Vibrational and electronic excitations of H(2)O on thymine films induced by low-energy electrons

We investigated vibrational and electronic excitations of 0.1-layer up to 2.4-layer film of H(2)O deposited on a 1.4-layer film of thymine condensed on Ar at a temperature of 18 K using high-resolution electron-energy loss (EEL) spectroscopy at the incident energy of 12 eV. The spectral contribution originating essentially from the H(2)O overlayer is obtained by separating the measured contribution from the underlying film of thymine, considering the electron beam attenuation in the H(2)O overlayer. The vibrational EEL spectrum of submonolayer amount of H(2)O on thymine, which excepts for small energy shift of the vibrational bands, is found to compare in intensity to that of the same amount of H(2)O deposited directly on the argon. The electronic energy-loss intensity near 8.6 eV, which is attributed to the excitation of (3,1)B(1) states of H(2)O in condensed phase, is observed to decrease by a factor of about 3 by the presence of the underlying film of thymine. This indicates that the corresponding cross section for excitation the (3,1)B(1) states of H(2)O by the electron impact is reduced significantly by the close proximity of the thymine molecules.     

H/D isotopic exchange between water molecules at ice surfaces

H/D isotopic exchange between H(2)O and D(2)O molecules was studied at the surface of ice films at 90-140 K by the technique of Cs(+) reactive ion scattering. Ice films were deposited on a Ru(0001) substrate in different compositions of H(2)O and D(2)O and in various structures to study the kinetics of isotopic exchange. H/D exchange was very slow on an ice film at 95-100 K, even when H(2)O and D(2)O were uniformly mixed in the film. At 140 K, H/D exchange occurred in a time scale of several minutes on the uniform mixture film. Kinetic measurement gave the rate coefficient for the exchange reaction, k(140 K)=1.6(+/-0.3) x 10(-19) cm(2) molecule(-1) s(-1) and k(100 K)< or =5.7(+/-0.5) x 10(-21) cm(2) molecule(-1) s(-1) and the Arrhenius activation energy, E(a)> or =9.8 kJ mol(-1). Addition of HCl on the film to provide excess protons greatly accelerated the isotopic exchange reaction such that it went to completion very quickly at the surface. The rapid reaction, however, was confined within the first bilayer (BL) of the surface and did not readily propagate to the underlying sublayer. The isotopic exchange in the vertical direction was almost completely blocked at 95 K, and it slowly occurred only to a depth of 3 BLs from the surface at 140 K. Thus, the proton transfer was highly directional. The lateral proton transfer at the surface was attributed to the increased mobility of protonic defects at the molecularly disordered and activated surface. The slow, vertical proton transfer was probably assisted by self-diffusion of water molecules.     

Influence of monolayer amounts of HNO3 on the evaporation rate of H2O over ice in the range 179 to 208 K: a quartz crystal microbalance study

The evaporation flux J(ev) of H2O from thin H2O ice films containing between 0.5 and 7 monolayers of HNO3 has been measured in the range 179 to 208 K under both molecular and stirred flow conditions in isothermal experiments. FTIR absorption of the HNO3/H2O condensate revealed the formation of metastable alpha-NAT (HNO(3).3H2O) converting to stable beta-NAT at 205 K. After deposition of HNO3 for 16-80 s on a 1 mum thick pure ice film at a deposition rate in the range (6-60) x 10(12) molecules s(-1) the initial evaporative flux J(ev)(H2O) was always that of pure ice. J(ev)(H2O) gradually decreased with the evaporation of H2O and the concomitant increase of the average mole fraction of HNO3, chi(HNO3), indicating the presence of an amorphous mixture of H2O/HNO3 that is called complexed or (c)-ice whose vapor pressure is that of pure ice. The final value of J(ev) was smaller by factors varying from 2.7 to 65 relative to pure ice. Depending on the doping conditions and temperature of the ice film the pure ice thickness d(D) of the ice film for which J(ev) < 0.85J(ev)(pure ice) varied between 130 and 700 nm compared to the 1000 nm thick original ice film at 208 and 191 K, respectively, in what seems to be an inverse temperature dependence. There exist three different types of H2O molecules under the present experimental conditions, namely (a) free H2O corresponding to pure ice, (b) complexed H2O or c-ice, and (c) H2O molecules originating from the breakup of NAT or amorphous H2O/HNO3 mixtures. The significant decrease of J(ev)(H2O) with increasing chi(HNO3) leads to an increase of the evaporative lifetime of atmospheric ice particles in the presence of HNO3 and may help explain the occurrence of persistent and/or large contaminated ice particles at certain atmospheric conditions.     

