Preparation and Physical Properties of LLDPE Grafted with Novel Nonionic Surfactants

Copolymers of linear low-density polyethylene (LLDPE) grafted with two novel nonionic surfactants, acrylic glycerol monostearate ester (AGMS) and acrylic polyoxyethylenesorbitan monooleate ester (ATW-EEN80), containing hydrophilic and hydrophobic groups and 1-olefin double bond were prepared by using a plasticorder at 190 degrees C. To evaluate the grafting degree, two different approaches based on H-1-NMR data were proposed, and FTIR calibration was showed to validate these methods. The rheological response of the molten polymers, determined under dynamic shear flow at small-amplitude oscillations, indicated that crosslinking formation of the chains could be decreased with increasing the monomer concentration. Their thermal behavior was studied by DSC and polarization microscope (PLM): The crystallization temperature (T-C) of grafted LLDPE shifted to higher temperature compared with neat LLDPE because the grafted chains acted as nucleating agents. Water and glycerol were used to calculate the surface free energy of grafted LLDPE films.

Crystallization Behavior and Mechanical Properties of Crosslinked Plasticized Poly(L-lactic acid)

Enhancing the stability of plasticized poly(L-lactic acid) (PLLA) with poly (ethylene glycol) (PEG) is necessary for its practical application. In this study, plasticized PLLA (PLLA/PEG 80/20 wt/wt) was crosslinked under I-ray (Co-60) in the presence of triallyl isocyanurate (TALC) as crosslinking agent. FTIR analysis revealed that PLLA, PEG, and TALC formed a cocrosslinking structure. Crystallization behavior and mechanical properties of the crosslinked plasticized PLLA were investigated by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), and tensile tests. Experimental results indicated that the crystallization behaviors of both PEG and PLLA in the blends were restrained after irradiation. The melting peak of PEG in the crystallized samples disappeared at a low irradiation doses about 10 kGy. Although PLLA still owned the behavior of crystallize, its cold crystallization temperature and glass transition temperature shifted to higher temperature. Mechanical properties of the plasticized PLLA were strengthened through crosslinking. Both yield strength and elastic modulus of the samples increased after crosslinking.

Effective enhancement of peroxydisulfate electrochemiluminescence on C-60/DDAB films

Effective enhancement of electrochermluminescence (ECL) of peroxydisulfate on a C-60/didodecyldimethyl ammonium bromide (C-60/DDAB) film coated glassy carbon electrode (GCE) surface is reported in this paper. The C60/DDAB film gave lower cathodic current in the presence of peroxydisulfate than that from a bare GCE. To our surprise, electrochemiluminescent intensity from peroxydisulfate reduction was effectively enhanced on the C60/DDAB film, which was 50 times and 250 times higher than those from a DDAB film coated and bare GCE, respectively. Moreover, the ECL onset potential on the C60/DDAB film was about -0.9 V, which positively shifted 200 mV compared with that from the bare GCE. Dissolved oxygen and the applied potential also affected the electrochemiluminescent intensity. The presence of oxygen decreased the intensity, and the intensity reached maximum at the applied potential of -1.7 V. The unique property will greatly enrich ECL studies and applications based on fullerenes.

Nanostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles: Polyol-mediated synthesis and luminescent properties

Nano-submicrostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles were prepared by polyol method and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectra (FT-IR), thermogravimetry-differential thermal analysis (TG-DTA), photoluminescence (PL), cathodo-luminescence (CL) spectra and PL lifetimes. The results of XRD indicate that the as-prepared samples are well crystallized with the scheelite structure of CaWO4. The FE-SEM images illustrate that CaWO4 and CaWO4 : Pb2+ and CaWO4 : Tb3+ powders are composed of spherical particles with sizes around 260, 290, and 190 nm respectively, which are the aggregates of smaller nanoparticles around 10-20 nm. Under the UV light or electron beam excitation, the CaWO4 powders exhibits a blue emission band with a maximum at about 440 nm. When the CaWO4 particles are doped with Pb2+, the intensity of luminescence is enhanced to some extent and the luminescence band maximum is red shifted to 460 nm. Tb3+-doped CaWO4 particles show the characteristic emission of Tb3+ D-5(4)-F-7(J) (J=6-3) transitions due to an energy transfer from WO42- groups to Tb3+.

Synthesis and chain-length dependent properties of monodisperse oligo(9,9-di-n-octylfluorene-2,7-vinylene)s

A series of monodisperse oligo(9,9-di-n-octylfluorene-2,7-vinylene)s (OFVs) with fluorene units up to 11 has been synthesized following a divergent approach. Chain length was found to affect not only photophysical properties but also thermal properties. Absorption and photoluminescence spectra are red-shifted with increasing chain length. The effective conjugated length has been extrapolated to be as long as 19 fluorene vinylene units, indicative of a well-conjugated system. With the number of fluorene units > 5, the oligomers exhibit nematic mesomorphism. Glass transition temperature (T-g) and clearing point temperature (T-c) increase with increasing molecular length and with those of OFV11 up to 71 and 230 degrees C, respectively. The oligomers can form uniform films by solution casting for fabrication of light-emitting diodes. With a device structure of ITO/ PEDOT:PSS/OFV11/Ca/Al, a current efficiency of 0.8 cd.A(-1) at a brightness of 1300 cd.m(-2) along with a maximum brightness of 2690 cd.m(-2) have been realized. This performance is notably superior to that of the corresponding polymer.

