This review describes the basic theory and some recently developed techniques for the study of quadrupole nuclei with half integer spins in powder materials. The latter is connected to the introduction of the double rotation (DOR) by A. Samoson et al. (1) and to the introduction of the multiple quantum magic-angle spinning (MQ MAS) technique by L. Frydman et. al. (2). For integer spins, especially the solid-state deuterium magnetic resonance, we refer to the review of G.L. Hoatson and R.L. Vold: ''"2H-NMR Spectroscopy of Solids and Liquid Crystals'' (3). For single crystals we refer to O. Kanert and M. Mehring: ''Static quadrupole effects in disordered cubic solids''(4) and we would like also to mention the ''classic'' review of M.H. Cohen and F. Reif: ''Quadrupole effects in NMR studies of solids'' (5). Some more recent reviews in the field under study are D. Freude and J. Haase ''Quadrupole effects in ...
High resolution structural elucidation of macromolecular structure by solid-state nuclear magnetic resonance requires the preparation of uniformly aligned samples that are isotopically labeled. In...Full Text Available
Hydrogen cyanide polymerizes readily under a variety of conditions and significant prebiotic roles have been suggested for these polymers due to the abundance of HCN in universe. However, the structures...Full Text Available
Orientational constraints obtained from solidstateNMR experiments on anisotropic samples are used here in molecular dynamics (MD) simulations for determining the structure and dynamics of several different membrane-bound molecules. The new MD technique is based on the inclusion of orientation dependent pseudo-forces in the COSMOS-NMR force field. These forces drive molecular rotations and re-orientations in the simulation, such that the motional time-averages of the tensorial NMR properties approach the experimentally measured parameters. The orientational-constraint-driven MD simulations are universally applicable to all NMR interaction tensors, such as chemical shifts, dipolar couplings and quadrupolar interactions. The strategy does not depend on the initial choice of coordinates, and...
This report covers the progress made on the title project for the project period. Four major areas of inquiry are being pursued. Advanced solidstateNMR methods are being developed to assay the distribution of the various important functional groups that determine the reactivity of coals. Special attention is being paid to methods that are compatible with the very high magic angle sample spinning rates needed for operation at the high magnetic field strengths available today. Polarization inversion methods utilizing the difference in heat capacities of small groups of spins are particularly promising. Methods combining proton-proton spin diffusion with [sup 13]C CPMAS readout are being developed to determine the connectivity of functional groups in coals in a high sensitivity relay type of experiment. Additional work is aimed at delineating the role of methyl group rotation in the proton NMR relaxation ...
Orientational constraints obtained from solidstateNMR experiments on anisotropic samples are used here in molecular dynamics (MD) simulations for determining the structure and dynamics of several different membrane-bound molecules. The new MD technique is based on the inclusion of orientation dependent pseudo-forces in the COSMOS-NMR force field. These forces drive molecular rotations and re-orientations in the simulation, such that the motional time-averages of the tensorial NMR properties approach the experimentally measured parameters. The orientational-constraint-driven MD simulations are universally applicable to all NMR interaction tensors, such as chemical shifts, dipolar couplings and quadrupolar interactions. The strategy does not depend on the initial choice of coordinates, and is in principle suitable for any flexible molecule. To test the method on ...
Orientational constraints obtained from solidstateNMR experiments on anisotropic samples are used here in molecular dynamics (MD) simulations for determining the structure and dynamics of several different membrane-bound molecules. The new MD technique is based on the inclusion of orientation dependent pseudo-forces in the COSMOS-NMR force field. These forces drive molecular rotations and re-orientations in the simulation, such that the motional time-averages of the tensorial NMR properties approach the experimentally measured parameters. The orientational-constraint-driven MD simulations are universally applicable to all NMR interaction tensors, such as chemical shifts, dipolar couplings and quadrupolar interactions. The strategy does not depend on the initial choice of coordinates, and is in principle suitable for any flexible molecule. To test the method on ...
Orientational constraints obtained from solidstateNMR experiments on anisotropic samples are used here in molecular dynamics (MD) simulations for determining the structure and dynamics of several different membrane-bound molecules. The new MD technique is based on the inclusion of orientation dependent pseudo-forces in the COSMOS-NMR force field. These forces drive molecular rotations and re-orientations in the simulation, such that the motional time-averages of the tensorial NMR properties approach the experimentally measured parameters. The orientational-constraint-driven MD simulations are universally applicable to all NMR interaction tensors, such as chemical shifts, dipolar couplings and quadrupolar interactions. The strategy does not depend on the initial choice of coordinates, and is in principle suitable for any flexible molecule. To test the method on ...
Solid-state nuclear magnetic resonance (NMR) has been used to explore the nanometer-scale structure of Nafion, the widely used fuel cell membrane, and its composites. We have shown that solid-stateNMR can characterize chemical structure and composition, domain size and morphology, internuclear distances, molecular dynamics, etc. The newly-developed water channel model of Nafion has been confirmed, and important characteristic length-scales established. Nafion-based organic and inorganic composites with special properties have also been characterized and their structures elucidated. The morphology of Nafion varies with hydration level, and is reflected in the changes in surface-to-volume (S/V) ratio of the polymer obtained by small-angle X-ray scattering (SAXS). The S/V ratios of different Nafion models have been evaluated numerically. It has been found that only the water channel model gives the ...
The heterogeneous solid catalyst, mercaptopropylsilica (MPS), has been prepared by a modified procedure in water and its structure confirmed by solidstate carbon-13 CP-MAS NMR spectrum. This catalyst has been efficiently utilized for the synthesis of a wide variety of tri-, tetrasubstituted imidazoles and their bis-analogues at room temperature. The protocol was further explored for the synthesis of the drug trifenagrel.
Phospholamban (PLB) is a 52-amino acid integral membrane protein that helps to regulate the flow of Ca2+ ions in cardiac muscle cells. Recent structural studies on the PLB pentamer...Full Text Available
Summary: The surface coverage of amorphous silica gels used in the synthesis of silica polyamine composites has been investigated by 29Si NMR. By diluting the polyamine anchor silane, chloropropyl trichlorosilane, with methyl trichlorosilane it was found that surface coverage could be markedly improved for a range of amine polymers after grafting to the silica surface. The commensurate decrease in the number of anchor points and increase in the number of free amines results in an increase in metal capacity and/or an improvement in capture kinetics. Solidstate CPMAS-13C NMR has been employed to investigate the structure and metal ion binding of a series of these composite materials. It is reported that the highly branched polymer, poly(ethyleneimine) (PEI) exhibits much broader 13C NMR res...
An inclusion complex between imazalil (IMZ), a selected fungicide, and cyclomaltoheptaose (beta-cyclodextrin, betaCD) was obtained using supercritical fluid carbon dioxide. The best preparation conditions were determined, and the inclusion complex was investigated by means of 1H NMR spectroscopy in aqueous solution and 13C CPMAS NMR spectroscopy in the solidstate. Information on the geometry of the betaCD/IMZ complex was obtained from ROESY spectroscopy, while the dynamics of the inclusion complex in the kilohertz range was obtained from the proton spin-lattice relaxation times in the rotating frame, T(1rho) (1H). PMID:14553984
It is the intention of this paper to point to some of the problems due to molecular motion and to suggest a few solutions to those problems. A few examples will be presented of model systems which demonstrate the effects of motion on the NMR spectroscopy and a very qualitative example of severe spectral distortion in fulvic acids will be shown. In the following discussions we will use concepts derived from the oft repeated thermodynamic picture shown in figure 1. When dealing with a homogeneous, pure compound this picture is sufficient but in a heterogeneous mixture, it is likely that there will be different compounds and different domains all with slightly different versions of figure 1 with poor thermodynamic contact between them. Thus optimal conditions for cross polarization in one domain may be totally inappropriate for another. 59 refs., 10 figs.
This report covers the progress made on the title project for the project period. Four major areas of inquiry are being pursued. Advanced solidstateNMR methods are being developed to assay the distribution of the various important functional groups that determine the reactivity of coals. Special attention is being paid to methods that are compatible with the very high magic angle sample spinning rates needed for operation at the high magnetic field strengths available today. Polarization inversion methods utilizing the difference in heat capacities of small groups of spins are particularly promising. Methods combining proton-proton spin diffusion with {sup 13}C CPMAS readout are being developed to determine the connectivity of functional groups in coals in a high sensitivity relay type of experiment. Additional work is aimed at delineating the role of methyl group rotation in the proton NMR relaxation ...
The surface coverage of amorphous silica gels used in the synthesis of silica polyamine composites has been investigated by 29Si NMR. By diluting the polyamine anchor silane, chloropropyl trichlorosilane, with methyl trichlorosilane it was found that surface coverage could be markedly improved for a range of amine polymers after grafting to the silica surface. The commensurate decrease in the number of anchor points and increase in the number of free amines results in an increase in metal capacity and/or an improvement in capture kinetics. Solidstate CPMAS-13C NMR has been employed to investigate the structure and metal ion binding of a series of these composite materials. It is reported that the highly branched polymer, poly(ethyleneimine) (PEI) exhibits much broader 13C NMR resonances than the linear polymers poly(allylamine) (PAA) and poly(vinylamine) (PVA). These results are ...
A dense silica glass was prepared by consolidating a highly dispersed silicic acid powder (particle size 1H magic-angle spinning (MAS) NMR confirmed an increase in hydroxyl groups in the sample prepared by SPS relative to that of the conventional SiO2 reference glass. Aside from the comparably high water content, we conclude from the similarity of the IR-reflectance and the 29Si MAS NMR spectra of the SPS sample and the corresponding spectra of the conventionally prepared silica glass, that the short- and medium-range order is virtually the same in both materials. Raman spectroscopy, however, suggests that the number of three- and four-membered rings is significantly smaller in the SPS sample compared to the conventionally prepared sample. Based on these results we conclude that it is possible to prepare glasses by compacting amorphous powders by the SPS process. The SPS process may therefore enable the preparation of glasses with compositions ...
Executive summaryForewordPublic awareness of solid-state chemistry, or more broadly solid-state science and technology rapidly grew along with the transistor revolution and the development of the integrated circuit. We are now at the half-way point in the solidstate century [Scientific American The Solid-State Century 1997;8(1) [special issue
Abstract Poly(butylene terephthalate) (PBT) composites containing multiwalled carbon nanotubes (MWCNTs) were prepared using a melt-blending process and used to examine the effects on the composite structure and properties of replacing PBT with acrylic acid-grafted PBT (PBT-g-AA). PBT-g-AA and multihydroxyl-functionalized MWCNTs (MWCNTs-OH) were used to improve the compatibility and dispersibility of the MWCNTs within the PBT matrix. The composites were characterized morphologically using transmission electron microscopy, and chemically using Fourier transform infrared, solid-state 13C NMR and UV-visible absorption spectroscopy. The antibacterial and electrical conductivity properties of the composites were also evaluated. MWCNTs or MWCNTs-OH enhanced the antibacterial activity and electric...
The crystal structure of Ca{sub 2}RuD{sub 6} has been determined by neutron powder diffraction: space group Fm3m, K{sub 2}PtCl{sub 6} structure, as found for other hexahydride salts of group 8 metals with alkaline earth or lanthanide counter ions. No structural phase transition was observed between 340 K and 50 K. The deuterium nuclear quadrupole coupling constant, 54.7 kHz, leads to an ionic character of the Ru-D bond of 76%. The known trends in the behaviour of A{sub 2}MH{sub 6} salts are interpreted in terms of the ionization energies of the cation and the central metal atom.
The crystal structure of Ca2RuD6 has been determined by neutron powder diffraction: space group Fm3m, K2PtCl6 structure, as found for other hexahydride salts of group 8 metals with alkaline earth or lanthanide counter ions. No structural phase transition was observed between 340K and 50K. The deuterium nuclear quadrupole coupling constant, 54.7kHz, leads to an ionic character of the Ru-D bond of 76%. The known trends in the behaviour of A2MH6 salts are interpreted in terms of the ionization energies of the cation and the central metal atom.
Selected derivatives of cyclophosphamide (CP) metabolites were synthesized and the solution chemistry of each was studied by "3"1P nuclear magnetic resonance (NMR) spectroscopy under a standard set of reaction conditions at physiological pH (7.4) and temperature (37"0C). Complementary "2H and "1"3C NMR spectral data was obtained using isotopically ("2G and "1"3C) enriched CP metabolites. The CP derivatives were synthesized by the ozonolysis of substituted 3-butenyl phosphorodiamidates, and were isolated as analogues of either cis and trans 4-hydroperoxy-CP or aldophosphamide (AP). The relative ratios of the tautomeric species, 4-hydroxy-CP and AP, and their half-lives (T/sub 1/2/) were measured by "3"1P NMR spectroscopy. The influence of CP metabolites on perfused U-937 cells, a CP-sensitive human lymphoma, was observed by high resolution "3"1P NMR spectroscopy. ...
Ferroelectric [Pb_0_._9_2(La_1_-_zSb _z)_0_._0_8][Zr_0_._6_0Ti_0_._4_0]O_3 for z = 0.0, 0.3, 0.6, 0.9 and 1 were prepared from their constituent oxides by a solidstate reaction technique. The powders were calcined in the temperature range of 1000 deg. C for 6 h. Phase formation, crystal structure and lattice parameter were investigated by X-ray diffraction (XRD) technique. The compacts were sintered at 1250 deg. C for 2h and their dielectric, ferroelectric and conductive properties were measured. The ferroelectric behavior of the doped samples was studied from their hysteresis loop.
The dealumination of mordenite by acidification (HCl, HNO/sub 3/) and by SiCl/sub 4/ and steaming treatments is followed by high-resolution magic-angle-spinning solid-state /sup 29/Si and /sup 27/Al NMR spectroscopy. The combined use of these techniques leads to the determination of the silicon-aluminum ordering. It is demonstrated that aluminum atoms preferentially occupy tetrahedral positions in the four-membered rings of the mordenite structure. In addition, a mechanism of dealumination can be inferred, consisting in removing the aluminum atoms two by two from the four-membered rings. It is also possible to compute the number of SiOH groups left in the unit cell after the progressive removal of aluminum atoms: four groups per extracted Al atom are generated in the beginning of dealumination and this number gradually decreases to two, suggesting that a structural reorganization must necessarily occur for substantial dealumination. These ...
"2"7Al and "2"9Si solid-stateNMR spectra and X-ray diffraction (XRD) patterns were obtained for #alpha#-SiAlON powders prepared by combustion synthesis, according to which the phase transformation and structure evolution of #alpha#-SiAlON were studied. It was found that in #alpha#-SiAlON "2"9Si chemical shift values (-48 < #delta# _S_i < -47) were close to those in #beta#-Si_3N_4 and #alpha#-Si_3N_4, indicating that Si atoms kept SiN_4 coordination to a large extent in #alpha#-SiAlON despite the presence of O atoms. Dissimilarly, "2"7Al chemical shift values in #alpha#-SiAlON deviated clearly from that corresponding to AlN_4 coordination (#delta# _A_l #approx# 112) and occurred in a range from #delta# _A_l 95.5 to 99.9, which should be assigned to tetrahedral AlO _xN_4_-_x (0 #<=# x #<=# 4) coordination. The broadening effect of AlO _xN_4_-_x peaks was noticed, which was suggested to induced by slight dispersion of #alpha#-SiAlON ...
The aim of this work is to understand the reasons for the selectivity shown in the complexation by unsaturated heteropolyanions (HPA) of actinides (An) which are oxidized to the number +IV. Different studies have been carried out, both in solution and in solidstate, on P_2W_1_7O_6_1"1"0"- and its complexes with Zn"2"+, UO_2"2"+, Ce"4"+, Th"4"+ and U"4"+ to characterize the nature of the complexation site offered to the cation. Among the actinides(IV), the U"4"+ ion has been selected due to its singular spectroscopic and magnetic properties. An initial series of studies, in solution, using NMR"3"1P has thus enabled us to characterize these complexes and to compare them to those formed with the complexing agent PW_1_1O_3_9"8"-. This body of data allows to identify an identical complexation site for both ligands. An analysis of the NMR"3"1P spectrum of U(P_2W_1_7O_6_1)_2"1"6"- has shown a plane of ...
Correlations between structural aspects of solid materials and their behavior as catalysts are relatively recent. This 20-chapter book focuses on understanding of solid-state mechanisms in heterogeneous catalysis and relationship between catalytic behavior and solidstate structure, emphasizing catalysis with oxides, sulfides, and zeolites.
The effect is reported of seven inorganic oxide additives on both the formation mechanism and the densification of X-Sialon prepared by a silicothermal process. The oxides were added to the starting mixture of halloysite clay, alumina and elemental silicon at a level of 1 wt% of the calculated final product, and fired in nitrogen at 1200-1500 deg C. The formation of X-Sialon was monitored by thermal analysis, powder XRD and 2"7"Al and "2"9Si solidstate MAS NMR The effects of the additives are temperature dependent and influence the various stages of the reaction by differing degrees. The oxides which best promote the formation of crystalline X-Sialon (Y_2O_3, CaO and MgO) are also those which facilitate the conversion of initially-formed Si_3N_4 to SiO_2N_2 and SiO_3N units. Densification is most enhanced by Y_2O_3 CaO and CeO_2; MgO exerts its maximum effect on sintering at lower temperatures. Copyright (1998) ...
The interaction of the herbicide paraquat dichloride (P Q, substrate) with p-tert-butylcalix arenas (L, receptor) was investigated in both the solution and solidstates. The isolated paraquat calixarene complexes were characterised by UV-visible, 1H NMR, ESI-Ms, Luminescence and IR spectroscopies and elemental analysis. The stoichiometry of complexes 1 and 2 was 1:1 (1 herbicide: 1 calixarene) and both revealed a biexponential luminescence decay with lifetimes depending on the size and the conformational particularity of the calixarenes. Molecular modelling suggested that both calixarenes interact with the herbicide through cation-? interaction. P Q in included in the p-tert butylcalix a rene cavity, a situation favoured by its pinched conformation in polar solvent while it is partially included in the p-tert butylcalix a rene cavity because of its in-out cone conformation. The theoretical results, in particular using Mopac ...
Pretreatment of brown coal in oil was conducted using 1-methyl naphthalene or mixture of tetralin and 1-methyl naphthalene as solvent at temperatures ranging from 300 to 430{degree}C under nitrogen atmosphere. Effects of the solvent properties on the structural change of oxygen-functional groups (OFG) and coal liquefaction were investigated by means of quantitative analysis of OFG and solidstate {sup 13}C-NMR measurement. When hydrogen transfer from solvent was insufficient, it was suggested that brown coal molecules loose their hydrogen to be aromatized. While, at lower temperatures ranging from 300 to 350{degree}C, hydrogen contained in brown coal molecules was consumed for the stabilization of pyrolytic radicals, and the deterioration of liquefaction was not observed. When hydrogen transfer from solvent was insufficient at higher temperatures above 400{degree}C in nitrogen atmosphere during pretreatment in oil, ...
The structural change of the (100-x)(0.6Li{sub 2}S{center_dot}0.4SiS{sub 2})centre dotxLi{sub 3}PO{sub 4} oxysulfide glassesduring crystallization was analyzed by means of solid-state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS). The unique tetrahedral units of SiO{sub n}S{sub 4-n} (n=1,2,3) and PO{sub n}S{sub 4-n} (n=1,2,3) present in the glass samples vanished and the SiS{sub 4}, PS{sub 4}, SiO{sub 4} units increased with proceeding of the crystallization process. Nonbridging sulfur and oxygen atoms decreased while bridging oxygens and S{sup 2-} increased with proceeding of the crystallization process. Large structural difference between the glass and the corresponding crystallized sample explained the high stability against crystallization found in the oxysulfide glass with the composition of X=5. (author)
The structural change of the (100-x)(0.6Li[sub 2]S[center dot]0.4SiS[sub 2])centre dotxLi[sub 3]PO[sub 4] oxysulfide glassesduring crystallization was analyzed by means of solid-state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS). The unique tetrahedral units of SiO[sub n]S[sub 4-n] (n=1,2,3) and PO[sub n]S[sub 4-n] (n=1,2,3) present in the glass samples vanished and the SiS[sub 4], PS[sub 4], SiO[sub 4] units increased with proceeding of the crystallization process. Nonbridging sulfur and oxygen atoms decreased while bridging oxygens and S[sup 2-] increased with proceeding of the crystallization process. Large structural difference between the glass and the corresponding crystallized sample explained the high stability against crystallization found in the oxysulfide glass with the composition of X=5. (author)
New palladium(II) and platinum(II) complexes of saccharinate (sac), trans-[Pd(py)"2(sac)"2] (1), cis-[Pt(py)"2(sac)"2] (2), trans-[Pd(3-acpy)"2(sac)"2] (3) and cis-[Pt(3-acpy)"2(sac)"2] (4) (py=pyridine and 3-acpy=3-acetylpyridine) have been synthesized. Elemental analysis, UV-Vis, IR, NMR and TG/DTA characterizations have been carried out. The structures of 1-4 were determined by X-ray diffraction. The palladium(II) and platinum(II) ions are coordinated by two N-bonded sac ligands, and two nitrogen atoms of py or 3-acpy, forming a distorted square-planar geometry. The palladium(II) complexes (1 and 3) are trans isomers, while the platinum(II) complexes (2 and 4) are cis isomers. The mononuclear species in the solidstate are connected by weak intermolecular C-H...O hydrogen bonds, C-H...@...
Accomplishments for the quarter are presented for the following areas of research: oil shale, tar sand, coal, advanced exploratory process technology, and jointly sponsored research. Oil shale research includes; oil shale process studies, environmental base studies for oil shale, and miscellaneous basic concept studies. Tar sand research covers process development. Coal research includes; underground coal gasification, coal combustion, integrated coal processing concepts, and solid waste management. Advanced exploratory process technology includes; advanced process concepts, advanced mitigation concepts, and oil and gas technology. Jointly sponsored research includes: organic and inorganic hazardous waste stabilization; development and validation of a standard test method for sequential batch extraction fluid; operation and evaluation of the CO[sub 2] HUFF-N-PUFF Process; fly ash binder for unsurfaced road aggregates; solidstate ...
A series of oxine ligands, 5-X, 8 OH C9H6N (X = H, Cl, SO3H) have been covalently bound to a silica gel polyamine composite made from a silanized amorphous silica xerogel and poly(allylamine) (BP-1) by the Mannich reaction. The resulting modified composites WP-4(X = H), CB-1(X = Cl), and SB-1(X = SO3H) were characterized by elemental analysis, FTIR, and solidstate CPMAS-13C-NMR. Using the analytical data before and after the ligand modification, the ligand loading could be estimated and in combination with metal ion capacities a metal to ligand ratio could be obtained. The composites WP-4 and CB-1 both showed ratios of approximately 1 : 1 while the sulfonate modified composite, SB-1, showed a metal to ligand ratio of 1 : 2. This is tentatively interpreted in terms of a zwitterionic oxine ...
A new preparation method for LiNiVO{sub 4} has been developed. LiNiVO{sub 4} can be readily obtained from the solidstate reaction of LiNiO{sub 2} and V{sub 2}O{sub 3} or V{sub 2}O{sub 5} at 700 C for 2h in air. The quarternary Li-Ni-V-O reaction is strongly dependent on vanadium starting materials, reaction environment atmosphere, reactant stoichiometry and synthesis temperature. Individual particles of LiNiVO{sub 4} powders are well-formed crystallites shown clearly by scanning electron microscopy results to be in the shape of an octahedron. Powder X-ray diffraction studies of this crystalline material indicate that LiNiVO{sub 4} has an inverse spinel structure different from that of known cathode materials such as LT-LiCoO{sub 2} and LiMn{sub 2}O{sub 4}. The Li/LiNiVO{sub 4} cell can be charged and discharged at about 4.8 V versus metallic Li. To our knowledge, this is the Li intercalation reaction ...
A number of high voltage cathode materials are now being considered for their ability to increase the energy density of lithium-ion batteries. In this study, a lithium-nickel composite alloy (LiNiVO{sub 4}) was synthesized using a rheological phase reduction method that incorporated mixtures of LiOH-H{sub 2}O, Ni(CH{sub 3}COO){sub 2}, 4H{sub 2}O, NH{sub 4}VO{sub 3} and C{sub 2}H{sub 2}O{sub 4}-2H{sub 2}O. The rheological phase method was used to prepare the compounds from a solid-liquid rheological mixture. Solid reactants were first mixed in a proper molar ratio, and water or solvents were added to the solid-liquid rheological body. X-ray powder diffraction (XRD) and Fourier Transform (FT) analyses were conducted to characterize the powders. Scanning electron microscopy (SEM) was used to characterize the morphological features and particle sizes of the powders. Results of the analyses indicated that ...
Angelin Pedra is a specie found in the north of Mato Grosso State in Brazil, where an expressive volume of waste of this wood is produced. An alternative to recycle this waste is to produce wood plastic composites. However, structural and chemical investigations are fundamental to generate information for this use. In the present work, low field NMR was used to determine the spin-lattice and spin-spin relaxation times with objective to investigate the molecular dynamic behavior of the alburnu and cerne regions of Angelin Pedra aiming at a potential use of this waste wood in polymeric composites. The results of the proton spin-lattice relaxation time (T1H) and the proton spin-spin relaxation time (T2H) showed at least three different mobility domains for both regions. Among the values, one was very flexible and other was rigid. Knowing that wood is a polymer composite basically constituted by cellulose, hemicellulose and ...
Integration of solid-state biosensors and lipid bilayer membranes is important for membrane protein research and drug discovery. In these sensors, it is critical that the solid-state sensing...Full Text Available
... materials science and engineering, condensed-matter or materials physics, solid-state or materials ... include materials theory, condensed-matter and materials physics, solid-state and materials ...
The monoanionic bidentate Schiff base, N-(phenolyl)-benzaldimine (HL), has been employed to synthesize a new vanadium(IV) complex of general composition [VO(L)2] (where L = O, N donor of Schiff base). The ligand and complex have been fully characterized by elemental analyses, molar conductance data, FT-IR, 1H- and 13C-NMR, and UV-Vis spectroscopies. Oxidation of alcohols to their corresponding aldehydes and ketones was conducted by this complex catalyst using Oxone as oxidant under biphasic reaction conditions (CH2Cl2/H2O) and tetra-n-butylammonium bromide as phase transfer agent under air at room temperature.
Purpose Study the radiolysis of solid-state metoclopramide hydrochloride at various absorbed doses. Elucidate the structure of the degradation products to gain information on the radiolysis mechanisms. Methods Solid-state metoclopramide samples were irradiated at several doses with gamma rays and high-energy electrons to evaluate the influence of the dose rate. High-performance liquid chromatography with a diode array detector was used to measure the chemical potency as a function of the absorbed dose and to quantify the degradation products. The characterization of degradation products was performed by liquid chromatography/atmospheric pressure chemical ionization/tandem mass spectrometry. Results The degradation of solid-state metoclopramide after irradiation was negligible. No qualitati...
... nent to the design and construction of metal-semiconductor solar cells, in that both the photovoltage and the efficiency of metal-semiconductor cells ...
Silanization of the silica gel surface in the synthesis of silica gel polyamine composites uses (chloropropyl)-trichlorosilane (CPTCS). It is possible to substitute a molar fraction of reagent CPTCS with methyltrichlorosilane (MTCS), creating a mixed silane surface layer. Two types of silica gels were modified with a series of MTCS:CPTCS molar ratios. Solid-state CP/MAS 29Si and 13C NMR spectroscopies were used to evaluate the surface silane composition. Surface silane coverage was markedly improved for the resulting gels. When polyamines were grafted to the resultant MTCS:CPTCS silane layers, it was shown that the decrease in the number of propyl attachments to the polyamine resulted in increased quantities of ''free amines''. Optimum MTCS:CPTCS ratios were determined for three polyamines grafted onto one silica gel. A substantial free amine increase was observed for poly(allylamine) (PAA). Metal uptake ...
Silanization of the silica gel surface in the synthesis of silica gel polyamine composites uses (chloropropyl)-trichlorosilane (CPTCS). It is possible to substitute a molar fraction of reagent CPTCS with methyltrichlorosilane (MTCS), creating a mixed silane surface layer. Two types of silica gels were modified with a series of MTCS:CPTCS molar ratios. Solid-state CP/MAS 29Si and 13C NMR spectroscopies were used to evaluate the surface silane composition. Surface silane coverage was markedly improved for the resulting gels. When polyamines were grafted to the resultant MTCS:CPTCS silane layers, it was shown that the decrease in the number of propyl attachments to the polyamine resulted in increased quantities of ''free amines''. Optimum MTCS:CPTCS ratios were determined for three polyamines grafted onto one silica gel. A substantial free amine increase was observed for poly(allylamine) (PAA). Metal uptake ...
The organization of organic semiconductor molecules in the active layer of organic electronic devices has important consequences to overall device performance. This is due to the fact that molecular organization directly affects charge carrier mobility of the material. Organic field-effect transistor (OFET) performance is driven by high charge carrier mobility while bulk heterojunction (BHJ) solar cells require balanced hole and electron transport. By investigating the properties and device performance of three structural variations of the fluorenyl hexa-peri-hexabenzocoronene (FHBC) material, the importance of molecular organization to device performance was highlighted. It is clear from {sup 1}H NMR and 2D wide-angle X-ray scattering (2D WAXS) experiments that the sterically demanding 9,9-dioctylfluorene groups are preventing {pi}-{pi} intermolecular contact in the hexakis-substituted FHBC 4. For bis-substituted FHBC compounds 5 and 6, {pi}-{pi} intermolecular ...
An interest in electronic materials has led me to investigate new synthetic approaches to III-V' type semiconducting (13-15, current IUPAC designation for B and N groups in the Periodic Table) and magnetic (3-15) compounds. It is now possible to prepare binary (GaAs and GdP) and ternary mixed-metal (Al[sub x]Ga[sub 1-x]As) and mixed-pnictide (GaP[sub x]As[sub 1-x]) compounds in seconds from rapid, low-temperature-initiated metathesis reactions between a metal (III) trihalide and a trisodium pnictide, exemplified by MX[sub 3] + Na[sub 3]Pn [yields] MPn + 3 NaX, where M is Al, Ga, In, (Al,Ga), or a lanthanide; X is F, Cl, or I; and Pn is P, As, Sb, or (P,As). The precursors are mixed together in a dry box and ignited by light grinding with a mortar and pestle, or by brief, local heating from a hot filament. These reactions are very exothermic (calculated [Delta]H[sub rxn] (GaAs) = 138 kcal/mol) and typically reach temperatures in excess of 700[degrees]C within seconds of ...
Accomplishments for the quarter are presented for the following areas of research: oil shale, tar sand, coal, advanced exploratory process technology, and jointly sponsored research. Oil shale research includes; oil shale process studies, environmental base studies for oil shale, and miscellaneous basic concept studies. Tar sand research covers process development. Coal research includes; underground coal gasification, coal combustion, integrated coal processing concepts, and solid waste management. Advanced exploratory process technology includes; advanced process concepts, advanced mitigation concepts, and oil and gas technology. Jointly sponsored research includes: organic and inorganic hazardous waste stabilization; development and validation of a standard test method for sequential batch extraction fluid; operation and evaluation of the CO{sub 2} HUFF-N-PUFF Process; fly ash binder for unsurfaced road aggregates; solidstate ...
Low-temperature catalytic pretreatment is a promising approach to the development of an improved liquefaction process- This work is a fundamental study on effects of pretreatments on coal structure and reactivity in liquefaction. The main objectives of this project are to study the coal structural changes induced by low-temperature catalytic and thermal pretreatments by using spectroscopic techniques; and to clarify the pretreatment-induced changes in reactivity or convertibility of coals in the subsequent liquefaction. This report describes the recent progress of our work. Substantial progress has been made in the spectroscopic characterization of structure and pretreatment-liquefaction reactions of a Montana subbituminous Coal (DECS-9), and thermochemical analysis of three mw and reacted bituminous coals. Temperature programmed liquefaction has been performed on three low-rank coals both in the presence and absence of dispersed molybdenum sulfide catalyst. We also performed a ...
In-situ methods are well known as powerful tools in studying catalyst formation processes, their solidstate properties under working conditions and the interaction with the feed, intermediates and products to reveal reaction mechanisms. This paper gives a short overview on results of intense studies using in-situ techniques to reveal VPO catalyst generation processes, interaction of educts, intermediates and products with VPO catalyst surfaces and mechanistic insights. Catalytic data of the ammoxidation of toluene on different VPOs complete these findings. The precursor-catalyst transformation processes were preferently investigated by in-situ XRD, in-situ Raman and in-situ ESR spectroscopy. The interaction of aromatic molecules and intermediates, resp., and VPO solid surfaces was followed by in-situ ESR and in-situ FTIR spectroscopy. Mechanistic information was mainly obtained using in-situ FTIR spectroscopy and the ...
The rate of the oxygen-exchange reaction in an aqueous solution of a heterocyclic oxygen compound, 2,4,6-trimethylpyrylium perchlorate, was quantitated. The /sup 18/O isotope effect in /sup 13/C NMR spectroscopy affords a direct, continuous, and relatively simple analysis of the reaction and was used to obtain data on the incorporation of /sup 18/O from solvent H/sub 2//sup 18/O into the pyrylium salt. Due to the low solubility of this salt in aqueous solutions, 2,4,6-trimethyl(2-/sup 13/C)pyrylium perchlorate and 2,4,6-trimethyl(2,6-/sup 13/C/sub 2/)pyrylium perchlorate were synthesized to facilitate the acquisition of the data on an NTC-200 spectrometer operating at 50.31 MHz. Upon incorporation of /sup 18/O into the pyrylium salt, the /sup 13/C NMR signal of the directly bonded carbon atom is shifted upfield 0.038 ppm. A /sup 13/C isotope effect is also detected in the doubly /sup 13/C-enriched pyrylium salt where the /sup 13/C ...
This report summarizes the progress of the SolidState Photovoltaic Research Branch of the Solar Energy Research Institute (SERI) from October 1, 1988, through September 30,l 1989. Six technical sections of the report cover these main areas of SERIs in-house research: Semiconductor Crystal Growth, Amorphous Silicon Research, Polycrystalline Thin Films, III-V High-Efficiency Photovoltaic Cells, Solid-State Theory, and Laser Raman and Luminescence Spectroscopy. Sections have been indexed separately for inclusion on the data base.
The fundamental product of tetracycline hydrochlorine gamma radiolysis was separated in its solidstate. From the results of spectroscopic studies it has been established that it is des-N,N-dimethylaminotetracycline.
Solidstate lasers, particularly neodymium glass systems, have undergone intensive development during the last decade. In this paper, we review solidstate laser technology in the context of high-peak-power systems for inertial confinement fusion. Specifically addressed are five major factors: efficiency, wavelength flexibility, average power, system complexity, and cost; these factors today limit broader application of the technology. We conclude that each of these factors can be greatly improved within current fundamental physical limits. We further conclude that the systematic development of new solidstate laser madia, both vitreous and crystalline, should ultimately permit the development of wavelength-flexible, very high average power systems with overall efficiencies in the range of 10 to 20%.
Solid-state single-photon sources have many desirable features that make them attractive for applications in quantum information processing. However, the phase coherence of such devices can be severely compromised by coupling to the solid-state environment. Here, we study the effects of realistic dephasing environments on a pair of solid-state single photon sources in the context of quantum interference effects such as the Hong-Ou-Mandel dip. By means of exact solutions for the non-Markovian dynamics of the sources, we show that the resulting loss of visibility depends crucially on the timing of photon detection events. Our results demonstrate that the effective visibility can be improved via temporal post-selection, and also that time-resolved interference can be a useful probe of the interaction between the emitter and its host environment.
