Structural evolution of tensile-deformed high-density polyethylene during annealing: Scanning synchrotron small-angle X-ray scattering study

The structural evolution of high-density polyethylene subjected to uniaxial tensile deformation was investigated as a function of strain and after annealing at different temperatures using a scanning synchrotron small-angle X-ray scattering (SAXS) technique. The results confirm that in the course of tensile deformation intralamellar block slips were activated at small deformations followed by a stress-induced fragmentation and recrystallization process yielding thinner lamellae with their normal parallel to the stretching direction. The original sheared lamellae underwent severe internal deformation so that they were even less stable than the newly developed thinner lamellae. Accordingly, annealing results in a melting of the original crystallites even at moderate strains where the stress-induced fragmentation and recrystallization just sets in and generates a distinctly different form of lamellar stacks aligned along the drawing direction. It was found that the lamellae newly formed during stretching at moderate strains remain stable at lower temperature. Only at a very high annealing temperature of 120 degrees C can they be melted, leading to an isotropic distribution of the lamellar structure.

The magnetic and structural properties of hydrothermal-synthesized single-crystal Sn1-xFexO2 nanograins

The crystal structure and magnetic properties of Sn1-xFexO2 nanograins synthesized by simple hydrothermal method using SnCl4 center dot 5H(2)O and FeCl3 center dot 6H(2)O as raw materials are studied. No secondary phase was found in the XRD spectrum. The linear change of lattice volume for different Fe content strongly supports that the Fe3+ substitutes Sn4+ in SnO2 lattice. A Raman and IR spectra study indicated that the Fe incorporates into the SnO2 lattice. Both ferromagnetic and paramagnetic signals are detected in the Mossbauer spectra. The Sn1-xFexO2 (x <= 0.10) samples show room-temperature ferromagnetism (RTFM) and the saturation magnetization increased with increasing Fe percent. Fe ions present three kinds of magnetic behaviors including paramagnetic, ferromagnetic, and antiferromagnetic in the samples observed by investigation of the M-H and M-T curves. The weak RTFM was due to only a fraction of Fe ions contributing to magnetic-order coupling mediated by oxygen vacancy.

Synthesis and structural characterization of new tungsten(VI) complexes with polycarboxylate ligands

The reactions of (NH4)(2)WS4 and three polycarboxylate ligands {including nitrilotriacetate (nta(3-)), citrate (Hcit(3-)) and ethylenediaminetetra acetate (EDTA(4-))} in H2O/EtOH at ambient temperature have resulted in three new trioxotungsten (VI) complexes, K-3[WO3(nta)]center dot H2O 1, (NH4)(4)[WO3(cit)]center dot 2 H2O 2 and K-2(NH4)(2)[W2O6(EDTA)]center dot 4H(2)O 3, respectively. These three complexes have been characterized by IR, XPS, TGA-DTA, H-1 and C-13 NMR spectroscopy. And their structures have been determined by X-ray crystallographic studies, which confirm that I and 2 are mononuclear compounds and 3 is a binuclear compound. Each tungsten atom in 1-3 is coordinated to three unshared oxygen atoms, which adopt fac stereochemistry, while the remaining fac positions are occupied by three atoms from the ligands. The electrochemical properties of 2 and 3 have been investigated.

Structural analysis of selected characteristic flavones by electrospray tandem mass spectrometry

Seven structure analogical flavonoid aglycones have been analyzed using electrospray ionization tandem mass spectrometry (ESI-MSn) in the negative-ion mode. The spectra obtained ESI-MSn allowed us to propose plausible schemes for their fragmentation mechanism. By analyzing the product ions spectra of deprotonated molecule ions [M-H](-), some neutral diagnostic losses and specific retro Diels-Alder fragments were obtained. By using all of these characteristic fragment ions we can specially differentiate the flavone isomer.

Structural determination of a new phase of monoclinic BaTb2Mn2O7

A new phase of monoclinic BaTb2Mn2O7 with extra superlattice lines in addition to the usual orthorhombic X-ray diffraction patterns was prepared and a Rietveld refinement was applied to analyze the crystal structure using X-ray powder diffraction data at room temperature. The refined lattice parameters were a = 0.54918(8) nm, b = 2.0149(5) nm, c = 0.54922(9) nm, and beta = 90.62degrees with the space group A2/m (no. 12). The MnO6 oxygen octahedron has distortion and tilts around a-axis by about 7degrees each other in the reverse direction.

Structural analysis of PEKEKK(T/I) using WAXD, imaging plates and SAXS

Structures and crystal form transition of the novel aryl ether ketone polymer containing meta-phenylene linkage: PEKEKK(T/I) were investigated by wide angle X-ray diffraction (WAXD), imaging plates (IPs) and small angle X-ray scattering (SAXS). The energy of activation of the decomposition reaction and degree of crystallinity of PEKEKK(T/I) were determined by WAXD and thermo-gravimetric analysis (TGA), respectively. Results obtained from WAXD and IPs show that crystal forms I and II coexist in the PEKEKK(T/I) samples isothermally cold crystallized in the temperature range from 180degreesC to 240degreesC and only form I occurs in PEKEKK(T/I) samples isothermally cold crystallized at 270degreesC. The radius of gyration (Rg), thickness of microregions with electron-density fluctuations (E) and distribution of particle sizes were investigated by SAXS.

