紫外光下纳米TiO2 薄膜亲水性机理的电化学研究

The nanometer films of TiO2 were prepared by sol-gel method on ITO（Indium-tin oxide,SnO2:In） substrate. The TiO2 film was the anatase phase with a particle size of 100 nm from the measurements of X-ray diffraction and AFM（Atomic-Force-Microscope）. Electrochemical characteristics of ITO/ TiO2 electrode under UV（ultraviolet）irradiation were investigated using the method of cyclic voltammetry. A new oxidative peak was observed at 0.035 V when the TiO2 electrode was irradiated by 253.7 nm UV light for a certain time. The peak current increased with the irradiation time. It was assumed that the new oxidative peak resulted from Ti3+,which was formed during the UV illumination. The changes of hydrophilicity of the TiO2 thin film on ITO under UV light were also observed. It was assumed that the changes of hydrophilicity of the films may be related with the formation of Ti3+ on the surface when the film was irradiated by UV light.     

Elucidating the Reaction Kinetics of Hydrophobic Porphyrin Nanoaggregates Dispersed in PVA Films Exposed to HCl Vapors

The behavior of the absorbance profiles of free‐base 5,10,15,20–tetraphenylporphyrin (TPPH₂) and zinc 5,10,15,20‐tetraphenylporphyrinate (ZnTPP) under exposure to HCl vapors was investigated to establish in detail the mechanism of protonation of these porphyrinic compounds and their potential for use as HCl sensors. We show that the intensities of diprotonated tetraphenylporphyrin absorption bands that arise at 444–446 and 662–666 nm increase as a function of the HCl exposure time. Reactions of free‐base meso‐tetraphenylporphyrin protonating and of zinc meso‐tetraphenylporphyrinate demetalation and subsequent protonating are discussed, and the solutions of the corresponding kinetic equations and respective reaction rates are also obtained. Finally, from a theoretical analysis we deduce the presence of intermediated monoprotonated porphyrin that helps us to explain why the isosbestic point in the TPPH₂ reaction with HCl is not well defined.     

Synthesis of Carboxylated Monodisperse Latexes and Their Self-Organization in Thin Films

The capability of carboxylated latexes of poly(methyl methacrylate) and copolymers of styrene with glycidyl methacrylate or methacrylic acid for self-organization in thin films was studied in relation to the compositions of the dispersion medium and polymer and to the latex particle size.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 1, 2005, pp. 161–167.Original Russian Text Copyright © 2005 by Men’shikova, Shabsel’s, Evseeva, Shevchenko, Bilibin.     

纳米TiO2薄膜的热致亲水性与光致亲水性机理

应用真空磁控溅射，溶胶－凝胶方法和电沉积方法分别在玻璃和导电玻璃表面制备了纳米TiO2薄膜，纳米TiO2薄膜的热致亲水性研究表明，这是由于热处理对TiO2薄膜表面的清洁作用除去了吸附的水和有机污染物而产生的。TiO2薄膜的光致亲水性可能也源于紫外光照产生的活性粒子对TiO2薄膜的“光清洁作用”所致。     

Structure Prediction Based on Hydrophobic to Hydrophilic Volume Ratios in Small Molecule Amphiphilic Organic Crystals

<正>The structure type for the crystal of 4,4'-bis-(2-hydroxy-ethoxyl)-biphenyl 1 has been predicted by using the previously developed interfacial model for small organic molecules. Based on the calculated hydrophobic to hydrophilic volume of 1, this model predicts the crystal structure to be of lamellar or bicontinuous type, which has been confirmed by the X-ray single-crystal structure analysis (C20H26O6, monoclinic, P21/C, a = 16.084(1), b = 6.0103(4), c = 9.6410(7) A, β9 = 103.014(2)°, V= 908.1(1) A3, Z = 2, Dc= 1.325 g/cm3, F(000)=388,μ = 0.097 mm-1, MoKα radiation, λ = 0.71073 A, R = 0.0382 and wR = 0.0882 with I > 2σ(I) for 7121 reflections collected, 1852 unique reflections and 170 parameters). As predicted, the hydrophobic and hydrophilic portions of 1 form in the lamellae. The same interfacial model is applied to other amphilphilic small molecule organic systems for structural type prediction.     

Thin Films and Interfaces of Electroactive Organic Materials: The Surface Science Approach

 We highlight the importance of interfacial properties in determining the performance of devices based on electroactive organic materials. Investigations of the interfaces of benzene with Al(111) and In₂O₃ are presented as a model of interface properties for devices based on complex aromatic molecules. At both interfaces the binding is shown to be electrostatic, with the resulting interface dipole determining the band alignment. It is also argued that chemical modification of substrates can be used to tailor both electronic and structural properties.     