A detailed kinetic study of the epoxidation of 1-octene with hydrogen peroxide catalyzed by Pt(II) complexes is reported. The two systems analyzed were (diphoe)Pt(CF/sub 3/)(OH)/1-octene/H/sub 2/O/sub 2//THF and ((diphoe)Pt(CF/sub 3/)(CH/sub 2/Cl/sub 2/))BF/sub 4//1-octene/H/sub 2/O/sub 2//H/sub 2/O/CH/sub 2/Cl/sub 2/. Rate data were determined with GLC from epoxide formed vs time plots. Evidence for many of the organometallic intermediates and the individual steps involved was gained from IR studies, /sup 19/F NMR studies, and especially designed experiments including studies of the acidity effect. In both cases the kinetic analysis suggests a mechanism in which the actual oxidant is a PtOOH species that interacts with a Pt-olefin complex in the oxygen-transfer step (second-order dependence on platinum). 29 references, 12 figures, 3 tables.
Since information has been regarded os a physical entity, the field of quantum information theory has blossomed. This brings novel applications, such as quantum computation. This field has attracted the attention of numerous researchers with backgrounds ranging from computer science, mathematics and engineering, to the physical sciences. Thus, we now have an interdisciplinary field where great efforts are being made in order to build devices that should allow for the processing of information at a quantum level, and also in the understanding of the complex structure of some physical processes at a more basic level. This thesis is devoted to the theoretical study of structures at the nanometer-scale, 'nanostructures', through physical processes that mainly involve the solid-state and quantum optics, in order to propose reliable schemes for the processing of quantum information. Initially, the main results of quantum information theory and quantum ...
Data resulting from a continuing effort to provide system/subsystem definition data to aid in the evaluation of the SPS program concept is presented. The specific data described relate to the proposed use of solidstate devices as microwave power amplifiers in the satellite microwave power transmission subsystem.
Modifications to the reference concept were studied and the best approaches defined. The impact of the high efficiency multibandgap solar array on the reference concept design is considered. System trade studies for several solidstate concepts, including the sandwich concept and a separate antenna/solar concept, are described. Two solidstate concepts were selected and a design definition is presented for each. Magnetrons as an alternative to the reference klystrons for dc/rf conversion are evaluated. System definitions are presented for the preferred klystron and solidstate concepts. Supporting systems are analyzed, with major analysis in the microwave, structures, and power distribution areas. Results of studies for thermal control, attitude control, stationkeeping, and details of a multibandgap solar cell study are included. Advanced laser concepts and the ...
Using carbon-paste-CuFeS{sub 2} electrodes and a cyclic voltammetric technique, it was found that a large number of intermediate electrochemical oxidation reactions were associated with the dissolution of chalcopyrite in presence and absence of bacteria. The effects of concentrations of copper, ferrous and ferric ions, as well as of agitation on the peaks of cyclic voltammograms were measured. It was established that chalcopyrite oxidation was solid-state controlled as suggested by the data of chronopotentiometric and chronoamperometric measurements. The activation energy of solidstate diffusion of chalcopyrite leaching was determined by the Sand's method to be {triangle}E{sub a} = 20.5 kJ. The leaching mechanism is discussed in terms of solid-state properties (energy bonding) of the n-type semiconductor chalcopyrite and energy density states of redox systems of acidic bacterial leach media. A ...
The production of {alpha}-amylase by Bacillus licheniformis M27 in submerged fermentation was completely inhibited due to catabolic repression in medium containing 1% glucose. In contrast, the enzyme production in a solidstate fermentation system was 19,550 units/ml extract even when the medium contained 15% glucose. The peak in enzyme titre was, however, shifted from 48 to 72 h. The ability of the solidstate fermentation system to significantly overcome catabolic repression was not known earlier and is probably conferred by various physico-chemical factors and culture conditions specific to the system. (orig.).
Summary Solidstate nuclear track detectors are used to determine the concentration of a particles in the environment. The standard method for assessing exposed detectors involves 2D image analysis. However 3D imaging has the potential to provide additional information relating to angle as well as to differentiate clustered hit sequences and possibly energy of a particles but this could be time consuming. Here we describe a new method for rapid high-resolution 3D imaging of solidstate nuclear track detectors. A `LEXT' OLS3100 confocal laser scanning microscope (Olympus Corporation, Tokyo, Japan) was used in confocal mode to successfully obtain 3D image data on four CR-39 plastic detectors. Three-dimensional visualization and image analysis enabled characterization of track features. This ...
Improved NMR detection of mass limited samples can be obtained by taking advantage of the mass sensitivity of microcoil NMR, while throughput issues can be addressed using multiple, parallel...Full Text Available
High resolution of NMR spectroscopic data of biosamples are a rich source of information on the metabolic response to physiological variation or pathological events. There are many advantages...Full Text Available
An indoor radioactive survey is being conducted in an Italian district. Preliminary results identified a zone with significant radioactive levels, in which a new specific survey has been planned. In this paper attention is dedicated mainly to radon measurement technique and results.
The Anglo-Danish programme of research on materials for advanced vehicular transport and other storage batteries is about to enter its fifth year. Here, the results of the work to date on solid electrolytes, electrode materials and cell design are reviewed and discussed as a systematic programme of cell testing gets underway.
Feb 23, 2011 ... THEMIS-D: The SolidState Telescope (SST) measures the incoming ... Each single sensor covers an angle of 36 degrees. .... The five small satellites were launched together on a Delta II rocket and they carry identical ...
Barbara), Arto Nurmikko (Brown U), Ed Petrow (DOE), Jim Brodrick (DOE), John Carrano (DARPA), Bob Karlicek (Gelcore), John Zolper (DARPA), and Steve Johnson (LBNL). This project...
This section of the report is concerned with the study of the metallisation, oxidation and doping of materials which are of importance to the micro-electronics industry. The Van de Graaff accelerator and radioactive tracers are used for studying surface and sub-surface behaviour of these materials.
... Oliver, j. Egekeze, m. 7. Kennedy, JW Jorgenson, J. F. Parcher and ... 9. .:. W. Thackeray, HS White and MS Wrighton, J. Phys ... Dr. Harold H. Singerman ...
Using a coplanar, end-mounted antenna as a baseline, various configuration trades were performed to select a preferred solidstate concept. The increase in efficiency that could be realized by use of multi bandgap solar cells, either with klystron or solidstate antenna was evaluated. Satellite configurations were developed to exploit the sandwich antenna concept wherein solar cells are located on one side of the antenna panel and solidstate dc/RF converters on the other side. These concepts entailed various primary and secondary reflector arrangements for directing solar energy to the solar cell side of the antenna with higher concentration ratios than used on the coplanar configurations. Operations analysis included development of a satellite construction scenario, a concept for the SCB, a top-level satellite construction operation, construction operation, ...
THEMIS-A: The SolidState Telescope (SST) measures the incoming intensity ... units (heads), each SST unit has two pairs of opposing ion and electron sensors. .... The five small satellites were launched together on a Delta II rocket and they ...
We have demonstrated that the SSSE pulverization process can convert multicomponent plastic waste into a powder with very promising properties. A variety of mixed color plastic chips have been pulverized.
The results of the radon concentration measurements in dwellings in Belgrade were shown in this paper. The measurements were done using long term method with diffusion cups equipped with solidstate nuclear track detector LR-115-II or CR-39. (author).
Science and technology could be revolutionized by quantum computers, but building them from solid-state devices will not be easy. Robert W Keyes of IBM's research division outlines the challenges in scaling up the technology from lab experiments to practical devices. (U.K.)
Various energy sources and motors of divers types can be used in electric cars with operating modes subjected to a number of particular constraints. As a result, the possible structures of the converters, that are analysed in detail, are about a dozen in number. Also considered is the use of solid-state components - thyristors, power transistors and new components.
Natural abundance 13C solid-state nuclear magnetic resonance spectroscopy was used to investigate the effect of the incorporation of cholesterol on the dynamics of dimyristoylphosphatidylcholine (DMPC)...Full Text Available
A method for recycling laser flashlamp radiation in selected wavelength ranges to decrease thermal loading of the solidstate laser matrix while substantially maintaining the pumping efficiency of the flashlamp.
... Science: London, 1987; p. 237; (b) Ratner, MA; Shriver, D. F. Chem. ... 11. Lofton, EP; Thackeray, JW; Wrighton, MS J. ... (1) Dr. Harold H. Singerman (1) ...
Within about 10 years, microelectronic devices will be made with more than a billion (10"9) electronic components per chip. To implement such a sophisticated technology it will be essential to have a fundamental understanding of the solidstate interaction between the different materials in thin film semiconductor structures. This is the main purpose of this research program. Characterization and analysis is carried out mainly by Rutherford backscattering spectrometry and channelling using accelerated nuclear particles from the Van de Graaff accelerator, while radioactive isotopes provide information about interaction mechanisms. 6 figs., 1 ref.
Indoor radon is a potential health hazard for the general public, especially in buildings with poor ventilation. A variety of dosemeters have been developed and used in surveys of radon concentration measurements. In this article the passive dosemeters which are based on solidstate nuclear track detectors are reviewed. The principle of passive dosimetry and the factors affecting their performance are discussed. The characteristics of SSNTD materials in relation to their behaviour under different environmental conditions are tabulated and discussed. Results of radon surveys from selected studies are also presented. (Author).
This invention pertains to passivation-free solid-state rechargeable batteries composed of Li.sub.4 Ti.sub.5 O.sub.12 anode, a solid polymer electrolyte and a high voltage cathode. The solid polymer electrolyte comprises a polymer host, such as polyacrylonitrile, poly(vinyl chloride), poly(vinyl sulfone), and poly(vinylidene fluoride), plasticized by a solution of a Li salt in an organic solvent. The high voltage cathode includes LiMn.sub.2 O.sub.4, LiCoO.sub.2, LiNiO.sub.2 and LiV.sub.2 O.sub.5 and their derivatives.
This invention pertains to passivation-free solid-state rechargeable batteries composed of Li{sub 4}Ti{sub 5}O{sub 12} anode, a solid polymer electrolyte and a high voltage cathode. The solid polymer electrolyte comprises a polymer host, such as polyacrylonitrile, poly(vinyl chloride), poly(vinyl sulfone), and poly(vinylidene fluoride), plasticized by a solution of a Li salt in an organic solvent. The high voltage cathode includes LiMn{sub 2}O{sub 4}, LiCoO{sub 2}, LiNiO{sub 2} and LiV{sub 2}O{sub 5} and their derivatives. 5 figs.
New lithium ion composite electrolyte, LiI?Li2S?La2O2Sm (m=1, 2) was synthesized from the binary Li2S?LaOI system through solidstate reaction. The lithium ion conductive property was investigated by AC impedance spectroscopy. And the highest conductivity of the obtained electrolyte at room temperature was found to be 3.0?10?6?S cm?1. The notable ionic conduction was attributed to the in situ formed amorphous LiI.
The fire protection practices adopted at nuclear power stations generally follow the well established principles used throughout industry. Unfortunately, there is one particular area - the interaction with heating, ventilation and air conditioning (HVAC) services - where nuclear power stations pose a seemingly insoluble conflict: that between the need to contain and the need to ventilate. Now, however, solidstate fire dampers using power fluidics may promise a solution. One of the key characteristics of a fluidic device is that it is 'solidstate', i.e. it has no moving parts. Because of this, its inherent reliability is orders of magnitude greater than a mechanical device. (U.K.).
Barbiturates substituted at the 5-position with organyltelluroalkyl or organylselenoalkyl groups were prepared by ring annulation of appropriately substituted diethyl malonates with urea or thiourea. The substituted diethyl malonates (phenyltellurobutyl(ethyl), i-propyltelluropropyl(ethyl), i-propyltelluropropyl(allyl), i-propyselenopropyl(ethyl), and phenylselenohexyl(methyl)) were prepared in 55-91% yield by reaction of diethyl omega-bromoalkyl(alkyl)malonates with organyltellurolates or selenolates (RXNa; X = Se, Te) in ethanol/benzene. The following barbiturates were obtained in 28-84% yield: phenyltellurobutyl(ethyl), m.p. 100/sup 0/C; i-propyltelluropropyl(ethyl), m.p. 119/sup 0/C; i-propylselenopropyl(ethyl), m.p. 137/sup 0/C; phenyl-selenohexyl(methyl), m.p. 124/sup 0/C. The 5-substituted thiobarbiturates i-propyltelluropropyl(ethyl)-(m.p. 75/sup 0/C) and i-propylselenopropyl(ethyl)thiobarbiturate (m.p. 83/sup 0/C) were isolated in 32 and 20% yield, respectively. The ...
The conductance in ferromagnetic Ni nano-wire is quantized in units of 2e{sup 2}/h in the absence of magnetic field, while the units switch to e{sup 2}/h in the magnetic field. The fractional units of 0.7e{sup 2}/h and 1.4e{sup 2}/h with and without magnetic field appear under the application of high bias-voltage. The spin polarization and bias-voltage play an important role in the electric conduction.
The paper studies the effect of crystal structure of LiNbO_3 monocrystals on NMR spectra of "7 Li and "9"3 Nb. Models of defect structure are analyzed via comparison of NMR experimental spectra and gradients of electrical field predicted on the basis of the calculations on "7 Li and "9"3 Nb nuclei using the relevant model. It is shown that no one of the main models of lithium niobate defect structure explains the peculiarities of NMR spectra. Conclusions are made about the independence of the reasons of occurrence of NMR additions lines "7 Li and "9"3 Nb, as well as, about links of "9"3 Nb NMR weak additional lines with the ranges of a different crystalline phase that may form while growing. 18 refs., 2 figs., 3 tabs.
Nuclear magnetic resonance (NMR) techniques coupled with multivariate data analysis were used to conduct monitoring of biochemical changes of black raspberry fruits at different stages of maturation and under various extraction and NMR dissolution solvent conditions: extraction with 50% methanol and D"2O as an NMR dissolution solvent, extraction with 50% methanol and 50% methanol-d"4 as an NMR dissolution solvent, and extraction with 100% ethyl acetate and 100% methanol-d"4 as an NMR dissolution solvent. Partial least-squares discriminant analysis reliably distinguished black raspberry fruits according to the maturation stage, whereby the relative levels of various compounds such as amino acids, organic acids, sugars and phenolic compounds were compared using analysis of variance. Sucrose ...
For the first time, rheological phase method, a simple and effective route, is applied to synthesize novel cathode material LiCoPO{sub 4}. X-ray diffraction spectrometer (XRD), X-ray photoelectron spectrometer (XPS), transmission electron microscope (TEM) and electrochemical impedance spectroscopy (EIS) are taken to investigate this material, respectively. XRD figure shows that the rheological sample is better crystallized than the solid-state one. XPS result of the rheological sample exhibits that the valence of Co is 2+. TEM images show that better dispersed particles with smaller size can be formed by rheological method comparing to the solid-state route. Charge-discharge test is carried out in the range of 3.0-5.0 V at 0.2 mA cm{sup -2}. The initial discharge capacity for rheological phase and solid-state powder is 71.5 and 30.9 mAh g{sup -1}, respectively. The better electrochemical property should be ascribed to the ...
For the first time, rheological phase method, a simple and effective route, is applied to synthesize novel cathode material LiCoPO4. X-ray diffraction spectrometer (XRD), X-ray photoelectron spectrometer (XPS), transmission electron microscope (TEM) and electrochemical impedance spectroscopy (EIS) are taken to investigate this material, respectively. XRD figure shows that the rheological sample is better crystallized than the solid-state one. XPS result of the rheological sample exhibits that the valence of Co is 2+. TEM images show that better dispersed particles with smaller size can be formed by rheological method comparing to the solid-state route. Charge-discharge test is carried out in the range of 3.0-5.0 V at 0.2 mA cm-2. The initial discharge capacity for rheological phase and solid-state powder is 71.5 and 30.9 mAh g-1, respectively. The better electrochemical property should be ascribed to the better crystallized ...
Solid-state lithium batteries with a unique construction are reported in this paper. These batteries contain two kinds of lithium ion-conductive solid electrolytes, LiI-Li{sub 2}S-P{sub 2}S{sub 5} glass contacted with the anode material and Li{sub 3}PO{sub 4}-Li{sub 2}S-SiS{sub 2} glass or Li{sub 2}S-GeS{sub 2}-P{sub 2}S{sub 5} crystalline material contacted with the cathode. The former electrolyte was selected as that stable to electrochemical reduction, and the latter two to oxidation. This construction made it possible to use graphite as the anode and LiCoO{sub 2} as the cathode in the solid-state lithium battery. The energy density of the battery is 390 W h{center_dot}l{sup -1} and 160 W h{center_dot}kg{sup -1} per total volume and weight of the cathode and anode layers, respectively, which are comparable to those of commercialized Li-ion batteries.
Radiation from an ultrastable 240 GHz solidstate source has been injected, through an isolator, into the cavity of the University of California, Santa Barbara millimeter-wave free-electron laser (FEL). High-power FEL emission, normally distributed among many of the cavity's longitudinal modes, is concentrated into the single mode to which the solidstate source has been tuned. The linewidth of the FEL emission is 0.5 MHz, consistent with the Fourier transform limit for the 2 #mu#s pulses. This demonstration of frequency-stable, ultranarrow-band FEL emission is a critical milestone on the road to FEL-based pulsed electron paramagnetic resonance spectroscopy.
With the preeminence of A-15 superconducting multifilamentary wires in magnet technology, it has become important to understand the thermodynamic factors influencing the formation of these compounds under solid-state reaction conditions. The six systems Nb--Sn, Nb--Ga, Nb--Ge, Nb--Al, V--Si, and V--Ga were prepared as single filament bronze wires and heat treated in an attempt to precipitate the appropriate A-15 compound. The compounds observed to form were categorized using a formation temperature ratio (stability index) based on the melting temperatures of the constituents which make up the single filament composites. This study has led to several predictions regarding the formation of A-15 compounds using a solid-state bronze diffusion technique. The results of experimentation based on these predictions are presented.
Abstract Trametes hirsuta, a filamentous basidiomycete, was successfully cultivated in solid-state fermentation (SSF) on a mixture of pine wood chips and orange peel in a novel bioreactor that allows mixing of the inoculated solid material during the fermentation. Copper sulfate or xylidine (2,5-dimethylaniline) were added to enhance the production of enzymes, especially laccases. For comparison, Trametes hirsuta was also cultivated in submerged conditions. The effect of additives in SSF was low, whereas the choice of the solid material and the rotation of the reactor vessel showed a significant influence on the enzyme production. The space-time yields for the fermentations were calculated and showed that SSF on low-cost substrates can effectively produce extracellular enzymes at a suffici...
Efforts concentrated on updating of the Rockwell reference concept, definition of new system options, studies of special emphasis topics, further definition of the transportation system, and further program definition. The Rockwell reference satellite concept has a gallium arsenide (GaAs) solar cell array having flat concentrators with an effective concentration ratio of 1.83at end of life. Alternatives to this concept includes solidstate power amplifiers or magnetrons for dc/RF conversion and multibandgap solar cells for solar to dc energy conversion. Two solidstate concepts were studied. It was determined that the magnetron approach was the lowest mass and cost system.
Radon appears mainly by diffusion processes from the point of origin following #alpha#- decay of "2"2"6Ra in underground soil and building materials used, in the construction of floors, walls, and ceiling. The transport phenomenon of radon through diffusion is a significant contributor to indoor radon entry. In the present study radon diffusion through sand, cement, mixtures of sand + cement (1:1), sand + cement (2:1), sand + cement (3:1), sand + cement (4:1) has been carried out using LR-115 type II solidstate nuclear track detectors (SSNTDs). The radon diffusion coefficient and diffusion lengths have been calculated for different materials. The effect of compaction, which changes the porosity and permeability of the materials, on radon diffusion has also been studied. (author)
In the formation of A-15 superconducting compounds by solidstate diffusion, the time exponent in the growth law under different experimental conditions varies widely from about 0.25 to 1.0. Specific models of growth for different operative rate-controlling conditions are proposed. When the diffusion of B atoms in the matrix is rate-controlling, the thickness of the reacted compound layer increases as tsup(1/2) or tsup(2/3). When the diffusion of B atoms through the compound layer is rate controlling, a tsup(1/2) dependence both for bulk diffusion and grain-boundary diffusion is predicted. When substantial grain growth occurs in the reacted layer during the diffusion anneal, the time exponent observed could be as low as 1/4. Experimental data in support of the predictions of the proposed models are presented. (author).
An all solid-state kicker pulser for a proton radiography system has been designed. Multiple solid-state modulators stacked in an inductive-adder configuration are utilized in this kicker pulser design. Each modulator is comprised of multiple metal-oxide-semiconductor field-effect transistors (MOSFETs) which quickly switch the energy storage capacitors across a magnetic induction core. Metglas is used as the core material to minimize loss. Voltage from each modulator is inductively added by a voltage summing stalk. A circuit model of a prototype inductive adder kicker pulser modulator has been developed to predict the performance of the pulser modulator. The modeling results are compared with experimental data.
Super light and high performance Mg{sub 2}Si/Mg composites, which had excellent mechanical properties, were developed via the combination of solid-state synthesis and hot extrusion process. In this study, cold compacting (CP) and repeated plastic working (RPW) were firstly carried out for the mixture of Mg-Si powders, and the refinement of both Mg grains and dispersoids. Each specimen was evaluated by observation of microstructure and tensile test. As a result, it was understood that Mg{sub 2}Si dispersoids were refined and dispersed into Mg matrix, and were flowed along extrusion direction. And their mechanical properties were higher than the conventional die casting alloys. Also the effect of RPW as the improvement of properties and the decrease of synthesis temperature were confirmed. (orig.)
Abstract Here we propose a software for the estimation of the occupied area and volume of fungal cultures. This software was developed using a Matlab platform and allows analysis of high-definition images from optical, electronic or atomic force microscopes. In a first step, a single hypha grown on potato dextrose agar was monitored using optical microscopy to estimate the change in occupied area and volume. Weight measurements were carried out to compare them with the estimated volume, revealing a slight difference of less than 1.5%. Similarly, samples from two different solid-state fermentation cultures were analyzed using images from a scanning electron microscope (SEM) and an environmental SEM (ESEM). Occupied area and volume were calculated for both samples, and the results obtained w...
Chapter one is a review of the relevant literature. In chapter two the coordination chemistry of biphenyl-tailed terpyridines with octahedral metal dications is investigated. The effect of different metal ions on their aggregation modes in the solidstate is also investigated. In chapter three the coordination chemistry of polyaryl-tailed terpyridines with octahedral metal dications is investigated. The effect of different aryl tails on their aggregation modes in the solidstate is investigated. In chapter four the pi-pi aggregation of molecular boxes through biphenyl tails is studied. In chapter five the immobilisation of aryl tailed complexes into polyelectrolyte films has been investigated, and the arrangement of these complexes in the films has been compared with same complexes in the crystal, thus moving from three dimensional aggregation to two dimensions.
Solidstate nuclear track detectors (SSNTD) are widely used for radon measurements and CR-39 is one of the most popular SSNTD. In this work it was determined the calibration factor for radon concentration measurements through the passive method with CR-39 detectors. The detectors were put in a proper device (an adapted Lucas cell) and exposed to the standard radon concentration through the Pylon Model RN-150 flow through radon gas source. After exposure, the detectors were etched for 5.5 hours in a KOH solution at 80 deg C in a bath at a constant temperature. The track density was read in an Axiolab-Zeiss optical microscope, with nominal magnification of X10 connected to a video camera and to a personal computer. The calibration factor was obtained through the relation between standard radon concentration, track density and exposure time. (author)
Solidstate nuclear track detectors (SSNTD) are widely used for radon measurements and CR-39 is one of the most popular SSNTD. In this work it was determined the calibration factor for radon concentration measurements through the passive method with CR-39 detectors. The detectors were put in a proper device (an adapted Lucas cell) and exposed to the standard radon concentration through the Pylon Model RN-150 flow through radon gas source. After exposure, the detectors were etched for 5.5 hours in a KOH solution at 80 deg C in a bath at a constant temperature. The track density was read in an Axiolab-Zeiss optical microscope, with nominal magnification of X10 connected to a video camera and to a personal computer. The calibration factor was obtained through the relation between standard radon concentration, track density and exposure time. (author)
Blow forming characteristics of 5083 Al alloy and AZ31 Mg alloy recycled by solidstate recycling were investigated. Scraps with different volume were recycled by hot extrusion and hot rolling in air. Oxide layers, which were contaminants from scrap surface, were distributed parallel to the extrusion direction in the recycled specimens. In the blow-forming test, the specimen from smaller scraps exhibited lower formability. The oxygen concentration in the recycled specimens was approximately proportional to the total surface area of scraps in the recycled specimen per unit volume. The low formability of the recycled specimens is likely to be attributed to contamination level of oxide. (orig.)
This report summarizes the progress of the Basic Sciences Branch of the National Renewable Energy Laboratory (NREL) from October 1, 1989, through September 30, 1990. Six technical sections of the report cover these main areas of NREL's in-house research: Semiconductor Crystal Growth, Amorphous Silicon Research, Polycrystalline Thin Films, III-V High-Efficiency Photovoltaic Cells, Solid-State Theory, and Solid-State Spectroscopy. Each section of the report was written by the group leader principally in charge of the work. The task in each case was to explain the purpose and major accomplishments of the work in the context of the US Department of Energy's National Photovoltaic Research Program plans.
This report summarizes the progress of the Basic Sciences Branch of the National Renewable Energy Laboratory (NREL) from October 1, 1989, through September 30, 1990. Six technical sections of the report cover these main areas of NREL`s in-house research: Semiconductor Crystal Growth, Amorphous Silicon Research, Polycrystalline Thin Films, III-V High-Efficiency Photovoltaic Cells, Solid-State Theory, and Solid-State Spectroscopy. Each section of the report was written by the group leader principally in charge of the work. The task in each case was to explain the purpose and major accomplishments of the work in the context of the US Department of Energy`s National Photovoltaic Research Program plans.
The binding of amphiphilic molecules to lipid bilayers is followed by 19F NMR using chemical shift and line shape differences between the solution and membrane-tethered states of...Full Text Available
A technique of low-field pulsed proton nuclear magnetic resonance (NMR) spin relaxation is described for assessment of age-related structural changes (dentin and pulp) of human teeth in...Full Text Available
Addition of the silane PPh[sub 2]CH[sub 2]CH[sub 2]SiMe[sub 2]H (chelH, 1a) to Pt(COD)[sub 2] (COD = cycloocta-1,5-diene) affords in high yield the cis-bis chelate Pt(chel)[sub 2] (2); formation of the same product from Pt(COD)(X)Y (X = Y = Me; X = Me, Y = Cl) has been shown by NMR spectroscopy ([sup 1]H, [sup 31]P, [sup 195]Pt) to proceed via prior coordination of chelH through P to afford Pt(chelH)[sub 2](X)(Y) (cis and trans isomers) and through intermediacy of PtH(chel)[sub 2]Cl (22) in which P trans to Si at Pt(IV) leads to an exceptionally low [sup 2]J(Pt-P) = 1084 Hz. Cleavage of Pt-Si bonds in 2 by HCl can be controlled to give the monochelate species Pt(chel)(chelH)Cl (7), from which chelH is displaced by PMe[sub 2]Ph, or trans-PtH(PPh[sub 2]CH[sub 2]SiMe[sub 2]Cl)[sub 2]Cl (9). Products related to 9 result from Pt-Si bond cleavage by I[sub 2] or MeI. Using the analogue PPh[sub 2]CH[sub 2]CH[sub 2]SiMe(Ph)H (1c) of ...
The hyperfine splitting in the rotational levels of the C/sub 2/H molecule is calculated as far as N = 10. Line strengths and transition probabilities are determined for permitted transitions with DN = 1, DF = 0, +- 1.
A multi-technique approach was employed to study a decorated Egyptian wooden sarcophagus (XXV?XXVI dynasty, Third Intermediate Period), belonging to the Museo del Vicino Oriente of the Sapienza University of Rome. Portable non-invasive unilateral NMR was applied to evaluate the conservation state of the sarcophagus. Moreover, using unilateral NMR, a non-invasive analytical protocol was established to detect the presence of organic substances on the surface and/or embedded in the wooden matrix. This protocol allowed for an educated sampling campaign aimed at further investigating the state of degradation of the wood and the presence of organic substances by 13C cross polarization magic angle spinning (CPMAS) NMR spectroscopy. The composition of the painted layer was analysed by optical micr...
The known biological functions of RNA have expanded in recent years and now include gene regulation, maintenance of sub-cellular structure, and catalysis, in addition to propagation of genetic information. As for proteins, RNA function is tightly correlated with structure. Unlike proteins, structural information for larger, biologically functional RNAs is relatively limited. NMR signal degeneracy, relaxation problems, and a paucity of long-range {sup 1}H-{sup 1}H dipolar contacts have limited the utility of traditional NMR approaches. Selective isotope labeling, including nucleotide-specific and segmental labeling strategies, may provide the best opportunities for obtaining structural information by NMR. Here we review methods that have been developed for preparing and purifying isotopically labeled RNAs, as well as NMR strategies that have been employed for signal assignment and structure ...
The solidstate reaction between a Pd thin film and a Si substrate produces a single new phase, Pd/sub 2/Si, for temperatures <700/sup 0/C. When the substrate is a single crystal of (111) surface orientation, this process is particularly interesting because the silicide grows epitaxially. Growth of epitaxial interfacial Pd/sub 2/Si was the focus of this study using X-ray diffraction techniques.
Single phase amorphous Al_xHf_1_0_0_-_x alloys with a wide amorphization range (33#<=#x#<=#75) were synthesized by the solid-state interdiffusion of pure polycrystalline Al and Hf powders at room temperature using a rod-milling technique. The mechanisms of metallic glass formation and competing crystallization processes in the mechanically deformed composite powders were investigated by means of X-ray diffraction, differential thermal analysis, scanning electron microscopy and transmission electron microscopy. The numerous intimate layered composite particles of the diffusion couples that formed during the first and intermediate stages of milling (0-173 ks) are intermixed to form amorphous phase(s) upon heating to about 980 K by so-called thermally assisted solid-state amorphization (TASSA). The amorphization heat formation for the binary Al_xHf_1_0_0_-_x system via TASSA, #DELTA#H"T"A"S"S"A_a, was measured directly as a function of the ...
Powder mold type solidstate battery was fabricated, and positive electrode compounding ratio and the battery characteristics were studied. The current density depended greatly on the TiS2 content of positive electrode material, and the current density showed maximum value of 800 {mu}A/cm{sup 2} at a TiS2 content of 40 wt%. This composition is expected to be the best to provide better charge-discharge characteristics. The rate capability of TiS2 is dominated by Li{sup +} ion in positive electrode. Further, the diffusion of lithium ion is greatly dominated by TiS2 in positive electrode, compounding ratio of solidstate electrolyte and its particle size. Results of charge-discharge characteristics studied for various charge-discharge current densities revealed that the rate capability of TiS2 was more than 50% for a current density of less than 254 {mu}A/cm{sup 2}, and this battery system proved the ...
Research investigating applicability of lithium salts for solid electrolyte batteries was described. The studies included determinations of lithium ion conductivities in solid electrolyte systems based on Li4SiO4, LiTi2(PO4)3, and ceramic materials. Research on all solidstate lithium cells utilizing TiS2 NiPS3 electrodes was also reported.
Radon concentration measurements were made in the interior of the great pyramid of ''Cheops'' at Giza. Measurements were carried out using CR-39 as a solidstate nuclear track detector. The CR-39 sheets were placed inside the Queen's and King's chambers and along the ascending corridor leading to them. An evaluation of the radon concentration is presented and discussed. (author).
Radon concentration measurements were made in the interior of the great pyramid of ''Cheops'' at Giza. Measurements were carried out using CR-39 as a solidstate nuclear track detector. The CR-39 sheets were placed inside the Queen's and King's chambers and along the ascending corridor leading to them. An evaluation of the radon concentration is presented and discussed. (author).
Radon concentration measurement in the ground can be used for the prospecting for uranium and earthquake prediction. Some results of radon concentration measurement in the soil are presented here. The moisture condensation at the detector surface can affect on the detection efficiency. Due to this problem we tested a few filter papers on water permeability. The ratio of track densities on solidstate nuclear track detector (SSNTD) in the open and the closed diffusion chamber is also determined. (author)
We describe the continued development of a portable, real-time neutron spectrometer. The spectrometer is composed of two distinct detector systems: a Helium 3 gas filled proportional counter for the lower neutron energy interval between 20 KeV and 2 MeV and a bulk silicon solidstate detector for the higher energy interval between 2 MeV and 500 MeV. Modeling and experimental results with mono-energetic neutron beams are reported.
We describe the early stage of development of an engineering model portable, real-time neutron spectrometer. Several systems of two distinct detector types, a helium 3 gas filled proportional counter and a bulk silicon solidstate detector, will be necessary to cover the energy range from thermal to 500 MeV. The advantages and disadvantages of using a moderator were investigated experimentally.
We report acceleration of electrons moving in free space near an active Nd:YAG slab. The power of a non-relativistic beam of electrons has increased by more than 30% when the medium was excited. It is demonstrated experimentally that the energy gained by the electrons is linearly proportional to the energy stored in the medium. Moreover, the energy gain traces closely the population inversion inferred by monitoring the spontaneous radiation.
In the present study the Pb content in Bi(2223) phase by regression or curve fitting method are optimized. The best fitting curve can be obtained by the method of least square. To study the effect of Pb content in Pb substituted Bi (2223) superconductors, prepared by solidstate reaction method data is obtained. The deviation of T_c from the target value for different Pb content is summarized
AC/DC voltage standards based entirely on solid-state references used as secondary, working, or transfer standards is widespread, although metrological performance is typically defined only via comparison with a higher level standard. The present report shows the improvements of the output metrological characteristics of an ac/dc calibrator by establishing three internal hierarchical levels of dc voltage references and by constant calibration of ac measuring circuits.
The hard-sphere radial distribution functions, g_H_S(r/d,#eta#), for the face-centered cubic and hexagonal close-packed phases have been computed by the Monte Carlo method at nine values of the packing fraction, #eta#[=(#pi#/6)#rho#d"3], ranging from 4% below the melting density to 99% of the close-packed density. The Monte Carlo data are used to improve available analytic expressions for g_H_S(r/d,#eta#). By utilizing the new g_H_S(r/d,#eta#) in the Henderson and Grundke method [J. Chem. Phys. 63, 601 (1975)], we next derive an expression for y_H_S(r/d,#eta#) [=g_H_S(r/d)exp#left brace##beta#V_H_S(r)#right brace#] inside the hard-sphere diameter, d. These expressions are employed in a solid-state perturbation theory [J. Chem. Phys. 84, 4547 (1986)] to compute solid-state and melting properties of the Lennard-Jones and inverse-power potentials. Results are in close agreement with Monte Carlo and lattice-dynamics calculations performed in this ...
An apparatus for sensing chemicals over extended range of concentrations. In particular, first and second sensors each having separate, but overlapping ranges for sensing concentrations of hydrogen are provided. Preferably, the first sensor is a MOS solidstate device wherein the metal electrode or gate is a nickel alloy. The second sensor is a chemiresistor comprising a nickel alloy.
Effect of ultrasonic-wave irradiation on the Mn-Zn ferrite powder suspension prepared by solid-state reaction and alcoholic dehydration methods was investigated. Size, distribution, and morphology of the powders prepared at different temperatures were examined, as a function of irradiation time. It was observed that the powders were reduced in size by ultrasonic energy through distinct routes. 8 refs., 7 figs., 1 tab.
Solidstate effects are taken into account in an internal conversion coefficients computation by using Wigner-Seitz boundary conditions. Both the bound and free electron wave functions are calculated from an atomic Dirac-Hartree-Fock-Slater self consistent potential. These internal conversion coefficients are compared with those obtained from the usual free atom boundary conditions.
Solidstate effects are taken into account in an internal conversion coefficients computation by using Wigner-Seitz boundary conditions. Both the bound and free electron wave functions are calculated from an atomic Dirac-Hartree-Fock-Slater self consistent potential. These internal conversion coefficients are compared with those obtained from the usual free atom boundary conditions. (orig.).
Surface barrier detectors may be damaged, because of microplasma breakdown, in rapid application of bias voltage. The high performance FETs of very low noise preamplifiers may also be damaged by rapid changes of the bias voltage. The electronic device described permits the gradual application and removal of the bias voltage, without any influence on the power supply specification. (Auth.).
