SEARCH · Search PubMed
Search indexed PubMed citations on genomics, clinical trials, systematic reviews and public health. Explore titles, authors and supplied subject terms, then open the PubMed record.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Ammonolysis of reactive oxide precursors affords the vanadium(V) phase Ba(2)VO(3)N that is shown by X-ray and neutron powder diffraction and Raman spectroscopy to contain pseudotetrahedral VO(3)N(4-) anions. This is the first example of such species for the first transition series metals.
The transformation of ammonium cyanate into urea, first studied over 170 years ago by Wöhler and Liebig, has an important place in the history of chemistry. To understand the nature of this solid state reaction, knowledge of the crystal structure of ammonium cyanate is a prerequisite. Employing neutron powder diffraction, we demonstrate conclusively that, in the structure of ammonium cyanate, the NH(4)(+) cation forms N-H...N hydrogen bonds to four cyanate N atoms at alternate corners of a distorted cube, rather than our previously proposed alternative arrangement with N-H...O hydrogen bonds to cyanate O atoms at the other four corners.
The crystal structure of the superconducting (ND(3))(x)()NaA(2)C(60) (0.7 < or = x < or = 1, A= K, Rb) fullerides (T(c)= 6-15 K) has been studied by synchrotron X-ray and neutron powder diffraction. It is face-centered cubic (fcc) to low temperatures with Na(+)-ND(3) pairs residing in the octahedral interstices. These are disordered over the corners of two "interpenetrating" cubes with the Na(+) ions and the N atoms displaced by approximately 2.0 A and approximately 0.5 A from the center of the site and statically disordered over the corners of the inner and outer cube, respectively. Close contacts between the D atoms of the ND(3) molecules and electron rich 6:6 C-C bonds of neighboring C(60) units provide the signature of weak N-D.pi hydrogen-bonding interactions, which control the intermolecular packing in the crystal and may determine the unusual superconducting properties.
Lithium intercalation into the oxide slabs of the cation-deficient n = 2 Ruddlesden-Popper oxysulfide Y(2)Ti(2)O(5)S(2) to produce Li(x)Y(2)Ti(2)O(5)S(2) (0 < x < 2) is described. Neutron powder diffraction measurements reveal that at low levels of lithium intercalation into Y(2)Ti(2)O(5)S(2), the tetragonal symmetry of the host is retained: Li(0.30(5))Y(2)Ti(2)O(5)S(2), I4/mmm, a = 3.80002(2) A, c = 22.6396(2) A, Z = 2. The lithium ion occupies a site coordinated by four oxide ions in an approximately square planar geometry in the perovskite-like oxide slabs of the structure. At higher levels of lithium intercalation, the symmetry of the cell is lowered to orthorhombic: Li(0.99(5))Y(2)Ti(2)O(5)S(2), Immm, a = 3.82697(3) A, b = 3.91378(3) A, c = 22.2718(2) A, Z = 2, with ordering of Li(+) ions over two inequivalent sites. At still higher levels of lithium intercalation, tetragonal symmetry is regained: Li(1.52(5))Y(2)Ti(2)O(5)S(2), I4/mmm, a = 3.91443(4) A, c = 22.0669(3) A, Z = 2. A phase gap exists close to the transition from the tetragonal to orthorhombic structures (0.6 < x < 0.8). The changes in symmetry of the system with electron count may be considered analogous to a cooperative electronically driven Jahn-Teller type distortion. Magnetic susceptibility and resistivity measurements are consistent with metallic properties for x > 1, and the two-phase region is identified as coincident with an insulator to metal transition.
