Structural study of ammonium metatungstate

Several techniques have been used to study the structure of the Keggin-type polyoxometalate salt ammonium metatungstate (AMT)—(NH₄)₆[H₂W₁₂O₄₀]*nH₂O, a potential fuel cell catalyst. The dehydrated salt is comprised of a mixture of crystallites of different unit cells in a centered eutactic cubic configuration, with an average unit cell of a≅12.295. Varied orientations of the Keggin ions in the cubic arrangement create the differences, and orientational variation within each unit cell size represents an energy well. Progressive hydration of each crystallite leads to expansion of the lattice, with the degree of expansion depending on the locations of the water added in relation to the Keggin ion, which is influenced by cation location and hydrogen bonding. The structural hypothesis is supported by electron diffraction of single and multicrystal samples, by powder density measurements, X-ray powder diffraction studies, synchrotron powder X-ray diffraction, and a priori structural modeling studies. Based on the structure, projected active site densities are compared with nanostructured platinum catalysts for fuel cell application.     

Structural study of gold clusters

Density functional theory (DFT) calculations were carried out to study gold clusters of up to 55 atoms. Between the linear and zigzag monoatomic Au nanowires, the zigzag nanowires were found to be more stable. Furthermore, the linear Au nanowires of up to 2 nm are formed by slightly stretched Au dimers. These suggest that a substantial Peierls distortion exists in those structures. Planar geometries of Au clusters were found to be the global minima till the cluster size of 13. A quantitative correlation is provided between various properties of Au clusters and the structure and size. The relative stability of selected clusters was also estimated by the Sutton-Chen potential, and the result disagrees with that obtained from the DFT calculations. This suggests that a modification of the Sutton-Chen potential has to be made, such as obtaining new parameters, in order to use it to search the global minima for bigger Au clusters.     

Structural study on polymorphism of cis-unsaturated triacylglycerol: triolein

To clarify the influence of cis-unsaturation on solid-state structures of triacylglycerols (TAGs), the crystal structures of three crystalline phases (alpha, beta' and beta) of triolein [C3H5(OCOC17H33)3] were investigated by powder X-ray diffractometry and IR and Raman spectroscopy. The influence on the structural change of the alpha phase in the course of cooling was also studied. With respect to the subcell structure and conformational order of hydrocarbon chains in the beta and beta' phases, triolein resembles saturated TAGs; trans-zigzag hydrocarbon chains are adopted in the T(parallel) subcell for the beta phase and in the O(perpendicular) subcell for the beta' phase. The influence of cis-unsaturation was most obvious in the structure of the alpha phase and its temperature dependence. The alpha phase of triolein does not form the ordinary hexagonal subcell but a rather loose distorted subcell, which hardly changes in cooling, forming a striking contrast to the hexagonal-->pseudohexagonal subcell transformation found in the alpha phase of saturated TAGs.     

Structural study of potential controlled deposited Langmuir-Blodgett-films on metal substrates

Summary A Langmuir-Blodgett-Film-Balance was modified, in order to obtain electrochemical potential control of metal substrates during film deposition. With this balance octadecylmercaptan (ODM) was brought onto gold substrates under different potentials. The mercaptan monolayer was investigated by means of surface analytical techniques (XPS, ARXPS). Initial results concerning the potential dependence of the LB-layer are presented.     

姜黄素衍生物电子结构及光谱性质的理论研究

在B3LYP/6-31G**和TD B3LYP/6-31G**水平上对标题化合物电子结构和光谱性质进行了研究,为模拟真实条件,计算还考虑了甲醇溶液对电子结构和光谱性质的影响。研究结果表明:标题化合物存在A、B、C三类互变异构体,异构体稳定性为BAC。以ΔU、ΔH作为比较依据,则在气相和甲醇溶液中,A3、B3、C3分别为其异构体的能量最低构象,且B3为最稳定构型。以ΔG作为比较依据,气相中B3为最稳定构型;而甲醇溶液中B4为最稳定构型。异构体A的红外光谱在2503 cm-1处存在特征吸收峰,该吸收峰为其分子内缔合氢键的νO-H;异构体B的红外光谱在1627 cm-1处存在很强的特征吸收峰,该吸收峰为螯合羰基的νC=O。甲醇溶液使分子的ELUMO、EHOMO、ΔEgap均下降,电子光谱λmax发生红移。异构体A、B在气相和甲醇溶液中的λmax均都主要来源于H→L的π→π*跃迁;异构体C在气相中的λmax主要来源于H→L+1、H-1→L的π→π*跃迁,而在甲醇溶液中则主要来源于H-1→L的π→π*跃迁;以上跃迁存在分子内电荷转移现象。     