The authors present design methodology and initial experimental results for a high power microwave switch. The switch is designed for application to the pulse compression system associated with the Next Linear Collider Test Accelerator (NLCTA). The switch is based on the excitation of a plasma layer within a silicon wafer by either a laser or an electron beam. They investigate problems associated with high power operation of such a switch. They explore solutions to the problems of thermal runaway, avalanche breakdown, photo-emission, and secondary emission.
We propose a novel scheme for scalable solidstate quantum computing, where superconducting microwave transmission line resonators (cavities) are arranged in a two-dimensional grid on the surface of a chip, coupling to superconducting qubits (charge or flux) at the intersections. We analyze how tasks of quantum information processing can be implemented in such a topology, including efficient two-qubit gates between any two qubits on the grid and elements of fault-tolerant computation.
An attempt to determine lysozyme hydration by employing a proton nuclear magnetic resonance (NMR) spin-echo technique and to correlated such measurements with the 20 "0C sorption equilibrium data is made. Determinations of specific site hydration for lysozyme, as well as proton NMR transverse relaxation rates for five different types of water populations in the lysozyme-water system, are presented over the whole range of lysozyme concentrations. The proton spin-echo NMR results are consistent with a three-component analysis of the sorption isotherm up to 70% water content, above which two additional water populations are identified by 360-MHz proton NMR spin-echoes. On the basis of the proton NMR results, a major component (III) of the lysozyme sorption isotherm is assigned to the water trapped between lysozyem molecules, whose relaxation rate is increased by diffusion barriers. The ...
As part of efforts to develop improved methods for NMR protein sample preparation and structure determination, the Northeast Structural Genomics Consortium (NESG) has implemented an NMR screening pipeline for protein target selection, construct optimization, and buffer optimization, incorporating efficient microscale NMR screening of proteins using a micro-cryoprobe. The process is feasible because the newest generation probe requires only small amounts of protein, typically 30-200 ?g in 8-35 ?l volume. Extensive automation has been made possible by the combination of database tools, mechanization of key process steps, and the use of a micro-cryoprobe that gives excellent data while requiring little optimization and manual setup. In this perspective, we describe the overall process used by the NESG for screening NMR samples as part of a sample optimization process, assessing optimal construct design and ...
One-electron reduction of the square-planar nickel precursor (PNP)NiCl ( 1) (PNP (-) = N[2-P(CHMe 2) 2-4-methylphenyl] 2) with KC 8 effects ligand reorganization of the pincer ligand to assemble a Ni(I) dimer, [Ni(mu 2-PNP)] 2 ( 2), containing a Ni 2N 2 core structure, as inferred by its solid-state X-ray structure. Solution magnetization measurements are consistent with a paramagnetic Ni(I) system likely undergoing a monomer dimer equilibrium. The room-temperature and 4 K solid-state X-band electron paramagnetic resonance (EPR) spectra display anisotropic signals. Low-temperature solid-state X-band EPR data at 4 K reveal rhombic values g z = 1.980(4), g x = 2. 380(4), and g y = 2.225(4), as well as a forbidden signal at g = 4.24 for the Delta M S = 2 half field transition, in accord with 2 having two weakly interacting metal centers. Utilizing an S = 1 model, full spin Hamiltonian simulation of the low-temperature EPR ...
The fluorescence properties of protopine and allocryptopine in aqueous and organic environments are described for the first time. The fluorescence of alkaloids and their pH-dependent interconversion to cationic forms (transannular interaction) were studied using steady-state and time-resolved fluorescence techniques. For the analysis of tricyclic base and cis/trans tetracyclic cations of the alkaloids, NMR and X-ray crystallography were used. - Highlights: ? We describe fundamental fluorescence characteristics of alkaloids protopine and allocryptopine. ? We analyzed the pH-dependent transitions and cis/trans isomerization. ? These two alkaloids can be better distinguished by their fluorescence decay characteristics. ? The fluorescence parameters are related to the NMR and crystallographic structural data.
This work has carried out a molecular structure characterization of two Brazilian plants, Harpalyce brasiliana Benth and Bredemeyera floribunda Wild, using {sup 1} H and {sup 13} C NMR spectroscopy. NMR spectra were presented and analysed, then several structures have been proposed based on spectral data, and finally the structural determination was done 3 refs., 4 figs., 1 tab.
A method to achieve NMR of dilute samples in the earth's magnetic field by applying para-hydrogen induced polarization is presented. Maximum achievable polarization enhancements were calculated by numerically simulating the experiment and compared to the experimental results and to the thermal equilibrium in the earth's magnetic field. Simultaneous 19F and 1H NMR detection on a sub-milliliter sample of a fluorinated alkyne at millimolar concentration (1018 nuclear spins) was realized with just one single scan. A highly resolved spectrum with a signal/noise ratio higher than 50:1 was obtained without using an auxiliary magnet or any form of radio frequency shielding.
The product-operator formalism is the most commonly used tool for describing and designing multidimensional NMR experiments. In spite of its relative simplicity and sound theoretical underpinnings,...Full Text Available
Copper deficiency is associated with impaired brain development and mitochondrial dysfunction. Perinatal copper deficiency was produced in Holtzman rats. In vivo proton NMR...Full Text Available
An assessment is made of the biological effects and physical hazards of static and time-varying fields associated with the NMR devices that are being used for clinical imaging and in vivo spectroscopy. A summary is given of the current state of knowledge concerning the mechanisms of interaction and the bioeffects of these fields. Additional topics that are discussed include: (1) physical effects on pacemakers and metallic implants such as aneurysm clips, (2) human health studies related to the effects of exposure to nonionizing electromagnetic radiation, and (3) extant guidelines for limiting exposure of patients and medical personnel to the fields produced by NMR devices. On the basis of information available at the present time, it is concluded that the fields associated with the current generation of NMR devices do not pose a significant health risk in themselves. However, rigorous guidelines must be followed to avoid ...
Solid-state fermentation of soybean hulls supplemented with wheat bran using a co-culture of Trichoderma reesei and Aspergillus oryzae was performed. Three parameters - initial moisture content, incubation temperature, and initial pH - were optimized in culture flasks using response surface methodology. Parameter optimization was carried out with respect to filter paper activity and b-glucosidase activity in the culture. Temperature of 30^oC, pH of 5, and moisture content of 70% were found to be optimum. Optimized parameters were used for laboratory scale-up in static tray fermenters. The maximum filter paper activity of 10.7FPU/g-ds and b-glucosidase of 10.7IU/g-ds were obtained after 96-h incubation period in static tray fermenters in agreement with optimized activities at shake flask le...
We discuss the possibility of extending solidstate laser technology to high average power and of improving the efficiency of such lasers sufficiently to make them reasonable candidates for a number of demanding applications. A variety of new design concepts, materials, and techniques have emerged over the past decade that, collectively, suggest that the traditional technical limitations on power (a few hundred watts or less) and efficiency (less than 1%) can be removed. The core idea is configuring the laser medium in relatively thin, large-area plates, rather than using the traditional low-aspect-ratio rods or blocks. This presents a large surface area for cooling, and assures that deposited heat is relatively close to a cooled surface. It also minimizes the laser volume distorted by edge effects. The feasibility of such configurations is supported by recent developments in materials, fabrication processes, and optical pumps. Two types of ...
Abstract Lithium-indium oxide is one of the candidate materials as solid-state scintillators for solar neutrinos due to an inverse --decay of 115In to 115Sn. On the other hand, when doped with rare-earth ions such as Eu3+ or Sm3+, it becomes a promising phosphor material. In this report we present a simple solid-state procedure for preparation of LiInO2:Eu3+ powders. X-ray diffraction confirmed prod-uct in tetragonal structural form (space group: I41/amd) and no impurity phases were detected. Then, high resolution photoluminescence emission measurements were performed at room and low temperatures to find 5D0 - 7FJ. Emission kinetics from 5D0 level exhibited pure single exponential behavior with lifetime of about 1.5 ms. Maximum energy splitting of 7F1 manifold is recorded as a function of ...
The growth of SrBi{sub 2}Ta{sub 2}O{sub 9} (SBT) films on top of Pt electrode substrates is an important issue for the fabrication of ferroelectric based memories. In a recent publication, SBT thin films grown using seeded and unseeded procedures were studied by PIXE and RBS. Difficulties and misfits found in the comparison of results from both techniques were, at that time, overcome by physical considerations. These, although not rendering interpretation impossible, left out the possibility of understanding the exact nature of the differences between the interface behavior in each case. In the present work it is shown that the reanalysis of the same data using the recently developed RBS-PIXE simultaneous and self-consistent calculation present in NDF leads to stronger conclusions on the solidstate reaction occurring during the deposition stage for both types of samples. Allowing for the occurrence of solid ...
Useful bipolar transistor action over the full temperature range from 78 to 823K has been demonstrated for mesa-isolated, liquid-phase epitaxial n/sup +/npn, GaP/Al/sub 0/ /sub 35/Ga/sub 0/ /sub 65/P/GaP/GaP structures. This represents both the highest temperature and the widest temperature range (745K) over which useful solid-state transistor action has ever been demonstrated in any III-V compound semiconductor system. These results imply that the GaP/Al/sub x/Ga/sub 1-x/P chemical system is an excellent materials candidate in which to base a technology for high-temperature electronics and the results also imply the very real possibility of functional solid-state devices and circuits at temperatures in excess of 500/sup 0/C.
The relationship between processing, microstructure, and properties was studied for A-15 compounds in multifilamentary composites produced by solid-state diffusion and in thin-film samples produced by vapor deposition. Grain sizes of A-15 superconducting compounds were measured by transmission electron microscopy of multifilamentary composites reacted at various temperatures. Critical current densities at 4.2 K and fields up to 6 T were found to be similar for niobium-tin, vanadium-gallium, and vanadium-silicon of the same grain size. Study of the Cu-V-Si phase diagram led to the production of improved multifilamentary vanadium-silicon conductors. The effects of various alloying elements on A-15 layers produced by solid-state diffusion were studied. The most promising new observation was that tantalum can be incorporated into niobium-tin reaction layers, leading to an enhancement of critical currents at high fields. The critical temperature of ...
A Ni3Al coating was prepared by plasma spraying technique on the surface of titanium alloy. Ni-Al mixed powders, coatings and reaction products were investigated by scanning electron microscope, EDS, DSC and XRD. A tight bonding between the coating and the substrate was formed. The X-ray diffraction analysis of the patterns showed that the coating not only had Ni3Al phase, but also had NiO and Al2O3 phase microcontent. Comparing Ni coated Al to Ni3Al at 900^oC, the diffusion was stronger and the diffusion layer was thicker. A minute pore structure was formed at 1200^oC in the front edge of solid-state reaction layer. So Ni3Al restrained the solid-state reaction of the coating with the substrate, and as a whole weakened the entry of oxygen atoms into the substrate and quenched the out-diffu...
We investigated the effect of pretreatment on the physicochemical characteristics-crystallinity, bed porosity, and volumetric specific surface of soybean hulls and production of cellulolytic enzymes in solid-state fermentation of Trichoderma reesei and Aspergillus oryzae cultures. Mild acid and alkali and steam pretreatments significantly increased crystallinity and bed porosity without significant change inholocellulosic composition of substrate. Crystalline and porous steam-pretreated soybean hulls inoculated with T. reesei culture had 4 filter paper units (FPU)/g-ds, 0.6?IU/g-ds ?-glucosidase, and 45?IU/g-ds endocellulase, whereas untreated hulls had 0.75?FPU/g-ds, 0.06?IU/g-ds ?-glucosidase, and 7.29?IU/g-ds endocellulase enzyme activities. In A. oryzae steam-pretreated soybean hulls had 47.10?IU/g-ds endocellulase compared to 30.82?IU/g-ds in untreated soybean hulls. Generalized linear statistical model fitted to enzyme activity data showed that effects of ...
A new two-step solid-state process was developed for synthesis of a pure phase 4.7 V LiMn{sub 1.5}Ni{sub 0.5}O{sub 4-{delta}} (LMNO) spinel of good electrochemical properties. This process which was based on formation of stable Ni{sub 1-x}Mn{sub 2}O{sub 4-{delta}} (x {<=} 0.33) spinel followed by subsequent lithiation, demonstrated the emerging of LiMn{sub 1.5}Ni{sub 0.5}O{sub 4-{delta}} frame work at temperatures of as low as 350 C. During this lithiation process, migration of metal ions (Ni/Mn) from partially occupied tetrahedral 8a sites (in Ni{sub 0.67}Mn{sub 2}O{sub 4-{delta}}) toward octahedral 16d site occurred. The resultant spinel material displayed low irreversible loss, a 97% columbic efficiency and 6% loss in discharge capacity after 100 cycles at 60 C. (author)
We propose triplet superconductors, such as ruthenates, as prospective materials for qubit construction. The vectorial nature of the order parameter in triplet superconductors makes it conceptually easy to estimate the performance of the qubits. The Cooper condensate of pairs in triplet superconductors has all the attributes of Bose-Einstein condensates and should facilitate long decoherence times for these qubits, relative to other vectorial schemes for qubits, such as small ferromagnets. There are other benefits, which the superconducting state provides for requirements such as entanglement between qubits via the proximity effect, etc. We consider these benefits in detail, although our consideration is only preliminary and further experimental and theoretical research will undoubtedly introduce correctives.
The aim of the report is to describe the state and prospects of the experimental and stand base (ESB) for fundamental investigations in the RF Ministry for Atomic Energy. The ESB includes the following scientific directions: high energy physics, nuclear physics, solidstate physics (including superconductivity), plasma physics and controlled thermonuclear synthesis, nuclear reactors and reactor materials testing, lasers, energy conversion and others. Main economical, scientific and technical data on the ESB as a whole and on its most large scientific centers are presented
We have synthesized ozone by irradiating thin solid films of oxygen and oxygen-water mixtures with 100 keV protons, motivated by recent reports of condensed O_3 on icy satellites in the outer Solar system. We measured the depth of the Hartley absorption band in the ultraviolet by reflectance spectroscopy and used it to quantify the column density of ozone. We analyzed the results using a three-component (O, O_2 and O_3) model that successfully explains the fluence dependence of ozone production.
A solid electrolyte cell comprises an alkali metal anode, e.g. lithium, a halogen-containing organic polymer cathode and a solid elecrolyte between the anode and the cathode. The cathode comprises iodine-containing vacuum-cyclised polyacrylonitrile, and the solid electrolyte is preferably lithium iodide and halogen-free vacuum-cyclised polyacrylonitrile. This patent also discloses the use of isotactic polyacrylonitrile, a method of making a cathode comprising iodine-containing vacuum-cyclised polyacrylonitrile, and novel methods of making the solid elecrolyte cells described.
Lithium orthosilicate (Li_4SiO_4) powder was synthesized by the solid-state reaction of lithium oxide with amorphous silica, and the effects of fabrication parameters on the structural characteristics of the product were investigated. Processing considerations such as milling media, drying technique, calcination time and temperature, pressing behavior, sintering time and temperatures, and impurity concentration were addressed. The initial powder particle size was observed to be important in achieving high sintered density, with densities as high as 98% TD achieved with a particle size of approximately 1 #mu#m. 9 refs., 6 figs.
Methylmethacrylate polymerisation in the presence of 4 wt% butadiene-acrylonitrile rubber was carried out at fixed dose-rate and temperature. The effect of irradiation was investigated with respect to the mechanical and dynamic-mechanical properties in the solidstate. A general increase of the 'compatibilisation' on irradiation is obtained. In fact both rubber and polymethylmethacrylate glass transition temperatures, determined through dynamic-mechanical analysis, reveal the presence of strong interactions between the components. Furthermore an improvement of the mechanical tensile properties of the blends is observed when irradiation is continued after polymerisation, at least until a certain absorbed dose.
Tb3+-activated Sr3AlO4F phosphors were synthesized by a high-temperature solid-state reaction method. The investigation of photoluminescence and cathodoluminescence indicates that these phosphors can be effectively excited by ultraviolet light and low-voltage electron beam. The phosphors exhibit a tunable-green emission. The luminescence behaviors are explained by the site occupancy of Tb3+ ions in the host crystal and the cross-relaxation of 5D3 to 5D4 state.
Tb3+-activated Sr3AlO4F phosphors were synthesized by a high-temperature solid-state reaction method. The investigation of photoluminescence and cathodoluminescence indicates that these phosphors can be effectively excited by ultraviolet light and low-voltage electron beam. The phosphors exhibit a tunable-green emission. The luminescence behaviors are explained by the site occupancy of Tb3+ ions in the host crystal and the cross-relaxation of 5D3 to 5D4 state.
It is discussed here how trustworthy predictions of etched track parameters in nuclear track detection technique can be made? Problems involved in doing so are described along with discussion about their possible solutions. Arguments are presented using 5.2 MeV alpha particle track etching experiments with CR-39 detector and corresponding calculations using computer programs TRACK{sub V}ISION and TRACK{sub T}EST. Experimental and computational results in the present paper are useful for further basic research and technology applications of solidstate nuclear track detection technique.
Cr_2O_3 scales are found to form on Alloy 800 and a similar pure ternary alloy in air, and 1 and 50 atm. helium containing oxidizing impurities typical of those in an SGHTR. The strong temperature dependence and neglibible helium overpressure dependence indicate that gas transport through the scales is not rate controlling. Surface oxidation rates are therefore controlled by solidstate diffusion and the low oxygen partial pressure dependence of the oxidation rate in Alloy 800 is ascribed to the presence of extrinsic defects in the Cr_3O_3 (due to doping by alloying elements) or to the presence of short circuit diffusion paths. (Auth.).
High-power diode laser arrays emitting at 690 nm have been developed for solid-state laser pumping. The laser diode bars (fill factor [approx]0.7) have been fabricated from single quantum well AlGaInP-based heterostructures. Using silicon microchannel heatsinks, a record high 360 W/cm[sup 2] per emitting aperture is achieved under continuous wave operation.
Compton backscattering of laser photons near the interaction point of an e"+e"- or e"-e"- collider can be used to produce a #gamma#-#gamma# or #gamma#-e"- collider. This paper describes the laser requirements, including pulse duration, intensity, energy, and wavelength, for such a collider. For most of the proposed, next generation, e"+e"- colliders, the laser wavelength should be in the near-infrared, with a pulse duration of 1 ps or less and an energy of similar 1 J per pulse. Current chirped pulse amplification laser systems in solidstate lasing materials are well suited to meet these requirements. These systems are described. ((orig.)).
The development status of the EE-1 Small Community Solar Thermal Power Experiment (SCSE Program) is presented. Current activities on the Phase II single module development effort are presented, together with plans for a Phase III 1 MW/sub e/ demonstration plant. A description of the various subsystems and components is given with a brief review of their development background. Latest performance figures are given for a 1 MW/sub e/ plant, based on 56 power modules, each consisting of a 12m parabolic dish concentrator, a cavity receiver, an organic Rankine power conversion subsystem and a ground-mounted solid-state rectifier.
The authors present design methodology for high power microwave switches. Among all possible applications for such a switch they emphasize the design parameters for application to the pulse compression system associated with the Next Linear Collider (NLC). The switch is based on the excitation of a plasma layer within a silicon wafer by either a laser or an electron beam. They investigate problems associated with high power operation of such a switch. Mainly, they explore solutions to the problems of thermal runaway, avalanche breakdown, photo-emission, and secondary emission. Different design methodologies are presented.
This is the homepage of "an Australian multi-university collaboration undertaking research on the fundamental physics and technology of building, at the atomic level, a solidstate quantum computer in silicon together with other high potential implementations." Although attempts to develop a quantum computer have met with limited success, the centre has substantial resources invested in advancing toward practical uses of quantum computing technology. The site provides a very good introduction to the principles and implications of quantum computing, as well as details about various research projects underway at the Australian universities. Links to conference and journal papers produced by members of the centre, many from 2003, are also provided.
Calcium stannate (CaSnO3) powders with the distorted perovskite structure have been synthesized by solidstate and the sol-gel methods and their electrochemical performance was compared. The sol-gel CaSnO3 shows stable cycling performance with a reversible capacity of 430-440 mAh/g (0.005-1.0 V; 60 mA/g) up to 50 cycles. The role of preparatory conditions, morphology and cycling conditions (current density and potential window) on the anodic performance of the compounds are addressed.
The proposed short wavelength coherent light source driven by the SLAC 3 km linac might be used to induce transitions between nuclear isomeric states. If an isotope were found with energetically adjacent isomeric states, one short-lived and one long-lived, and it were possible to separate and concentrate the long-lived species, and other nuclear and solid-state parameters were favorable, it might be possible to convert sufficient population to the short-lived state to realize [gamma]-ray lasing. Even if the x-ray intensity were insufficient, study of such driven transitions would be quite valuable.
The proposed short wavelength coherent light source driven by the SLAC 3 km linac might be used to induce transitions between nuclear isomeric states. If an isotope were found with energetically adjacent isomeric states, one short-lived and one long-lived, and it were possible to separate and concentrate the long-lived species, and other nuclear and solid-state parameters were favorable, it might be possible to convert sufficient population to the short-lived state to realize {gamma}-ray lasing. Even if the x-ray intensity were insufficient, study of such driven transitions would be quite valuable.
Solid-state acoustic sensors for monitoring conditions at a surface immersed in a liquid and for monitoring concentrations of species in a liquid and for monitoring electrical properties of a liquid are formed by placing interdigital input and output transducers on a piezoelectric substrate and propagating acoustic plate modes therebetween. The deposition or removal of material on or from, respectively, a thin film in contact with the surface, or changes in the mechanical properties of a thin film in contact with the surface, or changes in the electrical characteristics of the solution, create perturbations in the velocity and attenuation of the acoustic plate modes as a function of these properties or changes in them.
We describe a scheme for quantum error correction that employs feedback and weak measurement rather than the standard tools of projective measurement and fast controlled unitary gates. The advantage of this scheme over previous protocols (for example Ahn et. al, PRA, 65, 042301 (2001)), is that it requires little side processing while remaining robust to measurement inefficiency, and is therefore considerably more practical. We evaluate the performance of our scheme by simulating the correction of bit-flips. We also consider implementation in a solid-state quantum computation architecture and estimate the maximal error rate which could be corrected with current technology.
We have developed a new type personal dosemeter by using a B-10 doped silicon p-n junction detector with a polyethylene radiator and a polyethylene moderator. The purpose of this study was to develop a real time neutron dosemeter with a nearly flat response in the energy range from thermal to 15 MeV and low angular dependence to the incident neutron direction. The neutron response of the dosemeter was obtained with the Monte Carlo calculation and the monoenergetic neutron experiment in a free air field and also under a condition attached on a phantom.
The existence of n-particle n-hole deformed yrare bands in the N=28 isotones is explored using full pf-shell diagonalizations and the Lanczos Strength Function method. We find different 2p-2h and 4p-4h collective bands that, when allowed to mix, more often disappear. Only the 2p-2h yrare band in Cr-52 and the 4p-4h yrare band in Ni-56 survive, and only in this latter case, due to the reduced density of 2p-2h states, can the band be seen as a gamma-cascade.
The Wind2H2 system is fully functional and continues to gather performance data. In this report, specifications of the Wind2H2 equipment (electrolyzers, compressor, hydrogen storage tanks, and the hydrogen fueled generator) are summarized. System operational experience and lessons learned are discussed. Valuable operational experience is shared through running, testing, daily operations, and troubleshooting the Wind2H2 system and equipment errors are being logged to help evaluate the reliability of the system.
Ethanol has excellent fuel properties, such as high octane, high heat of vaporization and low photochemical reactivity in the atmosphere. It is less volatile than gasoline and there is lower smog formation from evaporative emissions of pure ethanol compared to gasoline. As such, ethanol has emerged as an important alternative energy source that is sustainable, efficient, cost effective, convenient and safe. In 2006, global production of ethanol reached 13.5 billion gallons, up from 12.1 billion gallons in 2005. However, in light of the current debate of food versus fuel, the industry must shift to non-food feedstocks. This paper described an emerging technology to cost-effectively produce ethanol from sweet sorghum stalks, the most promising alternative feedstock to corn, via solidstate fermentation (SSF). Experiments of advanced solidstate fermentation (ASSF) for ethanol production from sweet sorghum ...
Molar excess enthalpies and molar excess volumes are reported for the systems H_2O + (C_2H_5)_3N and D_2O + (C_2H_5)_3N at temperatures below and above their lower critical solution temperatures. The molar excess enthalpies are slightly less exothermic for the D_2O system. The molar excess volumes of the H_2O and D_2O systems are within experimental error of one another. Compositions of conjugate solutions estimated from the calorimetric and volumetric measurements agree with those obtained from published liquid-liquid phase diagrams. (Auth.).
Moessbauer spectra of the Fe(III) compounds (C[sub 2]H[sub 5])[sub 4]NFeX[sub 4] (X = Cl, Br) exhibit the following anomalies above [approx] 260 K: (i) the f-factor drops with respect to normal thermal behavior, (ii) the second-order Doppler shift drops similarly, (iii) the single-line spectrum broadens, becoming asymmetric at room temperature. These phenomena are discussed in relation to possible phase transitions in these systems. (orig.)
In this study, bone mineral density (BMD) of normal (CON), ovariectomized (OVX) and partially nephrectomized (NFR) rats was measured by 31P NMR spectroscopy; bone matrix density was...Full Text Available
Lithium tetrachloroaluminate solutions in thionylchloride, methylacetate and their mixtures are studied by "7Li and "2"7Al NMR. It is found that introduction of methylacetate in the LiAlCl_4-SOCl_2 system results in a change of lithium tetrachloroaluminate formation constant. In the ternary system, Li"+ is solvated by methyl-acetate after complete destruction of tetrachloroaluminate anion. Refs. 9, figs. 2.
Here we report the first 1H NMR metabolomics studies on excised lungs and bronchoalveolar lavage fluid (BALF) from mice exposed to crystalline silica. High resolution 1H...Full Text Available
Interactions of myristic acid with bovine serum albumin were studied by 13C NMR spectroscopy at 50.3 MHz using 90% isotopically substituted [1-13C]-, [3-13C]-, and [14-13C]myristic acids, either individually...Full Text Available
The bioenergetic capacity of skeletal muscle in a 17-year-old patient with a severe defect in complex III of the electron transport chain has been examined by 31P NMR measurements of the molar ratio...Full Text Available
31P nuclear magnetic resonance (NMR) spectroscopy was used to monitor the response of oil palm (Elaeis guineensis) and carrot (Daucus carota) cell suspensions...Full Text Available
The shifts induced by equimolar mixture of typical lanthanide shift reagent such as 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octadionato europium with silver trifluoroacetate in /sup 1/H NMR spectra of aromatic hydrocarbons have been used for analytical purposes; the NMR determination of m- and p-xylenes in mixtures has been chosen as an example. The use has been made of the difference between induced shifts of methyl group signals in the /sup 1/H NMR spectra of m- and p-xylenes. The magnitude of induced shifts of methyl groups signal in m-xylene is always larger than that of p-isomer, irrespective of contents of m- and p-xylenes in mixture.
A general method for stable-isotope labeling of large proteins is introduced and applied for studies of the E. coli GroE chaperone proteins by solution NMR. In addition to enabling the residue-specific {sup 15}N-labeling of proteins on a highly deuterated background, it is also an efficient approach for uniform labeling. The method meets the requirements of high-level deuteration, minimal cross-labeling and high protein yield, which are crucial for NMR studies of structures with sizes above 150 kDa. The results obtained with the new protocol are compared to other strategies for protein labeling, and evaluated with regard to the influence of external factors on the resulting isotope labeling patterns. Applications with the GroE system show that these strategies are efficient tools for studies of structure, dynamics and intermolecular interactions in large supramolecular complexes, when combined with TROSY- and CRINEPT-based experimental ...
MRI diagnosis for malignant tumors are made possible by direct comparison to the results obtained by the brain and it seems possible to differentiate malignant tumors from other benign lesions. Cystic lesions, and mycotic sinusitis sometimes resemble malignant tumors in MR Image. In the present report, we investigated the relationships between the biochemical contents of cystic lesions and NMR-parameters to clarify why some inflammatory lesions appeared similar to malignant tumors in MRI. The variation of relaxation time depends upon the amount of protein in the cystic contents and the amount of glucose affects the relaxation time. We conclude that NMR-parameters are useful for the differential diagnosis of malignant tumors, cystic lesions and mycositic sinusitis by using the multiple variation analysis.
{sup 1}H, {sup 13}C, {sup 27}Al, and {sup 29}Si magic-angle-spinning (MAS) NMR was used to elucidate the nature of the catalytic activity of zeolite H-ZSM-5. {sup 1}H MAS NMR of sealed samples after mild hydrothermal dealumination shows that the enhanced activity for n-hexane cracking is not due to an enhanced Bronstead acidity. The concentrations of the various OH groups and aluminous species suggest that the reason for the enhanced catalytic activity is the interaction of the n-hexane molecule with a bridging hydroxyl group and with extra-framework aluminium species, which give rise to the enhanced activity, cannot be easily removed from their positions, and are therefore immobilized by the zeolitic framework.
The effect of treatment of Na-forms of zeolites with HCl solutions and of heat treatment of their NH/sub 4/-forms on the stability of aluminum-oxygen tetrahedra has been studied in this work by high-resolution NMR on /sup 29/Si nuclei, using the synthetic zeolites X, Y, and M (mordenite) as the objects of the study. The exchange capacity with respect to Na/sup +/ ions was determined by analyzing the equilibrium solutions after contact of the samples with 0.5 NH/sub 4/Cl solution on a flame photometer. The high-resolution /sup 29/Si NMR spectra of polycrystalline samples were recorded on an SKhR-200 spectrometer with a superconducting solenoid at a frequency of 39.75 MHz with ultrafast mechanical rotation (3 kHz) of the sample at the magic angle to the external magnetic field. The results obtained are given.
This study compares the microstructure and mechanical properties of plain and 0.9 or 3.6 wt% VC- or Cr{sub 3}C{sub 2}-doped WC-12 wt% Co hardmetals with 40 wt% NbC, prepared by pulsed electric current sintering (PECS) in the solidstate for 4 min at 1240 deg. C and conventional pressureless liquid phase sintering (CS) for 1 h at 1420 deg. C. The addition of VC or Cr{sub 3}C{sub 2} was found to inhibit grain growth of the residual WC grains, whereas the size of the solid solution (Nb,W,V/Cr)C grains was hardly influenced. The type of grain growth inhibitor and densification temperature however, strongly influenced the composition of the NbC solid solution formed, which was thermodynamically and experimentally assessed.
Mesoporous films of platinized carbon nanotube-zirconia-Nafion composite have been used for the immobilization of tris(2,2prime-bipyridyl)ruthenium (II) (Ru(bpy)32+) on an electrode surface to yield a solid-state electrogenerated chemiluminescence (ECL) sensor. The composite films of Pt-CNT-zirconia-Nafion exhibit much larger pore diameter (3.55 nm) than that of Nafion (2.82 nm) and thus leading to much larger ECL response for tripropylamine (TPA) because of the fast diffusion of the analyte within the films. Due to the conducting and electrocatalytic features of CNTs and Pt nanoparticles, their incorporation into the zirconia-Nafion composite films resulted in the decreased electron transfer resistance within the films. The present ECL sensor based on the Pt-CNT-zirconia-Nafion gave a lin...
A new method for kinetic experiments with neutrons is described. This method combines the conventional triple-axis neutron spectroscopy with relaxation-type experiments. Whereas the former method yields information about the microscopic dynamics of solids, the latter provides macroscopic relaxation times. The combination of both methods allows to determine the microscopic mechanism of relaxation processes. The time-resolved triple-axis spectroscopy is limited to reversible processes and to time scales from 10"-"3 to 10"4 s. Typical applications are the kinetics of phase transformations (structural and dynamical changes), kinetics of domain distributions, kinetics of (spinodal) decomposition, reversible solidstate reactions, time-dependent occupation of phonon states or phonon lifetimes. (orig.).
Abstract Thermomechanical behavior of membranes based on blends of poly(vinyl alcohol) (PVA) with different weight percentage (wt %) of glycerol has been studied. Solid-state PVA/Glycerol polymer membranes were prepared by a solution casting method. The films were studied for thermal characteristics by differential scanning calorimetry (DSC) and thermogravimetric analysis and for the mechanical properties including hardness and modulus by nanoindentation method. The dispersion of glycerol within the polymer matrix was examined using scanning electron microscopy. Fourier transform infrared spectroscopy was used to confirm the formation of hydrogen bonding between the plasticizer and PVA in their blends and also to provide information on compatibility and physical interactions between the gl...
La{sub 1-x}Sr{sub x}MnO{sub 3} (LSMO) compounds (0.175{<=}x{<=}0.30) were prepared by conventional solid-state reaction method. Temperature dependence of the total hemispherical emittance ({epsilon}{sub H}) of the compounds from 173 to 373 K was measured on a calorimetric emissometer (CE) which was constructed based on the steady-state calorimetric method. The compounds show thermochromic properties and {epsilon}{sub H}'s have low value at low temperature and have high value at high temperature, because the compounds are dominated by metallic phase and insulator phase, respectively. We use the phase separation model to interpret the temperature dependence of {epsilon}{sub H}. (author)
Three classes of solar emanations, namely, photon radiation from solar flares, solar energetic particles, and inhomogeneities in the solar wind that drive magnetic storms, are examined, and their effects on humans and technological systems are discussed. Solar flares may disrupt radio communications in the HF and VLF ranges. Energetic particles pose a special hazard at low-earth orbit and above, where they can penetrate barriers such as spacesuits and aluminum and destroy cells and solidstate electronics. Energetic solar particles also influence terrestrial radio waves propagating through polar regions. Magnetic storms may disturb the operation of navigation instruments, power lines and pipelines, and satellites; they give rise to ionospheric storms which affect radio communication at all latitudes. There is also a growing body of evidence that changes in the geomagnetic field affect biological systems. 3 refs.
We have investigated the effect of excimer laser annealing (ELA) on transient enhanced diffusion (TED) and activation of boron implanted in Si during subsequent rapid thermal annealing (RTA). It is observed that ELA with partial melting of the implanted region causes reduction of TED in the region that remains solid during ELA, where the diffusion length of boron is reduced by a factor of #approx#4 as compared to the as-implanted sample. This is attributed to several mechanisms such as liquid-state annealing of a fraction of the implantation induced defects, introduction of excess vacancies during ELA, and solid-state annealing of the defects beyond the maximum melting depth by the heat wave propagating into the Si wafer. The ELA pretreatment provides a substantially improved electrical activation of boron during subsequent RTA.
Gas and plasma nitriding processes were executed in the magnesium with modification by titanium in search for an effective surface treatment method for magnesium alloys. Magnesium-nitrogen system has completely no solid solution or solubility, so that nitride should be only formed by eutectic reaction in the liquid phase. Hence, magnesium is difficult or nearly impossible to have its surface modified by nitriding. Addition of nitride forming element into magnesium enables us to lower the onset temperature of nitriding. Magnesium-titanium alloys with 1 to 5 wt% are yielded by the bulk mechanical alloying and, subjected to gas nitriding for various process conditions. Successful co-formation of Mg{sub 3}N{sub 2} as well as TiN becomes a proof to demonstrate the possibility of gas/plasma nitriding in the solid-state magnesium with aid of nitride former. (orig.)
Bilayers of pure palladium and gold films were evaporated alternatively on (100) and (111) monocrystalline silicon substrates. After annealing, in a vacuum furnace from 100 to 650degreeC during 30min, the growth sequence of the Pd2Si and PdSi phases that evolved as the result of the diffusion reaction was examined by means of Rutherford backscattering spectrometry (RBS), X-ray diffraction (XRD), whereas the surface morphology was investigated by scanning electron microscopy (SEM) technique. The effect of the intermediate gold layer is investigated in order to test its effectiveness as barrier for Cu and Si atoms interdiffusion and its influence on the morphology of the formed palladium silicides. The effect of substrate orientation on the palladium silicides growth and formation was also e...