The calculated structures of furan as a monomer, a dimer that was isolated from the crystal structure, and the full crystal structure have been thoroughly investigated by a combination of density functional theory (DFT) calculations and inelastic neutron scattering (INS) measurements. To improve our understanding of the nature and magnitude of the intermolecular interactions in the solid, the atoms in molecules (AIM) theory has been applied to the dimer and a cluster of eight monomers. After a careful topological study of the theoretical charge density and of its Laplacian, we have established the existence of C-H...pi, C-H...O, and H...H interactions between adjacent molecules in solid furan. The electron distribution has also been analyzed by performing natural bond orbital (NBO) calculations for the monomer and a H-bonded dimer. When the hydrogen bond is established between two adjacent furan rings, some electron charge is transferred from the pi electronic system of one furan ring to the other molecule in the dimer. This result provides a model of the interaction between end groups of neighboring chains of polyfuran and could be applicable to other conjugated polymers where the pi system is responsible for their conducting properties. To determine how the intermolecular bonds in the solid affect the vibrational dynamics in the periodic system, INS data were analyzed by performing molecular and periodic density functional calculations. Reasonable agreement is achieved, although we note that the poorest agreement is for modes involving hydrogen atoms.
We report the results of a neutron powder diffraction study of the La(0.62)Li(0.16)TiO3 perovskite that determined the diffusion path of lithium cations at room temperature. At 77 K, the Li cations are located at the 2c site (Wycoff notation of the Cmmm space group) on the (002) La deficient layer, while, at room temperature, they are spread over a wide area and migrate following the 2c-4f-2c or 2c-2d-2c tie line on the (002) layer. The probability density of Li cations has a minimum between the 2c and 4f or between the 2c and 2d positions on the diffusion path in contrast to the previous reports where the bottleneck has been thought to be located at the 2c, 2d, and 4f positions. On the basis of the present structural model, the Li-cation conductivity is discussed in terms of a two-dimensional bond-percolation model for Li-cation diffusion. It was found that the vacancy at the La site is essential for the Li-cation conduction.
The new binary antimonide Ti(2)Sb was found to crystallize in a distorted variant of the La(2)Sb type, which contains a square planar La net with short La-La bonds. In the Ti(2)Sb structure, the corresponding Ti net is deformed to squares and rhombs in order to enhance Ti-Ti bonding, as proven by single-crystal X-ray investigation in combination with the real-space pair distribution function technique utilizing both X-ray and neutron powder diffraction data. Electronic structure calculations revealed a lowering of the total energy caused by the disorder, the major driving force being strengthened Ti-Ti interactions along the diagonal of the Ti(4) rhombs.
The hindered rotor transitions of H(2) adsorbed in the chemically related and prototypical porous metal-organic frameworks IRMOF-1, IRMOF-8, IRMOF-11, and MOF-177 were studied by inelastic neutron scattering to gain information on the specifics of H(2) binding in this class of adsorbents. Remarkably sharp and complex spectra of these materials signify a diversity of well-defined binding sites. Similarities in the spectral features as a function of H(2) loading and correlations with recent crystallographic studies were used to assign transitions ranging in rotational barrier from <0.04 to 0.6 kcal/mol as corresponding to localized adsorption sites on the organic and inorganic components of these frameworks. We find that binding of H(2) at the inorganic cluster sites is affected by the nature of the organic link and is strongest in IRMOF-11 in accord with our adsorption isotherm data. The sites on the organic link have lower binding energies, but a much greater capacity for increases in H(2) loading, which demonstrates their importance for hydrogen uptake by these materials.
With neutron powder diffraction, electron diffraction, and second-harmonic generation, we have shown that BiScO3 has a structure closely related to that of multiferroic BiMnO3, but BiScO3 crystallizes in the centrosymmetric space group of C2/c. These results bring up a question about the origin of ferroelectricity in BiMnO3. BiScO3 may serve as a model system to understand the role of Mn3+ ions in the ferroelectricity of BiMnO3.
Unilamellar vesicles are observed to form in aqueous solutions of the cationic surfactant, cetyl trimethylammonium bromide (CTAB), when 5-methyl salicylic acid (5mS) is added at slightly larger than equimolar concentrations. When these vesicles are heated above a critical temperature, they transform into long, flexible wormlike micelles. In this process, the solutions switch from low-viscosity, Newtonian fluids to viscoelastic, shear-thinning fluids having much larger zero-shear viscosities (e.g., 1000-fold higher). The onset temperature for this transition increases with the concentration of 5mS at a fixed CTAB content. Small-angle neutron scattering (SANS) measurements show that the phase transition from vesicles to micelles is a continuous one, with the vesicles and micelles coexisting over a narrow range of temperatures. The tunable vesicle-to-micelle transition and the concomitant viscosity increase upon heating may have utility in a range of areas, including microfluidics, controlled release, and tertiary oil recovery.