Structural study on the carbohydrate moiety of calf intestinal alkaline phosphatase

Surprisingly alkaline phosphatase (AP) (EC 3.1.3.1) of calf intestine is found in large amounts, e.g. 80%, within chyme. Most of the enzyme is present as a mixture of four differently hydrophobic anchor-bearing forms and only the minor part is present as an anchorless enzyme. To investigate whether changes in the N-glycosylation pattern are signals responsible for large-scale liberation from mucosa into chyme, the glycans of the two potential glycosylation sites predicted from cDNA were investigated by matrix-assisted laser desorption/ionization and electrospray ionization mass spectrometry in combination with exoglycosidase treatment after tryptic digestion and reversed-phase chromatography. The glycans linked to Asn249 are at least eight different, mainly non-fucosylated, biantennary or triantennary structures with a bisecting N-acetylglucosamine. For the most abundant glycopeptide (40%) the following glycan structure is proposed: [carbostructure: see text]. The glycans linked to Asn410 are a mixture of at least nine, mainly tetraantennary, fucosylated structures with a bisecting N-acetylglucosamine. For the most abundant glycopeptide (35%) the following glycan structure is proposed: [carbostructure: see text]. For the structures the linkage data were deduced from the reported specificities of the exoglycosidases used and the specificities of the transglycosidases active in biosynthesis. The majority of glycans are capped by alpha-galactose residues at their non-reducing termini. In contrast to the glycans linked to other AP isoenzymes, no sialylation was observed. Glycopeptide 'mass fingerprints' of both glycosylation sites and glycan contents do not differ between AP from mucosa and chyme. These results suggest that the observed large-scale liberation of vesicle-bound glycosylphosphatidylinositol (GPI)-anchored AP from mucosa into chyme is unlikely to be mediated by alteration of glycan structures of the AP investigated. Rather, the exocytotic vesicle formation seems to be mediated by the controlled organization of the raft structures embedding GPI-AP. (c) 2001 John Wiley & Sons, Ltd.     

Structural and thermal study of calcium undecanoate

In the present work, an X-ray diffraction (XRD) and thermal study of calcium undecanoate is presented. The measured high-resolution XRD powder pattern of the synthesized salt at room temperature, using synchrotron radiation, showed that the salt is a mixture of monohydrated and anhydrous calcium undecanoate. Calcium undecanoate monohydrate proved to have a monoclinic cell with a symmetry described by the P2₁/a space group. The structure dehydrates at about 100°C. After dehydration, the salt undergoes a phase transformation which results in a thermotropic mesophase. Further heating of the salt leads to decomposition and melting. Ketones are the probable products of decomposition at 400°C.     

Structural study of supercooled liquid transition metals

Local structural models for supercooled liquid transition metals (Ti, Ni, and Zr) are proposed based on a reverse Monte Carlo analysis of high-energy x-ray diffraction data taken from the electrostatically levitated liquids. The resulting structures are characterized by their bond angle distributions, Honeycutt and Andersen indices [J. Phys. Chem. 91, 4950 (1987)], and bond orientational order parameters. All analyses suggest that an icosahedral short-range order is present in these supercooled liquids, but it is distorted in liquid Ti. These results are in agreement with the observed evolution of the high-q shoulder on the second peak in the structure factor S(q) and with an earlier analysis based on a local cluster model.     

Structural study of ternary iron-lead-germanate glass ceramics

Glass ceramics with the composition xFe(2)O(3)·(100-x)[7GeO(2)·3PbO(2)] where 0≤x≤60 mol% were obtained and studied using XRD, FTIR and UV-vis spectroscopy investigations. Heat treatment of glass samples at 400°C for 8 h led to the formation of α, γ-PbGe(4)O(9), Pb(3)Fe(2)Ge(4)O(14) and PbO(1.44) crystalline phases. The content of these crystalline phases depends of Fe(2)O(3) concentration. FTIR spectroscopy data suggest that the lead ions have a pronounced affinity towards [GeO(5)] structural units containing non-bridging oxygens and [FeO(4)] anions producing formation of the Pb(3)Fe(2)Ge(4)O(14) crystalline phase. The introduction of low concentrations of Fe(2)O(3) into the host matrix results in the formation of new absorption UV bands between 320 and 450 nm. These bands arise from to the d-d transitions of the Fe(+3) ions. The light absorption in the range from 250 to 600 nm increases with increasing iron oxide content in matrix network, accompanied with the changes on color from white to brown yellow and darker brown.     