A number of materials of composition YSr{sub 2}Cu{sub 3-x}MxO{sub 7{+-}y} with M = Ti, Fe, Co, Al, Ga and Pb were prepared by solidstate reactions. They belong to the tetragonal P4/mmm space group and their unit cell parameters were determined and refined from X-ray powder data. The infrared spectra of the compounds were also recorded and are briefly discussed on the basis of their structural characteristics and by comparison with those of related materials. (orig.) 23 refs.
We suggest and study designed defects in an otherwise periodic potential modulation of a two-dimensional electron gas as an alternative approach to electron spin based quantum information processing in the solid-state using conventional gate-defined quantum dots. We calculate the band structure and density of states for a periodic potential modulation, referred to as an antidot lattice, and find that localized states appear, when designed defects are introduced in the lattice. Such defect states may form the building blocks for quantum computing in a large antidot lattice, allowing for coherent electron transport between distant defect states in the lattice, and for a tunnel coupling of neighboring defect states with corresponding electrostatically controllable exchange coupling between different electron spins.
The development of solidstate chemical sensors, and more specifically of gas sensors, is carried out with great strength in the present time since the environmental pollution and the security in work and domestic ambient are problems of great interest and social impact. The main fields of application, are: automobile, domestic sensors, control of industrial process, bio medicine, environment. These chemical sensors are experimenting a great advance because of the advantages they offer, as low cost, simple operation, possibility of measure continuous and ''In situ'' and small size, in contrast with analytical techniques that need complex instrumentation and large size equipments. In the present work, a sensor for CO detecting concentrations as low as 50 p.p.m., is studied showing great interest since this gas is highly toxic even to such a low concentration. (Author)
Results that contradict known physics, data manipulated, lack of vigilance by co-authors, failures in the system for scientific publication... Last September a US Committee of Enquiry unveiled one of the most serious frauds in the history of physics. Over a two year period, a young researcher at Bell Laboratories had published a large number of articles with exciting results for solidstate physics, but which, alas, were fraudulent! Obviously a fraud of this magnitude is exceptional. However, it did serve to focus attention on the problem of integrity and honesty in research practices. This subject, crucial to the well-being and credibility of scientific research, will be the central theme of the lecture given by Nicholas Steneck, Professor of History at the University of Michigan. A leading expert on this issue, on which he has published extensively, he is a consultant to the Office of Research Integrity in the US, and has been closely ...
Radon concentration in the bed rooms, kitchens, sitting rooms and TV lounges in some houses in the Lahore has been measured using CN-85 SolidState Nuclear Track Detectors in box type dosimeters. Maximum value of radon concentration is 93 Bq/m/sup 3/ in a bed room whereas the minimum value is 25 Bq/m/ sup 3/ in a TV lounge. The average value of radon concentration in bed rooms, kitchens, sitting rooms and TV lounges varies between 43 Bq/m/sup 3/ and 55 Bq/m/sup 3/. Comparison of radon concentration in the old and new houses has been done and no specific relationship has been observed. (author).
The spectroscopic properties of Cr{sup 2+}, Co{sup 2+}, and Ni{sup 2+}-doped single crystals of ZnS, ZnSe, and ZnTe have been investigated to understand their potential application as mid-IR tunable solid-state laser media. The spectroscopy indicated divalent Cr was the most favorable candidate for efficient room temperature lasing, and accordingly, a laser-pumped laser demonstration of Cr:ZnS and Cr:ZnSe has been performed. The lasers` output were peaked at {approximately} 2.35 {mu}m and the highest measured slope efficiencies were {approximately} 20% in both cases.
A kind of polymer-metal complex gel electrolyte is successfully prepared and is used in dye-sensitized solar cells. Raman and X-ray photoelectron spectroscopy confirm the structure of this complex and is found that the metal ion reacts with nitrogen in the polymer. This novel electrolyte shows apparent diffusion coefficient of iodide of 8.37 x 10-7 cm2 s-1 and the energy conversion efficiency of 6.10% when the amount of ZnI2 is 0.04 M. By studying the dissociation active energy of the inorganic salt in electrolytes, we find that the metal salts can dissociate more easily after reacting with polymer and as a result can provide extra free iodide ion. The cell maintains ca. 93% of its initial efficiency after 20 d without further sealing, which shows good long-time stability.
Polarized electron sources for high energy accelerators took a significant step forward with the introduction of a new laser-driven photocathode source for the SLC in 1992. With an electron beam polarization of >80% and with {approximately}99% uptime during continuous operation, this source is a key factor in the success of the current SLC high-energy physics program. The SLC source performance is used to illustrate both the capabilities and the limitations of solid-state sources. The beam requirements for future colliders are similar to that of the SLC with the addition in most cases of multiple-bunch operation. A design for the next generation accelerator source that can improve the operational characteristics and at least minimize some of the inherent limitations of present sources is presented. Finally, the possibilities for producing highly polarized electron beams for high-duty-factor accelerators are discussed.
The Paul Scherrer Institute is a centre for multidisciplinary research in the natural and engineering sciences. It collaborates closely with universities, other research institutions, technical colleges, and industry, both in Switzerland and abroad. It is the largest research institute in Switzerland, with about 1'200 members of staff. Its particular areas of specialisation are solid-state research and material sciences, elementary particle physics and astrophysics, biology and medicine, and energy and environmental research. This annual report presents an overview of the work performed by the PSI research departments including information on new developments connected with the various accelerators and on the status of the Swiss Light Source project (SLS). Details on the organizational and financial structure of the Institute are also provided.
We report the fabrication of p"+/n junctions using Ge"+, C"+, and B"+ co-implantation and a spike anneal. The best junction exhibits a depth of 26 nm, vertical abruptness of 3 nm/decade, and sheet resistance of 520 Ohm/square. The junction location is defined by where the boron concentration drops to 10"1"8 cm"-"3. These junctions are close to the International Technology Roadmap specifications for the 65 nm technology node and are achieved by careful engineering of amorphization, stresses, and point defects. Advanced simulation of boron diffusion is used to understand and optimize the process window. The simulations show that the optimum process completely suppresses the transient-enhanced diffusion of boron and the formation of boron-interstitial clusters. This increases the boron solubility to 20% above the equilibrium solid-state solubility.
Materials and processing designs for advanced magnesium alloys with fine microstructures and superior properties were established by the combination of the repeated plastic working and the Mg{sub 2}Si synthesis in solid-state. The grain size was less than 1 {mu}m via RPW process due to its severe plastic working on raw powder. The hot extruded magnesium alloys produced in industries showed high ultimate tensile strength, e.g. 420{proportional_to}450 MPa, when employing Mg-Zn-Al-Ca-RE (Rare Earth) alloy coarse powder, having 0.5{proportional_to}2 mm diameter, as input materials. (orig.)
Magnetic pulse welding, a cold solidstate bonding process, is becoming a viable replacement for conventional fusion welding processes and explosive welding. The process is presented here along with its fundamental equations and applications of similar and dissimilar welds are illustrated along with typical interface microstructures. (orig.) [German] Magnetimpuls-schweissen, ein Verbindungsverfahren im kalten Festzustand, wird ein funktionsfaehiger Ersatz fuer das herkoemmliche Schmelzschweissverfahren und das Explosionsschweissverfahren. Das Verfahren wird hier mit seinen grundlegenden Gleichungen vorgestellt, und Anwendungen von aehnlichen und unaehnlichen Schweissungen werden mit typischen Schnittstellen-Mikrostrukturen veranschaulicht. (orig.)
Ultrathin solid polymer electrolyte membranes containing sulfonic ester groups were prepared by polymerization of methyl benzenesulfonate and octamethylcyclotetrasiloxane in a glow discharge plasma. The sulfonic ester groups of the plasma polymer were transformed to lithium sulfonate groups by treatment with lithium iodide. Hybridization of this plasma polymer containing the lithium sulfonate groups with poly(ethylene oxide) (average Mw 300) resulted in the formation of a single lithium ion conductive film. The hybrid polymer electrolyte films were about 1 #mu#m thick, pinhole-free, adherent to various substrates, and showed ionic conductivities at 60 degrees C of the order of 10"- "6 S cm"- "1 (10"2 #OMEGA# cm"2 resistance per unit area of as-prepared solid polymer electrolyte). This material shows promise for electrochemical applications such as all solid-state lithium batteries, sensors, and electrochemical display devices.
Magnetic pulse welding is a solidstate impact welding process, similar to explosive welding, which produces metallurgical bond by oblique high-speed impact between two metal bodies. This violent impact removes the metal surface oxide layers and then joins the two atomic level clean metal surfaces together by the incidental compression pressure. The impact velocity is at 200?400?m/s and the being welded metal surface undergoes severe plastic deformation with strain rate in the order of 106?107?s?1. The ultrafine-grained structure was observed on the welded interface. This article studied two types of similar material lap joint interfaces and the base metals were aluminum alloy 6061 and copper alloy 110. Nano-indentation testing shows that the welded interfaces have significantly greater ha...
A poly(ether urethane) (PEUR)/poly(ethylene oxide) (PEO)/SiO2 based nanocomposite polymer is prepared and employed in the construction of high efficiency all-solid-state dye-sensitized nanocrystalline solar cells. The introduction of low-molecular weight PEUR prepolymer into PEO electrolyte has greatly enhance the electrolyte performance by both improving the interfacial contact properties of electrode/electrolyte and decreasing the PEO crystallization, which were confirmed by XRD and SEM characteristics. The effects of polymer composition, nano SiO2 content on the ionic conductivity and I3- ions diffusion of polymer-blend electrolyte are investigated. The optimized composition yields an energy conversion efficiency of 3.71% under irradiation by white light (100 mW cm-2).
Compton backscattering of laser photons near the interaction point of an e{sup +}e{sup -} or e{sup -}e{sup -} collider can be used to produce a {gamma}-{gamma} or {gamma}-e{sup -} collider. This paper describes the laser requirements, including pulse duration, intensity, energy, and wavelength, for such a collider. For most of the proposed, next generation, e{sup +}e{sup -} colliders, the laser wavelength should be in the near-infrared, with a pulse duration of 1 ps or less and an energy of similar 1 J per pulse. Current chirped pulse amplification laser systems in solidstate lasing materials are well suited to meet these requirements. These systems are described. ((orig.)).
Ferrite of system, namely Ni_1_-_xZn_xFe_2O_4 with x = (0.0, 0.2, 0.4, 0.6, 0.8, 1.0), have been prepared by solidstate reaction to investigate the effect of gamma rays irradiations using Co"6"0 source on the cation distribution, structural and magnetic properties. The unirradiated and irradiated samples were then subjected to characterization techniques such as X-ray diffraction, magnetization and AC susceptibility. The results of these characterizations are found to be different for irradiated from that of the pristine sample. The modifications in respect of irradiated samples are explained in terms of the ion-induced disorder. The important result of #gamma#-irradiation on the cation distribution, structural and magnetic properties is the change of ratio Fe"2"+/Fe"3"+. Possible reasons on the results are proposed.
Useful bipolar transistor action over the temperature range from -195 to 550 /sup 0/C has been demonstrated for heterojunction bipolar transistors in the GaP/AlGaP chemical system. This represents the highest temperature at which useful bipolar solid-state transistor action has ever been demonstrated in any material. Improvements in the materials technology and in the understanding of device characteristics at high temperatures were essential to the successful fabrication of these devices. These results demonstrate that the GaP/AlGaP heterojunction system is an excellent technology for active electronic components operated at high temperatures.
Polymer-coated magnetic nanoparticles (MNPs) have been prepared and used as an immobilization matrix for the fabrication of solid-state tris(2,2prime-bipyridyl)ruthenium(II) (Ru(bpy)32+) electrogenerated chemiluminescence (ECL) sensor. The pre-synthesized maghemite (g-Fe2O3) MNPs were coated with poly(3-thiopheneacetic acid) based on an oxidative polymerization method using KMnO4. The poly(3-thiopheneacetic acid)-coated MNPs have formed the clusters with average diameter of 200-500nm. The multilayer films of poly(3-thiopheneacetic acid)-coated MNPs were uniformly formed on the surface of a Pt electrode by an external magnet. The Ru(bpy)32+ was rapidly incorporated into the multilayer films within 5min through the electrostatic interaction between the Ru(bpy)32+ and the negatively charged c...
As a new high-voltage cathode candidate for post 4V cathodes, ordered-olivine LiCoPO{sub 4} and fluoride phosphate, Li{sub 2}CoPO{sub 4}F were synthesized by solid-state reaction. Their structures were identified by neutron diffraction. The 5V discharge profiles were demonstrated using coin-type cells. Two important issues for commercial use, metal dissolution and oxygen release at elevated temperatures, were also tested with an atomic absorption spectrophotometer and differential scanning calorimeter, respectively. (author)
We report significant enhancement in superconducting properties of yttrium substituted Ce1-xYxOFFeAs superconductors. The polycrystalline samples were prepared by two step solidstate reaction technique. X-ray diffraction confirmed tetragonal ZrCuSiAs structure with decrease in both a and c lattice parameters on increasing yttrium substitution (with fixed F content). With smaller ion Y in place of Ce, the transition temperature increased by 6 K. Yttrium doping also lead to higher critical fields as well as broader magnetization loops, particularly at elevated temperature.
This paper aimed to the evaluation of different kinds of sorbent material preparation and to the evaluation of their characteristics at different pH conditions by X-ray fluorescence analysis. This method is suitable for identification and determination of elements in samples of different character, state and origin because it is a polycomponent, non-destructive, fast and simple analytical method. Moreover, it allows timeadvantageous and reliable measurements. This paper studies problems concerning the determination of some selected elements (Mn, Fe, Ni, Cu, Zn, Pb) in pharmaceutical samples of sodium chloride in the solidstate as well as in its solution by sorption on chelating extraction membrane 3M Empore"T"M and on the strongly acidic ion-exchanger Dowex 50Wx8. Conditions for the most effective sorption of determined elements are also interpreted. (author)
This paper aimed to the evaluation of different kinds of sorbent material preparation and to the evaluation of their characteristics at different pH conditions by X-ray fluorescence analysis. This method is suitable for identification and determination of elements in samples of different character, state and origin because it is a polycomponent, non-destructive, fast and simple analytical method. Moreover, it allows time-advantageous and reliable measurements. This paper studies problems concerning the determination of some selected elements (Mn, Fe, Ni, Cu, Zn, Pb) in pharmaceutical samples of sodium chloride in the solidstate as well as in its solution by sorption on chelating extraction membrane 3M Empore? and on the strongly acidic ion-exchanger Dowex 50Wx8. Conditions for the most ef...
The aim of this study is to evaluate the specificities of the irradiation of drugs in frozen aqueous solution. The structures of the degradation products were determined to gain insight into the radiolysis mechanisms occurring in frozen aqueous solutions. Metoclopramide hydrochloride and metoprolol tartrate were chosen as models. The frozen solutions were irradiated at dry ice temperature by high energy electrons at various doses. The drug purity (chemical potency) and the radiolysis products were quantified by HPLC-DAD. Characterization of the degradation products was performed by LC-APCI-MS-MS. The structures of the radiolysis products detected in irradiated frozen aqueous solutions were compared to those detected in solid-state and aqueous solutions (previous studies). For both metoclop...
Nowadays, diamond and the nitrogen-vacancy (NV) colour centres constitute the best solid-state system in view of quantum-computing applications. It has also been shown recently that single NV centres could be used as nanoscale magnetic sensors. Such applications require the creation of single NV centres with very high resolution and with a high efficiency. The nano-implanter at the university of Bochum provides low energy nitrogen ions which can be implanted through a hole pierced in the tip of an atomic force microscope. Ultrapure diamond samples have been implanted with spot sizes of 50nm and less. Stimulated Emission Depletion (STED) microscopy has been used to characterise and resolve the implanted spots.
The electronic structure of small niobium clusters Nb/sub n/ (n = 2, 4, 6, 9) has been calculated applying two different quantum-chemical approximation methods (Extended Hueckel (EH) method; SW-X/sub alpha/ method). It was found that both the methods led to the same results concerning equilibrium structures, energy level schemes, Fermi energies and band widths as well as the densities of states of the clusters. In solving solidstate problems of transition metals with the aid of the cluster model a better adaptation of the EH method should be expected by adjusting the EH parameters to the SW-X/sub alpha/ results.
Purpose To study the chemical modifications induced upon irradiation of solid human insulin at radiosterilization doses and investigate the influence of the absorbed dose on radiolysis. Materials and Methods Volatile radiolytic products were monitored by gas chromatography coupled with mass spectrometry (GC-MS) and non-volatile products by two different high performance liquid chromatography (HPLC) methods: the formation of higher molecular weight proteins was assessed by size exclusion liquid chromatography whereas assays for related compounds and chemical potency tests were carried out using reverse-phase HPLC-UV. Conformational changes were investigated by measurements of circular dichroism. Results After gamma irradiation at 10?kGy, the recovery of insulin was 96.8%; higher molecular w...
The 5-th International conference 'Nuclear and Radiation Physics' was held in Almaty (Kazakhstan) 26-29 September 2005. Besides basic problems of nuclear and solidstate physics the conference paid considerable attention to applied topics important for industry and science in Kazakhstan; they include fuel and construction materials for nuclear power production, new technologies and materials for their production, materials for hydrogen power production, handling and utilization of radioactive waste, analytical methods for combating with illicit trafficking of nuclear and radioactive materials, technologies for reduction and assessment of environmental risk from radiation-hazardous materials and sites, production and application of isotopes, application of nuclear technologies in medicine and industry. On the conference more than 300 papers were presented by participants from 20 countries.
Abstract Despite the fact that oxidation is the second most frequent degradation pathway for pharmaceuticals, means of evaluating the oxidative stability of pharmaceutical solids, especially effective stress testing, are still lacking. This paper describes a novel experimental method for peroxide-mediated oxidative stress testing on pharmaceutical solids. The method utilizes urea-hydrogen peroxide, a molecular complex that undergoes solid-state decomposition and releases hydrogen peroxide vapor at elevated temperatures (e.g., 30C), as a source of peroxide. The experimental setting for this method is simple, convenient, and can be operated routinely in most laboratories. The fundamental parameter of the system, that is, hydrogen peroxide vapor pressure, was determined using a modified spect...
A non-resonant RF cavity loaded with amorphous alloy cores has been designed and tested. The cavity has a re-entrant structure loaded with 8 amorphous alloy toroidal core and its characteristic impedance is designed as 450 Omega . The RF power is fed by 1 kW solidstate amplifier using a step-up transformer with 1:9 impedance ratio. In the high power test, an accelerating gap voltage of more than 900 V was measured with input power of 1 kW in the frequency range of 1 to 10 MHz. The voltage standing wave ratio (VSWR) was less than 2.0. The results prove that the cavity may be used successfully within a compact proton synchrotron for a cancer therapy facility. (3 refs).
During a Workshop on Gamma-Gamma Colliders in Lawrence Berkeley Laboratory, it was pointed out that an 1-#mu#m laser that can produce 1-J, 1-ps pulses at a few hundred hertz is required. With high-power scalability and ease of formatting, an FEL can be a promising candidate for such a laser. The authors propose an FEL scheme based on chirped-pulsed regenerative amplification to achieve this high peak-power laser. The 1-ps pulse of a solid-state laser will be stretched, amplified, and recompressed to achieve the high peak power. The system is relatively simple and consists of mostly components that have already been demonstrated. This paper will describe the proposal and the important issues of such a scheme.
During a Workshop on Gamma-Gamma Colliders in Lawrence Berkeley Laboratory, it was pointed out that an 1-{mu}m laser that can produce 1-J, 1-ps pulses at a few hundred hertz is required. With high-power scalability and ease of formatting, an FEL can be a promising candidate for such a laser. The authors propose an FEL scheme based on chirped-pulsed regenerative amplification to achieve this high peak-power laser. The 1-ps pulse of a solid-state laser will be stretched, amplified, and recompressed to achieve the high peak power. The system is relatively simple and consists of mostly components that have already been demonstrated. This paper will describe the proposal and the important issues of such a scheme.
We present a single solid-state laser system to cool, coherently manipulate and detect $^{25}$Mg$^+$ ions. Coherent manipulation is accomplished by coupling two hyperfine ground state levels using a pair of far-detuned Raman laser beams. Resonant light for Doppler cooling and detection is derived from the same laser source by means of an electro-optic modulator, generating a sideband which is resonant with the atomic transition. We demonstrate ground-state cooling of one of the vibrational modes of the ion in the trap using resolved-sideband cooling. The cooling performance is studied and discussed by observing the temporal evolution of Raman-stimulated sideband transitions. The setup is a major simplification over existing state-of-the-art systems, typically involving up to three separate laser sources.
Here we present evidence that in water/acetonitrile solvent detailed structural and dynamic information can be obtained for important proteins that are naturally present as oligomers under native conditions. An NMR-derived human insulin monomer structure in H{sub 2}O/CD{sub 3}CN, 65/35 vol%, pH 3.6 is presented and compared with the available X-ray structure of a monomer that forms part of a hexamer (Acta Crystallogr. 2003 Sec. D59, 474) and with NMR structures in water and organic cosolvent. Detailed analysis using PFGSE NMR, temperature-dependent NMR, dilution experiments and CSI proves that the structure is monomeric in the concentration and temperature ranges 0.1-3 mM and 10-30 deg. C, respectively. The presence of long-range interstrand NOEs, as found in the crystal structure of the monomer, provides the evidence for conservation of the tertiary structure. Starting from structures calculated by the ...
The homologous sequences observed for many calcium binding proteins such as parvalbumin, troponin C, the myosin light chains, and calmodulin has lead to the hypothesis that these proteins have homologous...Full Text Available
The conformation of the self-complimentary DNA dodecamer d(br5CGbr5CGAATTbr5CGbr5CG) has been investigated in a variety of salt and solvent conditions by one and two-dimensional 1H NMR. In low salt...Full Text Available
Major breakthroughs have recently been reported that can help overcome two inherent drawbacks of NMR: the lack of sensitivity and the limited memory of longitudinal magnetization. Dynamic nuclear polarization...Full Text Available
The bulky octahedral complex, Rh(bpy)2chrysi3+ (chrysi = 5, 6- chrysenequinone diimine), binds single base mismatches in a DNA duplex with micromolar binding affinities...Full Text Available
... the hydroxyl group with the benzene ring. The molar extinction coefficients for the various species at their respective absorption ... Glya Recorded by 1H-NMR Spectroscopy TABLE 2 Molar Extinction Coeff...
A quantum computer (QC) can operate in parallel on all its possible inputs at once, but the amount of information that can be extracted from the result is limited by the phenomenon of wave function...Full Text Available
The passage of a vascular-injected paramagnetic contrast reagent (CR) bolus through a region-of-interest affects tissue 1H2O relaxation and thus MR image intensity. For longitudinal...Full Text Available
Despite their structural resemblance, a pair of cyclic halogenated compounds, 1-chloro-1,2,2-trifluorocyclobutane (F3) and 1,2-dichlorohexafluorocyclobutane (F6), exhibit completely different anesthetic...Full Text Available
The pattern of biodegradation and the chemical changes occurring in the macromolecular fraction of domestic sludge during autothermal thermophilic aerobic digestion (ATAD) was monitored and characterised...Full Text Available
BackgroundPathophysiological mechanisms involved in amyotrophic lateral sclerosis (ALS) are complex and none has identified reliable markers useful in routine patient evaluation....Full Text Available
The objectives of this study were to estimate symbiotic nitrogen fixation by two common pasture legumes, Trifolium subterraneum L. and Medicago truncatula Gaertn., and an Australian native legume, Acacia dealbata Link, growing in pots using an indirect isotopic method. This method was also used to calibrate the C2H2 reduction assay of the intact plants. In addition, hydrogen evolution was measured in an attempt to explain the variations in C2H2:N2 ratios between the species. 25 refs.; 1 figure; 4 tabs.
The effect of complexing agents DTPA and H2C2O4 on the extraction-chemical behavior of Tc, as applied to extractive splitting of U and Pu in the Purex process, was studied. The kinetic relationships of catalytic decomposition of N2H5NO3 under the action of Tc in the presence of these agents were determined. Variation of the ratio of the oxidized and reduced Tc species in the course of this process at various HNO3 concentrations was examined. In the final step of the reaction of N2H5NO3 with Tc in a nitric acid solution, when the reductant content is stabilized, the oxidation of reduced Tc also stops or continues at a considerably lower rate than before stabilization. The presence of DTPA decreases the rate of Tc(IV) oxidation owing to its binding in a complex and decreases the fraction of ...
This study concerns the thermotolerance of spores of mesophilic fungi isolated from a tropical semi-arid habitat subject to dry season fire in the Western Ghats, southern India. Among 25 species of Ascomycota isolated from leaf litter, nine were able to grow after incubation in a drying oven for 2h at 100degreeC; the spores of two of these species survived 2h incubation at 110degreeC, and one survived exposure to 115degreeC for 2h. The range of thermotolerance among mesophilic fungi isolated from the leaf litter was surprising: filamentous fungi from other habitats, including species that colonize scorched vegetation after fires and thermophilic forms occurring in self-heating plant composts, cannot survive even brief exposure to such high temperatures. It is possible that the exceptional ...
The research has involved the characterization of catalyst acidity, [sup 2]D NMR studies of Bronsted acid sites, and kinetic, calorimetric, and spectroscopic studies of methylamine synthesis and related reactions over acid catalysts. Approach of this work was to explore quantitative correlations between factors that control the generation, type, strength, and catalytic properties of acid sites on zeolite catalysts. Microcalorimetry, thermogravimetric analysis, IR spectroscopy, and NMR spectroscopy have provided information about the nature and strength of acid sites in zeolites. This was vital in understanding the catalytic cycles involved in methylamine synthesis and related reactions over zeolite catalysts.
Conduction properties of Rb"+ ion in Rb-Al-priderite and K"+ ion and Rb"+ ion in (K,Rb)-Al-priderite, were investigated by NMR using "2"7Al in the framework as a probe. Size effect was observed remarkably in the activation energies. Frequency dependence of T_1 in Rb-Al-priderite at a low temperature indicates that the relaxation behavior of "2"7Al in Rb-Al-priderite can be described by the continuum model. Barrier height distributions and 'attempt frequencies' in both samples obtained by a curve-fitting method are discussed in comparison with those of K-Al-priderite. (orig.).
Synaptobrevin is a synaptic vesicle protein that has an essential role in exocytosis and forms the SNARE complex with syntaxin and SNAP-25. We have analyzed the structure of isolated synaptobrevin and its binary interaction with syntaxin using NMR spectroscopy. Our results demonstrate that isolated synaptobrevin is largely unfolded in solution. The entire SNARE motif of synaptobrevin is capable of interacting with the isolated C-terminal SNARE motif of syntaxin but only a few residues bind to the full-length cytoplasmic region of syntaxin. This result suggests an interaction between the N- and C-terminal regions of syntaxin that competes with core complex assembly.
In Nuclear Magnetic Resonance (NMR) imaging, contrast is dependent on the emission of radiofrequency waves by atomic nuclei, balanced by several parameters. The high information content of NMR images is due to the multiplicity of its parameters. However, this advantage introduces a difficulty in the interpretation of the contrast. There are three contrast parameters for each tissue: hydrogen nuclei density; relaxation time T1; relaxation time T2. Contrast may be enhanced towards any of these parameters by increasing the emission of radiowaves by atomic nuclei using particular pulse sequences.
The authors have performed a preliminary design for a persistent GHz NMR magnet at 23.5 T and 1.8 K operating conditions. In this paper the authors shall address the issues of realistic conductor selection, the coil design, the magnetic and mechanical analysis of the coil, and the required field uniformity. In addition, they shall describe the GHz magnet cryostat with a practical 1.8 K J-T refrigerator system. Finally vibration isolation system and field shield design and its associated field harmonics will be analyzed.
The authors studied the flow of carbon ({sup 14}C) from CO{sub 2} through sucrose to oligofructans in wheat (Triticum aestivum L.) leaves that had been induced by excision to accumulate fructan. Leaves were either labeled for 30 min and then chased in ambient air for 2h or labeled continuously for 2h. Fructans were chromatographed on BioGel P2 column. During continuous labeling, the specific activity was highest in sucrose and decreased for fructans with DP 3 to 5, and each increased linearly with time for 2h. During the chase period, sucrose specific activity increased for 60 min and then declined while oligofructans gained in specific activity through the 2h period. After 30 min of labeling, the specific activity of fructose moiety of sucrose was equal to glucose but, in oligofructans, those of the individual ...
Plasma nitriding in glow discharge is a process of modifying surface properties of a material by which surface hardness, corrosion resistance, fatigue strength etc. of a material can be improved
It is well established from experiments in premixed, laminar flames, jet-stirred reactors, flow reactors, and batch reactors that SO2 acts to catalyze hydrogen atom removal at stoichiometric and reducing conditions. However, the commonly accepted mechanism for radical removal, SO2 + H(+M) reversible arrow HOSO(+M), HOSO + H/OH reversible arrow SO2 + H-2/H2O, has been challenged by recent theoretical and experimental results. Based on ab initio calculations for key reactions, we update the kinetic model for this chemistry and re-examine the mechanism of fuel/SO2 interactions. We find that the interaction of SO, with the radical pool is more complex than previously assumed, involving HOSO and SO, as well as, at high temperatures also HSO, SH, and S. The revised mechanism with a high rate constant for H + SO2 recombination and with SO + H2O, rather than ...
1 The plasma protein binding of theophylline was determined after addition of [14C]-theophylline (15 micrograms/ml) to plasma from 24 healthy drug-free volunteers and equilibrium dialysis for 2h at...Full Text Available
The flybys of Jupiter by the Voyager spacecraft in 1979, and over two decades later by Cassini in 2000, have provided us with unique datasets from two different epochs, allowing the investigation of seasonal change in the atmosphere. In this paper we model zonal averages of thermal infrared spectra from the two instruments, Voyager 1 IRIS and Cassini CIRS, to retrieve the vertical and meridional profiles of temperature, and the abundances of the two minor hydrocarbons, acetylene (C2H2) and ethane (C2H6). The spatial variation of these gases is controlled by both chemistry and dynamics, and therefore their observed distribution gives us an insight into both processes. We find that the two gases paint quite different pictures of seasonal change. Whilst the 2-D cross-section of C2H6 abundance is slightly increased and more symmetric in 2000 (northern summer ...
Six uranyl coordination compounds, UO_2(OH)(PYCA) (1), UO_2(PYCA)_2(H_2O).2H_2O (2), UO_2(PIC)_2 (3), UO_2(H_2O)_2(NIC)_2 (4), UO_2(OH)(HINIC)(INIC) (5), and UO_2(PYTAC)_2(H_2O)_2 (6) were grown as single crystals via hydrothermal synthesis (PYCA - pyrazine-2-carboxylate, PIC - picolinate, NIC - nicotinate, INIC - iso-nicotinate, and PYTAC - 2-(pyridin-4-yl)thiazole-5-carboxylate) to study their optical properties. All six compounds have been identified via single crystal X-ray diffraction and fully characterized via powder X-ray diffraction, infrared spectroscopy, UV-Vis spectroscopy, and fluorescence spectroscopy. Three of the complexes, 1, 3, and 6, represent new structures, and their synthesis and structural characterization is detailed within. The structures of 2, 4, and 5 have previously been reported in the ...
Crystallization points of aqueous solution of the systems M(ClO_4)_2-H_2O (M"2 = Mg"2"+, Ca"2"+, Sr"2"+, Ba"2"+), depending on the salt concentration, were identified by visual-polythermal method. Relying on model notions on the structure of the electrolyte solutions, specific features of strontium perchlorate solubility polytherm and concentration dependence of the relative dynamic viscosity of the salt aqueous solutions are discussed
The new nonlinear optical crystal Rb3V5O14 has been synthesized by solidstate reaction and characterized by single-crystal X-ray diffraction, IR and thermogravimetric analysis. The crystal Rb3V5O14 crystallizes in the trigonal system with space P31m (No. 157), a=b=8.7134(12) A, c=5.2807(11) A and ?=90o, ?=90o, ?=120o, Z=1, ?=3.516 g/cm3. It is a layered structure that is very flat and strongly parallel to c. The V5O14 layer structure consists of corner-linked square and triangular pyramids. The layers are separated by Rb+ ions, which fit equally well on the V5O14 layer. The Kurtz powder SHG measurement, using 1064 nm radiation, showed that the second-harmonic generation efficiency of Rb3V5O14 is about two times that of KDP. -- Graphical abstract: The new nonlinear optical crystal Rb3V5O14 has been synthesized by solidstate reaction and characterized by single-crystal X-ray diffraction, IR and ...
Nitrogen has been added to stainless steels to improve mechanical strength and corrosion resistance. High nitrogen steel production is limited by high gas pressure requirements and low nitrogen solubility in the melt. One way to overcome this limitation is the addition of nitrogen in solidstate because of its higher solubility in austenite. However, gas and salt bath nitriding have been done at temperatures around 550 C, where nitrogen solubility in the steel is still very low. High temperature nitriding has been, thus proposed to increase nitrogen contents in the steel but the presence of oxide layers on top of the steel is a barrier to nitrogen intake. In this paper a modified plasma nitriding process is proposed. The first step of this process is a hydrogen plasma sputtering for oxide removal, exposing active steel surface improving nitrogen pickup. This is followed by a nitriding step where high nitrogen contents are introduced in the ...
Nitrogen has been added to stainless steels to improve mechanical strength and corrosion resistance. High nitrogen steel production is limited by high gas pressure requirements and low nitrogen solubility in the melt. One way to overcome this limitation is the addition of nitrogen in solidstate because of its higher solubility in austenite. However, gas and salt bath nitriding have been done at temperatures around 550 C, where nitrogen solubility in the steel is still very low. High temperature nitriding has been, thus proposed to increase nitrogen contents in the steel but the presence of oxide layers on top of the steel is a barrier to nitrogen intake. In this paper a modified plasma nitriding process is proposed. The first step of this process is a hydrogen plasma sputtering for oxide removal, exposing active steel surface improving nitrogen pickup. This is followed by a nitriding step where high nitrogen contents are introduced in the ...
The anodic reaction kinetics and interfacial mass transport of a direct polymer electrolyte membrane formic acid fuel cell have been investigated in an all solid-state electrochemical cell using a highly active nanostructured palladium-gold alloy microelectrode as an in situ probe. Well-defined 'S-shaped' steady-state cyclic voltammograms exhibiting current-rising region at lower overpotentials and limiting current region at higher overpotentials have been first obtained for the electrochemical oxidation of formic acid at varying temperature. The 'S-shaped' steady state polarization curves and chronoamperometric curves enable convenient measurements of the anodic reaction kinetics and interfacial mass transport of formic acid under real polymer electrolyte membrane conditions. It is encouragingly found that formic acid can be directly oxidized to CO2 with the first electron transfer being the likely rate-determining step and the formation of surface poison can be ...
In this paper, we report the electrochemical characteristics of a novel cathode material, Li{sub 2}CoPO{sub 4}F, prepared by solid-state reactions. The solid-state reaction mechanism involved in synthesizing the Li{sub 2}CoPO{sub 4}F also is analyzed in this paper. When cycled between 2.0 V and 5.0 V during cyclic voltammetry measurements, the Li{sub 2}CoPO{sub 4}F samples present one, fully reversible anodic reaction at 4.81 V. When cycled between 2.0 V and 5.5 V, peaks occurring at 4.81 V and 5.12 V in the first anodic scan evolved to one broad oxidative, mound-like pattern in subsequent cycles. Correspondingly, the X-ray diffraction (XRD) pattern of the Li{sub 2}CoPO{sub 4}F electrode discharged from 5.5 V to 2.0 V is slightly different from the patterns exhibited by a fresh sample and the sample discharged from 5.0 V to 2.0 V. This difference may correspond to a structural relaxation that appears above 5 V. In the constant current cycling ...
LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} was prepared through a solid-state reaction using various Ni precursors. The effect of precursors on the electrochemical performance of LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} was investigated. LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} made from Ni(NO{sub 3}){sub 2}.6H{sub 2}O shows the best charge-discharge performance. The reversible capacity of LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} is about 145 mAh g{sup -1} and remained 143 mAh g{sup -1} after 10 cycles at 3.0-5.0 V. The XRD results showed that the precursors and the dispersion methods had significant effect on their phase purity. Pure spinel phase can be obtained with high energy ball-milling method and Ni(NO{sub 3}){sub 2}.6H{sub 2}O as precursor. Trace amount of NiO and Li{sub 2}MnO{sub 3} phase were detected in LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} with manual-mixture method and using Ni(CH{sub 3}COO){sub 2}.6H{sub 2}O, NiO and Ni{sub 2}O{sub 3} as precursors. (author)
Single-phased Sr3B2SiO8:Eu3+ phosphor was prepared by a solid-state method at 1020 oC. The luminescence spectra showed that Sr3B2SiO8:Eu3+ phosphor can be effectively excited by near ultraviolet light (393 nm) and blue light (464 nm). When excited at 393 or 464 nm Sr3B2SiO8:Eu3+ exhibited the main emission peaks at 611 and 620 nm, which resulted from the supersensitive 5D0#->#7F2 transition of Eu3+. The luminescence intensity of Sr3B2SiO8:Eu3+ at 611 and 620 nm reached the maximum when the doping content of Eu3+ was 4.5 mol%. Its chromaticity coordinates (0.646, 0.354) were very close to the NTSC standard values (0.67, 0.33). Thus, Sr3B2SiO8:Eu3+ is considered to be an efficient red-emitting phosphor for long-UV InGaN-based light-emitting diodes. - Highlights: ? Sr3B2SiO8:Eu3+ was synthesized using solid-state reaction method for the first time. ? The phosphor can be efficiently excited by the near-UV chips and gives strong red emission. ? ...
The x-ray diffraction technique described previously for measurement of growth kinetics of Pd/sub 2/Si layers from their solidstate reaction couples has been extended by the use of a one-dimensional position-sensitive detector (PSD). Additionally, the method has been extended to include measurement of the Pd layer. A detailed description of the experimental arrangement and analytical procedures is presented. The kinetics of epitaxial Pd/sub 2/Si film growth were measured in situ over a range of 170--230 /sup 0/C. The PSD results, using data obtained from both the Pd/sub 2/Si and Pd layers, were able to confirm parabolic growth behavior for the Pd/sub 2/Si film. The rate constants followed Arrhenius behavior and yielded an activation energy of E = 1.32 +- 0.07 eV with a prefactor k/sub 0/ = 0.49 cm/sup 2//s for the Pd/sub 2/Si layer analysis and E = 1.34 +- 0.17 eV with a prefactor of 0.72 cm/sup 2//s for the Pd layer analysis. The PSD ...
A solid-state precipitation process was used to prepare superconducting tapes containing an A15 phase, V/sub 3/Ga or Nb/sub 3/Al, in a ductile niobium or vanadium containing BCC matrix. Ingots weighing as large as 30 to 50 gms of V-(14 approx. 19 at. %) Ga and Nb-(13 approx. 22 at. %) Al were prepared by arc-melting, homogenized, quenched, warm-rolled over 99% into tape, and aged at temperatures in the range 600/sup 0/C to 1000/sup 0/C to precipitate the superconducting A15 phase. The features demonstrated by the process are very attractive for practical applications. In the V-Ga system, transmission electron microscopy (TEM) studies revealed the A15 precipitates in an elongated form. However, for the Nb-Al samples, deformed and aged at 750/sup 0/C, TEM studies revealed A15 precipitation in fine equi-axed particles which formed as a semi-continuous network over sub-grain boundaries formed by the recovery of deformation-induced dislocations. In the V-Ga system, the ...
Several lanthanide shift reagents (LSR) were synthesized from praseodymium, europium, dysprosium, and terbium using ethylenediaminetetraacetic acid, trans-1,2-diaminocyclohexane-N,N,N[prime],N[prime]-tetraacetic acid, and diethylenetriaminepentaacetic acid for the purpose of separating overlapping [sup 31]P FT-NMR spectral signals of dissolved organic phosphorus compounds present in concentrated lake-water samples. The extent of change in signal position and line width of several known phosphorus compounds dissolved in pure water was examined as a function of solution pH and the molar ratio of LSR to phosphorus. Praseodymium ethylenediaminetetraacetate (PrEDTA) was determined to be the most effective LSR. Concentrated lake-water samples mixed with PrEDTA were examined with [sup 31]P FT-NMR. The use of PrEDTA provided separation of overlapping signals, indicated that phosphorus compounds were becoming isolated from the solution environment ...
NMR and CD studies indicate that Mg/sup 2 +/ and Ca/sup 2 +/ are able to change the conformation of tetracycline in DMSO solution. This may affect the in vivo effect of tetracycline. Using /sup 23/Na NMR, the formation constant of NaLAS (LAS represents the anion of lasalocid A) was found to be 80 M/sup -1/ which is much smaller than that in less polar solvents. Spin-lattice relaxation measurements were made to study the binding sites of Gd/sup 3 +/ on Las in ChCl/sub 3/-DMF mixed solvent system. No intermediate conformation (between cyclic and open-chain) was found. LAS was found to be a good second-sphere ligand to inert transition-metal amines. NMR studies suggest that LAS is in cyclic conformation when bound to these metal amines. A new method for the synthesis of spin-labeled anticancer Pt(II) complexes was developed. It is very simple and gives high yield of pure spin-labeled Pt(II) complexes.
#beta#-SiAlON was synthesized from a zeolite by NH_3 gas nitridation and its formation mechanism was investigated using X-ray diffraction and "2"9Si and "2"7Al NMR spectroscopy. It was revealed that most of the Si and Al atoms react to form #beta#-SiAlON via amorphous forms of Si-Al-O-N and O-SiAlON. Nitridation using NH_3 gas is an effective means of preventing mullite formation and promoting the introduction of nitrogen into aluminosilicate materials at lower temperatures than temperatures required by the carbothermal reduction nitridation process. Further, the NMR spectra showed that the siliceous part of the system changed into low z-value of Si_6_-_zAl_zO_zN_8_-_z (#beta#-SiAlON) and the incorporation of Al components into the #beta#-SiAlON was promoted in the later stages of the reaction. (author)
Trichlorfon is an organophosphorus insecticide, which is extensively being used for protection of fruit crops. Trichlorfon is a thermal labile compound, which cannot be easily determined by gas chromatography (GC) and has no suitable group for sensitive detection by high performance liquid chromatography (HPLC). In this study, a {sup 31}P nuclear magnetic resonance ({sup 31}P NMR) has been described for monitoring of trichlorfon without any separation step. The quantitative works of {sup 31}P NMR spectroscopy has been performed in the presence of an internal standard (hexamethylphosphoramide). Limit of detection (LOD) for this method has been found to be 55 mg L{sup -1}, without any sample preparation, and the linear working range was 150-5500 mg L{sup -1}. Relative standard deviation (R.S.D.%) of the method for three replicates within and between days was obtained {<=}9%. The average recovery efficiency was approximately 99-112%. This ...
We report $^{7}$Li pulsed NMR measurements in polycrystalline and single crystal samples of the quasi one-dimensional S=1 antiferromagnet LiVGe$_2$O$_6$, whose AF transition temperature is $T_{\\text{N}}\\simeq 24.5$ K. The field ($B_0$) and temperature ($T$) ranges covered were 9-44.5 T and 1.7-300 K respectively. The measurements included NMR spectra, the spin-lattice relaxation rate ($T_1^{-1}$), and the spin-phase relaxation rate ($T_2^{-1}$), often as a function of the orientation of the field relative to the crystal axes. The spectra indicate an AF magnetic structure consistent with that obtained from neutron diffraction measurements, but with the moments aligned parallel to the c-axis. The spectra also provide the $T$-dependence of the AF order parameter and show that the transition is either second order or weakly first order. Both the spectra and the $T_1^{-1}$ data show that $B_0$ has at most a small effect on the alignment of the AF ...
Crystalline bis(O,O'-di-sec-butyldithiophosphato)platinum(II) was prepared and studied by means of 13C, 31P CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. The unit cell of the platinum(II) compound is comprised of one centrosymmetric mononuclear molecule [Pt{S2P(O-sec-C4H9)2}2], in which the dithiophosphate groups display structural equivalence in both 31P NMR and XRD data. A pair of the dithiophosphate ligands exhibit the same S,S'-bidentate chelating structural function and form two planar four-membered chelate rings, [PtS2P], in this molecule. The planar configuration of the [PtS4] chromophore in structure 1 is governed by the dsp2-hybrid state of platinum(II). The structural states of the dithiophosphate groups in two different samples of complex 1 (one crystallised from...
The nature of extralattice aluminum and its effect on acidity in zeolites was studied. A series of zeolites (some commercial), dealuminated by various methods, were obtained having Si/Al ratios between 1.5 and 20. These were characterized using volumetric sorption, XRD, AA, NMR, and reaction studies. Samples dealuminated using ammonium hexafluorosilicate were found to contain little or no extralattice aluminum. In contrast, steam-dealuminated zeolites had large amounts of extralattice aluminum. In some cases a significant portion of the extralattice aluminum was unobservable by [sup 27]Al NMR, suggesting the existence of an aluminum species of low symmetry. Proton NMR indicated that all the protons were associated with the lattice aluminum atoms. Depending on the preparation history, different groups of H-Y zeolites exhibited different maxima in catalytic activity as a function of aluminum content. The maxima in catalytic ...
We have examined the theory of NMR multiple echoes developed for solid {sup 3}He to determine whether multiple echoes could be observed in solid hydrogen. We were particularly interested in the possibility of testing for low frequency quantum tunneling motions in solid hydrogen by the observation of multiple echoes. We find that for easily accessible nuclear spin polarizations, P > 12%, multiple echoes would be observed for HD impurities in solid parahydrogen if motional narrowing is effective in increasing the HD nuclear spin-spin relaxation time T{sub 2} to the order of 1 msec. These values for T{sub 2}, which have been observed for HD impurity concentrations of the order of 1%, are larger than the calculated rigid lattice values and can be attributed to quantum tunneling at frequencies of the order of 1kHz.
Effects of #gamma#-irradiation on synthetic polymers and paper used as packaging materials for irradiated food have been studied by NMR. Polystyrene, polybutadiene and some copolymers were studied before and after the #gamma#-irradiation treatment and in the presence or absence of antioxidants and stabilisers. In the absence of additives, the effect of #gamma#-irradiation on polystyrene is negligible even irradiating at high doses. In turn, the role of antioxidants and stabilisers is crucial in polybutadiene and butadiene-containing copolymers. Wood pulp paper was also studied by NMR. Preliminary measurements on #gamma#-irradiated wood pulp sheets show a shortening in the T_2 relaxation time component due to the bound water, i.e. some of the bound water is lost. (author)
Two new triterpene glycosides, patagonicosides B and C (2 and 3, resp.), together with the known patagonicoside A (1), have been isolated from the EtOH extract of the sea cucumber Psolus patagonicus. The structures of the new compounds were established on the basis of extensive NMR spectroscopic analysis ((1)H- and (13)C-NMR, (1)H,(1)H-COSY, HMBC, HSQC, TOCSY, and NOESY), HR-ESI-MS data, and chemical transformations. Compounds 1-3 and their desulfated analogs showed antifungal activities against the phytopathogenic fungus Cladosporium cladosporoides in a dose-dependent fashion. PMID:21404430
The effects of spin diffusion on the free induction decay (FID) of protons associated with the noncrystalline domains of two polymers, polyethylene and blended Nylon 66 (ZYTEL-408), have been examined using Goldman--Shen NMR pulse sequence ((1/2)..pi..x-t/sub 0/-(1/2)..pi..x-bar-tau-(1/2)..pi..x-t). At tau< or approx. =100 ..mu..s, the FID is drastically distorted from the exponential form while at longer tau(tau> or approx. =500 ..mu..s) an exponential FID is observed; but its transverse spin relaxation rate is smaller than that of the FID obtained after a single (1/2)..pi..x pulse and approaches this value at the limit of large tau. These findings are interpreted in terms of the theory of rapid spin diffusion. The spatial variation in the spin relaxation rate within the noncrystalline domain is inferred.
The purpose of this work is the elucidation of the f"n electronic structure of neutral mono base adducts derived from tris(#eta#"5-cyclopentadienyl)-lanthanide(III) (Cp_2Ln). The available data on related compounds like bis adducts and anionic mono adducts of the same moiety was also analyzed. The first aim was to derive the experimental crystal field splitting pattern from optical, magnetooptical and magnetochemical measurements and to reproduce it using an empirical Hamiltonian operator. The eigenvalues and eigenvectors obtained in this manner were used for a quantitative interpretation of the magnetochemical, EPR- and NMR-spectroscopic properties. For the latter subject it was necessary to develop an own procedure for the NMR analysis of paramagnetic compounds. This method is based on factor analysis and as demonstrated in the second part of this work, is clearly superior to all previous procedures. (orig.).
Chitosan was acetylated during 2, 5 and 10 h and physical gels were obtained at different polymer concentrations in N,N-dimethylacetamide containing 5% of LiCl. Acetylation was confirmed by infrared spectroscopy and "1"3C NMR, and degrees of acetylation in the range of 0.82-0.91 were determined by NMR. The O-acetylation degree (0.12-0.15) was exclusively determined by a volumetric method. Rheological studies showed that the storage modulus values were smaller for the more acetylated samples and increased with the temperature and the polymer concentration. All the gels presented storage modulus superior to loss modulus, evidencing more elastic than viscous characteristics. The results obtained in this work suggest a gelation process based on a balance between O and N-acetylation and intermolecular bonds. (author)
The endophytic fungus Trichothecium roseum LZ93 from Maytenus hookeri was found to antagonize other pathogenic fungi in vitro. To identify which compound contributed substantially to the antagonism, we fermented the strain and purified its fermentation products. Eleven compounds were obtained, including two trichothecenes, five rosenonolactones, two cardiotonic cyclodepsipeptides, and two sterols. Compound 11?-hydroxyrosenonolactone (1) was assigned according to 1D and 2D-NMR data for the first time. At the same time, the 1H and 13C-NMR assignments for 6?-hydroxyrosenonolactone (2) were revised. Of all of them, only trichothecin (6) showed strong antifungal activity. Based on our observations of the antagonistic activity and the other experimental results, we suggest that the antifungal co...
Cyclization of deproteinized natural rubber (DPNR) or purified natural rubber latex was effectively performed in latex phase by using trimethylsilyl-trifluoromethane sulfonate or trimethylsilyl triflate (TMSOTF) as a novel catalyst, which is still not reported in the case of natural rubber latex. Various cyclization conditions affecting the degree of cyclization were studied, such as dry rubber contents, temperature, TMSOTF concentrations, and time. The cyclized products were characterized by FTIR, Raman, 1H-, and 13C-NMR spectroscopies, as well as DSC and TGA. The degree of cyclization was estimated by 1H-NMR spectrum. It was found that the degree of cyclization in NR was a function of cyclization conditions. The thermal stability of cyclized DPNR increased with the degree of cyclization....
The mechanism of the IndolPhos-Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows an unsaturate/dihydride mechanism according to Michaelis-Menten kinetics. A large value of KM (KM=5.01+-0.16 M) is obtained, which indicates that the Rh-solvate complex is the catalyst resting state, which has been observed by high-pressure NMR spectroscopy. DFT calculations on the substrate-catalyst complexes, which are undetectable by experimental means, suggest that the major substrate-catalyst complex leads to the product. Such a mechanism is in accordance with previous studies on the mechanism...
One of the stiffest challenges in structural studies of proteins using NMR is the assignment of sidechain resonances. Typically, a panel of lengthy 3D experiments are acquired in order to establish connectivities and resolve ambiguities due to overlap. We demonstrate that these experiments can be replaced by a single 4D experiment that is time-efficient, yields excellent resolution, and captures unique carbon-proton connectivity information. The approach is made practical by the use of non-uniform sampling in the three indirect time dimensions and maximum entropy reconstruction of the corresponding 3D frequency spectrum. This 4D method will facilitate automated resonance assignment procedures and it should be particularly beneficial for increasing throughput in NMR-based structural genomics initiatives.
The effects of TANOL radical have been examined on chemical shifts and relaxation rates of /sup 109/Ag NMR in aqueous solution of silver salts. The silver ion in aqueous solution is found to coordinate with TANOL radical. A small amount of TANOL is added as a doping agent(0.020M), since /sup 109/Ag signals are obtained for (1.0M) silver ion within 30 minutes. The /sup 109/Ag chemical shifts of silver salt in aqueous solutions were found within the range of 0 to -1000 ppm relative to that of 1.0M AgNo/sub 3/.
In this paper nickel acetate catalyzed sodium borohydride cartridges have been prepared and hydrolyzed with water for hydrogen production. Two technological solutions have been tested to increase the overall hydrogen yield, namely a porous water diffuser and a hydrophobic membrane. The first was used to improve water diffusion inside the hydride while the second to confine water inside the cartridge. The generated hydrogen flow showed a very reproducible behavior. Hydrogen promptly evolved just after water was pumped into the cartridge. After some initial peaks, a constant hydrogen flow has been recorded for the whole reaction time. The constant flow was related to the presence of the porous diffuser. The use of a hydrophobic membrane to confine the water inside the cartridge allowed to increase the overall hydrogen yield: about 6 water molecules per mol of hydride were required to complete the reaction. The reaction product was identified by XRD as Na{sub 2}B{sub 2}O{sub 4}*8H{sub ...
The detector for retrospective radon exposure measurements is developed. The detector consists of the multilayer package of solid-state nuclear track detectors LR-115 type. Nitrocellulose films works both as {alpha}-particle detector and as absorber decreasing the energy of {alpha}-particles. The uncertainties of implanted {sup 210}Pb measurements by two- and three-layer detectors are assessed in dependence on surface {sup 210}Po activity and gross background activity of the glass. The generalized compartment behavior model of radon decay products in the room atmosphere was developed and verified. It is shown that the most influencing parameters on the value of conversion coefficient from {sup 210}Po surface activity to average radon concentration are aerosol particles concentration, deposition velocity of unattached {sup 218}Po and air exchange rate. It is demonstrated that with the use of additional information on surface to volume room ratio, air exchange rate ...
Mesoporous V2O5/Nafion composite films have been used for the immobilization of tris(2,2prime-bipyridyl)ruthenium (II) (Ru(bpy)$\\rm{ {_{3}^{2+}}}$) on an electrode surface to yield a solid-state electrogenerated chemiluminescence (ECL) sensor. The electrochemical and ECL behavior of Ru(bpy)$\\rm{ {_{3}^{2+}}}$ ion-exchanged into the composite films has been characterized as a function of the amount of Nafion incorporated into the V2O5/Nafion composite. The composite film with 80% Nafion content has the largest pore diameter (4.19 nm) and yields the maximum ECL response for tripropylamine (TPA) because of the fast diffusion of analyte into the film with large pores. Due to the enlarged pore size and enhanced conductivity of the V2O5/Nafion composite, the present ECL sensor based on the compo...
Our research in the general area of acid catalysis involves the characterization of solid acidity and the corresponding assessment of catalytic performance of acidic materials. Acid characterization studies are required to provide essential information about the type of acid site (i.e., Lewis versus Bronsted), the strength of the sites, and the mobility of molecules adsorbed on the acid sites. An accurate measure of acid strength is given by the heat of adsorption of a basic probe molecule on the acid site. A thermodynamic representation of the mobility of adsorbed species on these sites is given by the entropy of adsorption. Important techniques used in these acid site characterization studies include microcalorimetry, thermogravimetric measurements, temperature programmed desorption, infrared spectroscopy and solidstate nuclear magnetic resonance. The combination of these acid site characterization studies with reaction kinetics measurements ...
The high temperature solid-state reaction between LiNiO{sub 2} and V{sub 2}O{sub 3} (or V{sub 2}O{sub 5}) in air used to prepare LiNiVO{sub 4} has been further studied. This quaternary Li-Ni-V-O reaction is strongly dependent on reaction temperature and lithium stoichiometry in Li{sub x}Ni{sub 2-x}O{sub 2} and has produced a highly crystalline LiNiVO{sub 4} material whose structure has been confirmed to be an inverse spinel by Rietveld analysis with a Bragg R-factor of 1.18 in the absence of crystal orientation preference. The cell performance of LiNiVO{sub 4} prepared at various temperatures or by varying x-values in Li{sub x}Ni{sub 2-x}O{sub 2} has been examined in lithium coin cells and indicated that preparation at low temperatures or when x=0.89 provided an electrode material with higher cell capacity. (orig.)
In this work, new LaSi3N5:Ce3+ phosphors have been synthesized by solid-state reaction. Rietveld refinement of the crystal structure of La1-xCexSi3N5 reveals that Ce atoms substituted for La atoms occupy 4a crystallographic positions. Broad emission and excitation bands observed were attributed to the transitions between the doublet ground state of the 4f1 configuration and the crystal field components of the 5d1 excited state. At 77 K, the centroid and crystal field splitting ?cfs of the 5d levels of Ce3+ in LaSi3N5:Ce3+ compounds were valuated at 33.4x103 and 11.3x103 cm-1, respectively. The zero-phonon line and the Stokes shift were measured to be 26.0x103 and 5.0x103 cm-1, respectively.
The Schiff base ligand, 4-isopropylbenzaldehyde[N-(3-oxo-3,4-dihydro-2-quinoxalinyl)hydrazone] (Ipbh), the 1:1 condensation product of 4-isopropylbenzaldehyde and 2-hydroxy-3-hydrazinoquinoxiline, has been synthesized and characterized by X-ray crystallography. A series of complexes of Ipbh with Nickel(II), viz., [Ni(Ipbh)2]Cl2 (1), [Ni(Ipbh)2]Br2 (2), [Ni(Ipbh)2]I2 (3), [Ni(Ipbh)2(CH3OH)2](NO3)2(CH3OH)2 (4) and [Ni(Ipbh)2ClO4]ClO4 (5) have been synthesized. All the complexes were characterized by elemental analysis, molar conductivity, CHN analysis, spectroscopic studies, magnetic susceptibility measurements and TG/DTA methods. The solid-state structure of the complex 4 was established by single crystal X-ray crystallography. In all the complexes, Ipbh acts as a bidentate NO chelating age...
YIG precursor powder was obtained by homogeneous precipitation in chloride salt solution by thermal decomposition of urea. It was found that ferric ions precipitated prior to yttrium ions. The precipitate was minute and spherical in shape. The precipitate formed consisted of the mixture of amorphous and ferric oxyhydroxide. Crystallization of YIG was proceeded by solidstate reaction of intermediate YFeO{sub 3} and Fe{sub 2}O{sub 3} in the temperature range of 850 deg. C to 1400 deg. C. Single phase of YIG was obtained by heat-treatment of the powder at 1400 deg. C for 6 hrs in air. The powder calcined was molded into pellets and sintered in air. The maximum density of 4.92 g/cm{sup 3} (95.1% of theoretical density) was obtainable for the pellet sintered at 1450 deg. C using the powder calcined at 900 deg. C. (author) 20 refs., 8 figs., 1 tab.
A newly carbon-doped Lithium titanate (Li4Ti5O12/C) spinel-type composite material was routinely prepared by a simple solid-state reaction method using carbonization of polyacrylonitrile (PAN) as carbon source in an inert atmosphere. Impedance measurement shows that the resistance of the composite electrode is substantially lower than that of the pure one. Electrochemical performances of the prepared materials were investigated. Results indicate that the composite materials obtained with 10wt.% PAN shows relatively higher specific capacity, better cycling and higher rate performance. The first discharge specific capacity of 158mAhg^-^1, 138mAhg^-^1, and 121mAhg^-^1 were obtained at 0.2C rate, 1/3C rate, and 3C rate at room temperature, respectively. And it was also found that tap density o...
Luminescence and reflection spectra as well as luminescence kinetics of the 1 mol% Sm3+-doped crystalline lanthanum magnesium meta borate (LaMgB5O10) and gadolinium magnesium meta borate (GdMgB5O10) were analyzed. Materials were synthesized by conventional solidstate route and showed bright orange-red emission under UV excitation. Emission spectra contain sharp and well resolved Sm3+4G5/2#->#6HJ transitions indicating a strong crystal-field effect. In case of gadolinium compound energy transfer between Gd3+ and Sm3+ was detected. The luminescent kinetics of the Sm3+ in analyzed powders is characterized by single exponential decay and experimental values vary in the range 2.2-2.4 ms. - Research highlights: ? Phosphorescence of samarium-doped lanthanide magnesium meta borates. ? Bright and well resolved orange-red emission of Sm3+ under UV excitation. ? Energy transfer from Gd3+ to Sm3+ in gadolinium magnesium meta borate is observed. ? The ...
The effect of flame temperature on the Moza-Austin sticking test has been evaluated by increasing the adiabatic flame temperature used to melt the pellet and make it drop. It was found that the variation of apparent contact angle with substrate temperature, for an oxidized steel substrate, was almost independent of flame temperature over the range of 1750-2500 C. However, the strength of adhesion to the substrate increased with higher flame temperature at each substrate temperature. The adhesion force of a drop frozen on the substrate at constant temperature also increased with time up to about one h. This indicated that the adhesion was not caused solely by mechanical anchoring of solidified glass in the pores of the oxide layer. Reduction of the substrate temperature to lower temperatures after attachment of the drop caused lower strength of adhesion, but this was partially restored by raising the temperature. This also suggested a continuing solid-state ...
The layered cobaltate La0.30CoO2 was prepared from NaxCoO2 precursor by a solid-state ionic exchange and was characterized by means of X-ray and neutron diffraction, magnetic, thermal and electric transport measurements. The compound consists of hexagonal sheets of edge-sharing CoO6 octahedra interleaved by lanthanum monolayers. Compared to Na+ in the parent system, the La3+ ions occupy only one-third of available sites, forming a 2-dimensional superstructure. The deviation from the ideal stoichiometry La1/3CoO2 introduces extra hole carriers into the diamagnetic LS Co3+ matrix making the sample Pauli paramagnetic. The temperature dependence of the electrical conductivity in La0.30CoO2 follows Mott's T?1/3 law up to about 400K, which is in contrast w...
Multilayer mirrors for the extreme ultraviolet (EUV) are keyelements for numerous applications of coherent EUV sources such as newtabletop lasers and free-electron lasers. However the field ofapplications is limited by the radiation and thermal stability of themultilayers. Taking into account the growing power of EUV sources thestability of the optics becomes crucial. To overcome this problem it isnecessary to study the degradation of multilayers and try to increasetheir temporal and thermal stability. In this paper we report the resultsof detailed study of structural changes in Sc/Simultilayers when exposedto intense EUV laser pulses. Various types of surface damage such asmelting, boiling, shockwave creation and ablation were observed asirradiation fluencies increase. Cross-sectional TEM study revealed thatthe layer structure was completely destroyed in the upper part ofmultilayer, but still survived below. The layers adjacent tothe substrateremained intact even through the ...
The paper discusses two petrochemical selective oxidation reactions namely the practised formation of styrene (STY) and the desired oxidative functionalisation of propane. The present knowledge about the mode of operation of oxide catalysts is critically considered. The dehydrogenation of ethylbenzene (EB) should be described by an oxidehydration with water acting as oxidant. The potential role of the coke formed during catalytic reaction as co-catalyst will be discussed. Selective oxidation is connected with the participation of lattice oxygen mechanism which transforms unselective gas phase oxygen into selective oxygen. The atomistic description of this process is still quite unclear as well as the electron structural properties of the activated oxygen atom. The Role of solidstate acidity as compared to the role of lattice oxygen is much less well investigated modern multiphase-multielement oxide (MMO) catalysts. The rationale is that the ...
The amorphization of a quenched sample of the GaSb-II high-pressure phase was studied at ambient pressure by real-time neutron diffraction in the course of the sample heating from 100 K to room temperature at a rate of 0.4 K min{sup -1}. The transformation to the amorphous state begins at 140 K and is completed near room temperature. The {beta}-Sn type structure was shown to represent only the mean lattice of the high-pressure GaSb-II phase. The superstructure of this phase widely varied with temperature and is caused by the ordered displacement of atoms. The temperature range of the metastable crystalline phase relaxation is divided into three intervals according to the temperature dependence of the tetragonality ratio (c/a). At the boundaries of these temperature intervals, i.e. temperatures T = 170 and 230 K, two second-order phase transitions are observed. Anomalous heat and volumetric effects were observed earlier by means of calorimetry and dilatometry in the same temperature ...
The amorphization of a quenched sample of the GaSb-II high-pressure phase was studied at ambient pressure by real-time neutron diffraction in the course of the sample heating from 100 K to room temperature at a rate of 0.4 K min-1. The transformation to the amorphous state begins at 140 K and is completed near room temperature. The ?-Sn type structure was shown to represent only the mean lattice of the high-pressure GaSb-II phase. The superstructure of this phase widely varied with temperature and is caused by the ordered displacement of atoms. The temperature range of the metastable crystalline phase relaxation is divided into three intervals according to the temperature dependence of the tetragonality ratio (c/a). At the boundaries of these temperature intervals, i.e. temperatures T = 170 and 230 K, two second-order phase transitions are observed. Anomalous heat and volumetric effects were observed earlier by means of calorimetry and dilatometry in the same temperature range. ...
Recently, the lithium ion-conductive solid electrolyte draws attention because there is a possibility of producing the maintenance-free battery which is characterized by having such advantages as high energy density and no possibility of electrolyte leak because of solidstate structure. The invented lithium ion-conductive solid electrolyte is formed by sintering the granular electrolyte expressed in the following general formula: Li(1+(4-n)x)MxTi(2-x)(PO4)3 (M = mono- or di-valent cation, x = 0.1 - 0.5). Examples of the monovalent cation are Na[sup +], K[sup +], Rb[sup +], Cs[sup +], and Cu[sup +]. Examples of divalent cation are Mg[sup 2+], Fe[sup 2+], Be[sup 2+], Ca[sup 2+], Sr[sup 2+], Ba[sup 2+], Ra[sup 2+], Mn[sup 2+], Co[sup 2+], Cu[sup 2+], Ni[sup 2+], Zn[sup 2+], and Cd[sup 2+]. The electric conductivity of lithium ion is increased with the increase in the content of Li[sup +] in the electrolyte. 4 figs.
Solid recycling of AZ31 Mg alloy with vapor deposition coating layer of high purity Mg was evaluated. In the open die forging experiments, two AZ31 Mg alloy specimens with the pure Mg layer were sufficiently bonded by forging at 673 K. Furthermore, the Al and Zn of the AZ31 substrate diffused up to the center of the pure Mg layer. By the theoretical analysis, it is suggested that the grain boundary diffusion enhanced by grain refinement due to hot forging contributes to the solidstate bonding of the specimens. Also, the solid recycled specimen was fabricated from the AZ31 Mg substrate with pure Mg layer by hot extrusion at 673 K. The solid recycled specimen showed almost the same tensile properties as the virgin extruded specimen. This is probably related not only to the grain boundary diffusion but also severe plastic deformation by hot extrusion. (orig.)
Radon concentration measurements were carried out using solid-state nuclear track-etch detectors (SSNTDs) type CA 80-15 cellulose nitrate films, in a Pleistocenic cave at Petralona, in Halkidiki, Northern Greece, at 55 km from the city of Thessaloniki. Radon levels as high as 88 kBqxm"-"3 (2.38 nCi x l"-"1) have been recorded inside the cave equivalent to 11.90 WL in terms of occupational exposure to radon and its decay products. Absorbed dose rates were performed using TL dosimeters, type TLD-200 (CaF_2-Dy) in a continuous monitoring program (integrated measurements). Dose rate levels as high as 110 nGy x h"-"1 were recorded inside the cave. In interpreting the high levels of radiation doses, radioactivity measurements regarding the naturally occurring "2"3"8U, "2"3"2Th and "4"0K radionuclides were carried out in various speleothems found at different sites in the cave. (author)
Recent developments in solid-state radio frequency (RF) power technologies allow for the practical consideration of RF heated plasmas for space propulsion. These technologies permit the use of any electrical power source, de-couple the power and propellant sources, and allow for the effcient use of both the propellant mass and power. Effcient use of the propellant is obtained by expelling the rocket exhaust at the highest possible velocity, which can be orders of magnitude higher than those achieved in chemical rockets. Handling the hot plasma exhaust requires the use of magnetic nozzles, and the basic physics of ion detachment from the magnetic eld is discussed. The plasma can be generated by RF using helicon waves to heat electrons. Further direct heating of the ions helps to reduce the line radiation losses, and the magnetic geometry is tailored to allow ion cyclotron resonance heating. RF eld and ion trajectory calculations are presented to give a reasonably ...
The present investigation deals with the fabrication of liquid petroleum gas (LPG) sensor based on semiconducting oxide SnO{sub 2}. The gas sensor elements have been prepared by conventional solidstate route. Addition of noble metal sensitizer, palladium and grain growth inhibitor, aluminum silicate to the base material SnO{sub 2}, not only improved the sensitivity towards LPG but also the selectivity in the presence of CO and CH{sub 4} gases. Out of various sensor compositions, SnO{sub 2}:Al{sub 2}Si{sub 2}O{sub 7} (35 wt.%):Pd (1.5 wt.%) sintered at 800 C for 5 h has shown high sensitivity (0.97) towards LPG at an operating temperature of 350 C. Different characterization techniques have been employed, such as differential thermal analysis (DTA), surface area analyzer, X-ray diffraction (XRD), to study the formation of SnO{sub 2}, surface area and crystallite size, respectively. The results suggested the possibility of utilizing the sensor ...
Samples of air-dust-concentration- and air-dust-deposit measurements were digested by a standardized wet digestion procedure and the amounts of substances in the dust according to class I TA Luft by Atomic Emission Spectroscopy with Inductively Coupled Plasma (AES-ICP). The characteristic values for procedures according to VDI 2449, sheet 1, were determined for lead, vanadium, cadmium, chromium, copper, nickel and zinc. By partial automatic control of the digestion procedure the personel expenditure of work could be reduced by a factor 13. Dust filter samples were analysed without sample preparation by evaporating the material with a solidstate laser. The absolute detection limit was between 1 and 100 ng/cm"2 for the elements arsenic, cadmium, cobalt, chromium, mercury, antimony, selen and thallium. For sampling by means of the Beta-Staubmeter the relative detection limits for the laser-ICP were 10-fold lower than by use of a nebulizer. ...
Abstract Many (K1-xNax)NbO3 (KNN)-based ceramics with high piezoelectric performance exhibit undesirable strong temperature dependence due to the orthorhombic-tetragonal polymorphic phase transition near room temperature. In order to improve the temperature stability of the ceramics, many additives have been added into the KNN-based ceramics to shift TO-T down to below room temperature. Contrary to the previous approach (Na0.53K0.47-xAgx)Nb1-xSbxO3 (NKANS) ceramics with TO-T well above room temperature have been prepared by a conventional solid-state reaction method. The density and the electrical properties are effectively improved by the addition of AgSbO3, and optimum piezoelectric properties are found in the ceramics with 0.05---x---0.07, with maximum kp---0.46 for NKANS5 and maximum d...
A novel visible light sensitive photocatalyst, AgSbO3 was prepared by a conventional solid-state reaction method. This oxide belonging to a cubic-pyrochlore structure can absorb visible light with wavelength up to about 480nm. From the band structure calculation, we found that the top of the valence band consists of the hybridized Ag 4d and O 2p orbitals and the bottom of the conduction band mainly consists of the Ag 5s and the Sb 5s orbitals. Photocatalytic activities were evaluated using O2 evolution from an aqueous silver nitrate solution and decomposition of gaseous 2-propanol under visible light irradiation. We found that AgSbO3 shows a higher O2 evolution activity than WO3 and 2-propanol can be mineralized by the AgSbO3 photocatalysis under visible light irradiation.
