Preparation of ZnO colloids by aggregation of the nanocrystal subunits

Colloidal ZnO particles with narrow size distribution were prepared via a sol-gel process by base-catalyzed hydrolysis of zinc acetate. The morphology of ordered arrays of the particles was recorded by SEM. SEM also reveals that these uniform particles were composed of tiny ZnO subunits (singlets) sized of several nanometers. The size of the singlets, which is confirmed by X-ray diffraction and UV-vis absorption spectra, increases as the aging time is prolonged. The size-selective formation of colloids by aggregation of nanosized subunits is proposed to consist of two-stage growth by nucleation of nanosized crystalline primary particles and their subsequent aggregation into polycrystalline secondary colloids. The aggregates are all spherical because the internal rearrangement processes are fast enough. The ZnO colloids, i.e., the aggregates, tend to self-assemble into well-ordered hexagonal close-packed structures. Room-temperature photoluminescence was characterized for green and aged ZnO.     

Photogeneration and quenching of reactive oxygen species by urocanic acid

Urocanic acid, UCA, is characterized by two electronic transitions in the UV-B (280-320 nm) which comprise its broad absorption spectrum and give rise to wavelength-dependent isomerization quantum yields. The absorption spectrum of UCA extends into the UV-A (320-400 nm). Given the UV-A component of sunlight is significantly greater than the UV-B component it is hypothesized even weak UV-A photochemistry of UCA could be important for in vivo responses to UV radiation. Degenerate pump-probe experiments performed on t-UCA at several wavelengths in the UV-A reveal an excited-state absorption that undergoes a rapid, approximately 1 ps decay. Photoacoustic experiments performed on both the cis and trans isomers reveal the formation of a long-lived intermediate following UV-A excitation. The efficiency and action spectra for this latter photoactive process are presented and are similar for both isomers of UCA. Cholesterol hydroperoxide assays designed to investigate the nature of the UV-A photoreactivity of t-UCA confirm the production of reactive oxygen species. The bimolecular rate constant for the quenching of singlet oxygen by t-UCA is determined to be 3.5 x 10(6) M(-1) s(-1). Taking into consideration recent theoretical calculations and jet expansion studies of the electronic structure of gas-phase t-UCA, a model is proposed to explain the isomerization and photoreactivity of t-UCA in solution over the UV-A region.     

Photocatalytic degradation of methylene blue on Fe3+-doped TiO2 nanoparticles under visible light irradiation

Fe³⁺-doped TiO₂ composite nanoparticles with different doping amounts were successfully synthesized using sol-gel method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and ultravioletvisible spectroscopy (UV-Vis) diffuse reflectance spectra (DRS). The photocatalytic degradation of methylene blue was used as a model reaction to evaluate the photocatalytic activity of Fe³⁺/TiO₂ nanoparticles under visible light irradiation. The influence of doping amount of Fe³⁺ (ω: 0.00%–3.00%) on photocatalytic activities of TiO₂ was investigated. Results show that the size of Fe³⁺/TiO₂ particles decreases with the increase of the amount of Fe³⁺ and their absorption spectra are broaden and absorption intensities are also increased. Doping Fe³⁺ can control the conversion of TiO₂ from anatase to rutile. The doping amount of Fe³⁺ remarkably affects the activity of the catalyst, and the optimum efficiency occurs at about the doping amount of 0.3%. The appropriate doping of Fe³⁺ can markedly increase the catalytic activity of TiO₂ under visible light irradiation. __________ Translated from Journal of Northwest Normal University (Natural Science), 2006, 42(6): 55–56 [译自: 西北师范大学学报(自然科学版)]     

Direct electrochemistry and enzymatic activity of hemoglobin in positively charged colloid Au nanoparticles and hemoglobin layer-by-layer self-assembly films

Alternate adsorption of positively charged colloid-Au nanoparticles (nano-Au⊕) and negatively charged hemoglobin (Hb) on L-cysteine (L-cys) modified gold electrode resulted in the assembly of {Hb/nano-Au⊕}n layer-by-layer films/L-cys modified gold electrode. The nano-Au⊕ was characterized by transmission electron micrograph (TEM) and microelectrophoresis. The modified electrode interface morphology was characterized by electrochemical impedance spectroscopy (EIS), atomic force mi- croscopy (AFM), cyclic voltammograms (CV) and chronoamperometry. Direct electron transfer between hemoglobin and gold electrodes was studied, and the apparent Michaelis-Menten constant ( km app) of the modified electrode was evaluated to be 0.10 mmol·L?1. Moreover, the higher activity of proteins in the nano-Au⊕ films could be retained compared with the electropolymerization membrane, since the pro- teins in nano-Au⊕ films retained their near-native structure. Direct electron transfer between hemoglo- bin and electrode and electrochemically catalyzed reduction of hydrogen peroxide on a modified elec- trode was studied, and the linear range was from 2.1×10-8 to 1.2 ×10?3 mol·L-1 (r = 0.994) with a detection limit of 1.1×10-8 mol·L-1 H2O2.     