Structural study on gold nanoparticle functionalized with DNA and its non-cross-linking aggregation

Hybridization of DNA tethered on colloidal nanoparticles with fully matched complementary one induces the aggregation of the particles in a non-cross-linking configuration. Here, we performed a structural study on DNA-functionalized gold nanoparticle and its non-cross-linking aggregation mainly using synchrotron radiation small-angle X-ray scattering. To understand the non-cross-linking aggregation, the nanoparticles with various DNA lengths and core sizes were used. In the aggregation, the surface distance between the gold nanoparticles increased with the length of DNA duplex, although the increment of the distance per base pair was not constant and showed the tendency to become small with increasing DNA length, meaning the interdigitation of DNA layers. The aggregation was also found to occur between the identical cores, without being affected by tethered DNA. Furthermore, it was proved that the relative increase in DNA length to core size leads to the increase in colloidal stability. Even the nanoparticles with full-matched DNA duplex were dispersed stably. These facts suggested that van der Waals interaction between core particles rather than end-to-end stacking between DNA duplexes is a dominant attractive interaction. The steric repulsion force arising from entropic loss of thermal fluctuation of DNA molecules might be a key factor to characterize the non-cross-linking aggregation.     

Structural and thermal study of mesomorphic dodecylammonium carrageenates

Structural characteristics and thermal stability of a series of dodecylammonium carrageenates formed by stoichiometric complexation of dodecylammonium chloride and differently charged carrageenans (κ-, ι- and λ-carrageenan, respectively) were investigated. IR spectral analysis confirmed the electrostatic and hydrogen bond interactions between the dodecylammonium and carrageenan species. X-ray diffraction experiments show increased ordering in the complexes compared to that in the parent carrageenans. Dodecylammonium carrageenates have a layer structure, in which a polar sublayer contains layers of carrageenan chains and a nonpolar sublayer consists of conformationally disordered dodecylammonium chains electrostatically attached to the carrageenan backbone. The major factor that determines the dodecylammonium carrageenate structure is cationic surfactant, while the carrageenans moiety plays a major role in determining thermal properties.     

Structural and thermal study of CuInSe2 films

Ternary copper indium Di-selenide (CISe) thin film has been deposited by spin-coating on non-conducting glass slide substrates and a solution prepared by the sol-gel process. At room temperature, correspondingly, CuCl2·2H2O, InCl3·3H2O, and H2SeO3 were employed as precursor source chemicals for Cu, In, and Se ions. The dark brown films adhered effectively to the glass substrates. Energy dispersive X-ray analysis is utilized to assess the thin film's chemical composition, which revealed that the film was close to the stoichiometric ratio and proved the proper elemental composition. The thin film's tetragonal unit cell structure was validated by XRD analysis, and all of the derived lattice parameters (a = 5.8512 A and c = 11.7268 A) are excellent consistent with the previous results. Scherrer's formula yields a crystallite size of 5.94 nm. SEM microtopography of the film surface revealed that the film is homogeneous on the substrate surface, and AFM revealed that the film has a spike-like morphology. UV–Vis spectroscopy was performed in the 300–1400 nm region. The obtained values of the absorption coefficient and band gap are 1.2eV. The thermal analysis is carried out by TGA.     

Structural study of arylsilanes using 29Si NMR

²⁹Si NMR data (σ and ¹H, ²⁹Si coupling constants) of a series of arylsilanes were studied in relation to their molecular structure. It is shown that silicon chemical shift variation is too weak to allow empirical attribution. In contrast, ²⁹Si, ¹H coupling constants across the aromatic ring, especially the ³J, allow structural assignment. Generally, SPT experiments are sufficient to obtain these values. However, full attribution of polysilylated derivatives sometimes needs other experiments to identify all the silicons. A 2D J-resolved INEPT experiment is described and has proven to be an efficient method for ²⁹Si NMR signal identification. The usefulness of this approach is demonstrated by the complete analysis of all the ²⁹Si lines in a trisilyl derivative. An easy-to-use INEPT decoupled-type sequence is also proposed for a rapid characterization of polysilylated derivatives or mixture of isomers.     

Structural study of the solutions of acidic polysaccharides

A study was made of the effect of NaCl on the counterion activity coefficient in solutions of acidic polysaccharide sodium salts. The counterion activity coefficient in the sodium salt solutions of polyuronic acids was shown to be determined by electrostatic interactions only. Consequently it can be supposed that the counterion-polyion interaction is also of an electrostatic nature. A method was proposed for determining the distribution patterns of nonionogenic groups along the polyelectrolyte chain. The structural transition ofχ-carrageenan, depending on NaCl concentration, was found to be accompanied by a nonelectrostatic binding of sodium ions by the polysaccharide.     