The combination of functional and morphological imaging technologies such as positron emission tomography (PET) and X-ray computed tomography (CT) has shown its value in the clinical and preclinical field. However, CT provides only very limited soft-tissue contrast and exposes the examined patient or laboratory animal to a high X-ray radiation dose. In comparison to CT, magnetic resonance tomography (MRI) provides excellent soft-tissue contrast and allows for nuclear magnetic resonance spectroscopy (NMRS) or functional MRI (fMRI). Thus, the combination of PET and MRI has been pursued for several years. First approaches have succeeded using conventional photo multiplier tube (PMT) technology together with light fibers to transfer scintillation light away from the high magnetic field. Latest PET/MRI developments use solid-state light detectors that can be operated even at high magnetic fields. Initial pilot studies with prototype animal PET/MRI systems have shown ...
The Savannah River Site is a Department of Energy facility. The facility stores, processes, and works with fissionable material at a number of locations. Technical standards and US Department of Energy orders, require these locations to be monitored by criticality alarm systems under certain circumstances. The Savannah River Site calls such instruments Nuclear Incident Monitors or NIMs. The Sole purpose of the Nuclear Incident Monitor is to provide an immediate evacuation signal in the case of an accidental criticality in order to minimize personnel exposure to radiation. The new unit is the third generation Nuclear Incident Monitor at the Savannah River Site. The second generation unit was developed in 1979. It was designed to eliminate vacuum-tube circuits, and was the first solidstate NIM at SRS. The major design objectives of the second generation NIM were to improve reliability and reduce maintenance costs. Ten prototype units have been ...
In this study a modified solidstate synthesis (auto-ignition method) is used to form nanosized spinel type material LiMg{sub 0.05}Ni{sub 0.45}Mn{sub 1.5}O{sub 4}. This material presents a high voltage plateau at 4.75 V vs. Li/Li{sup +}. Structural and electrochemical characterisations have been performed using a wide range of techniques (TEM, neutron diffraction, galvanostatic measurements, and impedance spectroscopy). Besides, in situ XAS has been performed to monitor the evolution of Ni and Mn oxidation state during Li intercalation. The material presents an ordered cubic spinel structure, good capacity retention upon cycling (131 mAh g{sup -1} at C/10 and 117 mAh g{sup -1} at 1C) and good electronic conductivity (10{sup -6} S cm{sup -1} at RT). The simultaneous presence of Mn{sup 3+}/Mn{sup 4+} in the structure has been investigated and explained by inclusion of disordered nanodomains in the structure. (author)
Monodisperse noble metal nanoparticles are of tremendous interest for numerous applications, such as surface-enhanced Raman spectroscopy, catalysis or biosensing. However, preparation of monodisperse metal nanoparticles is still a challenging task, because typical preparation methods yield nanoparticle ensembles with broad shape and/or size distributions. To overcome this drawback, tailoring of metal nanoparticles with laser light has been developed, which is based on the pronounced shape- and size-dependent optical properties of metal nanoparticles. I will demonstrate that nanoparticle tailoring with ns-pulsed laser light is a suitable method to prepare nanoparticle ensembles with a narrow shape and/or size distribution. While irradiation with ns-pulsed laser light during nanoparticle growth permits a precise shape tailoring, post-grown irradiation allows a size tailoring. For example, the initial broad Gaussian size distribution of silver nanoparticles on quartz substrates with a ...
The applicability of in situ, real-time RBS is demonstrated by characterizing the growth of thin Pd_2Si films on Si left angle 111 right angle substrates using isothermal as well as non-isothermal annealing. In contrast to the currently fashionable in situ ramped resistance technique, it is possible to extract the activation energy from a single run with a constant heating rate. The results, which are in excellent agreement with the literature, will be compared for isothermal annealing, fitting an appropriate model for the growth process to data from a single run and a Kissinger-like analysis with different ramp rates. In situ, real-time RBS was also used to study marker motion during CrSi_2 formation in the Si left angle 100 right angle /Pd_2Si/Cr system. It is possible to distinguish between the following mechanisms: (1) CrSi_2 formation via dissociation of the Pd_2Si at the Pd_2Si/Cr interface and subsequent reaction of Pd to form Pd_2Si at the Si/Pd_2Si interface and (2) CrSi_2 ...
Semiconductive crystalline PZT powders doped with Bi and K were synthesized by hydrothermal reaction at 200{degree}C for 48 hours. The synthesis of the crystalline powders became difficult with an increase in doped amount of Bi and K, and in Zr/(Ti+Zr) ratio. Since substantial amounts of Pb remained in solution after hydrothermal reaction, the addition of Pb in excess of 25% was necessary to obtain the stoichiometric composition of the PZT solid solution. Bi contents in the powders were identical to those in starting materials, while K contents were less than expected ones. The electromechanical properties of the sintered bodies could be precisely measured by an admittance-curve-fitting method. The electromechanical coupling factor and piezoelectric coefficient of the sintered bodies varied with the Bi content like those of specimens prepared by solidstate reaction, and showed the maximum values at a given Bi content. However, the change in ...
Ho{sub 2}CuTiO{sub 6} double pervoskite is synthesized by solidstate reaction method and the phase formation was confirmed by X-ray diffraction. Ho{sub 2}CuTiO{sub 6} crystallizes in space group P63 cm and are isostructural in AMnO{sub 3} structure. We have investigated the effect of the presence of a magnetic ion (Ho{sup 3+}{approx}10.4{mu}{sub B}) in Ho{sub 2}CuTiO{sub 6}, on the magnetic properties, compared to that of an isostructural double perovskite containing Y-ion (non-magnetic), i.e., Y{sub 2}CuTiO{sub 6}. Magnetization measurements on Ho{sub 2}CuTiO{sub 6} showed paramagnetic moment of 0.026{mu}{sub B}/Ho at room temperature in an applied field of 7 T although no saturation is observed at room temperature, whereas, at 5 K, the paramagnetic moment was 0.3{mu}{sub B}/Ho in the same field. Since this compound is non-centrosymmetric, it is of interest to look into the possibility of realizing multiferroicity (coexistence of magnetic and ...
We will report on a new type of tunable semiconductor laser, which is based on the electronic selection of one Bragg grating among an array of such gratings in silica. The device that we have built operates at 120 Mb/s but extension to 1 Gb/s for Gigabit-Ethernet applications would be straightforward. In comparison with tunable semiconductor lasers using gratings in the III-V materials, silica gratings offer two significant advantages: 1-wavelength stability and predictability, 2-the ability to phusically overlap many gratings in a compact space in order to enable the selection of a large number of wavelengths for wavelength division multiplexed communications systems. The time required to chagne the wavelength in our laser has not been measured for lack of the necessary electronics but it is expected to be in the microsecond range on the basis of a straightforward calculation. The robust all solid-state nature of our device and its expected microsecond ...
BaxSr1-xTiO3 (x=0.6, 0.75, 0.80, 0.85 and 0.9) compositions are prepared by solid-state reaction route using controlled heating and cooling. Density optimization by varying sintering temperature was achieved. X-ray diffraction (XRD) analysis shows the phase pure materials. The lattice constant decreases from 3.9868A (x=0.90) to 3.9449A (x=0.60) with increasing Sr2+; the tetragonal distortion also decreases. Dielectric constant show sharp peaks for samples having low strontium content (0.10, 0.15) and gets smeared out as the strontium content is increased (0.20, 0.25). For further higher Sr2+ composition (0.40), the dielectric peak could not be observed in the measured temperature range. The peak broadening in Sr2+ rich compositions indicates that diffused transitions and is attributed to t...
Phosphor material BaAl2O4:Eu2+, Dy3+ with varying compositions of Sr substitution were prepared by the solid-state synthesis method. The phosphor compositions were characterized for their phase and crystallinity by XRD, SEM and TEM. Photoluminescence (PL) properties were investigated measuring PL and decay time for varying Ba/Sr compositions. The PL results show the blue shift in the luminescence properties in Sr substituted BaAl2O4:Eu2+, Dy3+ compared to parent BaAl2O4:Eu2+, Dy3+. It is probably due to the influence of 5d electron states of Eu2+ in the crystal field because of atomic size variation causing crystal defects. Dy3+ ion doping in the phosphor generates deep traps, which results in long afterglow phosphorescence.
Makrofol-De 1-1 CC Polycarbonate is a class of polymeric solidstate nuclear track detectors which has many applications in various industrial fields. A study of the modification possibility of the dielectric properties of Makrofol polymer using laser irradiation has been carried out. In tbe present work, Makrofol samples were irradiated using different fluences between 0.47 and 10.4 J/cm"2 of 5 watt infrared pulsated laser. The mollifications in the laser irradiated Makrofol samples have been studied as a function of fluence using dielectric constant #epsilon#', dielectric loss #epsilon#"and AC conductivity #sigma#_AC measurements. Tbe frequency dependencies (100 Hz-5 MHz) of #epsilon#', #epsilon#"and #sigma#_AC at 35 degree c were investigated. The dielectric constant #epsilon#', dielectric loss #epsilon#"and AC conductivity #sigma#_AC were found to increase at heating up to 100 degree C. This indicates that #epsilon#', #epsilon#"#sigma#_AC ...
Holmium doped barium based hexaferrites BaFe12-2xHo2xO19 with (x=0.0-1.0) were synthesized by solidstate reaction method. Structural and magnetic characterization of these ferrites provide significant information about their reactive physical properties. X-ray analysis reveals that in all samples M-type structure exist with few secondary phases. Scanning electron microscope revealed the grain size of the specimen. The results show that grain size decreases with the substitution degree of Holmium. Thus rare earth element Holmium Ho^3^+ acts as a grain growth inhibitor. The magnetic hysteresis loops show the variation in the values of magnetic parameters like saturation magnetization (Ms), remanent magnetization (Mr) and coercivity (Hc) were observed by changing Ho^3^+ content in BaFe12-2xH...
Holmium doped barium based hexaferrites BaFe_1_2_-_2_xHo_2_xO_1_9 with (x = 0.0-1.0) were synthesized by solidstate reaction method. Structural and magnetic characterization of these ferrites provide significant information about their reactive physical properties. X-ray analysis reveals that in all samples M-type structure exist with few secondary phases. Scanning electron microscope revealed the grain size of the specimen. The results show that grain size decreases with the substitution degree of Holmium. Thus rare earth element Holmium Ho"3"+ acts as a grain growth inhibitor. The magnetic hysteresis loops show the variation in the values of magnetic parameters like saturation magnetization (M_s), remanent magnetization (M_r) and coercivity (H_c) were observed by changing Ho"3"+ content in BaFe_1_2_-_2_xHo_2_xO_1_9 ferrites. Coercivity showed a maximum value of 2230 Oe for (x = 0.4) and then decreasing trend were observed in the values of ...
We have developed a transportable container based direct detection Doppler lidar based on the double-edge molecular technique. The pulsed solidstate system was built at the University of Geneva. It was used to make range resolved measurements of the atmospheric wind field as part of the VALID campaign at the Observatoire de Haute Provence in Provence, France in July 1999. Comparison of our lidar wind measurements, which were analyzed without knowledge of the results of rawinsonde measurements made under the supervision of ESA, show good agreement with these rawinsondes. These are the first Doppler lidar field measurements made with an eyesafe direct detection molecular-based system at 355 nm and serve as a demonstrator for future spaceborne direct detection wind systems such as the Atmospheric Dynamics mission. Winds are an important contributor to sea surface temperature measurements made with the Tropical Rainfall Measuring Mission (TRMM) ...
The personal neutron dosimetry becomes more important with the increasing use of nuclear and accelerator facilities. The solidstate track detector, film badge and thermo-luminescent dosimeter have widely been used as passive-type personal neutron dosimeters, but the real-time neutron dosimeter is strongly needed. A real time personal dosimeter which could give neutron dose equivalent over wide energy range from thermal to 10 odd MeV by using two neutron sensors has been developed by our group. For practical commercial product, some changes from these prototype sensors have recently been done by Fuji Electric Co. Ltd. The purpose of this work is the final performance test of the dosimeter just before sale. We checked again about the sensitivity in the monoenergetic neutron field from 8 keV to 15 MeV and in the neutron fields around a few accelerator facilities. (author)
The University of Georgia, in collaboration with GE Global Research, has investigated the relevant quenching mechanism of phosphor coatings used in white light devices based on UV LEDs. The final goal of the project was the design and fabrication of a high-efficacy white light UV-LED device through improved geometry and optimized phosphor coatings. At the end of the research period, which was extended to seamlessly carry over the research to a follow-up program, we have demonstrated a two-fold improvement in the conversion efficiency of a white light LED device, where the increase efficacy is due to both improved phosphor quantum efficiency and lamp geometry. Working prototypes have been displayed at DOE sponsored meetings and during the final presentation at the DOE Headquarters in Washington, DC. During the first phase of the project, a fundamental understanding of quenching processes in UV-LEDs was obtained, and the relationships that describe the performance of the phosphor as a ...
The University of Georgia, in collaboration with GE Global Research, has investigated the relevant quenching mechanism of phosphor coatings used in white light devices based on UV LEDs. The final goal of the project was the design and fabrication of a high-efficacy white light UV-LED device through improved geometry and optimized phosphor coatings. At the end of the research period, which was extended to seamlessly carry over the research to a follow-up program, we have demonstrated a two-fold improvement in the conversion efficiency of a white light LED device, where the increase efficacy is due to both improved phosphor quantum efficiency and lamp geometry. Working prototypes have been displayed at DOE sponsored meetings and during the final presentation at the DOE Headquarters in Washington, DC. During the first phase of the project, a fundamental understanding of quenching processes in UV-LEDs was obtained, and the relationships that describe the performance of the phosphor as a ...
Measurements have been made of radon ("2"2"2Rn), release from diverse quaternary samples collected from different sediment deposits in the Errachidia and Beni-Mellal areas (Morocco). The radon diffusion coefficient as one of some important parameters of radon transport in the soil has been measured using solidstate nuclear track detectors (SSNTD). Radon #alpha#-activity, uranium content and radon exhalation rate have been determined in the studied samples. Uranium concentrations were found to vary from 0.14 to 9.52 ppm whereas the radon exhalation rate varied from 0.003 to 0.145 Bq x m"-"2 x h"-"1. A positive correlation has been found between radon exhalation rate and uranium content in the studied samples. The average radon diffusion coefficients were found to vary from (1.26 #+-# 0.09) x 10"-"6 m"2 x s"-"1 to (4.3 #+-# 0.36) x 10"-"6 m"2 x s"-"1. Furthermore, the correlation between "2"2"2Rn diffusion coefficient and porosity are also ...
Solidstate nuclear track detectors (SSNTD) record radiation in the form of tracks. In the case of high track density, however, it is not always possible to distinguish each track separately. The track density might then be underestimated unless the loss of track number due to overlapping is compensated. An elaborated 'erosion' or curve fitting process is applied usually, for the separation of the overlapping tracks, to automatic track counting systems. This paper shows a much simpler correction method which was developed by the analogy of the correction equation for the dead time of GM counters. From a set of about 10 data obtained from high track density detectors, the equation for SSNTD can be determined by a least square fitting. Once the equation is found, true track density could be derived easily without any help of complex image processing or calculation, such as the erosion or curve fitting. This method also provides ...
In the past, organic substance is generally deemed as electrical insulator, but in recent years, molecular crystals and polymers showing electroconductivity like metal were synthesized and even those showing superconductivity have appeared. These materials are called organic metals or synthetic metals and have peculiar solidstate physical properties. Examples of real application of organic electroconductive materials are becoming available, but in this article, a chip type aluminum solid electrolytic capacitor using polypyrrole is introduced. There are four kinds of capacitors including ceramic capacitors and aluminum electrolytic capacitors, etc. The aluminum electrolytic capacitor is most retarded than any other type of capacitor in introducing its chip type since its use of electrolytic solution becomes an obstacle. Polypyrrole synthesized by electrolytic polymerization through anode oxidation of pyrrole has good stability and high ...
Global meat and milk consumption is exponentially increasing due to population growth, urbanization and changes in lifestyle in the developing world. This is an excellent opportunity for developing countries to improve the livestock sector by using technological advances. Biotechnology is one of the avenues for improved production in the "Livestock revolution". Biotechnology developments applied to livestock health, nutrition, breeding and reproduction are improving with a reasonable pace in developing countries. Simple bio-techniques such as artificial insemination have been well implemented in many parts of the developing world. However, advanced technologies including transgenic plant vaccines, marker assisted selection, solidstate fermentation for the production of fibrolytic enzymes, transgenic fodders, embryo transfer and animal cloning are confined largely to research organizations. Some developing countries such as Taiwan, China and ...
An ever first attempt has been made to investigate the possible anode performance characteristics of LiFePO{sub 4}, popularly known so far as an environmentally compatible and economically viable lithium battery cathode material. The compound LiFePO{sub 4} has been synthesized via solidstate method and explored for the first time as an anode material against lithium metal through the present study. Surprisingly, an initial capacity of circa 620 mAh/g has been exhibited by LiFePO{sub 4} anode, which is about 4-5 times higher than the capacity of the corresponding LiFePO{sub 4} cathodes. Also an excellent coulombic efficiency value of 99% has been shown by the compound, especially upon extended cycling. The extraordinarily higher specific capacity values of LiFePO{sub 4} anodes may be exploited suitably for practical lithium battery applications.
There has been a good deal of interest in the sialon system of ceramics in recent years due to their combination of important engineering properties #beta# including strength, hardness, low thermal expansion and good thermal shock resistance. #beta#-sialon (Si_6_-_zAl_zO_zN_8_-_z ;0solid state Nuclear Magnetic Resonance techniques in determining the nature of intermediate phases which occur. 9 refs., 1 tab., 1 fig.
Isotherms have been measured for H(D){sub 2}(g) solution in crystalline Pd{sub 9}Si{sub 2} in the temperature range from 235 to 373 K. The solubilities are significant, e.g., at 1.0 MPa (298 K), (H/Pd) = 0.052 or Pd{sub 9}Si{sub 2}H{sub 0.47}, however, there is no indication of hydride phase formation even down to 235 K at 1.0 MPa. The thermodynamic values for hydrogen solutions at infinite dilution of hydrogen are {Delta}H{degrees}{sub H}= -11.9 kJ/mole {1/2}H{sub 2} and {Delta}S{degrees}{sub H} = -50 J/K mole {1/2}H{sub 2}. The former is more negative than for Pd-H{sub 2} and the latter is somewhat more positive; but generally the values are not that different from Pd-H{sub 2}. The isotope effect is similar to that found for Pd-H(D){sub 2}.
Methods for the synthesis and quantitation of the novel choline analogues, telluronium choline and acetyltelluronium choline, are described. An assay procedure utilizing pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) with cold trapping was developed with [2H4]telluronium choline and [2H4]acetyltelluronium choline as internal standards. The telluronium compounds were ion-pair extracted from tissue with dipicrylamine, washed with 2-butanone, and pyrolyzed prior to GC-MS analysis. The compounds were monitored using selected ion monitoring at m/z 232 and m/z 190 for acetyltelluronium and telluronium choline, respectively, and at m/z 236 and m/z 194 for the analogous deuterated internal standards. The assay was linear over a range of 20 pmol-20 nmol of compound taken through the assay. PMID:8130881
By methods of vibrational (infrared, Raman) and PMR spectroscopy, crystallohydrate forms of monosubstituted uranyl orthophosphate have been examined. The vibrational frequencies of the groupings from the compounds were identified. The existence of non-equivalent H_2PO_4"--groups in the substances under investigation was ascertained. It has been suggested that one of them is a bridged group, and the other is the end group. A fragment of the VO_2(H_2PO_4)_2 hydrate structure is given, its main constituents being uranylphosphate chains. The analysis of water vibrations assumes coordination of one mole of H_2O in VO_2(H_2PO_4)_2:3H_2O to uranium, while two other molecules are only hydrogen-bonded with phosphate anions. Absorption within the region of 2100-2550 cm"-"1 is assigned to vibrations of O...H...O groupings.
The ECP of construction materials in the water steam circuits of power plants is influenced by many parameters, including: reactions of oxidants, such as O{sub 2} or dissolved copper species; and reactions of reducing species, namely N{sub 2}H{sub 4}. Electrochemical measurements were performed to clarify the role of hydrazine for the open circuit potential in water/steam circuits. Current density electrode potential curves of the electrochemical oxidation of hydrazine and the reduction of oxygen in aqueous solutions were measured as a function of temperature in the range from room temperature to approximately 260{degrees}C. The electrode materials used were platinum, gold and Alloy 800 mod.. In addition, corrosion potentials were measured in water containing oxygen or hydrazine.
The effect of a series of complexing and reducing agents on the extraction-chemical behavior of technetium as applied to extraction splitting of uranium and plutonium in the Purex process was examined. Kinetic parameters of the catalytic decomposition of N2H5NO3 under the action of Tc in the presence of these agents were evaluated. Variation of the ratio of the oxidized and reduced Tc species in the course of the process and in the hydrazine-free systems was determined. Reagents preventing oxidation of the reduced technetium and decomposition of N2H5NO3 in nitric acid solutions (acetohydroxamic acid, hydroxylamine, ascorbic acid, etc.), inhibiting the reduction of Tc with hydrazine nitrate (H2O2, HN3, etc.), and known as complexing agents toward quadrivalent actinides but indifferent to Tc...
The reactions of the hydroxyl radical with hydrocarbons and fluoro hydrocarbons attract significant attention due to their importance in atmospheric chemistry. Its reactions with the two first hydrocarbons, methane and ethane are of special interest because, owing to the small size of these systems, they serve as a prototype for the theoretical studies of hydrogen abstraction reactions. In this work, the reaction and activation energies of the hydroxyl radical abstraction reaction with methane and ethane have been investigated by correlated ab initio and DFT methods. The DFT reaction energies are in good agreement with experimental values, but the activation energies may be in severe error. (authors) 22 refs.
Abstract Surface modification of topography and chemistry in order to achieve a specific water contact angle (CA) has been explored by using a novel combinatorial screening platform. The screening arrays consisted of 507 distinct combinations of micro-topographies and chemical compositions. By performing chemical modifications with 1H, 1H, 2H, 2H perfluoroethyltriethoxy-silane (PFS) and n-octadecyltriethoxysilane (ODS) on standard silicon wafers it was possible to include both superhydrophobic and very hydrophilic pad arrays in the same screening platform. Surfaces modified with PFS were more hydrophobic than surfaces modified with ODS, while the unmodified silicon surfaces were hydrophilic. For the PFS modified surfaces the largest CAs were achieved with a small pillar size of X-=-1-m and...
Reaction kinetics for the displacement of 5-aminoquinoline (5-Aq) and diethyl sulfide (SEt{sub 2}) from cis-[PtPh{sub 2}(CO)(L)] (L = 5-Aq or SEt{sub 2}) by aliphatic amines was measured for a wide array of amines. Reaction products were characterized by IR and NMR spectroscopies and crystalk structures of selected products were reported. Steric effects on the substitutions were discussed.
The wavefunction of a particle extends into the classically forbidden barrier region of the potential energy surface. The consequence of this partial delocalisation is the phenomenon of quantum tunnelling, an effect which enables a particle to penetrate a potential barrier of magnitude greater than the energy of the particle. The tunnelling probability is an exponential function of the particle mass. The effect is therefore an important contribution to the behaviour of light atoms, in particular the proton. The hydrogen bond has long been appreciated to be an essential component of many biological and chemical systems, and the proton transfer reaction in the hydrogen bond is fundamental to many of these processes. The proton behaviour in the hydrogen bonds of benzoic acid, acetylacetone and calix-4-arene has been studied. A variety of techniques, both experimental and computational, were adopted for the study of the three hydrogen bonded systems. The complementary spectroscopic ...
In this article, the authors recall the factors apt to influence image quality in NMR Imaging and present the european works that have been developed in MRIQA to set 5 quality assurance tests: EUROSPIN 1 to 5.
The marked difference between the intra- and extracellular "3"1P NMR chemical shifts of various phosphoryl compounds when added to a red cell suspension may be largely understood in terms of the effects of hemoglobin on the "3"1P NMR chemical shifts. The presence of [oxy- or (carbonmonoxy)-] hemoglobin inside the red cell causes the bulk magnetic susceptibility of the cell cytoplasm to be significantly less than that of the external solution. This difference is sufficient to account for the difference in the intra- and extracellular chemical shifts of the two phosphate esters trimethyl phosphate and triethyl phosphate. However, in the case of the compounds dimethyl methylphosphonate, diethyl methylphosphonate, and trimethylphosphine oxide as well as the hypophosphite, phenylphosphinate, and diphenylphosphinate ions, hemoglobin exerts an additional, much larger, effect, causing the "3"1P NMR resonances to shift to lower ...
Titanium and aluminum alkoxide derivatives with polymerizable ligands such as 2-(methacryloyloxy)ethylacetoacetate (HAAEMA), oleic acid and geraniol (HOGE) have been obtained. The various compounds have been characterized by FT-IR and NMR {sup 1}H. Copolymerization with styrene and divinylbenzene affords porous doped organic materials which have been characterized by scanning electron microscopy (SEM), elemental analysis, density measurements.
Analysis of published NMR relaxation data of /sup 6/Li and /sup 7/Li in Li/sub 3/N leads to a unique model fo Li/sup +/ hopping along the c-axis. It is one in which an ion goes directly from one Li(1) plane to another Li(1) plane by passing through the intermediate Li(2) plane.
Temperature-dependent (5-42 degrees C) 13C NMR spectra of albumin complexes with 90% isotopically substituted [1-13C]decanoic acids (3 mol of fatty acid per mol of albumin) showed a single peak at greater...Full Text Available
The susceptibility of solid "3He is deduced from multiple echoes observed in pulsed NMR experiments. It follows a Curie Weiss law at high temperature, increases faster than this law below 5 mK and drops abruptly around 1 mK. (Auth.).
A pulsed field gradient spin echo sequence has been incorporated in a nuclear magnetic resonance (NMR) imaging experiment to provide an image contrast dependent on local molecular self-diffusion. The...Full Text Available
A nonperturbing 13C nuclear magnetic resonance (NMR) method was used to monitor the equilibrium distribution of carboxyl 13C-enriched fatty acids (FA) between distinct binding sites on human serum albumin,...Full Text Available
Aqueous solutions of 2-amino-2-hydroxymethyl-1,3-propanediol (AHPD), a sterically hindered amine, was examined as a potential CO{sub 2} absorbent and compared with the most commonly used absorbent, monoethanolamine (MEA) solution, through equilibrium solubility measurements and {sup 13}C NMR spectroscopic analyses. The solubilities of CO{sub 2} in aqueous 10 mass % AHPD solutions were higher than those in aqueous 10 mass% MEA solutions above 4 kPa at 298.15 K, but lower below 4 kPa. The solubility difference between these two solutions increased with the CO{sub 2} partial pressures above the crossover pressure. Equilibrated CO{sub 2}-MEA-H{sub 2}O and CO{sub 2}-AHPD-H{sub 2} solutions at various CO{sub 2} partial pressures ranging from 0.01 to 3000 kPa were analyzed by {sup 13}C NMR spectroscopy. AHPD contains more hydroxyl groups than nonhindered MEA, and hence the chemical shifts in its {sup 13}C NMR spectra were strongly ...
We have measured, by {sup 1}H and {sup 13}C nuclear magnetic resonance (NMR), the percent deuteration, the tacticity and the purity of several polymers and one solvent used in the preparation of microcellular foams. The percent deuteration was measured for polystyrene, polyacrylonitrile and polyethylene. The tacticities of polystyrene and polyacrylonitrile were determined. The purity and degradation products of polyacrylonitrile and maleic anhydride were examined. This report documents the experimental procedures and results of these measurements.
For the intermetallic system CaCdsub(1-x)Tlsub(x), 0 <= x <= 1, the Knight shift Ksub(s) of the Cd-NMR and the Tl-NMR were calculated as a function of x, Ksub(s) = Ksub(s)(x). The theoretical investigations were performed on the basis of relativistic augmented-plane-wave (RAPW) band-structure calculations for the boundary phases CaCd and CaTl respectively, and by using the rigid band model for the ternary phases. The density of states and the matrix elements of the relativistic hyperfine operator for electron states at the Fermi surface were calculated in detail. The obtained values were compared with nonrelativistic calculations. The effect of using different exchange potentials was studied for Ksub(s)(Tl). For the Cd-NMR the relativistic effects enhance the nonrelativistic results by a factor of about 1.4. The theoretical value for the Knight shift is smaller than the experimental one by a factor of 1.13. The band ...
Besarhanamides A (1) and B (2) are fatty acid amides purified from the marine cyanobacterium, Lyngbya majuscula, collected from Pulau Hantu, Singapore. The structure determination of these secondary metabolites was carried out using extensive 2D NMR spectral data as well as chemical manipulations including the Marfey's method. In addition, besarhanamide A exhibited moderate toxicity with LD50 at 13mM in the brine shrimp toxicity bioassay.
One- and two-dimensional NMR techniques have been used to investigate the solution structures of (2S,6S,11S,15S)-2,6,11,15-tetramethyl-1,4,7,10,13,16-hexaoxacyclooctadecane (I) and (2R,3R,11R,12R)-2,3,11,12-tetramethyl-1,4,7,10,13,16-hexaoxyacyclooctadecane (II) macrocycle complexes of CaCl{sub 2} and Ca(NO{sub 3}){sub 2} in CDCl{sub 3}. Previous chiroptical studies of these and similar crown complexes by circularly polarized luminescence (CPL), total luminescence (TL), and circular dichroism (CD) spectroscopy have shown that the macrocycle asymmetric carbons in these complexes constrain the ring such that the sense of the ring twist in the S chiral ring complexes is opposite to that in the R chiral ring complexes. These studies have also shown that there is an added chirality element in the di- and trivalent (alkaline earth and lanthanide metal, respectively) nitrate complexes of I and II associated with the twist of the nitrate anions relative to one another as ...
By the example of CH2Cl2, CF2Cl2, CHF2Cl, C2F6, C2H6, SF6 and C6H12 we have investigated the isobaric thermal conductivity jump at crystal-liquid phase transition. It is shown that the reduction in the thermal conductivity at melting derives from the degree of orientational ordering of the crystals at pre-melting point.
An intermetallic compound Sm[sub 2]Fe[sub 17]N[sub x] was synthesized by plasma nitriding of Sm[sub 2]Fe[sub 17] in a stream of N[sub 2]-H[sub 2] mixed gas. The reaction proceeded at a lower temperature (around 423 K) than that of the conventional thermal technique, but not at room temperature. This is discussed on the basis of the difference between the reaction mechanisms of plasma and thermal nitridings. (orig.)
Brushite (CaHPO4·2H2O) was considered to govern the formation of renal calculus of calcium phosphate origin. The degree of saturation of urine with respect to this phase...Full Text Available
Methanobacterium thermoautotrophicum, M. ruminantium, and Methanosarcina barkeri were labeled with 14CO2 (14CO2 + H14CO3- + 14CO32-) for from 2 to 45 s. Radioactivity was recovered in coenzyme M derivatives,...Full Text Available
Molar extinction coefficients for the solid solutes in aqueous solutions of some alkaline earth chlorides such as MgCl_2.6H_2O, CaCl_2, SrCl_2.6H_2O and BaCl_2.2H_2O have been determined at 81, 356, 511, 662, 1173 and 1332 keV energies in different concentration using the narrow beam transmission methods. (author)
The effect of the non-selective, 1-aminoindan-1,5-dicarboxylic acid (AIDA), and selective (3,4-dihydro-2H-pyrano[2,3-b]quinolin-7-yl)-(cis-4- methoxycyclohexyl) methanone (JNJ16259685),...Full Text Available
Hydrology and hydrogeochemical are auxiliary techniques to valid conceptual hydrogeology an recharge models. Stable isotopes from water trace sources and path flow and Tritium indicates age. This paper is about the use of D 18, D2H y 3H to study the aquifer system on Bajo Cauca antioqueno.
The H-D exchange reaction has been measured with the D2-H2O system, for Rhodobacter capsulatus JP91, which lacks the hupSL-encoded hydrogenase, and R. capsulatus BSE16, which lacks the HupUV proteins....Full Text Available
Among the three modifications of calcium sulfite hemihydrate, two of them, hexagonal ..beta..-CaSO/sub 3/.1/2H/sub 2/O with a rhombohedral lattice and ..gamma..-CaSO/sub 3/.1/2H/sub 2/O with a simple triangular hexagonal lattice, were found in the authors' recent work. By heating ..cap alpha..- and/or ..gamma..-hemihydrate at 330-360/sup 0/C in a nitrogen atmosphere, the orthorhombic anhydrate ..cap alpha..-CaSO/sub 3/ was formed, with lattice constants of 6.472, 15.93, and 23.44 angstrom for a, b, and c respectively, while the body-centered tetragonal anhydrate ..beta..-CaSO/sub 3/, with lattice constants of 15.68 and 19.44 angstrom for a and c respectively, was formed by heating the ..beta..-hemihydrate. The dehydration of three hemihydrates and the hydration of two anhydrates were discussed. Calcium sulfite hemihydrate (CaSO/sub 3/.1/2H/sub 2/O) is ...
The advance in the analysis of very small amount (<= 1#alpha#/cm"2h) of #alpha#-emitters in the cited materials is reviewed. The review, for which 75 references are listed, covers the period from January, 1978, to June, 1982. The use of #alpha#-ray counting, #alpha#-ray spectrometry, #gamma#-ray spectrometry, neutron activation analysis and mass spectrometry is discussed, and their relative merit and limitation are outlined. (J.P.N.).
NO{sub x} compounds, specifically NO and NO{sub 2}, are pollutants and potent greenhouse gases. Compact and inexpensive NO{sub x} sensors are necessary in the next generation of diesel (CIDI) automobiles to meet government emission requirements and enable the more rapid introduction of more efficient, higher fuel economy CIDI vehicles. Because the need for a NO{sub x} sensor is recent and the performance requirements are extremely challenging, most are still in the development phase. Currently, there is only one type of NO{sub x} sensor that is sold commercially, and it seems unlikely to meet more stringent future emission requirements. Automotive exhaust sensor development has focused on solid-state electrochemical technology, which has proven to be robust for in-situ operation in harsh, high-temperature environments (e.g., the oxygen stoichiometric sensor). Solid-state sensors typically rely on yttria-stabilized zirconia (YSZ) as the ...
We have performed multicanonical Monte Carlo simulations of C-peptide of ribonuclease A. It is known by CD and NMR experiments that this peptide has high alpha-helix content in aqueous solution and that the side-chain charges of residues Glu-2$^-$ and His-12$^+$ play an important role in the stability of the alpha-helix. In order to confirm these experimental implications, we have used two analogues of the peptide with charged and neutral side chains of Glu-2 and His-12. Two dielectric functions, distance-dependent and constant, are considered to study the effects of solvent contributions. All the simulations were started from random initial conformations. Various thermodynamic quantities such as average helicity as a function of residue number and average distance between two side chains as a function of temperature are calculated. The results are found to be in accord with the implications of CD and NMR experiments. The lowest-energy ...
A general approach has been designed to synthesize some mononuclear and binuclear cyclometalated platinum(II) complexes, containing aromatic N-donor ligands with the presence of one Cl- trans to carbon. In this way, cyclometalated platinum(II) complex [Pt(C^N)Cl(dmso)], 1, C^N = N(1),C(2prime)-chelated, deprotonated 2-phenylpyridine and dmso = dimethylsulfoxide, was used as a precursor to react with imidazole derivatives (1-methylimidazole, 2a, imidazole, 2b,), monodentate pyridine derivatives (4-methylpyridine, 2c, pyridine, 2d,) and bidentate pyridine derivative (4,4prime-bipyridine, 3 and 4,). Synthesized complexes were fully characterized by using multinuclear NMR spectroscopy (1H, 13C{1H} and 195Pt), correlation NMR spectroscopy (1H-1H COSY, 13C{1H}-1H Heteronuclear Multiple Quantum C...