Thin Films and Interfaces of Electroactive Organic Materials: The Surface Science Approach

Summary.  We highlight the importance of interfacial properties in determining the performance of devices based on electroactive organic materials. Investigations of the interfaces of benzene with Al(111) and In₂O₃ are presented as a model of interface properties for devices based on complex aromatic molecules. At both interfaces the binding is shown to be electrostatic, with the resulting interface dipole determining the band alignment. It is also argued that chemical modification of substrates can be used to tailor both electronic and structural properties. Received May 30, 2000. Accepted September 21, 2000     

Functional Transformations on the Surface of Poly(ethylene terephthalate) Films under Exposure to Accelerated Electrons

The effect of the electron-beam treatment of poly(ethylene terephthalate) (PETP) films in an air atmosphere on the functional chemical composition of their surface and on the optical properties in the UV region was studied. The mutual functional transformations of surface sites (carbonyl, methyl, and hydroxyl groups) by the action of fast electrons were analyzed as functions of the absorbed dose over the range 25–500 kGy using the adsorption of acid–base indicators with the pK_a values ranging from –5 to 15. Correlation between the absorbed dose, the concentration of certain functional groups (centers with pK_a 5.0 (–CH₃) and 0.8 (–CH₂OH)), the hydrophilicity of films, and the transparency in the UV region of the spectrum was established. The transparency was found to exhibit a pronounced minimum at an absorbed dose of 150–200 kGy. A comparative analysis of PETP surfaces differing by the absence or presence of kaolin (0.1%) as an oxide material additive was performed. Differences in the pK_a distribution of adsorption sites were found, and their dependence on the absorbed dose was studied.     

Effect of Surface Roughness on Structure and Dynamics in Thin Films

We performed Monte Carlo simulations of free‐standing, amorphous polyethylene (PE) thin films at 509 K. The three films are constructed from 9, 36, or 144 independent parent PE chains, with 100 carbon atoms per chain. The two‐dimensional periodic cross‐sectional area of the simulation box is proportional to the number of independent parent chains, with the 144‐chain film having an area four times larger than the 36‐chain film. All three films have a similar bulk density and a comparable thickness between the two free surfaces. The 144‐chain film with the largest periodic surface area has a broader density profile due to the increased roughness of its surfaces. Snapshots of its surfaces along the trajectory indicate dynamic changes in the high and low regions of the rough surfaces. Diffusion of the chains parallel to the free surfaces is suppressed in the 144‐chain film, due to increased surface roughness. The tendency of bonds to orient parallel to the free surface is less pronounced in films with higher surface roughness.     

Immobilized Cytochrome c Sensor in Organic/Aqueous Media for the Characterization of Hydrophilic and Hydrophobic Antioxidants

A method for the characterization of antioxidants is introduced, which allows the measurement of pure hydrophilic and hydrophobic substances as well as complex cosmetic creams. The sensor is based on cytochrome c covalently immobilized on a gold wire electrode working in mixtures of phosphate buffer and organic solvents. It is combined with a superoxide generating enzyme system. The decrease of the superoxide concentration in the test solution by the added antioxidants is detected and used for the quantification of their antioxidative efficiency. Electrochemical properties of immobilized cytochrome c, such as formal potential and heterogeneous electron transfer rate constant, have been investigated in mixtures of aqueous buffer and DMSO, methanol, butanediol, and THF. The maximum organic solvent content for quasi‐reversible electrode behavior was correlated to spectroscopic measurements. The activity of the radical producing enzyme in such media was determined and the radical generation characterized. The antioxidative properties of pure substance such as ascorbic acid and Biochanin A as well as of five anti‐ageing cosmetic creams were studied. This showed also the influence of matrix composition on the efficiency of antioxidative supplements.     

Determination of Volatile Organic Compounds by a Novel Polymer Spin-Coated Thin Film and Surface Plasmon Resonance

Here, the synthesis, characterization, and volatile organic compound (VOCs) sensing of a 1,3-dimethyl polyphenylene vinylene polymer is reported. The synthesis was performed by a Witting condensation through the reaction of 1,4-terphthaldehyde with the phosphonium chloride of meta-xylene. The material was characterized by infrared spectroscopy, elemental analysis, and thermogravimetric analyses. Thin films of the polymer were prepared by spin coating at speeds from 1000 to 5000?rpm. Ultraviolet–visible spectroscopy and surface plasmon resonance were used to characterize the spin-coated films. The thicknesses of the films were estimated by fitting the curves and were between 4.5 and 24.5?nm depending on the speed. The refractive index of the new polymer was 1.72. The polymer spin-coated films were exposed to volatile organic vapors to characterize their sensing properties by surface plasmon resonance as a function of time. The results showed that the new material responded rapidly, sensitively, and reversibly to VOCs.     