Electrocatalysis of peroxide reduction by Au-stabilized, Fe-containing poly(vinylpyridine) films

We show that poly(vinylpyridine) (PVP) coated glassy carbon surfaces containing Fe(CN)6(3-) exhibit catalytic activity toward electroreduction of H2O2. While Fe(CN)6(3-) is catalytically inactive in solution phase, it exhibits catalytic activity upon incorporation into the PVP film, because film incorporation leads to an open coordination site in the otherwise inert Fe(CN)6(3-) molecule. However, this catalytic activity is quickly lost during H2O2 electroreduction due to leaching of the Fe species from the PVP film. The Fe catalyst in the PVP film could be stabilized by 1 order of magnitude in time by electrodeposition of small Au particles. Characterization of the film using scanning electron microscopy, secondary ion mass spectroscopy, and Raman spectroscopy shows that covalent attachment between the Au particle and the Fe-based catalyst is a likely mechanism for catalyst stabilization.     

Study of (TPP)H_2 Vapor Deposited Film on Iron

IntroductionCorrosioninhibitionofmetalsdependsupontheinhibitor'sabilityofformingbondstothemetalatomorionsofthesubstrate.Aporphyrinringligandpossessespowerfulcoordinationcapabilitytomanymetalionsthroughitsfournitrogenatoms.Additionally,someofthecoordinatedcefltered-metalionscanacceptanotheroneortWoligandstoformtheaxialcomplexes'-'.Athoughsomecorrosionsciefltistshavebeeninterestedininvestigatingthepotentialityofporphyrins(metal-freeporphyrins)ormetalporphyrinsasinhibitors,theinhibitedfilmsorinh…     

热处理对LiFe1-0.01xY0.005xAg0.005xPO4薄膜光波导传感元件气敏性的影响

以FeSO4.7H2O,H3PO4,LiOH.H2O,AgNO3及Y(NO3)3.6H2O为原料,利用水热法一步合成出了LiFe1-0.01xY0.005xAg0.005xPO4粉体(x=0.5,1.0),并将该材料作为敏感试剂,用旋转-甩涂法做成纳米薄膜固定在锡掺杂玻璃光波导表面,在不同温度下进行热处理。采用紫外-可见分光光度计、测厚仪以及自组装的玻璃光波导气敏测试仪研究了热处理对LiFe1-0.01xY0.005xAg0.005xPO4薄膜光学及气敏特性的影响。研究结果表明:在450℃下进行热处理的薄膜元件具有良好的光学透明及较好的气敏特性。相同浓度的不同挥发性有机气体中,该传感元件对二甲苯气体有很好的选择性响应,其检测响应范围为1×10-7～1×10-3(V/V),响应-恢复时间分别小于5和100 s。     

Liquid phase deposition of hemoglobin/SDS/TiO2 hybrid film preserving photoelectrochemical activity