Polypeptides, copolymers of #alpha#-amino acids and #alpha#-hydroxy acids, could prove to be a valuable new class of synthetic biodegradable polymers. In this paper. steps in synthesis of poly (dl-lactide-co-3, 6-dimethylmorpholine-2,5-dione) from dl-lactide and dl-3,6-dimethylmorpholine-2,5-dione was explained. dl-Lactide was synthesized from lactic acid. In the reaction of 2-bromopropionyl chloride and dl-alanine, N-(2-bromopropionyl)-dl-alanine was prepared and this material was converted to its salt and finally this salt was converted to 3,6-dimethylmorpholine-2,5-dione in a sublime r. These two monomers, that is d l-lactide and dl-3,6-dimethylmorpholine-2,5-dione was polymerized by ring-opening polymerization. F T-IR, "1H NMR, "1"3C NMR Spectra were used for structure elucidation of all intermediate compounds and final product.
The structure of the O-antigen polysaccharide (PS) from Escherichia coli O177 has been determined. Component analysis together with 1H and 13C NMR spectroscopy experiments was used to determine the structure. Inter-residue correlations were determined by 1H,13C-heteronuclear multiple-bond correlation and 1H,1H-NOESY experiments. PS is composed of tetrasaccharide repeating units with the following structure: 2)-a-l-Rhap-(13)-a-l-FucpNAc-(13)-a-l-FucpNAc-(13)-b-d-GlcpNAc-(1 An a-l-Rhap residue is suggested to be present at the terminal part of the polysaccharide, which on average is composed of 20 repeating units, since the 1H and 13C chemical shifts of an a-linked rhamnopyranosyl group could be assigned by a combination of 2D NMR spectra. Consequently, the biological repeating unit has a 3-...
Platinum(II) complexes (1-4) with bidentate N,Nprime-ligands, O,Oprime-dialkyl esters (alkyl = ethyl, n-propyl, n-butyl and n-pentyl), of (S,S)-ethylenediamine-N,Nprime-di-2-(4-methyl)pentanoic acid were synthesized and characterized by IR, 1H NMR and 13C NMR spectroscopy and elemental analysis. DFT calculations were performed for the complexes and it was found that only one diastereoisomer could be formed. Cytotoxic activity of complexes 1-4 was determined against chronic lymphocytic leukemia cells (CLL) and compared to the activity of ligand precursors L12HCl-L42HCl and corresponding palladium(II) complexes, [PdCl2L] (L = L1-L4). The complexes were found to exhibit significantly higher antitumor activities than cisplatin on CLL cells. Cytotoxic effect of platinum(II) complexes on CLL cel...
GSTD1 is one of several insect glutathione S-transferases capable of metabolizing the insecticide DDT. Here we use crystallography and NMR to elucidate the binding of DDT and glutathione to GSTD1. The crystal structure of Drosophila melanogaster GSTD1 has been determined to 1.1 {angstrom} resolution, which reveals that the enzyme adopts the canonical GST fold but with a partially occluded active site caused by the packing of a C-terminal helix against one wall of the binding site for substrates. This helix would need to unwind or be displaced to enable catalysis. When the C-terminal helix is removed from the model of the crystal structure, DDT can be computationally docked into the active site in an orientation favoring catalysis. Two-dimensional {sup 1}H,{sup 15}N heteronuclear single-quantum coherence NMR experiments of GSTD1 indicate that conformational changes occur upon glutathione and DDT binding and the residues that broaden upon DDT ...
Following the successful application of hydrostatic pressure in mechanistic investigations of organic reactions, chemists have launched a vigorous effort to apply this tool to substitution reactions of coordination compounds. The authors began to study pressure effects in the NMR spectra of keton-lanthanide combination with the hope that the increase shifts anticipated might enhance the utility of the method, perhaps even expand its applicability to new classes of compounds. 5-Phenyl- and 5-tert-butyladamantan-2-one, piperidine, tetrahydrofuran, and cyclopentanol exhibited pressure-reduced lanthanide-induced shifts with Eu(fod)/sub 3/; Yb(fob)/sub 3/ and the shielding reagent Pr(fod)/sub 3/ showed the same effect with adamantanone. Solvent variations (CD/sub 2/Cl/sub 2/, CCl/sub 4/) caused minor changes in the magnitude of these shifts but did not reverse any. With the objective of learning whether these effects are due to a suppressed equilibrium population or to ...
The pozzolanic behaviour of compound-activated red mud-coal gangue has been investigated through TG, DTA, XRD, FTIR and {sup 27}Al MAS NMR. From viewpoint of reaction kinetics, it is found that the pozzolanic reaction mechanism of the compound-activated red mud-coal gangue-lime system is clearly consistent with diffusion control up to 14 days, and the reaction rate constant calculated from Jander equation decreases with the increase of CaO addition in the system. The hydration products formed in the red mud coal gangue-lime systems at ambient temperature are essentially aluminous C-S-H and Ca{sub 3}Al{sub 2}O{sub 6} center dot xH{sub 2}O. From TG analysis results, it is thought that the high amount of Ca(OH){sub 2} in the pastes of studied system is not conducive to the continual increase of non-evaporable water content of the hydration products. Of particular interest. {sup 27}Al MAS NMR proved to be an effective technique to obtain valuable ...
The pozzolanic behaviour of compound-activated red mud-coal gangue has been investigated through TG, DTA, XRD, FTIR and 27Al MAS NMR. From viewpoint of reaction kinetics, it is found that the pozzolanic reaction mechanism of the compound-activated red mud-coal gangue - lime system is clearly consistent with diffusion control up to 14 days, and the reaction rate constant calculated from Jander equation decreases with the increase of CaO addition in the system. The hydration products formed in the red mud-coal gangue - lime systems at ambient temperature are essentially aluminous C-S-H and Ca3Al2O6.xH2O. From TG analysis results, it is thought that the high amount of Ca(OH)2 in the pastes of studied system is not conducive to the continual increase of non-evaporable water content of the hydration products. Of particular interest, 27Al MAS NMR proved to be an effective technique to obtain valuable information of Al[4] in C-S-H and Al[6] in ...
A tertiary structure of recombinant A22^G-B31^K-B32^R-human insulin monomer (insulin GKR) has been characterized by ^1H, ^1^3C NMR at natural isotopic abundance using NOESY, TOCSY, ^1H/^1^3C-GHSQC, and ^1H/^1^3C-GHSQC-TOCSY spectra. Translational diffusion studies indicate the monomer structure in water/acetonitrile (65/35vol.%). CSI analysis confirms existence of secondary structure motifs present in human insulin standard (HIS). Both techniques allow to establish that in this solvent recombinant insulin GKR exists as a monomer. Starting from structures calculated by the program CYANA, two different refinement protocols used molecular dynamics simulated annealing with the program AMBER; in vacuum (AMBER_VC), and including a generalized Born solvent model (AMBER_GB). From these calculation...
Ionic motion of a divalent cation, Ba"2"+, in a single crystal of Ba-Al-priderite was studied using "2"7Al as an NMR probe. Several pairs of satellite peaks due to electric quadrupole interaction were observed superposed on broad satellite tails on both sides of the main peak of "2"7Al. These peak pairs indicate the existence of some stable three-dimensional configurations of Ba"2"+ ions in the structure, and the broad shoulders show a random substitution of Al"3"+ for Ti"4"+ sites. The temperature dependence of the spin-lattice relaxation time T"*_l measured in the temperature range from 161 to 1176 K was analyzed by a curve fitting method on the assumption that there are two types of Ba"2"+ ions. An activation energy of 0.47 eV was obtained for the motion of Ba"2"+ ions which are easy to move, and a broad distribution of activation energies spread over a range from 0.95 to 2.45 eV was obtained for the motion of Ba"2"+ ions which form a three-dimensional honeycomb ...
Results of our systematic NMR study in high T_c cuprates are reviewed. The antiferromagnetic spin fluctuations (AFSF) decrease in the order of La_1_._8_5Sr_0_._1_5CuO_4. YBa_2Cu_3O_7 and Tl_2Ba_2CuO_6_+_y. 1/T_1 of "6"3Cu in the CuO_2 plane in the normal state follows essentially a Curie-Weiss law at high temperature and T_1T = const. law at low temperature. The temperature dependence of 1/T_1 and the Knight shift together with their impurity effect in the superconducting state strongly suggest d-wave pairing implying the AFSF to be responsible for the occurrence of superconductivity. From the NQR frequency measurement the density of Cu 3d and O 2p holes decreases and increases, respectively, in the order of La, Y and Tl compounds, which is consistent with the change of AFSF. The relation between T_c and #nu#_Q, and their pressure dependence suggest that there exists and optimum value of the ratio of Cu 3d and O 2p hole density to give a maximum in T_c. (orig.).
The available experimental data on the specific heat, magnetic susceptibility, magnetization, valence, NMR Knight shift and relaxation rate, and the quadrupolar moment of YbPd_2Si_2 are examined within the framework of the single-ion Anderson model. Such an analysis has previously given excellent agreement between theory and experiment for numerous other light heavy-fermion compounds, where crystalline fields do not play a dominant role. For YbPd_2Si_2, substantial crystalline-field splittings make difficult a quantitative comparison with existing exact solutions of the Anderson model. Inconsistencies with the interpretation that a nearly degenerate ground quadruplet determines the low-temperature thermodynamics are pointed out. It is concluded that at least three of the four Kramers doublets participate in the low-T properties. These three doublets should have a splitting of the order of the Kondo temperature, i.e., about 100 K. A simple resonant-level model ...
The available experimental data on the specific heat, magnetic susceptibility, magnetization, valence, NMR Knight shift and relaxation rate, and the quadrupolar moment of YbPd{sub 2}Si{sub 2} are examined within the framework of the single-ion Anderson model. Such an analysis has previously given excellent agreement between theory and experiment for numerous other light heavy-fermion compounds, where crystalline fields do not play a dominant role. For YbPd{sub 2}Si{sub 2}, substantial crystalline-field splittings make difficult a quantitative comparison with existing exact solutions of the Anderson model. Inconsistencies with the interpretation that a nearly degenerate ground quadruplet determines the low-temperature thermodynamics are pointed out. It is concluded that at least three of the four Kramers doublets participate in the low-{ital T} properties. These three doublets should have a splitting of the order of the Kondo temperature, i.e., about 100 K. A simple ...
The /sup 31/P NMR method was first applied to characterize in vivo phosphorylation of H1 and H5 in calf thymus and chicken erythrocytes as well as in vitro phosphorylation of H1 and H5 by cAMP-dependent protein kinase. The amino acid residues phosphorylated in vivo in the histones were exclusively serine residues, and the mole fraction of phosphoserine was estimated to be 0.34 and 0.27 per molecule of calf thymus H1 and chicken erythrocyte H5, respectively. Interestingly, chicken erythrocyte H1 was not phosphorylated in vivo. Three H1 subtypes from calf thymus H1 varied in the /sup 31/P NMR spectra, and the bisected fragments of calf thymus H1 and chicken erythrocyte H5 exhibited characteristic spectral patterns, indicating that there are considerable diversities of the degree of phosphorylation and phosphorylation sites in very-lysine-rich histones. Furthermore, it was found that the microenvironment of phosphoserine residues phosphorylated in ...
Monoclonal antibodies (MAbs) 19-9 and 73-3 specific for human colon adenocarcinoma were labelled with a high number of gadolinium atoms. Twenty five DTPA were chelated per MAb, with only slight loss of immunoreactivity. The NMR contrast agent Gd-25 DTPA-MAb 19-9 or 73-3 ((Gd) 17 mumole/kg, (MAb) 60 microM) was injected into nude mice bearing human colon adenocarcinoma (SW948). Tumors were removed 24 hr after injection and T1 was measured in vitro. T1 relaxation time varied according to MAb specificity against tumour targets; T1 decreased 20% for MAb 19-9 and MAb 73-3 with SW948 tumor. Imaging was performed with this model. Very good contrast was obtained 24 hr after Gd-25 DTPA-MAb injection.
The effect of the external pH on the intracellular pH in mung bean (Vigna mungo (L.) Hepper) root-tip cells was investigated with the T P nuclear magnetic resonance (NMR) method. The T P NMR spectra showed three peaks caused by cytoplasmic G-6-P, cytoplasmic Psub(i) and vacuolar Psub(i). The cytoplasmic and vacuolar pHs could be determined by comparing the Psub(i) chemical shifts with the titration curve. When the external pH was changed over a range from pH 3 to 10, the cytoplasmic pH showed smaller changes than the vacuolar pH, suggesting that the former is regulated more strictly than the latter. The H -ATPase inhibitor, DCCD, caused the breakdown of the mechanism that regulates the intracellular pH. H -ATPase appears to have an important part in the regulation of the intracellular pH.
The effect of the external pH on the intracellular pH in mung bean (Vigna mungo (L.) Hepper) root-tip cells was investigated with the "3"1P nuclear magnetic resonance (NMR) method. The "3"1P NMR spectra showed three peaks caused by cytoplasmic G-6-P, cytoplasmic Psub(i) and vacuolar Psub(i). The cytoplasmic and vacuolar pHs could be determined by comparing the Psub(i) chemical shifts with the titration curve. When the external pH was changed over a range from pH 3 to 10, the cytoplasmic pH showed smaller changes than the vacuolar pH, suggesting that the former is regulated more strictly than the latter. The H"+-ATPase inhibitor, DCCD, caused the breakdown of the mechanism that regulates the intracellular pH. H"+-ATPase appears to have an important part in the regulation of the intracellular pH. (author).
A mixture of long-chain hydrocarbons constituted by nonacosane (29C, 7.5%), hentriacontane (31C, 48.3%), and tritriacontane (33C, 30.1%), the ester 1?-acetyloxymethylpentacosa-20?-enyl 10-hydroxydecanoate (2), ?-amyrin (3), friedelin (4), and lupeol (5), and 3?-hydroxy-D:B-friedo-olean-5-ene (6) were identified as constituents of fruits of Maytenus salicifolia Reissek (Celastraceae). The structural formula and the stereochemistry of compound 6 were established by the data obtained through 1H and 13C NMR spectroscopy, including DEPT-135 and 2D (HMQC, HMBC, and NOESY) experiments. By analysis of the spectral data, it was possible to correct seven chemical shift assignments of compound 6, which were erroneous attributed and published in the scientific literature.
In our evaluation we utilized the Asahi Mark-J NMR-CT system, with a resistive vertical quadrupolar electromagnet (0.1 Tesla) and a proton resonance frequency of 4.5 MHz. Our main imaging methods are the inversion-recovery or IR, saturation-recovery, or SR, and calculated T/sub 1/. Difference, or D images, constructed by subtracting the data of the IR signal from that of the SR signal, have also been obtained in some cases. The system allows averaging of raw data. Hybrid images were constructed from two or more images to obtain clear definition of areas of interest. By using the hybrid image, several tissues of different relaxation times can be shown in the same image. Application in our study of the newly developed hybrid image indicates its importance in the detection and diagnosis of lesion, especially the detection of the differentiation of an edematous lesion from a tumor, and also abnormal fluid collection such as the pleural effusion or ascites. We hope that ...
A few metal complexes of isatin-isonicotinoylhydrazone with Ni(II), Cr(III), Co(II), Cu(II), Zn(II) and Cd(II) have been prepared and characterized on the basis of elemental analyses, infrared and electronic spectra as well as "1H NMR spectra, conductivity and magnetic measurements. In view of the results obtained, it has been found that two molecules of isatin-isonicotinoylhydrazone are chelated to the central metal ion as bis-uninegative ONO tridentate ligand forming non-electrolytic octahedral metal complexes. (author)
Syntheses of all five of the singly labeled (/sup 15/N)adenines are now provided. The presence or absence of two-bond /sup 15/N-/sup 1/H spin couplings in their /sup 1/H NMR spectra confirm the location of the isotope in each case. The fragmentation patterns in their mass spectra are indicative of the sequential losses of HCN units and of CH/sub 2/N/sub 2/ from adenine upon electron impact.
The first preparation and characterization of the platinum (II) complexes containing five phosphorus ligands are reported herein. The complexes are represented by the formulae (Pt(PP/sub 3/)(P(OR)/sub 3/)Cl/sub 2/, where R = Me or Et, and (Pt(PP/sub 3/)(PEt/sub 3/))Cl/sub 2/. The /sup 31/P spectra of the complexes are presented. 10 references, 2 tables.
Polytetrafluoroethylene was obtained by radiation induced polymerization of tetrafluoroethylene in acetone at 195 K. An average diameter of the products was very small compared with commercial one; it was about 0.3 micro-meters. The yield was reached to 100% with a dose of 4 kGy. The crystallinity of the products is decreasing with increasing dose. The products become amorphous, for higher irradiation doses. It was found that PTFE obtained by irradiation of TFE in acetone at 195 K has branching structure. This was demonstrated by means of "1"9F MAS NMR. (Author)
Our major goal of our work has been to develop and use NMR techniques to study how methanogenic archaebacteria deal with osmotic stress with the hope of providing insights into increasing the salt tolerance of other cells. The project has three main sections: (i) in vivo studies of methanogens; (ii) use of {sup l3}C- and {sup l5}N- labeled potential precursors and in vitro analyses of specific label uptake for elucidation of osmolyte dynamics and biosynthetic pathways of osmolytes in these organisms, and isolation of key biosynthetic enzymes; and (iii) collaborative studies on identification of organic solutes in other methanogens.
Our major goal of our work has been to develop and use NMR techniques to study how methanogenic archaebacteria deal with osmotic stress with the hope of providing insights into increasing the salt tolerance of other cells. The project has three main sections: (i) in vivo studies of methanogens; (ii) use of [sup l3]C- and [sup l5]N- labeled potential precursors and in vitro analyses of specific label uptake for elucidation of osmolyte dynamics and biosynthetic pathways of osmolytes in these organisms, and isolation of key biosynthetic enzymes; and (iii) collaborative studies on identification of organic solutes in other methanogens.
Zeolite Y is the active component of most commercial cracking catalysts. Interaction of H[sub 3]PO[sub 4] with extraframework aluminum of ultra-stable zeolite (USY) leads to the formation of different types of aluminum phosphates, while there is no indication of the formation of SAPO zeotype structures. The total acidity of USY slightly decreases upon the H[sub 3]PO[sub 4] treatment, while the maximum in the distribution of acid strength is shifted to milder acidities. Dealumination of the zeolite and creation of POH sites associated with AIPO[sub 4] are responsible for the modifications observed. 37 refs., 8 figs., 3 tabs.
XVTa and XXTa nuclei were oriented at low temperature as dilute impurities in Fe. The magnetic hyperfine splitting frequencies = B sub(HF)/Ih of the XVTa and XXTa ground states have been measured to be 320.45(11) and 317.552(55) MHz by using the technique of NMR-ON. Taking the known hyperfine field of Y Ta in Fe, the magnetic moments have been deduced: ( XVTa, 7/2 ) =2.270(45) and ( XXTa, 7/2 ) =2.250(45) sub(N). These values of the magnetic moments are discussed in the framework of the rotational model.
"1"7"5Ta and "1"7"7Ta nuclei as dilute impurities in Fe were oriented at low temperatures. Using the technique of NMR/ON the magnetic moments have been measured: "+#mu#("1"7"5Ta, 7/2"+,"+=2.270(45) #mu# sub(N) and "+#mu#("1"7"5Ta, 7/2"+)"+=2.250(45) #mu# sub(N). These values are discussed in the framework of the rotational model. (author).
The authors continued their efforts in studying the mechanism of carbalkoxylation of {sigma}-vinyls bound to platinum(II). In this work, the focus was specifically on the reductive elimination of {alpha},{beta}-unsaturated carboxylic esters form the carbonylated, alkoylated intermediates. Crystal structures of the carbonylated (12) and alkoxylated (13) intermediates were reported. Kinetic and NMR studies indicate that reductive elimination proceeds via a preequilibration involving phosphine dissociation, followed by a rate-determining trans-cis isomerization. 35 refs., 3 figs., 5 tabs.
Decomposition yields of tetracycline hydrochloride (TC.HCl) and chlorotetracycline hydrochloride (ClTC.HCl) in methanol solution saturated with Ar or N/sub 2/O were determined. Rate constants of the reaction esub(s)/sup -/ with some antibiotics were obtained. It was demonstrated by /sup 1/H NMR that the radical formed by degradation of 7-C-Cl group is recombined with the H atoms leading to ClTC.HCl being converted into tetracycline hydrochloride (TC.HCl).
We have designed a new nucleobase, benzodeazaadenine (BDA) that has a stronger charge transport ability than guanine and is not destroyed during charge transport process. By incorporating this new nucleobase into DNA, we demonstrated a protocol for real DNA nano-wire that is far superior to natural DNA. We also demonstrated that the selectivity for the interaction of Mn(II) ion with guanine N7 in G runs is a HOMO-controlled process, and as a consequence, the selectivity for G-metal ion interactions obtained by 15N-NMR studies would directly reflect the HOMO distribution of G-containing sequences in B-DNA. PMID:12903077
The first stage of the continuous coal hydrogenation unit has been used to test a number of coals with different processing strategies. This work has shown that conversion increases with product recycle, however after the second pass the increase is small but operability of the reactor is considerably improved. A kinetic model for the aromatic saturation of the recycle solvent in the second stage has been developed and will be used in the selection of conditions for oil upgrading processes. New insights into the structural composition of coal derived materials have been made due to the refinement of chromatographic or solubility separation analyses into routine operations and the development of a new technique in NMR spectroscopy.
This paper describes the chemical constituents isolated from aerial parts of the plant Galianthe brasiliensis. From a methanol extract, the iridoid glycosides asperuloside, deacetylasperuloside, mixture of Z- and E-6-O-p-coumaroylscandoside methyl ester, the triterpene ursolic acid and the steroids stigmasterol, campesterol, b-sitosterol and 3-O-b-glucopyranosyl sitosterol were isolated. The structures of the natural products were identified on the basis of spectral data, including 2D NMR experiments. The antiproliferative properties of the crude methanolic extract were investigated against a series of nine human cancer cell lines. (author)
The oxygen vacancies distribution in the rigid lattice and the thermally activated motion of oxygen atoms are studied in La1-xSrxGa1-xMgxO3-x (x=0.00; 0.05; 0.10; 0.15 and 0.20) compounds. For that 71Ga, 25Mg and 17O NMR was performed from 100 K up to 670 K, and ion conductivity measurements were carried out up to 1273 K. The comparison of the electric field gradients at the Ga- and Mg-sites evidences that oxygen vacancies appear exclusively near gallium cations as a species trapped below room temperature in local clusters, GaO5/2-#square#-GaO5/2. These clusters decay at higher temperature into mobile constituents of the structural octahedra Ga(O5/6#square#1/6)6/2. At the same time, the nearest octahedral oxygen environment of magnesium cations persists at different doping levels. The case of two adjacent vacant anion sites is found highly unlikely within the studied doping range. The thermally activated oxygen motion starts to develop above room temperature as is ...
NMR spectroscopy combined with paramagnetic relaxation agents was used to study the positioning of the 40-residue Alzheimer Amyloid {beta}-peptide A{beta}(1-40) in SDS micelles. 5-Doxyl stearic acid incorporated into the micelle or Mn{sup 2+} ions in the aqueous solvent were used to determine the position of the peptide relative to the micelle geometry. In SDS solvent, the two {alpha}-helices induced in A{beta}(1-40), comprising residues 15-24, and 29-35, respectively, are surrounded by flexible unstructured regions. NMR signals from these unstructured regions are strongly attenuated in the presence of Mn{sup 2+} showing that these regions are positioned mostly outside the micelle. The central helix (residues 15-24) is significantly affected by 5-doxyl stearic acid however somewhat less for residues 16, 20, 22 and 23. This {alpha}-helix therefore resides in the SDS headgroup region with the face with residues 16, 20, 22 and 23 directed away ...
This report seeks to address the role of hydrogen bonding with Bronsted acids and bases in proton-coupled electron transfer (PCET) as it pertains to concerted or stepwise pathways of quinone (Q) and hydroquinone (QH_2) electrochemistry. This study was performed using a series of techniques that included cyclic voltammetry (CV), digital simulations, computational chemistry and "1H NMR. Hydrogen bonding was inferred by a decrease in diffusion coefficient (D) values measured using a pulsed gradient echo- (PGE-) "1H NMR technique. Changes of 40.8% and 37.9% in D values were only noted after the addition of two equivalents of acetate to 1,4-hydroquinone (1,4-QH_2) and catechol (1,2-QH_2), respectively. In contrast, the D values for the addition of selected amines (pyridine, N,N-diisopropylethylamine and triethylamine) changed only 3.2% on average. Quantum mechanical calculations were conducted to determine the pK_a of all quinoid species to serve as ...
This paper proposes a model to explain tritium release behavior of an irradiated Li_4SiO_4 sample made by Forschungszentrum Karlsruhe. The release curves were obtained in a series of experiments carried out using out-pile temperature programmed desorption techniques in the Kyoto University Reactor (KUR). Tritium release curves obtained for different purge gas compositions (N_2, N_2 + H_2, N_2 + H_2O) were compared for selection of suitable conditions to determine the apparent diffusivity of tritium in a crystal grain of Li_4SiO_4.In the model formation, some mass transfer steps in the bulk of the crystal grain and those on the surface of the grain were taken into account, which were diffusion of tritium in the grain, adsorption and desorption of water on the surface of the grain, two types of isotope exchange reactions, and water formation reaction by the addition of hydrogen to the purge ...
The sulfur-iodine water-splitting cycle is characterized by the following three reactions: 2H/sub 2/O + SO/sub 2/ + I/sub 2/ ..-->.. H/sub 2/SO/sub 4/ + 2HI; H/sub 2/SO/sub 4/ ..-->.. H/sub 2/O + SO/sub 2/ + 1/2 O/sub 2/; and 2HI ..-->.. H/sub 2/ + I/sub 2/. This cycle was developed at General Atomic after several critical features in the above reactions were discovered. These involved phase separations, catalytic reactions, etc. Estimates of the energy efficiency of this economically reasonable advanced state-of-the-art processing unit produced sufficiently high values (to approx.47%) to warrant cycle development effort. The DOE contract was largely directed toward the engineering development of this cycle, including a small demonstration unit (CLCD), a bench-scale unit, engineering design, and costing. The work has resulted in a design that is projected to produce H/sub 2/ at prices not yet ...
Behavior to hydrogen damage caused by stress corrosion in a H_2S medium (SSC) and to intergranular corrosion (IGC) in different mediums, such as oxalic acid (C_2H_2.2H_2O), iron sulphate-50% sulfuric acid (Fe_2(SO_4)_3-50% H_2SO_4), nitric acid (HNO_3), copper sulphate-16% sulfuric acid (CuSO_4.5H_2O-16% H_2SO_4) and cooper sulphate-50% sulfuric acid (CuSO_4.5H_2O-50% H_2SO_4), is studied in an AISI 347 austenitic stainless steel stabilized with 0.61 mass % Nb and hot rolled to a seamless pipe with 273.1 mm in diameter and 18.2 mm in thickness. (Author) 12 refs.
The sycamore lace bug, Corythucha ciliata is a new, invasive pest of Platanus trees in China. Although C. ciliata is often subjected to acute low temperatures in early winter and spring in northern and eastern China, the cold tolerance of C. ciliata has not been well studied. The objectives of this study were to determine whether adults of C. ciliata are capable of rapid cold hardening (RCH), and to compare the benefits of RCH vs. cold acclimation (ACC) in the laboratory. When the adult females incubated at 26^oC were transferred directly to the discriminating temperature (-12^oC) for 2h, survival was only 22%. However, exposure to 0^oC for 4h before transfer to -12^oC for 2h induced RCH, i.e., increased survival to 68%. RCH could also be induced by gradual cooling of the insects at rates ...
Sucrose and mannitol are major photosynthetic products and translocates in celery. Assimilate partitioning and transport were studied by pulse-labeling leaves with /sup 14/CO/sub 2/ followed by different length chases in ambient air. After a 2h chase in the light there was more /sup 14/C in sucrose than mannitol in source leaves and their petioles. In contrast after a 2h dark chase leaves contained more /sup 14/C in mannitol than sucrose but petioles had more /sup 14/C in sucrose than mannitol. After a 15 h chase (6 h light; 9 h dark) labeled sucrose was higher in source petiole vascular bundles than in adjacent parenchyma tissue but label in glucose and fructose was higher in the parenchyma tissue. After the 15 h chase most of the /sup 14/C remaining in developing sink leaves and their petioles was in mannitol. Although in the light mannitol:sucrose ratios are the same in leaf and petiole tissues, in ...
Site measurements were collected at Mount John University Observatory in 2005 and 2007 using a purpose-built scintillation detection and ranging system. $C_n^2(h)$ profiling indicates a weak layer located at 12 - 14 km above sea level and strong low altitude turbulence extending up to 5 km. During calm weather conditions, an additional layer was detected at 6 - 8 km above sea level. $V(h)$ profiling suggests that tropopause layer velocities are nominally 12 - 30 m/s, and near-ground velocities range between 2 -- 20 m/s, dependent on weather. Little seasonal variation was detected in either $C_n^2(h)$ and $V(h)$ profiles. The average coherence length, $r_0$, was found to be $7 \\pm 1$ cm for the full profile at a wavelength of 589 nm. The average isoplanatic angle, $\\theta_0$, was $1.0 \\pm 0.1$ arcsec. The mean turbulence altitude, $\\bar{h_0}$, was found to be $2.0\\pm0.7$ km above sea level. No ...
Nitrogen is often provided to impoverished overburden dumps through the establishment of legumes. Low indigenous soil nutrient levels, summer drought conditions and an acidic mining overburden represent major obstacles to successful rehabilitation of open-cut coal mining at Collie in southwest Western Australia. In this study, Acacia pulchella, a native Western Australian species often used in rehabilitation of mined lands, was shown to nodulate and grow in coal mining overburden with pH values less than 4.0 under glasshouse conditions. Plant growth (both top and root dry weight), nodule fresh weight, and nodulation success was best at pH near 5.0, a value only slightly lower than the typical soil pH of the native jarrah (Eucalyptus marginata) forest. Acetylene reduction rates were reduced by acidity and ranged from 8.2..mu..m C/sub 2/H/sub 4//g hr at pH 6.77 to 3.0..mu..m C/sub 2/H/sub 4//g hr at a pH ...
The interfacial tension g of the hexane solution of 1H,1H,10H,10H-perfluorodecane-1,10-diol (FC10diol) and 1H,1H,2H,2H-perfluorododecanol (TFC12OH) mixture against water was measured as a function of the total molality m and composition of TFC12OH in the mixture X2 at 298.15K under atmospheric pressure. The interfacial pressure p vs. mean area per adsorbed molecule A curves and the phase diagram of adsorption (PDA) were constructed in order to shed light on the effect of the molecular orientation on the state of and the miscibility of FC10diol and TFC12OH in the adsorbed film. The p vs. A curves demonstrated that the mixed system exhibits three kinds of film states, parallel-condensed, normal-condensed, and multilayer states, depending on m and X2. The PDA indicated that film composition X...
The attenuation of gamma rays in some fatty acids, viz. formic acid (CH_2O_2), acetic acid (C_2H_4O_2), propionic acid (C_3H_6O_2), butyric acid (C_4H_8O_2), n-hexanoic acid (C_6H_1_2O_2), n-caprylic acid (C_8H_1_6O_2), lauric acid (C_1_2H_2_4O_2), myristic acid (C_1_4H_2_8O_2), palmitic acid (C_1_6H_3_2O_2), oleic acid (C_1_8H_3_4O_2) and stearic acid (C_1_8H_3_6O_2), has been measured at the photon energies 81, 356, 511, 662, 1173 and 1332 keV. Experimental values for the molar extinction coefficient, the effective atomic number and the electron density have been derived and compared with theoretical calculations. There is good agreement between experiment and theory.
Ferroelectric barium strontium titanate (Ba0.7Sr0.3TiO3)(BST) thin films have been prepared from barium 2-ethylhexanoate [Ba[CH3(CH2)3CH(C2H5)CO2]2], strontium 2-ethylhexanoate [Sr[CH3(CH2)3CH(C2H5)CO2]2] and titanium(IV) isopropoxide [TiOCH(CH3)2]4 precursors using a modified sol-gel technique. The precursor except [TiOCH(CH3)2]4 were synthesized in the laboratory. Transparent and crack-free films were fabricated on pre-cleaned quartz substrates by spin coating. The structural and optical properties of films annealed at different temperatures have been investigated. The as-fired films were found to be amorphous that crystallized to the tetragonal phase after annealing at 550degreeC for 1h in air. The lattice constants "a" and "c" were found to be 3.974A and 3.990A, respectively. The grain...
Polycrystalline silicon films have been grown from Si{sub 2}H{sub 6} by low-pressure chemical vapour deposition at 800 K and in situ laser annealing (LA) on amorphous silicon seed layers deposited on a metallic Ti/Pd/Ag multilayer. The crystalline volume fraction in the seed layer was controlled by thermal annealing. According to the metal-induced crystallization effect, the presence of the metal induces a lower-temperature crystallization of silicon in the seed layers. X-ray diffraction and scanning electron microscopy data show that the formation of palladium silicides in the seed layer drives the growth of wire-like columns which are found to change morphology depending on the seed layer microstructure and LA parameters. It is suggested that superficial palladium was found to affect also the growth rate by enhancing the Si{sub 2}H{sub 6} dissociation.
Polycrystalline silicon films have been grown from Si_2H_6 by low-pressure chemical vapour deposition at 800 K and in situ laser annealing (LA) on amorphous silicon seed layers deposited on a metallic Ti/Pd/Ag multilayer. The crystalline volume fraction in the seed layer was controlled by thermal annealing. According to the metal-induced crystallization effect, the presence of the metal induces a lower-temperature crystallization of silicon in the seed layers. X-ray diffraction and scanning electron microscopy data show that the formation of palladium silicides in the seed layer drives the growth of wire-like columns which are found to change morphology depending on the seed layer microstructure and LA parameters. It is suggested that superficial palladium was found to affect also the growth rate by enhancing the Si_2H_6 dissociation.
This study addresses the solar thermal decomposition of natural gas for the co-production of hydrogen and carbon black (CB) as a high-value nano-material with the bonus of zero CO2 emission. The work focused on the development of a medium-scale solar reactor (10kW) based on the indirect heating concept. The solar reactor is composed of a cubic cavity receiver (20cm-side), which absorbs concentrated solar irradiation through a quartz window by a 9cm-diameter aperture. The reacting gas flows inside four graphite tubular reaction zones that are settled vertically inside the cavity. Experimental results in the temperature range 1740-2070K are presented: acetylene (C2H2) was the most important by-product with a mole fraction of up to about 7%, depending on the gas residence time. C2H2 content i...
Abstract Series of typical -type and pseudo--type halogen-bonded complexes BClY and BBrY and hydrogen-bonded complex BHY (B = C2H4, C2H2, and C3H6; Y = F, Cl, and Br) have been investigated using the MP2/aug-cc-pVDZ method. A striking parallelism was found in the geometries, vibrational frequencies, binding energies, and topological properties between BXY and BHY (X = Cl and Br). It has been found that the lengths of the weak bond d(X)/d(H), the frequencies of the weak bond (X)/(H), the frequency shifts (XY)/(HY), the electron densities at the bond critical point of the weak bonds c(X)/c(H), and the electron density changes c(XY)/c(HY) could be used as measures of the strengths of typical -type and pseudo--type halogen/hydrogen bonds. The typical -type and pseudo--type halogen bond and hyd...
A procedure for high level tritium labelling at the C2-H position of adenosine 5`-triphosphate ([2-{sup 3}H]-ATP, 1), based on the tritiodehalogenation reaction of 2-bromoadenosine 5`-triphosphate (2) has been elaborated. This precursor was prepared in a six-step synthesis from guanosine. The tritiodehalogenation of (2) for three hours over palladium oxide in phosphate buffer yielded tritium labelled ATP with high specific activity, in good chemical yield. (author).
