Sol–gel preparation and properties of hydroxypropylcellulose–titania hybrid thin films

Hydroxypropylcellulose (HPC)–titania hybrid thin films were prepared by sol–gel method where titanium tetraisopropoxide Ti(OC₃H₇ ⁱ )₄ was hydrolyzed under acidic conditions in the presence of HPC, followed by dip-coating and drying at 120 °C for 24 h. The viscosity average molecular weight of HPC was 55,000–70,000 or 110,000–150,000, and the TiO₂/(HPC + TiO₂) mass ratio ranged from 0 to 1, which was calculated on the assumption that all Ti(OC₃H₇ ⁱ )₄ is converted into TiO₂. The films were 0.35–1.0 μm thick, transparent in visible region and opaque in ultraviolet (UV) region, where the optical absorption coefficient in UV region increased with increasing titania content. The refractive index increased with increasing titania content, ranging from 1.6 to 1.8 for the hybrid thin films. The pencil hardness increased from 6B to 5H, the durability in hot water significantly increased and the contact angle of water on films increased from 35° to 89° with increasing titania content. Crack-free films could be deposited on organic polymer substrates irrespective of titania or HPC contents, where cracking did not occur at higher HPC contents even when the substrate was bent.     

On the factors affecting the enhanced resonance light scattering signals of the interactions between proteins and multiply negatively charged chromophores using water blue as an example

Electrostatic interactions of proteins, including bovine serum albumin (BSA), human serum albumin (HSA), γ-globulin (γ-IgG), α-chymotrypsin (Chy), lysozyme (Lys) and cellulase (Cel), with multiply negatively charged chromophores were investigated based on the measurements of the enhanced resonance light scattering (RLS) signals. Using triply negatively charged water blue (WB) as an example, the factors were discussed that affect the enhanced resonance light scattering signals of the interactions between proteins and the negatively charged chromophores. It was found that the enhanced RLS signals with the maximum light scattering peak at 346.0 nm in these interacting systems are strongly dependent on the isoelectric points of proteins and show adverse linear relationships with increasing ionic strength depending on the positive charges of the inorganic metal ions used to control the ionic strength of the medium, sufficiently disclosing that the electrostatic attraction performs an important role in the combination of proteins with WB. Linear responses were discovered between the enhanced RLS signals and the protein molecular weights (M_w), displaying the dimensions of scattered particles formed by proteins and WB make a key contribution to the RLS enhancements. An empirical equation is proposed which possibly displays the factors affecting the enhanced RLS signals of the interactions between proteins with negatively charged chromophores.     

Influence of the cathodic polarization on the stability of Ti surface in concentrated KOH solutions

The stability of spontaneous thin layers and thin layers formed upon cathodical polarization of Ti in KOH solutions have been studied by potentiostatic and ellipsometric methods. At open circuit potential (OCP) the strongly adherent films, whose thickness depends on the concentration of the KOH solution, were formed. During the cathodic polarization the transformation of these films to weakly adsorbed precipitated layers on the electrode surface was observed. Comparing the theoretically computed curves with the experimental Ψ vs Δ loci measured ellipsometrically, the complex indices of refraction and the thickness of the generated films, from 3.6 to 60 nm in 1 M KOH and from 36 to 105 nm in 5 M KOH (adherent to the electrode surface), were determined. At OCP the rate of film growth increases with increasing the concentration of KOH solution. Cathodic polarizations change the chemical composition and retard the rate of film growth. Based on the ellipsometric and electrochemical data the chemical compositions of the formed films consisted of TiO₂, Ti₂O₃, TiO₂·H₂O, Ti(OH)₃ and TiOOH·nH₂O.     

Fuzzy Symmetries for Linear Molecules and their Molecular Orbitals

In this paper, the fuzzy symmetry of some prototypical linear molecules has been analyzed. The results show that some molecular orbitals (MOs) are less symmetrical but some others are more symmetrical than the molecular skeleton, which the MOs correspond to. The membership functions of space inversion for MOs are closely related to the chemical characteristics of the MOs. Sometimes, although the symmetry of a molecular skeleton is not obvious, however that of some MO is quite obvious. The membership functions of the fuzzy inversion symmetry depend on the choice of the position of the center of inversion. As compared to those of diatomic molecules and linear tri-atomic molecules, the linear polyatomic molecules in which a distinctive fuzzy symmetry of space translation may exist, and thus a significant effect on their properties can be expected.     