Surface Activities of Calix[4] resorcinarenes Bearing Four Hydrophobic Chains and Its Sol ubilization for Organic Compounds

ＩｎｔｒｏｄｕｃｔｉｏｎＩｎｃｌｕｓｉｏｎｃｏｍｐｏｕｎｄｓｈａｖｅｂｅｅｎｎｏｔｅｄｉｎｒｅｃｅｎｔｙｅａｒｓａｎｄｒｅｓｏｒｃｉｎｏｌ ｔｙｐｅｃａｌｉｘ [4 ]ａｒｅｎｅｈａｓｂｅｅｎｓｔｕｄｉｅｄｆｏｒｔｈｅｉｒｉｎｃｌｕｓｉｏｎａｂｉｌｉｔｉｅｓｂｙＳｃｈｅｉｄｅｒａｎｄＢｕｇｌｅｒｅｔａｌ[1— 3] .Ｔｈｅｐｏｌｙｏｌｍｏｉｅｔｉｅｓｉｎｃａｌｉｘ[4 ]ｒｅ ｓｏｒｃｉｎａｒｅｎｅｆｏｒｍｒｉｇｉｄｈｙｄｒｏｇｅｎ ｂｏｎｄｉｎｇｎｅｔｗｏｒｋｓ[4 ] ,ａｎｄｃａｌｉｘ [4 ]ｒｅｓｏｒｃｉｎａｒｅ…     

硅表面复合自组装膜的制备及其摩擦性能

采用自组装技术在单晶硅表面制备了3-氨基丙基三乙氧基硅烷(APTES)-SiO2-APTES复合膜,并对其表面的组成、结构及摩擦性能进行了表征.结果表明:复合膜表面对水的接触角约为63°,且表面平整、致密,其平均粗糙度(Ra)约为0.963nm.通过原子力显微镜(AFM)和透射电子显微镜(TEM)观察到夹层中SiO2颗粒的粒径约为20-50nm,较均匀地分布在第一层APTES膜的表面.与APTES自组装单层膜(SAMs)相比,APTES-SiO2-APTES复合膜由于纳米SiO2颗粒的引入而表现出更低的摩擦系数和更长的耐磨寿命.     

Self-Organization and Dynamics of Nanoparticles in Chemically Active Plasmas for Low-Temperature Deposition of Silicon and Carbon-Based Nanostructured Films

Self-organization and dynamic processes of nano/micron-sized solid particles grown in low-temperature chemically active plasmas as well as the associated physico-chemical processes are reviewed. Three specific reactive plasma chemistries, namely, of silane (SiH₄), acetylene (C₂H₂), and octafluorocyclobutane (c—C₄F₈) RF plasma discharges for plasma enhanced chemical vapor deposition of amorphous hydrogenated silicon, hydrogenated and fluorinated carbon films, are considered. It is shown that the particle growth mechanisms and specific self-organization processes in the complex reactive plasma systems are related to the chemical organization and size of the nanoparticles. Correlation between the nanoparticle origin and self-organization in the ionized gas phase and improved thin film properties is reported. Self-organization and dynamic phenomena in relevant reactive plasma environments are studied for equivalent model systems comprising inert buffer gas and mono-dispersed organic particulate powders. Growth kinetics and dynamic properties of the plasma-assembled nanoparticles can be critical for the process quality in microelectronics as well as a number of other industrial applications including production of fine metal or ceramic powders, nanoparticle-unit thin film deposition, nanostructuring of substrates, nucleating agents in polymer and plastics synthesis, drug delivery systems, inorganic additives for sunscreens and UV-absorbers, and several others. Several unique properties of the chemically active plasma-nanoparticle systems are discussed as well.     

Assessment of Aqueous Extraction Methods on Extractable Organic Matter and Hydrophobic/Hydrophilic Fractions of Virgin Forest Soils

The assessment of water-extractable organic matter using an autoclave can provide useful information on physical, chemical, and biological changes within the soil. The present study used virgin forest soils from Chini Forest Reserve, Langkawi Island, and Kenyir Forest Reserve (Malaysia), extracted using different extraction methods. The dissolved organic carbon (DOC), total dissolved nitrogen (TDN), total dissolved phosphorus (TDP), and ammonium-nitrate content were higher in the autoclave treatments, up to 3.0, 1.3, 1.2, and 1.4 times more than by natural extraction (extracted for 24 h at room temperature). Overall, the highest extractable DOC, TDN, TDP, ammonium and nitrate could be seen under autoclaved conditions 121 °C 2×, up to 146.74 mg C/L, 8.97 mg N/L, 0.23 mg P/L, 5.43 mg N mg/L and 3.47 N mg/L, respectively. The soil extracts became slightly acidic with a higher temperature and longer duration. Similar trends were observed in the humic and nonhumic substances, where different types of soil extract treatments influenced the concentrations of the fractions. Different soil extraction methods can provide further details, thus widening the application of soil extracts, especially in microbes.