A new oxidation state of aniline pentamer observed in water-soluble electroactive oligoaniline-chitosan polymer

A novel water-soluble electroactive polymer, aniline pentamer crosslinked chitosan (Pentamer-c-Chi), was prepared by condensation polymerization of the terminal carboxyl groups in aniline pentamer with the amino side groups in chitosan in aqueous solution. The carboxyl groups were activated by N-hydroxysuccinimide (NHS) and N,N'-dicyclohexylcarbodiimide (I)CC). The electrochemical behavior of aniline pentamer in this kind of crosslinked polymer was studied in acidic aqueous solution by means of cyclic voltammetry (CV), UV-vis, and electron spin resonance (ESR) spectroscopy.

Chain propagation kinetics on melt grafting reaction

Graft copolymerization in the molten state is of fundamental importance as a probe of chemical modification and reactive compatibilization. However, few grafting kinetic studies on reactive extrusion have been carried out because of the inherent difficulties, as expected. In this work, we have studied chain propagation kinetics on melt grafting using pre-irradiated linear low density polyethylene (LLDPE) and three monomers, acrylic acid (AA), methacrylic acid (MAA), and methyl methacrylate (MMA), as the model system. We measured the apparent chain propagation rate coefficients of grafting (k(p,g)) and homopolymerization (k(p,h)) at an initial stage for the melt grafting by FT-IR spectroscopy and electron spin resonance spectroscopy. It was observed that the convective mixing affected the rate coefficients. The magnitude of k(p,h) and k(p,g) were in the same order, but k(p,h) was slightly larger than k(p,g) The k(p,g) of the three grafting systems increased in the order: LLDPE/MMA < LLDPE/MAA < LLDPE/AA. These results are explained in terms of phase separation, solubility, and inherent reactivity of the monomer.

Modification of electrode surface through electrospinning followed by self-assembly multilayer film of polyoxometalate and its photochromic

Electrospun poly (vinyl alcohol) (PVA) nanofibers mat was collected on indium tin oxide (ITO) substrate. Heat crosslinked nanofibers mat became water-insoluble and firmly fixed on ITO substrate even in water. Oppositely charged poly (allylamine hydrochloride) (PAH) and Dawson-type polyoxometalate (POM), Na6P2Mo18O62 (P2Mo18), were alternately assembled on PVA nanofibers-coated ITO substrate to construct multilayer film through an electrostatic layer-by-layer (LBL) technique. The scanning electron microscope (SEM) images showed that P2Mo18 multilayer film was selectively deposited on PVA nanofibers while the unoccupied space by nanofibers on bare ITO was acted as substrate at the same time because the electrospun nanofibers have larger surface area and surface energy than the flat substrate. The cyclic voltammograms current responses of the P2Mo18 multilayer film on PVA/ITO electrode showed three well-defined redox couples of P2Mo18, but very small because P2Mo18 multilayer film was selectively deposited on PVA nanofibers with poor conductivity. In addition, the photochromic behavior of P2Mo18 multilayer film on PVA/ITO was investigated through UV-vis spectra and electron spin resonance (ESR). Fourier-transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) proved that the charge-transfer complex was formed between PAH and P2Mo18 after UV irradiation.

Graft chain propagation rate coefficients of acrylic acid in melt graft copolymerization with linear low density polyethylene

Graft chain propagation rate coefficients (k(p.g)) for grafting AA onto linear low density polyethylene (LLDPE) in the melt in ESR tubes have been measured via Fourier transform infrared (FTIR) spectroscopy and electron spin resonance (ESR) spectroscopy in the temperature range from 130 to 170 degrees C. To exclude the effect of homopolymerization on the grafting. the LLDPE was pre-irradiated in the air by electron beam to generate the peroxides and then treated with iodide solution to eliminating one kind of peroxides, hydroperoxide. The monomer conversion is determined by FTIR and the chain propagation free-radical concentration is deduced from the double integration of the well-resolved ESR spectra, consisting nine lines in the melt. The temperature dependence of k(p.g) is expressed:The magnitude of k(p.g) from FTIR and ESR analysis is in good agreement with the theoretical data deduced from ethylene-AA copolymerization, suggesting this method could reliably and directly provide the propagation rate coefficient. The comparison of k(p.g) with the data extrapolated from solution polymerization at modest temperature indicates that the extrapolated data might not be entirely fitting to discuss the kinetics behavior in the melt.