CHARGE-TRANSFER AND ENERGY-TRANSFER IN THE PHOTO-INDUCED COPOLYMERIZATION OF 2-VINYLNAPHTHALENE WITH MALEIC ANHYDRIDE

The initiation mechanism of the copolymerization of 2-vinylnaphthalene with maleic anhydride was studied under irradiation of 365 nm. The excited complex was formed from (1) the local excitation of 2-vinylnaphthalene followed by the charge-transfer interaction with maleic anhydride and (2) the excitation of the ground state charge-transfer complex, and then it collapsed to 1,4-tetramethylene biradical for initiation. A1: 1 alternating copolymer was formed in different monomer feeds. Addition of benzophenone could greatly enhance the rate of copolymerization through energy-transfer mechanism.     

Computer simulation of particle separation based on non-equilibrium swelling

Steric/hyperlayer field-flow fractionation (FFF) is an established analytical technique for separating and characterizing particles in the 1-100 microns diameter range. The separation can be based on differences in size, density, shape and mechanical properties of the particles. In the course of an analysis of the water transporter system of Chinese hamster ovary (CHO) cells and one of their high permeability mutants, the first successful attempt was made to use the steric/hyperlayer FFF system for the purpose of separating particles based on a time-dependent property, namely, the differential swelling of the two cell types. The present study was undertaken to simulate numerically the separation and suggest selection of operating conditions to minimize repetitive experiments. The computer simulation was developed using Maple V, a symbolic computing environment. It is shown that the model is able to predict an optimal velocity of carrier buffer that maximizes resolution. Predicted velocity/resolution pairs are in good agreement with available experimental data. Empirical models for the lift forces encountered in such FFF experiments, and for the zone broadening observed in work with cell sized particles, form the basis for this model.     

聚氨酯(PU)/聚乙烯醇(PVA)共混体系的有关性能及其模型研究

本文研究了聚氨酯(PU)-聚乙烯醇(PVA)共混体系的动态力学性质、相逆转现象和透气性能.发现当PVA重量含量为30-50％时,共混体系发生了连续相与分散相的逆转.进一步,通过力学模型描述了该共混体系的模量-组成关系、动态力学温度谱以及透气系数与PVA含量的关系曲线.所有实验数据都落在理论预测的范围内,并分别与改进的Kerner模型和组合Kerner模型相符合.     

SYNERGISTIC MODIFICATION OF EPDM AND CROSSLINKING AGENT IN IMMISCIBLE BLENDS OF POLYVINYL CHLORIDE WITH LOW DENSITY POLYETHYLENE

The synergism of ethylene-propylene-diene monomer copolymer （EPDM） and dicumyl peroxide （DCP, a crosslinking agent） in low density polyethylene （LDPE）/poly（vinyl chloride） （PVC） blends was investigated. When EDPM and DCP are added to the blends simultaneously, the tensile properties could be improved significantly, especially for the blends with LDPE matrix. For example, incorporation of 10/1 （mass ratio） EPDM/DCP improves the tensile strength of the LDPE/PVC （mass ratio 80/20） blend from 7.9 MPa to 8.5 MPa and the elongation at break from 25% to 503%. Results from selective extraction, phase-contrast microscopy and thermal analysis reveal that the improvement in the tensile properties of the blends with LDPE matrix is principally due to the formation of a fine crosslinking network of the LDPE and EPDM phase. The outstanding modification effect of EPDM is explained by its dual functions： molecular entanglement with LDPE and the enhanced efficiency of DCP in the blends.     

New efficient organocatalytic oxidation of benzylic compounds by molecular oxygen under mild conditions

Efficient aerobic oxidation of benzylic compounds has been achieved under no irradiation using a new organocatalytic system in the presence of acridine yellow and N-hydroxyphthalimide with assistance of a catalytic amount of molecular bromine. Various substrates, especially alkylaromatics, were effectively oxygenated to the corresponding carbonyl compounds with molecular oxygen as oxidant under mild conditions. For instance, indan was oxidized with 92% conversion and 79% selectivity for 1-indanone under 0.3 MPa of O₂ at 75 °C.