Butylene copolyesters based on aldaric and terephthalic acids. Synthesis and characterization

The synthesis, characterization, and some properties of new copolyesters analogous to poly(butylene terephthalate) (PBT), based on L ‐arabinaric and galactaric acids, are described. These copolyesters were obtained by polycondensation reaction in the melt of mixtures of methyl 2,3,4‐tri‐O‐methyl‐L ‐arabinarate or methyl 2,3,4,5‐tetra‐O‐methyl‐galactarate and dimethyl terephthalate with 1,4‐butanediol. Their weight‐average molecular weights ranged between 10,000 and 34,000, with polydispersities ranging from 1.4 to 2.2. The composition of all the copolymers was analyzed by NMR, and was found to have a statistical microstructure. All these copolyesters were thermally stable, with degradation temperatures well above 300 °C. The melting temperature and crystallinity decreased in both series, and the glass transition temperature increased and decreased respectively, for the PBTGa and PBTAr series with increasing amounts of aldaric units in the copolyester chain. Only PBT‐derived copolyesters containing a maximum of 30% aldaric units showed discrete scattering characteristic of crystalline material. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1168–1177, 2009     

Iron,copper and zinc ammonium-1-hydroxyalkylidene-diphosphonates with zero-, one- and two-dimensional covalent metal–ligand structures extended into three-dimensional supramolecular networks by charge-assisted hydrogen-bonding

Hydrothermal synthesis with MCl₂ (M = Fe, Cu, and Zn) and disodium 5-ammonium-1-hydroxypentylidene-1,1-bisphosphonate, (Na⁺)₂[⁺H₃N(CH₂)₄C(OH)(PO₃²⁻)(PO₃H⁻)] (Na₂HAC₅OHP₂) or sodium 3-ammonium-1-hydroxypropylidene-1,1-bisphosphonate hydrate, Na⁺[⁺H₃N(CH₂)₂C(OH)(PO₃H^–)(PO₃H^–)]·H₂O (NaH₂PAM·H₂O) the sodium salt of pamidronic acid, H₃PAM) yielded the one-dimensional (1D) iron, molecular copper and two-dimensional (2D) zinc compounds 1D-{[Fe(μ₃-η⁵-HAC₅OHP₂)]·H₂O}, 1, [Cu(η²-H₂AC₅OHP₂)₂], 2, 2D-{[Zn₂(μ₅-η⁷-AC₅OHP₂)Cl], 3, and 2D-{[Zn(μ₂-η³-H₂PAM)₂], 4, respectively. The bisphosphonate ligand bridges (μ_n) between 2–5 metal atoms and uses 2–7 oxygen donor atoms towards metal coordination (ηⁿ). The zwitterionic nature of the now bis- or tetrakis-deprotonated ammonium–bisphosphonate is retained in the metal complexes. From the reaction of NiCl₂ and Na₂HAC₅OHP₂ the zwitterionic 5-ammonium-1-hydroxypentylidene-1-phosphonic acid, ⁺H₃N(CH₂)₄CH(OH)PO₃H⁻, 5 was obtained as a product of the ligand P–C bond hydrolysis. Adjacent strands, molecules or layers in 1–4, respectively are organized through the Coulomb attraction between the positive ammonium group and the negative phosphonate groups, supported by hydrogen-bonding. Each protic H atom on the C–OH, NH₃⁺ and –PO₃H⁻ group is involved in charge-assisted hydrogen-bonding. The ammonium-pentylidene groups act as hydrophobic separators between the hydrophilic units with the polar M{C(OH)(PO₃)₂} and {NH₃} units. Bond valence sum calculations support the Fe(II) oxidation state in 1, which was experimentally determined from a quantitative polarographic Fe(II)/Fe(III) speciation analysis as well as a temperature variable magnetic study.     

Living fungal hyphae-templated porous gold microwires using nanoparticles as building blocks

Abstract  

A simple and environmentally benign green method is reported to decorate growing fungal hyphae with high loading of gold nanoparticles, which were initially produced using aqueous tea extract as a sole reducing/stabilizing agent. Inoculation of fungal spores in aqueous suspension of nanoparticles led to the growth of intensely red-coloured fungal hyphae due to the accumulation of gold nanoparticles. Heat treatment of these hybrid materials led to the formation of porous gold microwires. This report is thus an interesting example of using green and sustainable approach to produce nanostructured materials which have potential applications in catalysis, sensing and electronics.     

Study of dielectric and impedance properties of Mn ferrites

The paper reports on the effect of Al substitution on the structural and electrical properties of bulk ferrite series of basic composition MnFe_2−2xAl_2xO₄ (0.0≤x≤0.5) synthesized using solid state reaction method. XRD analysis confirms that all the samples exhibit single phase cubic spinel structure excluding presence of any secondary phase. The dielectric constant shows a normal behaviour with frequency, whereas the loss tangent exhibits an anomalous behaviour with frequency for all compositions. Variation of dielectric properties and ac conductivity with frequency reveals that the dispersion is due to Maxwell-Wagner type of interfacial polarization in general and hopping of charge between Fe⁺² and Fe⁺³ as well as between Mn⁺² and Mn⁺³ ions at octahedral sites. The complex impedance plane spectra shows the presence of two semicircles up to x=0.2, and only one semicircle for the higher values of x. The analysis of the data shows that the resistive and capacitive properties of the Mn ferrite are mainly due to processes associated with grain and grain boundaries.     