Synthesis and characterization of microencapsulated dicyclopentadiene with melamine–formaldehyde resins

Microcapsules containing healing agents have been used to develop the self-healing polymeric composites. These microcapsules must possess special properties such as appropriate strength and stability in surrounding medium. A new series of microcapsules containing dicyclopentadiene (DCPD) with melamine–formaldehyde (MF) resin as shell material were synthesized by in situ polymerization technology. These microcapsules may satisfy the requirements for self-healing polymeric composites. The chemical structure of microcapsule was identified by using Fourier transform infrared (FTIR) spectrometer. The morphology of microcapsule was observed by using optical microscope (OM) and scanning electron microscope. Size distribution and mean diameter of microcapsules were determined with OM. The thermal properties of microcapsules were investigated by using thermogravimetric analysis and differential scanning calorimetry. Additionally, the self-healing efficiency was evaluated. The results indicate that the poly(melamine–formaldehyde) (PMF) microcapsules containing DCPD have been synthesized successfully, and their mean diameters fall in the range of 65.2∼202.0 μm when the adjusting agitation rate varies from 150 to 500 rpm. Increasing the surfactant concentration can decrease the diameters of microcapsules. The prepared microcapsules are thermally stable up to 69 °C. The PMF microcapsules containing DCPD can be applied to polymeric composites to fabricate the self-healing composites.     

Synthesis,crystal structure,electrochemical properties and large optical limiting effect of a novel 3-(E)-ferrocenyl-vinyl-<Emphasis Type="BoldItalic">N</Emphasis>-hexyl carbazole

The novel compound, 3-(E)-ferrocenyl-vinyl-N-hexylcarbazole (FVHC) was first synthesized and fully characterized by elemental analysis, IR, ¹H-NMR, single-crystal X-ray diffraction, ultraviolet (UV) absorption, cyclic voltammograms (CV) and optical limiting (OL) measurements. The result of single crystal X-ray diffraction for the compound reveals that the ferrocenyl and carbazole groups are approximately coplanar, and bridged by double-bond with E configuration, showing that there is a well-delocalized π-electron system in the molecule. The electrochemical investigation indicated that the electron in the FVHC may partially be delocalized over the π-conjugated system and CT process in functionalized carbazole systems. Besides, the compound exhibited strong UV absorption and large optical limiting effect, indicating promising potential applications as useful OL materials.     

基于双氨基三唑硫醚为中性载体的汞离子选择性电极的研究

研制了基于双氨基三唑硫醚为中性载体的阳离子选择性电极。实验表明,该电极对Hg2 具有良好的电位响应特性,在pH 2.0硝酸盐缓冲液中,电极电位呈近能斯特响应,线性响应范围为4.0 mg/L~20 g/L,斜率为33.4 mV/dec.(25℃),检出限为1.7 mg/L。该电极响应时间短(<10 s),pH范围较宽(1.3~3.3)。将该电极用于实际水样和二元混合溶液中Hg2 的检测,其结果令人满意。     

Inhibition of the toxic byproduct during photocatalytic NO oxidation via La doping in ZnO

It is of a great challenge to develop semiconductor photocatalysts with potential possibilities to simultaneously enhance photocatalytic efficiency and inhibit generation of toxic intermediates.In this study,we developed a facile method to induce the La doping and cationic vacancie(V(Zn))on ZnO for the highly efficient complete NO oxidation.The photocatalytic NO removal efficiency increases from 36.2%to 53,6%.Most importantly,a significant suppressed NO2 production also has been realized.According to the DFT calculations,ESR spectra and in situ FTIR spectra,the introduction of La^3+induce the redistribution of charge carriers in La-ZnO,which promote the production of·O2^- and lead to the formation of V(Zn)for the formation of·OH,contributing to the complete oxidation of NO to nitrate.Besides,the conversion pathway of photocatalytic NO oxidation has been elaborated,This work paves a new way to simultaneously realize the photocatalytic pollutants removal and the inhibition of toxic intermediates generation for efficient and safe air purification.     

The first example of enantioselective isocyanosilylation of meso epoxides with TMSCN catalyzed by novel chiral organogallium and indium complexes

The desymmetrization ring opening of meso epoxides using trimethylsilyl cyanide catalyzed by organogallium and indium complexes with binaphthol monoether derivatives as chiral ligands gave beta-isocyanohydrins with moderate to excellent enantioselectivities of up to 95% ee.     

Carbon nanotube array-based biosensor

Aligned multi-wall carbon nanotubes (MWNT) grown on platinum substrate are used for the development of an amperometric biosensor. The opening and functionalization by oxidation of the nanotube array allows for the efficient immobilization of the model enzyme, glucose oxidase. The carboxylated open-ends of nanotubes are used for the immobilization of the enzymes, while the platinum substrate provides the direct transduction platform for signal monitoring. It is also shown that carbon nanotubes can play a dual role, both as immobilization matrices and as mediators, allowing for the development of a third generation of biosensor systems, with good overall analytical characteristics.