary milling. After this process the composite were compacted in stainless steel die with cylindrical county of 10 mm of diameter, at pressure 200 Mpa and sintered in a resistive furnace in argon atmosphere at 1400 oC for 5 min. The sintered composite were cutted, inlaid, sandpapered, and polished. The microestrutural parameters of the composite was analyzed by X-ray diffraction, scanning electronic microscopy, optical microscopy, hardness, magnetic propriety and Rietveld method analyze. The results shows, with milling time increase the particle size decrease, it possibility minor temperature of sintering. The increase of milling time caused allotropic transformation in cobalt phase and cold welding between particles. The cold welding caused the formation of the particle composite. The X-ray diffraction pattern of composite powders shows the WC peaks intensity decrease with the milling time increase. The X-ray diffraction pattern of the composite sintered samples shows the other phases. The magnetic measurements detected a significant increase in the coercitive field and a decrease in the saturation magnetization with milling time increase. The increase coercitive field it was also verified with decrease grain size with milling time increase. For the composite powders the increase coercitive field it was verified with particle size reduction and saturation magnetization variation is relate with the variation of free cobalt. The Rietveld method analyze shows at milling time increase the mean crystalline size of WC, and Co-cfc phases in composite sintered sample are higher than in composite powders. The mean crystallite size of Co-hc phase in composite powders is higher than in composite sintered sample. The mean lattice strains of WC, Co-hc and Co-cfc phases in composite powders are higher than in composite sintered samples. The cells parameters of the composite powder decrease at milling time increase this effect came from the particle size reduction at milling time increase. In sintered composite the cells parameters is constant with milling time increase

Síntese e caracterização da ferrita de MnZn obtida pelo método dos citratos precursores

It was synthesized MnZn ferrite with general formulae Mn1-xZnxFe2O4 (mol%), 0,3 ≤ x ≤ 0,7 by using the citrate precursor method. The precursors decomposition was studied by thermogravimetric analysis (TGA), differential thermogravimetric analysis (DTG), differential thermal analysis (DTA) and Fourier transform infrared (FTIR) of powder calcined at 350ºC/3,5h. X-ray diffraction pattern (XRD) of samples was done from 350 to 1200ºC/2h using various atmospheres. The power calcined at 350ºC/3,5h formed spinel phase. It is necessary atmosphere control to avoid secondary phase such as hematite. From 900 to 1200ºC was obtained 90,66 and 100% of MnZn spinel ferrite phase, respectively. Analysis by dispersive energy scanning (EDS) at 350ºC shows high Mn and Zn dispersion, indicating that the diffusion process was homogeneous. Semi-quantitative analysis by EDS verified that despite the atmosphere control during calcinations at high temperatures (< 800ºC) occurred ZnO evaporation causing stoichiometric deviation. Vibrating sample magnetometer (VSM) measures show soft ferrite material characteristics with Hc from 6,5 x 10-3 to 11,1 x 10-2 T. Saturation magnetization (Ms) and initial permeability (µi) of MnZn spinel phase obtained, respectively, from 14,3 to 83,8 Am2/kg and 14,1 to 62,7 (Am2/kg)T

Interface Formation and Electrical Transport in SnO2:Eu3+/GaAs Heterojunction Deposited by Sol-Gel Dip-Coating and Resistive Evaporation

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effect of enzymatic hydrolysis on some physicochemical properties of root and tuber granular starches