This work demonstrates that liquid phase deposition (LPD) technique provides a novel approach to the immobilization of hemoglobin (Hb) in TiO(2) film for studying the direct electron transfer of Hb. Using the LPD process, a hybrid film composed of Hb, TiO(2) and sodium dodecylsulfonate (SDS) is successfully prepared on the electrode surface. The surface morphology of as-deposited Hb/SDS/TiO(2) film shows a flower-like structure. The cyclic voltammetric measurement indicates that the LPD hybrid film facilitates the electron transfer of Hb, which yields a pair of redox peaks prior to the characteristic voltammetric peaks of TiO(2). Due to the electrocatalytic activity of Hb towards H(2)O(2), the Hb/SDS/TiO(2) hybrid LPD film can be utilized as an H(2)O(2) sensor, showing a sensitive response linearly proportional to the concentration of H(2)O(2) in the range of 5.0×10(-7)-4.0×10(-5) mol/L. At the same time, the Hb/SDS/TiO(2) hybrid film preserves the photoelectrochemical activity of TiO(2). The photovoltaic effect on the electrochemical behavior of Hb/SDS/TiO(2) film is observed after long-time UV irradiation on the film, which could improve the calibration sensitivity for H(2)O(2).     

Fabrication and Electrowetting Properties of Poly Si Nanostructure Based Superhydrophobic Platform

Poly-silicon based superhydrophobic surface (water contact angle >150°) is being fabricated and its electrowetting properties have been studied. The polysilicon thin film has been deposited over patterned gold electrodes. The polysilicon film is structured to form nanoscale features using Reactive Ion Etching. A thin film of HfO₂ high k-dielectric is deposited over the structured polysilicon surface. The surface was chemically modified with Trichloro (1H, 1H, 2H, 2H-perfluorooctyl) silane (PFOS). Such a surface showed Superhydrophobic behavior with water contact angle of 172° and roll off angle <3°. The electrowetting properties of the fabricated device was studied by applying a DC voltage between the gold electrode and the droplet. The electrowetting commences when the applied voltage was 18 V and the contact angle is reduced to 152°. As the applied voltage was increased there was decrease in contact angles.     

Palladium(II)-substituted tungstosilicate [Cs2K(H2O)7Pd2WO(H2O)(A--SiW9O34)2]9-

The palladium(II)-substituted tungstosilicate [Cs(2)K(H(2)O)(7)Pd(2)WO(H(2)O)(A-alpha-SiW(9)O(34))(2)](9)(-) (1) has been synthesized and characterized by IR, elemental analysis, and electrochemistry. Single-crystal X-ray analysis was carried out on Cs(3)K(2)Na(4)[Cs(2)K(H(2)O)(7)Pd(2)WO(H(2)O)(A-alpha-SiW(9)O(34))(2)].5H(2)O (1a), which crystallizes in the monoclinic system, space group P2(1)/n, with a = 16.655(3) A, b = 19.729(4) A, c = 25.995(5) A, beta = 95.46(3) degrees , and Z = 4. Polyanion 1represents the first structurally characterized palladium(II)-substituted tungstosilicate. The title polyanion consists of two (A-alpha-SiW(9)O(34)) Keggin moieties linked via a [WO(H(2)O)](4+) group and two equivalent, square-planar Pd(2+) ions leading to a sandwich-type structure with C(2)(v) symmetry. The central belt of 1 contains also one potassium and two cesium ions. Polyanion 1 was synthesized by reaction of Pd(CH(3)COO)(2) with K(10)[A-alpha-SiW(9)O(34)] in aqueous acidic medium (pH 4.8). A cyclic voltammetry study of polyanion 1 in a pH 5 medium shows a Pd(0) deposition process on the glassy carbon electrode surface. The corresponding wave and that of tungsten redox processes could be separated clearly during the first few runs before their merging into a broad composite wave. The film thickness increases with the number of potential cycles or the duration of potentiostatic electrolysis. As judged from hydrogen sorption/desorption pattern, the quality of the film deposited from polyanion 1 is better than that of a film deposited directly from Pd(2+) solutions.     