A magnetic study of the ThCr2Si2-type RPd2Ge2 (R=Pr, Nd) compounds. Magnetic structure of PrPd2Ge2 from powder neutron diffraction

The magnetic properties of the PrPd₂Ge₂ and NdPd₂Ge₂ compounds have been investigated by magnetic measurements, specific heat measurements and neutron diffraction experiments. The PrPd₂Ge₂ compound orders antiferromagnetically below T_N=5.0(2) with an original modulated magnetic structure characterized by a magnetic cell three times larger than the chemical one by tripling of the c parameter. The palladium atom is non magnetic and the Pr moments are parallel to the c-axis with a value of ≈2.0 μ_B at 2 K. The specific heat measurements clearly detect a low temperature transition for the NdPd₂Ge₂ compound, interpreted as a Nd sublattice antiferromagnetic ordering below 1.3(2) K.     

Influence of temperature on the electric,dielectric and AC conductivity properties of nano-crystalline zinc substituted cobalt ferrite synthesized by solution combustion technique

Cobalt–zinc nanoferrites with formulae Co $_{1-x}$ Zn $_{x}$ Fe $_{2}$ O $_{4}$ , where x = 0.0, 0.1, 0.2 and 0.3, have been synthesized by solution combustion technique. The variation of DC resistivity with temperature shows the semiconducting behavior of all nanoferrites. The dielectric properties such as dielectric constant ( $\varepsilon $ ’) and dielectric loss tangent (tan $\delta )$ are investigated as a function of temperature and frequency. Dielectric constant and loss tangent are found to be increasing with an increase in temperature while with an increase in frequency both, $\varepsilon $ ’ and tan $\delta $ , are found to be decreasing. The dielectric properties have been explained on the basis of space charge polarization according to Maxwell–Wagner’s two-layer model and the hopping of charge between Fe $^{2+}$ and Fe $^{3+}$ . Further, a very high value of dielectric constant and a low value of tan $\delta $ are the prime achievements of the present work. The AC electrical conductivity ( $\sigma _\mathrm{AC})$ is studied as a function of temperature as well as frequency and $\sigma _\mathrm{AC}$ is observed to be increasing with the increase in temperature and frequency.     

Crystal structure of tetrakisdiphenylammonium hexadecachlorotetrabismuthate(III)

[(C₆H₅)₂NH₂]₄ ⁺[Bi₄Cl₁₆]^4– crystallizes in the triclinic space group witha=11.835(2),b=12.393(2),c=12.625(3)Å, =108.37(3), =108.69(3), =96.00(3)° andD _c=2.135 g cm^–3 forZ=1. The [Bi₄Cl₁₆]^4– anion is a centrosymmetric cluster of four distorted edge-sharing BiCl₆ octahedra. The ranges of the Bi–Cl bonds are 2.484(4)–2.606(3)Å for Bi–Cl(terminal), 2.691(3)–2.956(4)Å for Bi-Cl(µ₂), and 2.960(3)–3.120(4)Å for Bi-Cl(µ₃). The cations and anions are held in place by weak hydrogen bonds.     

Rheological study of multilayer functionalized polymers: characterization of interdiffusion and reaction at polymer/polymer interface

Rheological behavior in molten state of multilayered polymers was investigated by dynamic mechanical measurements. The competition between polymer/polymer interdiffusion and interfacial reaction of functionalized polymers in a sandwich structure was followed by oscillatory mode under small amplitudes of deformation. The systems chosen for study were polyethylene (PE) grafted with glycidyl methacrylate/polyamide (PA) 6 as a reactive system and PE/PA6 as nonreactive one. Moreover, the interphase thickness was estimated by using thermodynamical models. Experimental results of bilayer systems were compared to existing models of multiphase systems. An expression of storage modulus as a function of welding time was also suggested. Thus, the fit between this one and the experimental data was satisfactory with the different appearing phenomena.     

Rheological studies of the gelation of aqueous solutions of acrylamide-acrylic acid copolymers in the presence of chromium chloride

The gelation kinetics of aqueous solutions of acrylamideacrylic acid copolymers in the presence of chromium ions was studied with different rheometers. The gel time is found to vary with the principle of the apparatus because of a low shear dependence of the elongation of the macromolecules. The variations of the gel time with the experimental conditions of the gel preparation were investigated and we conclude that the gelation is governed by the oligornerization kinetics of the chromium ions which are instantaneously, complexated by the carboxylate groups of the polymer. The variation laws of the gel time and of the elastic modulus with chromium and polymer concentrations, temperature and ionic strength are in qualitative agreement with the structure of the temporary network of the semi-dilute solutions of these copolymers.     

Ultrafast experiments on intermolecular electron transfer in the benzene - bromine atom charge transfer complex

Ultrafast pump - probe measurements have been made on the benzene - bromine atom charge transfer (CT) complex in CCl₄ and cyclohexane solutions. Ultrafast optical excitation of the CT band of the complex yields an ion pair, which is comprised of a benzene cation and a bromide anion. The rate of charge recombination between the bromide and the benzene cation in the ion pair has been observed to be much faster than the rate of diffusion apart. The charge recombination rate is accelerated at high benzene concentrations as a result of the formation of a benzene dimer cation - bromide ion pair which undergoes much faster charge recombination than the benzene cation - bromide ion pair.