A porous hybrid inorganic/organic material, NaNi3(OH)(SIP)2 [SIP = 5-sulfoisophthalate][1], is shown to strongly bind molecular hydrogen at coordinatively unsaturated metal sites. A combination of H2 sorption isotherms, temperature programmed desorption, and inelastic neutron scattering spectroscopy show the existence of a considerable number of such strong binding sites in [1] along with other sites where hydrogen is more weakly physisorbed. The overall capacity for hydrogen of this material as well as the much stronger binding of hydrogen than in typical porous material represent an important step toward a possible utilization of porous media for hydrogen storage.
Use of the tritopic bridging ligand 1,3,5-benzenetristetrazolate (BTT3-) enables formation of [Mn(DMF)6]3[(Mn4Cl)3(BTT)8(H2O)12]2.42DMF.11H2O.20CH3OH, featuring a porous metal-organic framework with a previously unknown cubic topology. Crystals of the compound remain intact upon desolvation and show a total H2 uptake of 6.9 wt % at 77 K and 90 bar, which at 60 g H2/L provides a storage density 85% of that of liquid hydrogen. The material exhibits a maximum isosteric heat of adsorption of 10.1 kJ/mol, the highest yet observed for a metal-organic framework. Neutron powder diffraction data demonstrate that this is directly related to H2 binding at coordinatively unsaturated Mn2+ centers within the framework.
It was found that a degree of the binding of alkylphenols to N-alkylacrylamide gel increased transitionally to induce the volume phase transition of gel. Binding isotherms of nonylphenol (n-Ph), propylphenol (p-Ph), ethylphenol (e-Ph), methylphenol (m-Ph), and phenol (Ph) to N-isopropylacrylamide (NIPA), N,N-diethylacrylamide (DEA), N,N-dimethylacrylamide (DMA), and acrylamide (AM) gels were examined. Two types of binding, the site binding at beta < 1 and the multimolecular binding at beta > 1, were observed, where beta was a degree of binding to a monomeric unit of the chain. The former binding was analyzed with the Hill equation applicable to the cooperative binding and the latter binding with the Brunauer-Emmett-Teller (BET) equation applicable to the multilayer adsorption. The binding constant, K, and the Hill coefficient, N, decreased and increased, respectively, in the order of DEA, NIPA, and DMA gels in the case where the binding alkylphenol was the same. The K value increased in the order of Ph, m-Ph, e-Ph, p-Ph, and n-Ph that bound to the same type of gel. The N value was found to change little with the type of binding alkylphenol. The complexes of N-alkylamide with alkylphenol were condensed to form the ordered nanostructures that were observed as broad scattering peaks in small-angle X-ray scattering experiments. The fluorescence excimer emission was observed for the phenol-binding DMA gel, which corresponded to the condensed state of phenol.
Analytical expressions for the scattering functions of ordered mesoscopic materials are derived and compared to experimentally determined scattering curves. Ordered structures comprising spheres (fcc, bcc, hcp, sc), cylinders (hex, sq), and lamellar structures are considered. The expressions take into account particle size distributions and lattice point deviations, domain size, core/shell structures, as well as peak shapes varying analytically between Lorentzian and Gaussian functions. The expressions allow one to quantitatively describe high-resolution synchrotron small-angle X-ray (SAXS) and neutron scattering (SANS) curves from lipid and block copolymer lyotropic phases, core/shell nanoparticle superstructures, ordered nanocomposites, and ordered mesoporous materials. In addition, the diffuse out-of-plane scattering of grazing incidence GISAXS and GISANS experiments of laterally ordered thin films can be quantitatively analyzed.