Diffusion of HDO in pure and acid-doped ice films

In these experiments, a few bilayers of D(2)O were vapor-deposited on a pure crystalline H(2)O ice film or an ice film doped with a small amount of HCl. Upon deposition, H/D isotopic exchange quickly converted the D(2)O layer into an HDO-rich mixture layer. Infrared absorption spectroscopy followed the changes of the HDO from the initial HDO mixture layer to HDO isolated in the H(2)O ice film. This was possible because isolated HDO in H(2)O ice has a unique, sharp peak in the O-D stretch region that can be distinguished from the broad peak due to the initial HDO mixture layer. The absorbance of isolated HDO displayed first-order kinetics and was attributed to diffusion of HDO from the HDO-rich mixture layer into the underlying H(2)O ice film. While negligible diffusion was observed for pure ice films and for ice films with HCl concentrations up to 1 x 10(-4) mole fraction, diffusion of HDO occurred for higher concentrations of (2-20) x 10(-4) mole fraction HCl with a concentration-independent rate constant. The diffusion under these conditions followed Arrhenius behavior for T = 135-145 K yielding E(a) = 25 +/- 5 kJ/mol. The mechanism for the HDO diffusion involves either (i) molecular self-diffusion or (ii) long-range H/D diffusion by a series of multiple proton hop and orientational turn steps. While these spectroscopic results compare favorably with recent studies of molecular self-diffusion in low-temperature ice films, the diffusion results from all the ice film studies at low temperatures (ca. T < 170 K) differ from earlier bulk ice studies at higher temperatures (ca. T > 220 K). A comparison and discussion of the various diffusion studies are included in this report.     

Epitaxial film growth and superconducting behavior of sodium-cobalt oxyhydrate, NaxCoO2.yH2O (x approximately 0.3, y approximately 1.3)

We have developed a unique multistep film growth technique, combining reactive solid-phase epitaxy (R-SPE) with an intercalation process, to fabricate epitaxial films of superconducting sodium-cobalt oxyhydrate, Na(0.3)CoO2.1.3H2O. An epitaxial film of Na(0.8)CoO2 grown on an alpha-Al2O3(0001) substrate by R-SPE was subjected to oxidation and hydration treatment, leading to the formation of a Na(0.3)CoO2.1.3H2O epitaxial film. The film exhibited metallic electrical resistivity with a superconducting transition at 4 K, similar to that of bulk single crystals. The present technique is suitable and probably the only method for the epitaxial growth of superconducting Na(0.3)CoO2.1.3H2O.     

Electrochemical properties of myoglobin deposited on multi-walled carbon nanotube/ciprofloxacin film

We report the direct electrochemical and electrocatalytic properties of myoglobin (MB) on a multi-walled carbon nanotube/ciprofloxacin (MWCNT/CF) film-modified electrode. A highly homogeneous MWCNT thin-film was prepared on an electrode surface using ciprofloxacin (CF) as a dispersing agent. MB was then electrochemically deposited onto the MWCNT/CF-modified electrode. The MB/MWCNT/CF film was characterized by scanning electron microscopy and UV-visible spectroscopy (UV-vis). UV-vis spectra confirmed that MB retained its original state on the MWCNT/CF film. Direct electrochemical properties of MB on the MWCNT/CF film were investigated by cyclic voltammetry. The formal potential and electron transfer rate constant were evaluated in pH 7.2 buffer solution as -0.327V and 300s(-1), respectively. In addition, the MB/MWCNT/CF-modified electrode showed excellent electrocatalytic properties for the reduction of hydrogen peroxide (H(2)O(2)). The MB/MWCNT/CF-modified electrode was used for the detection of H(2)O(2) at concentrations from 1×10(-6)M to 7×10(-4)M in pH 7.2 buffer solution. Overall, the MB/MWCNT/CF-modified electrode was very stable and has potential for development as a H(2)O(2) sensor.     

Formation of AlOOH and silica composite hierarchical nanostructures thin film by sol–gel dip-coating for superhydrophobic surface with high adhesion force

Nanosheet AlOOH and silica spheres composite thin film was deposited onto glass by sol–gel dip-coating method through hydrolysis of boiling water immersion. A silica sol and an alumina sol are employed in dipping process for the preparation of hierarchical nanostructures thin film. The morphology and structure of the films were characterized using field emission scanning electron microscopy and X-ray diffraction. The super-hydrophobicity with high adhesion forces can be attributed to both the rough multi-scale structural coating and surface enrichment of low surface energy with the chemical vapor deposition of 1H,1H,2H,2H-perfluorodecyltriethoxysilane.     