A hidrólise enzimática do amido pode fornecer informações importantes sobre sua estrutura granular. Amidos de mandioca, batata-doce, mandioquinha-salsa e batata foram hidrolisados por α-amilase bacteriana a 37 °C durante 48 horas, e algumas propriedades físico-químicas dos resíduos da hidrólise foram determinadas. O amido de mandioca foi o mais suscetível à enzima com 20,9% de hidrólise, enquanto o amido de batata foi o mais resistente com 5,9%. O tamanho médio dos grânulos variou de 10,8 a 23,4 μm para os amidos de mandioquinha-salsa e batata, respectivamente. Amidos de mandioca e batata-doce apresentaram um padrão de difração de raio-X tipo A, enquanto os amidos de mandioquinha-salsa e batata mostraram padrão tipo B. Todos os amidos nativos mostraram superfície granular lisa e, após hidrólise, os amidos de mandioca, batata-doce e mandioquinha-salsa mostraram alguns grânulos bastante degradados, enquanto o amido de batata apresentou sutil sinal de degradação. O teor de amilose dos amidos diminuiu com a hidrólise para os amidos de mandioca, batata-doce e mandioquinha-salsa, permanecendo inalterado para o amido de batata. Como esperado, a viscosidade intrínseca e as propriedades de pasta diminuíram para todos os amidos hidrolisados. Não houve diferença significativa entre as propriedades térmicas dos amidos nativos e hidrolisados. Estes resultados sugeriram que a hidrólise ocorreu nas áreas cristalinas e amorfas dos grânulos. O padrão de difração do tipo B e o grande tamanho dos grânulos do amido de batata podem ter contribuído para a maior resistência deste amido à hidrólise.

Crystallization and preliminary X-ray crystallographic analysis of the heterodimeric crotoxin complex and the isolated subunits crotapotin and phospholipase A(2)

Crotoxin, a potent neurotoxin from the venom of the South American rattlesnake Crotalus durissus terrificus, exists as a heterodimer formed between a phospholipase A(2) and a catalytically inactive acidic phospholipase A(2) analogue (crotapotin). Large single crystals of the crotoxin complex and of the isolated subunits have been obtained. The crotoxin complex crystal belongs to the orthorhombic space group P2(1)2(1)2, with unit-cell parameters a = 38.2, b = 68.7, c = 84.2 angstrom, and diffracted to 1.75 angstrom resolution. The crystal of the phospholipase A(2) domain belongs to the hexagonal space group P6(1)22 (or its enantiomorph P6(5)22), with unit-cell parameters a = b = 38.7, c = 286.7 angstrom, and diffracted to 2.6 angstrom resolution. The crotapotin crystal diffracted to 2.3 angstrom resolution; however, the highly diffuse diffraction pattern did not permit unambiguous assignment of the unit-cell parameters.

Synthesis of Ba0.5Sr0.5(Ti0.80Sn0.20)O-3 prepared by the soft chemical method

Single-phase Ba0.5Sr0.5(Ti0.80Sn0.20)O-3 (BST:Sn) powders with perovskite structure were prepared by the soft chemical method. Infrared data indicates that the BST:Sn powder is carbonate free while Raman analysis has shown that the transversal (TO) and longitudinal (LO) optical modes tend to disappear with tin addition. The electron diffraction pattern of the BST:Sn powder showed an interplanar distance of 3.94 angstrom characteristic of the pseudo-cubic structure. (c) 2007 Elsevier B.V. All rights reserved.

Structure study of Bi4Ti3O12 produced via mechanochemically assisted synthesis

Nanosized bismuth titanate was prepared via high-energy ball milling process through mechanically assisted synthesis directly from their oxide mixture of Bi2O3 and TiO2. Only Bi4Ti3O12 phase was formed after 3 h of milling time. The excess of 3 wt% Bi2O3 added in the initial mixture before milling does not improve significantly the formation of Bi4Ti3O12 phase comparing to stoichiometric mixture. The formed phase was amorphized independently of the milling time, The Rietveld analysis was adopted to determine the crystal structure symmetry, amount of amorphous phase, crystallite size and microstrains. With increasing the milling time from 3 to 12 h, the particle size of formed Bi4Ti3O12 did not reduced significantly. That was confirmed by SEM and TEM analysis. The particle size was less than 20 nm and show strong tendency to agglomeration. The electron diffraction pattern indicates that Bi4Ti3O12 crystalline powder is embedded in an amorphous phase of bismuth titanate. Phase composition and atom ratio in BIT ceramics were determined by X-ray diffraction and EDS analysis. (c) 2007 Elsevier Ltd. All rights reserved.