The growth behavior of aggregates formed in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS) in the presence of the cationic hydrophobic salts o-toluidine hydrochloride (OTHC) and m-toluidine hydrochloride (MTHC) has been studied by dynamic light scattering (DLS) and small-angle neutron scattering (SANS) techniques. DLS studies indicate a progressive growth of SDS micelles with addition of less than equimolar concentrations of hydrophobic salts. A prolate ellipsoidal model is used to analyze the DLS data, which is further supported by SANS measurements. We explain the propensity for the strong growth of micelles in the presence of OTHC and MTHC by the high charge neutralization provided by these salts as the aromatic counterions are adsorbed on the surface of the micelles. When the substitution is at the meta position, i.e., for MTHC, micellar growth is favored at lower salt concentrations than for OTHC. The variation in growth behavior is explained in terms of the difference in the chemical environments of the substituents at the ortho and meta positions. Micellar parameters obtained from SANS data at elevated temperature also support enhanced growth of micelles in the presence of MTHC as compared to OTHC.
Spontaneously formed unilamellar vesicles (ULV) composed of short- and long-chain phospholipids, dihexanoyl phosphorylcholine (DHPC) and dimyristoyl phosphorylcholine (DMPC), respectively, were doped with a negatively charged lipid, dimyristoyl phosphorylglycerol (DMPG), and studied with small-angle neutron scattering (SANS) and dynamic light scattering (DLS). Upon dilution, the spontaneous formation of vesicles was found to take place from bilayered micelles, or so-called "bicelles". SANS and DLS data show that ULV with narrow size distributions are highly stable at low lipid (C(lp) < 0.50 wt %) and NaCl salt (C(s)) concentrations. ULV size was found to be independent of both C(lp) and C(s) when they were below 0.33 and 0.5 wt %, respectively. Surface charge and salinity were found to be important factors in preparing ULV of a certain size. This observation is not in complete agreement with previous experimental results and cannot be completely explained with current theoretical predictions based on equilibrium calculations for catanionic surfactant mixtures. ULV size is found to be invariant over a wide range of temperatures, both below and above the phase-transition temperature, T(M), of DMPC, and was stable for periods of weeks and months, even after sonication.
The formation of associative networks in semidilute aqueous solutions of hydrophobically modified alginate (HM-alginate) is dependent on intermolecular hydrophobic interactions. Addition of beta-cyclodextrin (beta-CD) monomers to the system provides decoupling of these associations via inclusion complex formation with the polymer hydrophobic tails. This results in a dramatic decrease in the viscoelastic response of the system and a more extended local structure of the polymer chains, as shown by small-angle neutron scattering (SANS) measurements. The zero-shear viscosity decreases about an order of magnitude when the beta-CD concentration is increased from 0 to 12 mm. The lifetime of the associative network decreases strongly with increasing levels of beta-CD addition. These findings clearly demonstrate that the hydrophobic association effect is efficiently reduced as the amount of beta-CD is increased. In the framework of drug delivery, this effect may be useful to improve the release of therapeutic molecules that can be entrapped in the polymer matrix.
A detailed investigation on the nature of the relaxation processes occurring in a typical room temperature ionic liquid (RTIL), namely, 1-butyl-3-methyl imidazolium hexafluorophosphate ([bmim][PF(6)]), is reported. The study was conducted using both elastic and inelastic neutron scattering over a wide temperature range from 10 to 400 K, accessing the dynamic features of both the liquid and glassy amorphous states. In this study, the inelastic fixed energy scan technique has been applied for the first time to this class of materials. Using this technique, the existence of two relaxation processes below the glass transition and a further diffusive process occurring above the glass-liquid transition are observed. The low temperature processes are associated with methyl group rotation and butyl chain relaxation in the glassy state and have been modeled in terms of two Debye-like, Arrhenius activated processes. The high temperature process has been modeled in terms of a Kohlraush-Williams-Watts relaxation, with a distinct Vogel-Fulcher-Tamman temperature dependence. These results provide novel information that will be useful in rationalizing the observed structural and dynamical behavior of RTILs in the amorphous state.