Having simple and highly symmetric structure, solid hydrogen is a useful matrix on the study of radiation-chemical processes in solid phase which have been less understood in previous studies. We have found three outstanding findings: resonance effects on the tunneling reaction H+H{sub 2} {yields} H{sub 2} + H, effects of pressure on the dissociation and recombination of H{sub 2} molecules in solid hydrogen, and high-resolution ESR spectroscopy using a solid parahydrogen matrix. (author)
The "2H(#alpha#,p#alpha#)n reaction was investigated in a kinematically complete experiment with a #alpha#-beam at energy 27.2 MeV.The "5He excited state was observed and its parameters were determinate.Coincidence spectra were fitted by contribution of sequential decay through the "5He ground and excited states.The best agreement with the data was obtained assuming the following "5He excited state parameters: E_a_n=2.8 MeV #GAMMA#=2.5 MeV.
We evaluate the sphere level S-matrix element of two tachyons and two massless NS states, the S-matrix element of four tachyons, and the S-matrix element of two tachyons and two Ramond-Ramond vertex operators, in type 0 theory. We then find an expansion for theses amplitudes that their leading order terms correspond to a covariant tachyon action. To the order considered, there are no T4, T2(-bar T)2, T2H2, nor T2R tachyon couplings, whereas, the tachyon couplings FF-bar T and T2F2 are non-zero.
We describe a compact ultrafiltration system for the removal of pyrogens and bacteria from water labeled with the stable isotopes of deuterium and oxygen-18. The ultrafiltration system is constructed from readily available commercial components and can achieve complete removal of pyrogens and bacteria from 1L contaminated water within 30 min. By use of our procedure, loss of the isotopically labeled water by retention in the filtration system was minimal. The purified water is suitable for both oral and intravenous administration to healthy human subjects participating in nutrition studies.
With the aim of optimizing the nitriding process parameters (temperature and gas mixture ) experimental studies of the plasma nitriding of Ck 15 steel were carried out, using a D. C. glow discharge. Nitriding treatments were performed at 450, 500 and 550 and N_2/H_2 volume ratio of 3/1, 1/1 and 1/3 for 5 hours. Nitriding treatment produces modified surface layer consisting of an outer compound layer and an inner diffusion layer.The plasma nitriding of Ck 15 produce single white layer consisting of #gamma#-(Fe_4N).
Thermal desorption spectroscopy (TDS) was used to study outgassing from polycrystalline SiGe (poly-SiGe), SiC and SiO"2 films used for poly-SiGe-based MEMS thin film vacuum package technology. Primary desorption products were found to be H"2, H"2O and CO"2. The CO"2 outgassing could be correlated with CF"4 plasma interface cleaning used for thick SiGe PECVD, which can leave carbon at the CF"4-plasma-cleaned interface.
In the reaction sup(nat)Ag + /sup 40/Ar (285 MeV) there have been measured the energy spectra of the isotopes of elements from H to Cl at an emission angle of 40/sup 0/, the energy spectra and angular distributions of /sup 1/H, /sup 2/H, /sup 3/H, and /sup 4/He, and the angular distributions of Li, Be, B, and C. The contribution from multinucleon transfer reactions to the formation of light charged particles is discussed.
An analytical electron microscope study is presented on carbonaceous material in two chondritic porous aggregates, W7029* A and W7010* A2, from the Johnson Space Center Cosmic Dust Collection. The finding of well-ordered carbon-2H (lonsdaleite) in the two aggregates suggests that a record of hydrocarbon carbonization may be preserved in these materials. This carbon is a metastable phase resulting from hydrous pyrolysis below 300-350"0C and may be a precursor to poorly graphitized carbons in primitive extra terrestrial materials. (UK).
In this study, Multi-Walled Carbon Nanotubes (MWCNTs) / Hydroxylapatite (HAp) composites were made to improve mechanical properties by using Spark Plasma Sintering (SPS) method. Slurry 6 mol of CaHPO4#centre dot#2H2O (DCPD), 4 mol calcium hydroxide and MWCNTs were mixed and sintered by using SPS at 5-120 MPa pressure, 1200-1250 deg. C and in vacuum or N2 atmosphere. The fracture toughness of sintered MWCNTs/HAp composites was increased.
An analysis based on Jaroniec's theory of mixed gas adsorption showed that for two arbitrary adsorbing gas components the ratio of their surface coverages is a simple power function of the ratio of their partial pressures. This result was verified with available experimental data on the adsorption of C/sub 1/-C/sub 4/ hydrocarbon binary mixtures, CO/sub 2//C/sub 2/H/sub 4/, and N/sub 2//CO on various carbons, silica gel, and cesium iodide.
"2H, "4He, "1"6O, "4"0Ca, "8"0Zr, "1"4"0Yb, "2"2"4112, "3"3"6168 nuclei are invesigated in terms of flucton model. Effective numbers of nuclear fluctons and deuterons are calculated. Values of complete effective numbers of low-radius deuterons and fluctons with S=1 spin and T=0 isospin are presented. Investigation results of inclusive reactions of quasi-elastic knock-out of deuterons by fast protons are discussed. 9 refs.; 1 fig.; 1 tab.
A new phenylboric acid derivative entrapped lipiodol (PBAD-lipiodol) was developed as a boron carrier for the boron neutron capture therapy (BNCT) of hepatoma in Taiwan. The biodistribution of both PBAD-lipiodol and BPA-fructose was assayed in GP7TB hepatoma-bearing rat model. The highest uptake of PBAD-lipiodol was found at 2h post injection. The application of BNCT for the hepatoma treatment in tumor-bearing rats is suggested to be 2-4 h post PBAD-lipiodol injection.
The uptake of "2"3"8U and "2"3"2Th in different parts of some selected plants used in traditional treatment of hypertension and diabetes in south-eastern Morocco (Errachidia area) has been studied using two different types of solidstate nuclear track detectors (SSNTDs) LR-115 type II and CR-39. Plant uptake of radionuclides is one of many vectors for introduction of contaminants into the human food chain. Thus, it is critical to understand soil-plant relationships that control nuclide bioavailability. Soil concentrations of uranium ranged from 6.10 to 11.62 ppm, with a mean of 7.90 ppm. Soil concentrations of thorium ranged from 2.70 to 4.80 ppm, with a mean of 3.41 ppm. Mean uranium specific activities were 8.38 Bq kg"-"1 in root tissue, 5 Bq kg"-"1 in stem tissue and 6.02 Bq kg"-"1 in leaf tissue. Mean thorium specific activities were 2.53 Bq kg"-"1 in root tissue, 1.64 Bq kg"-"1 in stem tissue and 1.96 Bq kg"-"1 in leaf tissue. The transfer ...
The ortho-metalated Pt(II) complexes Pt(ppy)(CO)Cl (1), Pt(ptpy)(CO)Cl (2), and Pt(ppy)(Hppy)Cl (3) (where ppy and ptpy are respectively the ortho-C-deprotonated forms of 2-phenylpyridine and 2-p-tolylpyridine and Hppy is 2-phenylpyridine) have been prepared. The CO ligand is coordinated trans to the nitrogen atom of the ortho-metalated ligand and exerts a strong trans effect resulting in a relatively long Pt-N bond [2.114(19) {angstrom}]. This structure shows both the bidentate ppy ligand and the monodentate Hppy with the nitrogens of these ligands trans to each other. The UV/vis electronic absorption spectra of 1-3 have intense bands in the near-UV region ({approximately}375 nm) which have been assigned as metal to ligand charge transfer (MLCT) transitions, and higher energy bands were assigned as ligand-centered transitions. Each complex exhibits relatively long-lived structured emissions in the solidstate at ambient temperature and at 77 K ...
The n=4 Aurivillius phase, Bi5Ti3CrO15, was synthesised by solidstate reaction. Rietveld analysis of high resolution neutron diffraction data demonstrated this material to adopt the polar space group A21am at room temperature, transforming to the aristotype I4/mmm structure above 650 oC. This phase transition is coincident with an anomaly in DSC signal and relative permittivity, which are characteristic of a ferroelectric-paraelectric phase transition. Bi5Ti3CrO15 exhibits paramagnetic behaviour at low temperature, with short range antiferromagnetic interactions, but no evidence for long range magnetic ordering. This is considered a consequence of significant disorder of Ti and Cr over the available octahedral sites, as demonstrated by analysis of neutron diffraction data. -- Graphical abstract: We report here the synthesis, structure and characterisation of the n=4 Aurivillius phase Bi5Ti3CrO15. Analysis of neutron powder diffraction and ...
Solid oxide fuel cell (SOFC) is a promising source of power generation in terms of conversion efficiency which is higher than the conventional one, as it is not limited by the Carnot efficiency. Theoretically, the SOFC have an efficiency of the order of 60-80 % but it is limited by the number of active side available for the reaction i.e. TPB (triple phase boundary) at the electrode-electrolyte interface which depends on the particle size of the materials employed during the fabrication of SOFC components (i.e. the method employed during the synthesis). Literally, there are several methods used in the syntheses of oxide materials such as conventional solid-state reaction, co-precipitation, hydrothermal rout, sol-gel and Glycine nitrate process (GNP) but among these GNP found to be effective over the other because of homogeneity, phase purity and smaller particle size of final product. In this work, the Nano-crystalline Ln_0_._6Sr_0_._4Co_0_._8Fe_0_._2O_3_-_#delta# ...
The new compounds In_3_._7Mo_1_5S_1_9, In_1_._6Rb_2Mo_1_5S_1_9, In_2_._2CsMo_1_5S_1_9, and ScTl_2Mo_1_5S_1_9 have been synthesized by solid-state reaction in sealed molybdenum crucible at about 1250 deg. C. Their crystal structures were solved and refined from X-ray single-crystal data in the hexagonal space group P63/m. Their Mo-S framework consists of an equal mixture of Mo_6S_8S_6 and Mo_9S_1_1S_6 cluster units interconnected through Mo-S bonds. In In_3_._7Mo_1_5S_1_9, the In atoms occupy crystallographically different positions depending on their formal oxidation states of +1 or +3. This was confirmed by replacing partially or totally the monovalent indium by another monovalent cation such as the rubidium, cesium or thallium and the trivalent indium by the scandium to get the new In_1_._6Rb_2Mo_1_5S_1_9, In_2_._2CsMo_1_5S_1_9, and ScTl_2Mo_1_5S_1_9 compounds, respectively.
Mixed-conducting ceramic oxides have potential uses in high-temperature electrochemical applications such as solid oxide fuel cells, advanced batteries, sensors, and oxygen-permeable membranes. The Sr-Fe-Co-O system combines high electronic/ionic conductivity with appreciable oxygen permeability at elevated temperatures. Dense ceramic membranes made of this material can be used to separate high-purity oxygen from air without the need for external electrical circuitry, or to partially oxidize methane to produce syngas. Samples of Sr{sub 2}Fe{sub 3{minus}x}Co{sub x}O{sub y} (with x = 0, 0.6, 1.0, and 1.4) were prepared by solid-state reaction in atmospheres with various oxygen partial pressures (pO{sub 2}) and were characterized by X-ray diffraction, scanning electron microscopy, and electrical conductivity measurements. Phase components of the samples are dependent on cobalt concentration and synthesis pO{sub 2}. Total conductivity increases with increasing ...
Lithium (Li) plating-stripping reaction properties at the lithium phosphorus oxynitride glass electrolyte (LiPON)/copper thin film (Cu) interface is improved by the insertion of nano-thickness platinum (Pt) layer at the interface. The LiPON films are formed on mirror-polished lithium-ion conductive solid electrolyte sheets, and current collector thin films of Li, Cu-Pt multi layer, and Cu are formed on the LiPON films. The plating-stripping reactions at the LiPON/current collector films interface are carried out by galvanostatic and potential sweep measurements. Galvanostatic measurements reveal that Pt layer insertion reduces the overvoltage of the reaction and improves its coulomb efficiency. Also, cyclic voltammetry measurement suggests formation of Li-Pt alloys at higher voltages than 0 V (vs. Li/Li{sup +}) during the lithium plating process. Scanning electron microscopy observation clarifies that platinum insertion moderate non-uniform lithium plating reaction. Most probably, ...
Two electroactive polymeric arylene bisimides, namely poly[(4,7,10-trioxatrideca-1,13-diyl)-(1,4,5,8-naphthalenetetracarboxylic bisimide-N,N'-diyl)] and its perylene analogue - poly[(4,7,10-trioxatrideca-1,13-diyl)-(3,4,9,10-perylenetetracarboxylic bisimide-N,N'-diyl)] have been synthesized and studied by cyclic voltammetry, UV-vis-NIR as well as Raman spectroeletrochemistry. Contrary to low molecular weight arylene bisimides, which show a clear two electron, double-step electrochemical reduction (neutral form to radical anion and from radical anion to dianion), in the synthesized polymers multielectron transfers are observed, accompanied with a strong electrochromic effect. However, as probed by cyclic voltammetry, their first reduction step is retarded and covers a wider potential range. We attribute this effect to macromolecular nature of the compounds being reduced and their structural inhomogeneity caused by ?-stacking induced nanoaggregation of bisimide segments of the polymer ...
Single-crystalline nanostructures often exhibit gradients of surface (and/or interface) curvature that emerge from fabrication and growth processes or from thermal fluctuations. Thus, the system-inherent capillary force can initiate morphological transformations during further processing steps or during operation at elevated temperature. Therefore and because of the ongoing miniaturization of functional structures which causes a general rise in surface-to-volume ratios, solid-state capillary phenomena will become increasingly important: On the one hand diffusion-mediated capillary processes can be of practical use in view of non-conventional nanostructure fabrication methods based on self-organization mechanisms, on the other hand they can destroy the integrity of nanostructures which can go along with the failure of functionality. Additionally, capillarity-induced shape transformations are effected and can thereby be controlled by applied fields and forces (guided ...
This topical review provides an overview of quantum dot micropillars and their application in cavity quantum electrodynamics (cQED) experiments. The development of quantum dot micropillars is motivated by the study of fundamental cQED effects in solidstate and their exploitation in novel light sources. In general, light-matter interaction occurs when the dipole of an emitter couples to the ambient light field. The corresponding coupling strength is strongly enhanced in the framework of cQED when the emitter is located inside a low mode volume microcavity providing three-dimensional photon confinement on a length scale of the photon wavelength. In addition, coherent coupling between light and matter, which is essential for applications in quantum information processing, can be achieved when dissipative losses, predominantly due to photon leakage out of the cavity, are strongly reduced. In this paper, we will demonstrate that high-quality, low ...
In order to investigate interactions of (Ti,W)(C,N) and (Ti,Mo)(C,N) with binder metals solid/solid diffusion couples were annealed. These two-dimensional arrangements provide good access to phase reactions occurring upon sintering already in the solidstate. It was found in (Ti,W)(C,N)/Co- and (Ti,W)(C,N)/Ni-based couples that the reaction zone is thinner in contact with Co than with Ni. It was also observed that the reaction rate with both Co and Ni is lower if nitrogen is added to the hard phases. Beside a thickness variation of the diffusion zones a change in the microstructure was found. At the interface of nitrogen-free hard phases in contact with Co elongated microstructural constituents are formed with the main axis perpendicular to the interface, while at the interface of nitrogen-containing hard phases these elongated microstructural constituents were found in contact with Ni. Also phase reactions and the diffusion behavior between ...
Lithium-ion batteries are becoming more and more important not only for portable electronic devices, but also in prevision of high power electric vehicles. In such an optic, deep studies regarding all the components of a secondary battery are in development. In this study, high voltage cathode materials have been selected. Crystals with spinel structure have a 3D vacancy pathway suitable for Li-ions transport. The material under study was LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} doped with magnesium replacing the nickel. Various samples were synthesized via three different routes: a solid-state method, a modified sol-gel method and a xerogel method. The structure and morphology of the powders were analyzed with HRTEM and XRD. Electrochemical tests were also performed. A wide range of particle sizes (from micro to nanosize) was the result of the different synthesis routes. Unfortunately pure materials were not always obtained. The electrochemical tests showed improvement of ...
Magnetothermal measurements up to 1600 K have been made on alloys in the ternary Ni-Mn-Sb system with a constant ratio Mn/Sb=1/1, to which belong the two ferromagnetic Heusler phases Ni/sub 2/MnSb with L2/sub 1/ structure and NiMnSb with C1/sub b/ structure. The susceptibility-temperature curves show the constitution of the vertical section. At high temperatures the susceptibilities obey a Curie-Weiss law. In the solidstate the effective magneton number decreases with increasing Mn concentration from 4.9 (Ni/sub 2/MnSb) to 3.8 (NiMnSb). Simultaneously, on the transition from Ni/sub 2/MnSb to NiMnSb there is a strong increase of the susceptibility and of the Curie temperature from 292 to 686 K. In the heterogeneous range between 10 and 20 at.% Mn another phase part appears which is ferromagnetic at room temperature. By a heat treatment it undergoes a distinct development. In the liquid phase, the alloys can be characterized by an extended ...
Ionic conductive materials are of much interest as an electrolyte for solid-state lithium batteries. Poly(alkylene oxide) and lithium salt complex exhibits high ionic conductivity in terms of its high solubility for lithium salts. However, the temperature dependency of its ionic conductivity is quite large and non-linear, the ionic conductivity drops down at low temperature, especially below glass transition temperature of the polymer. Because its ionic conductive mechanism is derived from its segmental motion of polymer main chain. A novel ionic conductive material, poly[2,6-dimethoxy-N-(4-vinylphenyl)benzamide] is synthesized and confirm ionic conductivity even below glass transition temperature. Ionic conductivity of the polymer with lithium ditrifluoromethylsulfonate imide complex shows 10{sup -5}Scm{sup -1} from 0 to 60{sup o}C. Its temperature dependency is linear, namely Arrehnius type dependency. Evaluating from these data, activation energy of ionic ...
Lithium ion conducting glass ceramics composed of the crystalline conductive phase Li{sub 1.4}Al{sub 0.4}(Ge{sub 1-x}Ti{sub x}){sub 1.6}(PO{sub 4}){sub 3}(x=0-1.0) with the Nasicon-type structure have been synthesized and characterized by DTA, X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and complex impedance techniques. The experimental results indicated that the glass ceramics were mainly composed of solid solution Li(Ge{sub 1-x}Ti{sub x}){sub 2}(PO{sub 4}){sub 3} formed by LiGe{sub 2}(PO{sub 4}){sub 3} and LiTi{sub 2}(PO{sub 4}){sub 3} in the whole x range and showed conductivity over 10{sup -4} S/cm at room temperature. The maximum room temperature lithium ion conductivity of 6.21x10{sup -4} S/cm with an activation energy as low as 0.32 eV was obtained for the Li{sub 1.4}Al{sub 0.4}(Ge{sub 0.67}Ti{sub 0.33}){sub 1.6}(PO{sub 4}){sub 3} treated at 950 C for 18 h. Mechanisms for the enhancement of {sigma}{sub totle} in glass ceramics were given and ...
A technique involving shifting of core fuel loadings was investigated as a method for reducing the neutron flux at points of high damage accumulation in the pressure vessel wall of a light water reactor. Calculations were run for six types of commercial generic PWR. Information is provided on the progress being made to develop and apply the SolidState Track Recorder (SSTR) method for in-situ in- and ex-vessel measurements of neutron exposure parameter values, such as fluence (E > 1.0 MeV) and dpa in iron. A new technique of quantitative track counting, the Buffon needle method, is advanced. It is based on random sampling of the SSTR surface. A desensitized etching technique was developed that resulted in an excellent differential energy response for alpha particles in the 3- to 14-MeV energy range. The optical efficiency of Muscovite mica for manual fission track counting is being redetermined to form a data base for comparison with ...
The purpose of this memo is to give an update on our work on ceramic laser materials--feasibility proposal 04-FS-006. Transparent ceramic materials have several major advantages over single crystals in laser applications including, ease and robustness of manufacturing, large apertures, design flexibility, fracture toughness, high activator concentrations, uniformity of composition, no residual stress, and others discussed in the proposal. After a decade of working on making transparent YAG:Nd in 1995 Japanese workers demonstrated samples for the first time that performed as well in lasers as their single crystal counterparts. Since then several laser materials have been made and evaluated. For these reasons, developing ceramic laser materials is the most exciting and futuristic materials topic in today's major solid-state laser conferences. The highlights and executive summary of our work to date are: (1) Ordered a slab of transparent YAG:Nd from Konoshima ...
An x-ray diffraction approach has been developed for determination of the kinetics of growth of Pd/sub 2/Si layers. Epitaxial Pd/sub 2/Si films were grown on Si(111) substrates over a temperature range of 160-222/sup 0/C by a solid-state reaction between the substrates and the Pd overlayers. The parabolic rate equation was verified and rate constants showed Arrhenius behavior with an activation energy E/sub a/ = 1.06 eV and prefactor k/sub 0/ = 7 x 10/sup -4/ cm/sup 2//s. The low value of E/sub a/ suggests a short-circuit diffusion mechanism. It is reasonable to expect that impurities and microstructure may play important roles in the growth process. Impurity levels in the specimens were evaluated by analytic techniques suited to thin-film study: Rutherford backscattering spectrometry, secondary ion mass spectrometry, and Auger electron spectrometry. No impurities were present at concentrations approaching 1 at. %. Some O, C, and F were detected at the Pd/sub ...
Intermetallic compounds based on the Al-Co system were synthesized by solidstate method - mechanical alloying and their properties were investigated using XRD, SEM, and DSC. The powder was used to make new targets of irradiation for gamma sources in order to enhance the specific activity and to reduce the consumption of material. The intermetallic compound AlCo was formed in the first 4 hours of milling. After 8 hours of milling the medium size of crystallites were of 5.58 nm. This value decreases with the increase of milling time up to 3 nm, corresponding to the 28 hours of grinding. There was calculated and plotted the Gibbs function, #DELTA#_f"0, for the reaction of formation AlCo and Al_3Co from the Al-Co system. It had negative values over the entire range of temperatures for both investigated compounds. After 28 hours milling a phase composition was obtained as follows: 0.2% Al; 21%Co ; 55.5%AlCo; 23.3% Al_1_3Co_4. AlCo 98% has been ...
Holmium doped barium based hexaferrites BaFe{sub 12-2x}Ho{sub 2x}O{sub 19} with (x = 0.0-1.0) were synthesized by solidstate reaction method. Structural and magnetic characterization of these ferrites provide significant information about their reactive physical properties. X-ray analysis reveals that in all samples M-type structure exist with few secondary phases. Scanning electron microscope revealed the grain size of the specimen. The results show that grain size decreases with the substitution degree of Holmium. Thus rare earth element Holmium Ho{sup 3+} acts as a grain growth inhibitor. The magnetic hysteresis loops show the variation in the values of magnetic parameters like saturation magnetization (M{sub s}), remanent magnetization (M{sub r}) and coercivity (H{sub c}) were observed by changing Ho{sup 3+} content in BaFe{sub 12-2x}Ho{sub 2x}O{sub 19} ferrites. Coercivity showed a maximum value of 2230 Oe for (x = 0.4) and then ...
The radical cations from aziridine and azetidine have been characterized by ESR spectroscopy following their generation in the solidstate by #gamma# irradiation of dilute solutions of the parent compounds in the CFCl_3 matrix at 77 K. The ESR parameters of the azetidine radical cation are typical of those for nitrogen-centered amine radical cations such as Me_2NH*"+. On the other hand, the radical cation formed from aziridine has very different ESR parameters that compare closely to those for the isoelectronic C...C ring-opened form of the oxirane radical cation and the allyl radical. The radical cation formed from azetidine is therefore assigned a ring-closed structure with the unpaired electron in a 2p/sub z/ orbital on nitrogen perpendicular to the ring plane, whereas the cation from aziridine is an allylic C...C ring-opened planar isomer with the unpaired electron in a nonbonding #pi# orbital centered mainly on the two end carbon atoms. ...
The radical cations from aziridine and azetidine have been characterized by ESR spectroscopy following their generation in the solidstate by ..gamma.. irradiation of dilute solutions of the parent compounds in the CFCl/sub 3/ matrix at 77 K. The ESR parameters of the azetidine radical cation are typical of those for nitrogen-centered amine radical cations such as Me/sub 2/NH*/sup +/. On the other hand, the radical cation formed from aziridine has very different ESR parameters that compare closely to those for the isoelectronic C...C ring-opened form of the oxirane radical cation and the allyl radical. The radical cation formed from azetidine is therefore assigned a ring-closed structure with the unpaired electron in a 2p/sub z/ orbital on nitrogen perpendicular to the ring plane, whereas the cation from aziridine is an allylic C...C ring-opened planar isomer with the unpaired electron in a nonbonding ..pi.. orbital centered mainly on the two ...
Lead-free piezoelectric ceramics (1-x)K0.5Na0.5NbO3-xAgSbO3+0.75 mol % MnO2 were prepared by a conventional solid-state sintering technique, and the piezoelectric and dielectric properties of the ceramics were studied. The results of x-ray diffraction suggest that AgSbO3 diffuses into the K0.5Na0.5NbO3 lattices to form a new solid solution with a single-phase orthorhombic perovskite structure. After the addition of AgSbO3, the paraelectric cubic-ferroelectric tetragonal phase transition temperature (TC) and the ferroelectric tetragonal-ferroelectric orthorhombic phase transition temperature (TO-T) decrease, and the ceramics become ``softened,'' resulting in significant improvements in the ferroelectric and piezoelectric properties. The ceramics with x=0.03-0.10 exhibit excellent piezoelectric properties: d33=130-216 pC/N, kp=0.44-0.51, and kt=0.40-0.52. The ceramics also exhibit a good thermal stability up to high TO-T, suggesting that the ceramics are promising ...
A high resolution Compton telescope has been identified by the Gamma Ray Astronomy Program Working Group (GRAPWG) as the highest priority major mission in gamma ray astrophysics following GLAST. This mission should provide 25-100 times improved sensitivity, relative to CGRO and INTEGRAL, for MeV gamma ray lines. It must have good performance for narrow and broad lines and for discrete and diffuse emissions. Several instrumental approaches are being pursued to achieve these goals. We discuss issues relating to this mission including alternative detector concepts, instrumental configurations, and background reduction techniques. We have pursued the development of position-sensitive solid-state detectors (Ge, Si) for a high spectral resolution Compton telescope mission. A #approx#1 m2 germanium Compton telescope of position-sensitive germanium detectors was the basis for one of the GRAPWG concepts. Preliminary Monte Carlo estimates for the sensitivities of this ...
Element 97 was first produced in December 1949, by the bombardment of americium-241 with accelerated alpha particles. This new element was named berkelium (Bk) after Berkeley, California, the city of its discovery (Thompson, Ghiorso, and Seaborg, Phys. Rev. 77, 838 (1950); 80, 781 (1950)). In the 36 years since the discovery of Bk, a substantial amount of knowledge concerning the physicochemical properties of this relatively scarce transplutonium element has been acquired. All of the Bk isotopes of mass numbers 240 and 242 through 251 are presently known, but only berkelium-249 (..beta../sup -/ decay, 0.125 MeV, t/sub 1/2/ = 325 days) is available in sufficient quantities for bulk chemical studies. About 0.7 gram of this isotope has been isolated at the HFIR/TRU Complex in Oak Ridge, Tennessee in the last 18 years. Over the same time period, the scale of experimental work using berkelium-249 has increased from the tracer level to bulk studies at the microgram level to solution and ...
The object and the purpose of the present work was to develop, to assemble and to start running a new TOF (time of flight) mass spectrometer for imaging SNMS analytic which is optimized for the analysis of highly molecular secondary ions. The most important purpose was the characterization of the TOF mass spectrometer. The obtained mass spectra of indium, tantalum and silver clusters reflect the excellent properties of the TOF mass spectrometer for the detection of large clusters with good detection efficiency up to masses of 16000 amu. The possibility of the deflection of selected saturated atom and cluster peaks serves for further improvement of the detection efficiency for large molecules. The accessible mass resolution was determined to be of the order of m/{delta}m=1000 in the high mass region. Numerous measurements were carried out to characterize the useful yield of this spectrometer. For a best possible adaptation of the TOF mass spectrometer for the detection of highly ...
The thermal behaviour of 21 proteinaceous l-amino acids either as pristine samples and also as radiolyzed (3.2 MGy) samples was studied with the differential scanning calorimeter. The onset and peak melting point as well as the melting enthalpy of all samples before and after the radiation treatment was measured and reported. The residual amount of each amino acid survived to the radiation dose of 3.2 MGy (N_#gamma#) was measured from the melting enthalpies before and after radiolysis and hence the radiation resistance of each amino acid has been determined. The radiolysis causes a systematic reduction of the melting enthalpy and a shift of the onset and peak melting point to lower values. It is shown that N_#gamma# does not correlate with the melting points of the amino acids but shows a correlation with the entity of the shift of the melting point peaks occurred after radiolysis. Such correlation instead does not exist between the N_#gamma# parameter and the onset melting points of ...
A new iron phosphate (NH4)4Fe3(OH)2F2[H3(PO4)4] has been synthesized hydrothermally at HF concentrations from 0.5 to 1.2 mL. Single-crystal X-ray diffraction analysis reveals its three-dimensional open-framework structure (monoclinic, space group P21/n (No. 14), a=6.2614(13) A, b=9.844(2) A, c=14.271(3) A, ?=92.11(1)o, V=879.0(3) A3). This structure is built from isolated linear trimers of corner-sharing Fe(III) octahedra, which are linked by (PO4) groups to form ten-membered-ring channels along [1 0 0]. This isolated, linear trimer of corner-sharing Fe(III) octahedra, [(FeO4)3(OH)2F2], is new and adds to the diverse linkages of Fe polyhedra as secondary building units in iron phosphates. The trivalent iron at octahedral sites for the title compound has been confirmed by synchrotron Fe K-edge XANES spectra and magnetic measurements. Magnetic measurements also show that this compound exhibit a strong antiferromagnetic exchange below TN=17 K, ...
Experiments are reported in which a methane plasma is created, and the methyl ions and hydrogen ions are accelerated within a microchannel array so that they interact with neutral methane molecules on the inside surfaces of the microchannels. No catalysts are used, and the device operates at room temperature. Impact energies of the ions are in the range of 10 eV to greater than 100 eV, and the energy delivered in the interaction at the surfaces causes the production of larger hydrocarbon molecules, such as C{sub 2}H{sub 2}, C{sub 2}H{sub 4}, and C{sub 2}H{sub 6}, along with C{sub 3}, C{sub 4}, C{sub 5}m C{sub 6}, C{sub 7}m and C{sub 8} molecules. There is a decreasing percentage of larger molecules produced, in comparison with the C{sub 2} and C{sub 3} types. Conversion effectiveness is greater at higher pressure, due to the increased ionic activity. The yield ...
Homogeneous nucleation of CaSO{sub 4}{center_dot}2H{sub 2}O (gypsum) based on an optical diagnostic technique was studied within a supersaturation range of 1--4 at 25--90 C. The experiments were carried out using an experimental apparatus consisting of a batch crystallizer with the related measurement devices. Signals of scattered and transmitted light coming from a He-Ne laser source were analyzed to measure the induction period (t{sub ind}), that is, the time delay necessary for homogeneous nucleation to take place. As expected from theory, it was found that t{sub ind} decreases when either temperature or supersaturation increase; from the dependence of t{sub ind} on supersaturation, it was possible to distinguish between the mechanisms of homogeneous and heterogeneous nucleation. From the experimental data relative to homogeneous nucleation, the interfacial tension ({gamma}{sub s}) between CaSO{sub ...
A comparative test in mice for pulmonary toxicity between butylated hydroxytoluene (2,6-di-tert.-butyl-4-methylphenol, BHT) and 2,6-di-tert.-butyl-4-(alpha, alpha, alpha-2H3)methylphenol (BHT-d3) showed a significantly lower toxic potency of the latter. The rate of in vitro BHT metabolism to 2,6-di-tert.-butyl-4-methylene-2,5-cyclohexadienone (BHT-QM) was slowed by deuterating BHT in the 4-methyl group. On the other hand, the rate of in vitro metabolism to 2,6-di-tert.-butyl-4-hydroxy-4-methyl-2,5-cyclohexadienone (BHT-OH) was increased with the deuteration. A similar isotope effect of the deuterium substitution on the in vivo metabolic rates of BHT was observed. These observations support the concept that the lung damage caused by BHT is mediated by BHT-QM. The pulmonary toxicity of 2-tert.-butyl-4-ethylphenol (4-EP) and their deuterated analogs was also compared. 2-tert.-Butyl-4-(1,1-2H2)ethylphenol ...
The quality of molecular dynamics (MD) simulations of proteins depends critically on the biomolecular force field that is used. Such force fields are defined by force-field parameter sets, which are generally determined and improved through calibration of properties of small molecules against experimental or theoretical data. By application to large molecules such as proteins, a new force-field parameter set can be validated. We report two 3.5 ns molecular dynamics simulations of hen egg white lysozyme in water applying the widely used GROMOS force-field parameter set 43A1 and a new set 45A3. The two MD ensembles are evaluated against NMR spectroscopic data NOE atom-atom distance bounds, {sup 3}J{sub NH{alpha}} and {sup 3}J{sub {alpha}}{sub {beta}} coupling constants, and {sup 1}5N relaxation data. It is shown that the two sets reproduce structural properties about equally well. The 45A3 ensemble fulfills the atom-atom distance bounds derived from ...
Here we reported a two-step procedure for preparing a novel polymeric based solid-solid phase change heat storage material. Firstly, a copolymer monomer containing a polyethylene glycol monomethyl ether (MPEG) phase change unit and a vinyl unit was synthesized via the modification of hydrogen group of MPEG. Secondly, by copolymerization of the copolymer monomer and phenyl ethylene, a novel polymeric based solid-solid phase change heat storage material was prepared. The composition, structure and properties of the novel polymeric based solid-solid phase change material were characterized by IR, "1H NMR, DSC, WAXD, and POM, respectively. The results show that the novel polymeric based solid-solid phase change material possesses of excellent crystal properties and high phase change enthalpy.
Premnalatifolin A (1), a unique icetexane diterpene dimer was isolated from the stem-bark of Indian medicinal plant, Premna latifolia. Its structure and relative stereochemistry were elucidated on the basis of detailed spectroscopic analysis, including HRESIMS and 2D NMR (COSY, HSQC, HMBC, and NOESY) spectra. The compound has dimeric carbon skeleton composed of two icetexane skeletal diterpenes linked via ether bond. Further, premnalatifolin A (1) was also evaluated for its cytotoxicity against cancer cell lines (HT-29, A-431, MCF-7, Hep-G2, PC-3, A-549, B-16 F10, and ACHN), which displayed potent activity against HT-29 and MCF-7 cell lines with the IC50 values of 12.15 and 1.11mg/mL, respectively.
This paper describes the search for new potential chemotherapeutic agents based on transition metal complexes with planar ligands. In this study, palladium polypyridyl complexes were synthesized and characterized by elemental analysis, NMR, UV-VIS and IR spectroscopies. The interaction of the complexes with DNA was also investigated by spectroscopic methods. All metal-to-ligand charge transfer (MLCT) bands of the palladium polypyridyl complexes exhibited hypochromism and red shift in the presence of DNA. The binding constant and viscosity data suggested that the complexes [PdCl{sub 2}(phen)] and [PdCl{sub 2}(phendiamine)] interact with DNA by electrostatic forces. Additionally, these complexes induced an important leishmanistatic effect on L. (L.) mexicana promastigotes at the final concentration of 10 {mu}mol L{sup -1} in 48 h. (author)
Nuclear magnetic resonance (NMR) images of live rats with sterile and pyogenic abscesses, hematomas, and various implanted and spontaneous neoplasms demonstrated good contrast differentiation between pathologic and surrounding normal tissues. This differentiation was maximal when both the T1 and T2 tissue relaxation times were used as criteria. Neoplasms have a broad range of T1 and T2 values and may be confused with abscesses or hematomas. Tissue rate constants (1/T1 and 1/T2) are mainly dependent on total water content, the exception being fat, which has a 1/T2 value much shorter than that expected on the basis of water content alone.