The enhancement effect of Eu3+ on electro-oxidation of ethanol at Pt electrode

It is reported for the first time that the slow electrochemical kinetics process for the electro-oxidation of ethanol can be promoted by changing the electrochemical environment. The electro-oxidation of ethanol at a Pt electrode in the presence of Eu3+ cations was studied and an enhancement effect was exhibited. Cyclic voltammetry experiment results showed that the peak current density for the electro-oxidation of ethanol was increased in the presence of EU3+ in the ethanol solution. A preliminary discussion of the mechanism of the enhancement effect is given. This is based on a CO stripping experiment, which shows that either the onset potential or the peak potential of CO oxidation is shifted negatively after adding Eu3+ to the solution.

Electrosynthesis and characterization of 1,2-dibenzyl C-60: A revisit

A reinvestigation of the reaction between C-60(2-) and benzyl bromide in benzonitrile containing 0.1 M tetra-n-butylammonium perchlorate (TBAP) has shown that there are more reaction products than previously reported. Use of a silica rather than a "Buckyclutcher I" column for HPLC purification led to isolation of two previously unattained products in the reaction mixture, one of which was identified as 1,2-(PhCH2)(2)C-60 by UV-vis and NMR. The earlier incorrectly assigned 1,2-(PhCH2)(2)C-60 was identified as the methanofullerene C61HPh by X-ray single-crystal diffraction. The electrochemistry of genuine 1,2-(PhCH2)(2)C-60 shows that its first reduction potential in PhCN containing 0.1 M TBAP is cathodically shifted by 100 mV with respect to E-1/2 for reduction of 1,4-(PhCH2)(2)C-60, indicating that the addition pattern significantly affects the electrochemistry of derivatized C-60. Visible and near-IR spectra of the monoanion and dianion of 1,2-(PhCH2)(2)C-60 are also reported.

Surface charge influence on the surface plasmon absorbance of electroactive thiol-protected gold nanoparticles

Gold nanoparticles (3.1-5.0 nm in size) surface-derivatized with both electroactive and nonelectroactive self-assembled monolayers were synthesized. The surface-derivatized electroactive particles can be easily oxidized/reduced at an electrode surface based on the diffusion-controlled current-voltage curve observed in cyclic voltammetry measurements. Spectroelectrochemical investigation demonstrated that the maximum absorbance of the nanoparticles in their oxidized state red-shifted compared with their reduced state to a different extent according to their size distribution. In the case of the particles surface-derivatized with nonelectroactive monolayers, much less shift was observed. This study showed that surface plasmon absorbance of gold nanoparticles was not only related to core charge states but was also influenced by surface charge states as well.

Single-wall carbon nanotube-based voltammetric sensor and biosensor

The pH-sensitive property of the single-wall carbon nanotube modified electrode based oil the electroactive group on the single-wall carbon nanotube was explored by differential pulse voltammetry technique. In pH range 1-13 investigated in Britton-Robinson (B-R) buffer, the anodic peak shifted negatively along with the increase of pH exhibiting a reversible Nernstian response. Experiments were carried out to investigate the response of the single-wall carbon nanotube (SWNT) modified electrode to analytes associated with pH change. The response behavior of the modified electrode to ammonia was studied as an example. The potential response could reach equilibrium within 5 min. The modified electrode had good operational stability. Voltammetric urease and acetylcholinesterase biosensors were constructed by immobilizing the enzymes with sol-get hybrid material. The maximum potential shift could reach 0.130 and 0.220V for urea and acetylthiocholine, respectively. The methods for preparing sensor and biosensor were simple and reproducible and the range of analytes could be extended to substrates of other hydrolyases and esterases.

Electrocatalytic reduction of oxygen at multi-walled carbon nanotubes and cobalt porphyrin modified glassy carbon electrode

The multi-walled carbon nanotubes (MWNTs) modified glassy carbon electrode exhibited electrocatalytic activity to the reduction of oxygen in 0.1 M HAc-NaAc (pH 3.8) buffer solution. Further modification with cobalt porphyrin film on the MWNTs by adsorption, the resulted modified electrode showed more efficient catalytic activity to O-2 reduction. The reduction peak potential of O-2 is shifted much more positively to 0.12 V (vs. Ag/AgCl), and the peak current is increased greatly. Cyclic voltammetry (CV), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), were used to characterize the material and the modified film on electrode surface. Electrochemical experiments gave the total number of electron transfer for oxygen reduction as about 3, which indicated a co-exist process of 2 electrons and 4 electrons for reduction of oxygen at this modified electrode. Meanwhile, the catalytic activities of the multilayer film (MVVNTs/CoTMPyP)(n) prepared by layer-by-layer method were investigated, and the results showed that the peak current of O-2 reduction increased and the peak potential shifted to a positive direction with the increase of layer numbers.