六水合硝酸镁增塑改性淀粉-聚乙烯醇复合膜的合成与性能

以六水合硝酸镁[Mg(NO₃)₂·6H₂O]为增塑剂, 采用流延法制备了增塑改性的淀粉-聚乙烯醇(PVA)复合膜, 并研究了改性后淀粉-PVA复合膜的性能. 研究结果表明, Mg(NO₃)₂·6H₂O与淀粉和PVA发生一定的相互作用, 破坏了淀粉和PVA中的结晶结构. 因此, Mg(NO₃)₂·6H₂O的加入可提高淀粉与PVA间的相容性, 改变了淀粉-PVA复合膜的力学性能, 使其拉伸强度下降, 断裂伸长率提高.     

添加改性松香对生漆漆膜性能的影响

通过添加松香、改性松香对生漆漆膜进行改性,研究结果表明,加入改性松香能改善生漆漆膜性能,在反应温度为80℃时,加入生漆质量5％的聚合松香效果最佳,附着力为1级,抗冲击力为35kg／cm,铅笔划痕为3H。反应温度对漆膜性能有很大影响,当加入生漆质量5％的聚合松香,反应温度从50℃升至80℃时,附着力从3级提高到1级,抗冲击力从10kg／cm提高到35kg／cm,铅笔划痕从H升至3H。红外光谱分析表明,天然松香对生漆性能的增强效果是由于与生漆发生了化学反应,而聚合松香对生漆性能的增强效果是协同作用造成的。     

Effects of hydrogen peroxide on the electrochemical decomposition of layer-by-layer thin films composed of 2-iminobiotin-labeled poly(ethyleneimine) and avidin

The effects of hydrogen peroxide on the electrochemical decomposition of layer-by-layer thin films composed of 2-iminobiotin-labeled poly(ethyleneimine) (ib-PEI) and avidin were studied. An ib-PEI/avidin thin film prepared on the surface of a platinum (Pt) film-coated quartz resonator was electrochemically decomposed in the presence of hydrogen peroxide (H(2)O(2)) in the solution. The resonant frequency of the thin-film-deposited quartz resonator was increased upon application of electric potential (0.4-0.6 V vs Ag/AgCl) to the Pt layer, suggesting that the mass on the quartz resonator was decreased as a result of decomposition of the ib-PEI/avidin film. It was found that decomposition of the film is highly accelerated in the presence of H(2)O(2) compared to the decomposition in the same buffer solution without H(2)O(2), due to a pH change originating from electrochemical oxidation of H(2)O(2) on the Pt surface. The rate of electrochemical decomposition of the ib-PEI/avidin film was highly dependent on the concentration of H(2)O(2,) buffer capacity, and pH of the solution.     

Nanotribology of ethers: effects of molecular asymmetry and fluoroalkyl chains

The tribological properties of the molecularly thin films of asymmetric ether (1,3-dimethylbutyl octyl ether, AE) and fluorinated asymmetric ether (1H,1H,2H,2H-perfluorooctyl-1,3-dimethylbutyl ether, FAE) were investigated. Friction forces and dynamic thicknesses (thicknesses during sliding) were simultaneously measured using the surface forces apparatus, and the effects of molecular asymmetry and fluoroalkyl chains on the friction properties are analyzed. The friction forces (both kinetic and static) and dynamic thicknesses are larger for the AE film than for the FAE film. The two ethers exhibit stick-slip friction at low sliding velocity, but the stick-slip patterns are different. For the AE film, one stick-slip cycle consists of two or more spikes; a large spike is followed by one or more small spike(s) in the cycle. On the other hand, regular stick-slip spikes are observed for the FAE film. The results suggest that the responsible friction mechanisms are completely different between the two ether films. The asymmetric shape of the AE molecule results in a variety of shear-ordered liquid structures in confinement, and the friction (stick-slip) behavior follows the "phase-transition model". In contrast, the FAE molecule is rigid, and the shape of the molecule is rather close to a symmetric cylinder, which leads to a well-ordered two-layer film in confinement. The each molecular layer is strongly adsorbed on adjacent mica substrate and behaves as a fluorinated coating. The friction is governed by the molecular scale "bumpiness" of the fluoroalkyl chains lying on mica surfaces and basically follows the "cobblestone model". The advantage of the thin FAE film as a practical lubricant is also discussed.     