Nano-reactors for controlling the selectivity of the free radical grafting of maleic anhydride onto polypropylene in the melt

This paper reports on a successful application of the concept of nanoreactors to effectively controlling the selectivity of the free radical grafting of maleic anhydride (MAH) onto polypropylene (PP) in the melt, an industrially relevant process. More specifically, a free radical initiator of type ROOR was first confined into (or encapsulated by) the galleries of an organically modified montmorillonite (o-MMT) whose interdistance was 2.4 nm. Primary free radicals (RO center dot) formed inside the o-MMT galleries had to diffuse out before they could react with the PP backbone. The controlled release of the primary free radicals significantly increased the grafting degree of MAH onto PP and greatly reduced the level of the chain scission of the latter. Those results were better understood by electron spin resonance studies on model systems and by Monte Carlo simulations.

Synthesis, properties and X-ray crystal structure of a new heteropolyacid supermolecular charge-transfer complex [(VB1)(2)DMFHPMo12O40 center dot 5DMF]

The title complex [(VB1)(2)DMFHPMo12O40.5DMF, VB1 = vitamin B-1 (thiamine chloride), DMF = N,N-dimethylformamide] has been synthesized and characterized by elemental analysis, IR, UV-Vis, electron spin resonance, X-ray photoelectron spectroscopy and cyclic voltammetry methods. The X-ray crystal structure revealed that there is one independent molecule in the unit cell of the title complex that contains one mixed-valence heteropolyanion, two VB1+ cations and six DMF molecules. The title complex possesses a centrosymmetrical arrangement in the unit cell, with the P atom at the symmetry center of the heteropolyanion and with eight O atoms surrounding the central P atom, such that two sets of PO4 tetrahedra are formed. The PO4 tetrahedra and MoO66-(7-) octahedra are disordered in the heteropolyanion. The bond distances of P-O-a and Mo=O-d are in the ranges 1.57 (4)-1.70 (4) Angstrom and 1.61 (2)-1.67 (2) Angstrom, respectively.

Spectrometric investigation on the thermooxidative degradation of ethylene oxide and tetra-hydrofuran co-polyether

The thermooxidative degradtion of ethylene oxide and tetra-hydrofuran (EO-THF) co-polyether has been studied by electron spin resonance (ESR), Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy. The initial degradation site was found to be at the a-carbon of the ether bond. Two free radicals which derived from dehydrogenation and oxygen addition were successfully detected by spin-trapping technique which used alpha -phenyl-N-tert-butyl nitrone(PBN) as spin trap. Both FT-IR and NMR have been used to follow structural changes of the copolyether during degradation. Nearly 20 product fragments including formate, carbonate, methyl, alcohol, methylene-dioxy, hydroperoxide and semiformal have been characterized by D-1 and D-2 NMR. The thermooxidtion of co-polyether preferred to occur on the THF units especially at the alternating linkage of EO and THF. Antioxidant (BHT) not only retarded the thermooxidation but also modified the degradation products with less ester and methylene-dioxy groups hut more hydroxyl and methyl groups.

Production of active oxygen species from Taxus cuspidata induced by far-UV radiation

In order to understand the role of active oxygen species in mediating plant injuries induced by far-UV radiation, seedlings of Taxus cuspidata Sieb. et Zucc. were irradiated by far-UV rays in laboratory for 4 weeks. The production of organic free-radicals in detached needles, and the production of O-2(radical anion) and O-1(2) in isolated chloroplasts were detected weekly by electron spin resonance (ESR) to evaluate their relative importance. The results show that the cumulative effect of far-UV irradiation, is best indicated by the production of organic free radicals in the needles, O-2(radical anion) production in chloroplasts is the next. The enhancement of O-1(2) production in chloroplasts by the cumulative far-UV irradiation seems to be not so important as O-2(radical anion) in mediating injuries induced by, far-UV radiation because of its high background value.