Formation and photoluminescence of silver nanoparticles stabilized by a two-armed polymer with a crown ether core

Silver nanoparticles were synthesized by the use of a two-armed polymer with a crown ether core [poly(styrene)]-dibenzo-18-crown-6-[poly(styrene)] based on the flexibility of the polymer chains and the complex effect of crown ether with Ag+ and Ag. The size of silver nanoparticles could be tailored by controlling the initial concentrations of the polymer and Ag+, and the molecular weight of the polymer. The emission of silver nanoparticles was blue-shifted, and the intensity of the photoluminescence of silver nanoparticles stabilized by the polymer was significantly increased due to the complex effect between the crown ether embedded in the polymer and the silver nanoparticles.

Thermal analysis of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) irradiated under vacuum

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) was irradiated by Co-60 gamma-rays (doses of 50, 100 and 200kGy) under vacuum. The thermal analysis of control and irradiated PHBV, under vacuum was carried out by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The tensile properties of control and irradiated PHBV were examined by using an Instron tensile testing machine. In the thermal degradation of control and irradiated PHBV, a one-step weight loss was observed. The derivative thermogravimetric curves of control and irradiated PHBV confirmed only one weight-loss step change. The onset degradation temperature (T-o) and the temperature of maximum weight-loss rate (T-p) of control and irradiated PHBV were in line with the heating rate (degreesC min(-1)). T-o and T-p of PHBV decreased with increasing radiation dose at the same heating rate. The DSC results showed that Co-60 gamma-radiation significantly affected the thermal properties of PHBV. With increasing radiation dose, the melting temperature (T-m) of PHBV shifted to a lower value, due to the decrease in crystal size. The tensile strength and fracture strain of the irradiated PHBV decreased, hence indicating an increased brittleness.

Sol-gel-derived BPO4/Ba2+ as a new efficient and environmentally-friendly bluish-white luminescent material

In this paper, BPO4 and Ba2+-doped BPO4 powder samples were prepared by the sol-gel process using glycerol and poly(ethylene glycol) as additives. The structure and optical properties of the resulting samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FESEM), diffuse reflection spectra, photoluminescence (PL) excitation and emission spectra, quantum yield, kinetic decay, and electron paramagnetic resonance (EPR), respectively. It was found that the undoped BPO4 showed a weak purple blue emission (409 nm, lifetime 6.4 ns) due to the carbon impurities involved in the host lattice. Doping Ba2+ into BPO4 resulted in oxygen-related defects as additional emission centers which enhanced the emission intensity greatly (> 10x) and shifted the emission to a longer-wavelength region (lambda(max) = 434 nm; chromaticity coordinates: x = 0.174, y = 0. 187) with a bluish-white color. The highest emission intensity was obtained ;when doping 6 mol % Ba2+ in BPO4, which has a quantum yield as high as 31%. The luminescent mechanisms of BPO4 and Ba2+-doped BPO4 were discussed in detail according to the existing models for silica-based materials.

Viscous-force-dominated tensile deformation behavior of oriented polyethylene

High-density polyethylene with shish-kebab structure, prepared by a melt extrusion drawing, was employed to investigate the effect of the well-defined lamellar orientation on the deformation characteristics under uniaxial tensile deformation along the drawing direction. This was done by investigating the true stress-true strain dependencies at different strain rates, recovery properties, and stress relaxation measurements. Measurements were complemented by recording in-situ wide-angle X-ray scattering patterns during the deformation process. The oriented samples showed not only a higher modulus, but different from analogous isotropic samples, a homogeneous deformation without necking. The true strain associated with the onset of fibrillation was determined. Because of the preorientation, it is shifted to 0.3, which is below the value 0.6 of the isotropic counterpart. The main finding is a strong enhancement of the Viscous force, as was revealed by stress relaxation experiments; the viscous force takes up 70% of the total stress. The presence of shish-kebabs, i.e., interconnected lamellae in a stack, seems to be responsible for the high viscous force in the oriented samples. The absence of necking has to be ascribed to the high viscous force.

Multilayer films of carbon nanotubes and redox polymer on screen-printed carbon electrodes for electrocatalysis of ascorbic acid

Multilayer films containing multiwall carbon nanotubes and redox polymer were successfully fabricated on a screen-printed carbon electrode using layer-by-layer (LBL) assembled method. UV-vis spectroscopy, X-ray photoelectron spectroscopy, field-emission scanning electron microscopy and electrochemical method were used to characterize the assembled multilayer films. The multilayer films modified electrodes exhibited good electrocatalytic activity towards the oxidation of ascorbic acid (AA). Compared with the bare electrode, the oxidation peak potential negatively shifted about 350 mV (versus Ag/AgCl). Furthermore, the modified screen-printed carbon electrodes (SPCEs) could be used for the determination of ascorbic acid in real samples.