pH-responsive copolymer films by surface-catalyzed growth

We have engineered a new class of pH-responsive polymer films on gold surfaces by first developing a controlled, surface-catalyzed polymerization to prepare a copolymer film consistent with poly(methylene-co-ethyl acetate) and subsequently hydrolyzing the ester side chains to varying extents to yield carboxylic acids (denoted as PM-CO2H). When pH is increased, the acid groups become deprotonated or charged, dramatically increasing their water solubility and greatly altering the film properties. The carboxylic acid content within the copolymer film can be adjusted by changing the monomer concentration ratio used in the polymerization process or the length of time for the hydrolysis. We have designed PM-CO2H films to consist predominately (>95%) of polymethylene (PM) so that the film is hydrophobic in the uncharged state and, thereby, exhibits an extremely large pH-induced response in barrier properties once ionized. The effect of polymer composition on pH response was investigated by electrochemical impedance spectroscopy (EIS), reflectance-absorption infrared spectroscopy (RAIRS), and contact angle measurements. At a 1%-4% molar acid content, the copolymer film exhibits a 5 orders of magnitude change in its resistance to ion transport over 2-3 pH units. The pH at which this response begins can be tailored from pH 5 to pH 10 by decreasing the acid content in the film from 4% to 1%.     

Electrophoretic deposition of titanate nanotube films with extremely large wetting contrast

A facile electrophoretic deposition (EPD) process has been developed to prepare thin films consisting of titanate nanotubes (TNTs) that were synthesized by a hydrothermal approach. Such an EPD process offers easy control in the film thickness and the adhesion to the substrate was found to be strong. The chemical composition and structure of the products have been characterized by XRD, HRTEM, and FESEM. It was found that the functionalization of TNTs plays a key role on the electrolyte stability and the formation of a uniform TNT film with good adhesion. The as-prepared TNT films show exceptional superhydrophilic behavior with ultra-fast spreading, while it converts to superhydrophobicity yet with strong adhesion after 1H,1H,2H,2H-perfluorooctyl-triethoxysilane modification. This study provides an interesting method to prepare films with extremely high wettability contrast that are useful for producing different types of functional materials.     

Interaction of water with ordered theta-Al(2)O(3) ultrathin films grown on NiAl(100)

The structure of an ordered, ultrathin theta-Al(2)O(3) film grown on a NiAl(100) single-crystal surface was studied by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and low-energy electron diffraction (LEED), and its interaction with water was investigated with temperature programmed desorption (TPD) and XPS. Our results indicate that H(2)O adsorption on the theta-Al(2)O(3)/NiAl(100) surface is predominantly molecular rather than dissociative. For theta(H)()2(O) < 1 ML (ML = monolayer), H(2)O molecules were found to populate Al(3+) cation sites to form isolated H(2)O species aligned in a row along the cation sites on the oxide surface with a repulsive interaction between them. For theta(H)()2(O) > 1 ML, three-dimensional ice multilayers were observed to form, which then desorb during TPD with approximate zero-order kinetics as expected. A small extent of H(2)O dissociation was observed to occur on the theta-Al(2)O(3)/NiAl(100) surface, which was attributed to the presence of a low concentration of oxygen atom vacancies. Titration of these defect sites with adsorbed H(2)O molecules revealed an estimated defect density of 0.05 ML for the theta-Al(2)O(3)/NiAl(100) system consistent with the ordered nature of the synthesized oxide film.