Structural features of films based on star-shaped fullerene-containing polystyrenes: Small-angle neutron-scattering study

The structuring of films based on regular six-arm and twelve-arm polystyrenes with the arm characteristics M_n = 118 × 10³ and M_w/M_n = 1.06 and a fullerene (С₆₀) branching center in a weakly swollen state in a mixture of deuterated solvents (90 vol % D-methanol and 10 vol % D-toluene) is studied by small-angle neutron scattering. Analogous studies are performed for films based on linear polystyrene (M_n = 280 × 10³, M_w/M_n = 1.07) and its composites with fullerene С₆₀ (0.5 wt %). It is shown that, during saturation of the samples with the solvent D-toluene, filling of the free volume that forms chain-transport channels that have gyration radii of the order of diameters of macromolecules and unite to form submicron and micron structures occurs. The degree of filling of the free volume, which is maximum for the linear polymer, becomes minimum for polystyrene with the inserted free fullerene. In addition, the transition from the linear polymer to the six-arm polymer is related to a smaller degree of filling of the free volume due to the formation of thinner migration channels. As the amount of arms in macromolecules is increased to 12, permeability of the polymer matrix improves because molecular order partially appears in accordance with the model of the densest packing of solid spheres.     

Structural study on a bioactive fructan from the root of Achyranthes bidentata Blume

The structure of a saccharide component (Abs),with pronounced activity of improving immunity system,isolated from the root of Achyranthes bidentata Blume,a traditional Chinese herbal medicine,was studied.Based on 13C NMR,HPLC,and methylation analyses,Abs was shown to be a mixture of short-chain fructans with an average dp of 8,containing more (2→6) than (2→1) linked β-D-fructofuranosyl residues,with branching at O-6 or O-1 of 18% of the D-fructofuranoeyl residues.     

Structural study of lanthanum nickelate thin films deposited on different single crystal substrates

Fabrications of La₂NiO_4+δ thin film layers by liquid-injection metalorganic chemical vapor deposition were tried on different single crystals substrates: (001)Si, (001)MgO, (001)LaAlO₃ and (001)SrTiO₃. As results of structural characterizations, polycrystalline dendritic layers of La₂NiO_4+δ tetragonal (or orthorhombic) phase were observed on (001)Si substrates while layers of a perovskite-like cubic structure were observed on the other single crystal substrates. From a high-resolution TEM study of a layer deposited on (001)MgO, such a perovskite-like cubic structure exhibits many planar structural faults likely similar to planes of oxygen vacancies of the La₂NiO_4+δ orthorhombic structure. A thin intermediate epitaxial layer of NiO phase was also identified. Using a X-ray texture diffractometer, the layer structure on (001)MgO, (001)LaAlO₃ and (001)SrTiO₃ was confirmed to be of cubic structure with 〈100〉 axes parallel to those of the substrate. The T dependence of the resistivity of a layer deposited on (001)MgO substrate was found to be of a semi-conducting behavior.     

Structural and thermodynamic aspects of an electron-diffraction study on saturated thallium monofluoride vapor

Ivanovo Chemical Engineering Institute. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 1, pp. 42–49, January–February, 1989.     

Structural study of the solid-state photoaddition reaction of arylidenoxindoles

The photochemistry of isomeric 2-furyliden- and benzylidenoxindoles (2H-indol-2-ones) is examined. In solution E-Z isomerization is the only process via the excited singlet state (which fluoresces in glassy solution at 77 K and not at room temperature). In the crystalline state, the two (Z) derivatives are photostable, in accordance with the prediction based on the structural determination of the furylidene derivative, which adopts the unreactive Schmidt's gamma type arrangement. The (E) furylidene derivative (1a) gives efficiently (Phi = 0.3) the head-to-tail dimer, as indicated by the crystal structure, which is of the reactive alpha type, in full accord with the topochemical principles. In contrast, the corresponding benzylidene (1b) derivative reacts sluggishly (Phi < 0. 01) and mainly gives polymers, despite the fact that crystal structure determination shows that it likewise pertains to the alpha type and complies with the topochemical rules. The difference in reactivity is explained on the basis of (i) the twist of the phenyl ring with respect to the indole plane, and (ii) the higher overall cohesion energy and the lower interaction energy between facing molecules, as found from the charge density analysis for the crystals of 1b in comparison to those of 1a. This evidences a further stringent requirement for the occurrence of topochemical photodimerizations.