Effects of La3+ on lipid fluidity land structural transitions in human erythrocyte membranes

The effects of La3+ on the structure and function of human erythrocyte membranes were investigated by fluorescence polarization, spin-labeled electron spin resonance (ESR) and differential scanning calorimetry (DSC). The results showed that increasing concentrations of La3+ inhibited (Na++K+)-ATPase and Mg2+-ATPase activities. La3+ lowered the lipid fluidity of erythrocyte membranes and induced structural transitions in erythrocyte membranes.

Irradiation damage on BaLiF3 crystallites and its suppression by rare-earth ion doping

The x-ray and gamma-ray induced damage in BaLiF3 crystallites and its suppression by rare earth ion doping have been studied by electron spin resonance and thermally stimulated luminescence methods. It has been found that the x-ray irradiation damage is light and can be erased easily. This shows that the BaLiF3 crystallite is an ideal host for x-ray storage material. But the damage induced by gamma-ray has been found to be relatively hard to recover; however the gamma-ray irradiation hardness can be improved by rare earth (e.g., La3+, Yb3+) ion doping. So the BaLiF3 is also promising material for being used in detection of high-energy particles (e.g., gamma-ray).

ELECTROCHEMICAL REDUCTION PROCESS OF BILIRUBIN IN DIMETHYLFORMAMIDE

The electrochemical reduction behavior of bilirubin (BR) at platinum electrode in DMF was investigated by cyclic voltammetry, in situ electron spin resonance spectroscopy and in situ rapid scanning thin layer spectroelectrochemistry. Experimental results revealed that the reduction of BR firstly undergoes an ECE process: GRAPHICS The generated (BR)(2)(3-). can be re-oxidized to BR and then to purpurin (Pu) by a series of oxidation processes: GRAPHICS However, the re-reduction reactions of Pu are not the reverse processes. The different reduction mechanisms are discussed in detail.

INTERACTION OF LANTHANUM AND CALCIUM WITH HUMAN ERYTHROCYTE-MEMBRANES

The effect of lanthanum and calcium on the structure and function of human erythrocyte membranes was investigated by fluorescence polarization, spin- labeled electron spin resonance (ESR) and laser Raman spectroscopy. The results showed that low concentration of La3+ (0.5 mu mol/L) activated a Little (Na++K+)-ATPase and Mg2+-ATPase activities, and it inhibited obvi ously the ATPase activities with increasing its concentrations. La3+ lowered the lipid fluidity of human erythrocyte membranes and decreased the vibration intensity of alpha-helix of the protein in the Amide I '. The effect of Ca2+ on the lipid fluidity and alpha-helix of the protein in the Amide I ' was smaller than that of La3+.

PLASMA-INDUCED GRAFTING OF STYRENE ONTO NASCENT POLYETHYLENE POWDER

In this paper, the graft copolymers of styrene to nascent linear polyethylene reactor powders were prepared through plasma graft polymerization. The grafting reaction was initiated by the alkyl radicals formed on the surface of nascent polyethylene with plasma treatment as indicated by electron spin resonance spectra. In graft copolymerization by alkyl radicals, the grafting yield increased with either the plasma power or the plasma treatment lime. Compared with ordinary polyethylene powders, nascent polyethylene reactor powders were found to be more easily plasma-grafted. This has been attributed to the greater sensitivity to irradiation in producing reactive centres under the same conditions. High density polyethylene showed almost the same grafting yield as linear low density polyethylene at 50 degrees C. The surface morphology of nascent polyethylene observed by scanning electron microscope before and after the grafting showed that the silk-like fibrils were not destroyed by plasma treatment.

GAMMA-RADIATION DAMAGE TO POLYAMIDE-1010 CRYSTAL-STRUCTURE

Radiation effects on polyamide-1010 specimens having various states of aggregation were studied using wide angle X-ray diffraction, electron spin resonance, calorific and sol measurement techniques. Experimental results indicated that chain crosslinking

INVESTIGATION ON MECHANISMS FOR THE ELECTROOXIDATION OF SOME BILE-PIGMENTS BY SPECTROELECTROCHEMISTRY

The electrooxidation behavior of bilirubin (BR), biliverdin (BV), purpurin (Pu), and choletelin (Ch in dimethylformamide (DMF) have been investigated bv voltammetry, in situ electron spin resonance (ESR) thin-layer spectroelectrochemistry and especially i