Structural analysis of saponins from medicinal herbs using electrospray ionization tandem mass spectrometry

The underivatized saponins from Tribulus terrestris and Panax ginseng have been investigated by electrospray ionization multi-stage tandem mass spectrometry (ESI-MSn). In ESI-MS spectra, a predominant [M + Na](+) ion in positive mode and [M - H](-) ion in negative mode were observed for molecular mass information. Multi-stage tandem mass spectrometry of the molecular ions was used for detailed structural analysis. Fragment ions from glycoside cleavage can provide information on the mass of aglycone and the primary sequence and branching of oligosaccharide chains in terms of classes of monosaccharides. Fragment ions from cross-ring cleavages of sugar residues can give some information about the linkages between sugar residues. It was found that different alkali metal-cationized adducts with saponins have different degrees of fragmentation, which may originate from the different affinity of a saponin with each alkali metal in the gas phase. ESI-MSn has been proven to be an effective tool for rapid determination of native saponins in extract mixtures, thus avoiding tedious derivatization and separation steps.

Structural selectivity of aromatic diamidines

Competition dialysis was used to study the interactions of 13 substituted aromatic diamidine compounds with 13 nucleic acid structures and sequences. The results show a striking selectivity of these compounds for the triplex structure poly dA:(poly dT)(2), a novel aspect of their interaction with nucleic acids not previously described. The triplex selectivity of selected compounds was confirmed by thermal denaturation studies. Triplex selectivity was found to be modulated by the location of amidine substiuents on the core phenyl-furan-phenyl ring scaffold. Molecular models were constructed to rationalize the triplex selectivity of DB359, the most selective compound in the series. Its triplex selectivity was found to arise from optimal ring stacking on base triplets, along with proper positioning of its amidine substituents to occupy the minor and the major-minor grooves of the triplex. New insights into the molecular recognition of nucleic acid structures emerged from these studies, adding to the list of available design principles for selectively targeting DNA and RNA.

Structural features of the L-argininamide-binding DNA aptamer studied with ESI-FTMS

The 24-mer DNA aptamer of Harada and Frankel ( Harada, K.; Frankel, A. D. EMBO J. 1995, 14, 5798-5811) that binds L-argininamide (L-Arm) was studied by electrospray ionization Fourier transform mass spectrometry (ESI-FTMS). This DNA folds into a stem and loop such that the loop is able to engulf L-Arm. As controls, two derivatives of the same base composition, one with the same stem but a scrambled loop and the other with no ability to form a secondary structure, were studied. The two DNAs that could fold into stem-loop structures showed a more negatively charged distribution of ions than the linear control. This tendency was preserved in the presence of ligand; complexes expected to have more secondary structure had ions with more negative charges. Distinct species corresponding to no, one, and two bound L-Arm molecules were observed for each DNA. The fractional peak intensities were fit to a straightforward binding model and binding constants were obtained. Thus, ESI-FTMS can provide both qualitative and quantitative data regarding the structure of DNA and its interactions with noncovalent ligands.

Synthesis and structural characterization of beta-diketiminate-lanthanide Amides and their catalytic activity for the polymerization of methyl methacrylate and epsilon-caprolactone

The synthesis and catalytic activity of lanthanide monoamido complexes supported by a beta-diketiminate ligand are described. Donor solvents, such as DME, can cleave the chloro bridges of the dinuclear beta-diketiminate ytterbium dichloride {[(DIPPh)(2)nacnac]YbCl(mu-Cl)(3)Yb[(DIPPh)(2)nacnac](THF)} (1) [(DIPPh)(2)nacnac = N,N-diisopropylphenyl-2,4-pentanediimine anion] to produce the monomeric complex [(DIPPh)(2)nacnac]YbCl2(DME) (2) in high isolated yield. Complex 2 is a useful precursor for the synthesis of beta-diketiminate-ytterbium monoamido derivatives. Reaction of complex 2 with 1 equiv of LiNPr2i in THF at room temperature, after crystallization in THF/toluene mixed solvent, gave the anionic beta-diketiminate-ytterbium amido complex [(DIPPh)(2)nacnac]Yb(NPr2i)(mu-Cl)(2)Li(THF)(2) (3), while similar reaction of complex 2 with LiNPh2 produced the neutral complex [(DIPPh)(2)nacnac]Yb(NPh2)Cl(THF) (4). Recrystallization of complex 3 from toluene solution at elevated temperature led to the neutral beta-diketiminate-lanthanide amido complex [{(DIPPh)(2)nacnac}Yb(NPr2i)(mu-Cl)](2) (5). The reaction medium has a significant effect on the outcome of the reaction.

Non-affine structural evolution of soft colloidal crystalline latex films under stretching as observed via synchrotron X-ray scattering

A polymer dispersion consisting of soft latex spheres with a diameter of 135 nm was used to produce a crystalline film with face-centered cubic (fcc) packing of the spheres. Different from conventional small-molecule and hardsphere colloidal crystals, the crystalline latex film in the present case is soft (i.e., easily deformable). The structural evolution of this soft colloidal latex film under stretching was investigated by in-situ synchrotron ultra-small-angle X-ray scattering. The film exhibits polycrystalline scattering behavior corresponding to fcc structure. Stretching results not only in a large deformation of the crystallographic structure but also in considerable nonaffine deformation at high draw ratios. The unexpected nonaffine deformation was attributed to slippage between rows of particles and crystalline grain boundaries. The crystalline structure remains intact even at high deformation, suggesting that directional anisotropic colloidal crystallites can be easily produced.