Effects of the polarizability and packing density of transparent oxide films on water vapor permeation

The tin oxide and silicon oxide films have been deposited on polycarbonate substrates as gas barrier films, using a thermal evaporation and ion beam assisted deposition process. The oxide films deposited by ion beam assisted deposition show a much lower water vapor transmission rate than those by thermal evaporation. The tin oxide films show a similar water vapor transmission rate to the silicon oxide films in thermal evaporation but a lower water vapor transmission rate in IBAD. These results are related to the fact that the permeation of water vapor with a large dipole moment is affected by the chemistry of oxides and the packing density of the oxide films. The permeation mechanism of water vapor through the oxide films is discussed in terms of the chemical interaction with water vapor and the microstructure of the oxide films. The chemical interaction of water vapor with oxide films has been investigated by the refractive index from ellipsometry and the OH group peak from X-ray photoelectron spectroscopy, and the microstructure of the composite oxide films was characterized using atomic force microscopy and a transmission electron microscope. The activation energy for water vapor permeation through the oxide films has also been measured in relation to the permeation mechanism of water vapor. The diffusivity of water vapor for the tin oxide films has been calculated from the time lag plot, and its implications are discussed.     

The molecular structures of gaseous cyclopentene oxide,cyclohexene oxide and cycloheptene oxide as determined by electron diffraction

The molecular structures of gaseous cyclopentene oxide, cyclohexene oxide and cycloheptene oxide are investigated by electron diffraction. The boat conformation of cyclopentene oxide is confirmed, while a half-chair conformer is determined for cyclohexene oxide. Cycloheptene oxide is found to exist in a 66(2):34(2) conformational mixture of two chair forms.     

Parameters affecting carbofuran photocatalytic degradation in water using ZnO nanoparticles

Carbofuran photodegradation in water using zinc oxide nanoparticles as a catalyst was examined as well as some parameters influencing its percentage degradation rate such as zinc oxide load, initial concentration of carbofuran, the temperature of the reaction, the initial pH of the solution, and doping of zinc oxide nanoparticles with 5% (w:w) silver. Zinc oxide and Ag-doped zinc oxide nanoparticles were produced using solvothermal and photoreduction methods, respectively, and silver doping effects on the structural, optical, and photocatalytic properties of zinc oxide nanoparticles were investigated using XRD, UV-VIS spectrophotometer, TEM, SEM, SEM/EDX, and FTIR. The average diameter of the synthesized samples was 26.6, 30.55 nm for undoped zinc oxide and Ag-doped zinc oxide, respectively. Zinc oxide doping with silver did not change the shape of the zinc oxide crystal, but decreased the reflection in the visible region, as well as the energy of the bandgap, and increased the zinc oxide photocatalytic activity.     

Interaction of Zinc Oxide and Copper Oxide Nanoparticles with Chlorophyll: A Fluorescence Quenching Study

The present study aims to investigate the interactions of zinc oxide nanoparticles and copper oxide nanoparticles with the major photosynthetic pigment chlorophyll using ultraviolet-visible, steady state, and time resolved laser induced fluorescence spectroscopy. The steady state fluorescence measurements show that zinc oxide and copper oxide nanoparticles quench the fluorescence of chlorophyll in concentration-dependent manner. The Stern-Volmer plot for the chlorophyll-zinc oxide nanoparticles is linear, and the value of quenching constant has been observed to increase with temperature indicating the possibility of dynamic quenching. A decrease in the lifetime of chlorophyll with increase in the concentration of zinc oxide nanoparticles confirms the involvement of dynamic quenching in the chlorophyll–zinc oxide nanoparticle interaction. In the case of copper oxide nanoparticles, the Stern-Volmer plot deviates from linearity observed in the form of upward curvature depicting the presence of both static and dynamic quenching. In addition, the lifetime of chlorophyll decreases with increase in the concentration of copper oxide nanoparticles displaying the dominance of dynamic quenching in the chlorophyll-copper oxide nanoparticle interaction. The decrease observed in the value of binding constant with increasing temperature and negative values of change in enthalpy, entropy, and Gibb’s free energy indicates that van der Waal and hydrogen bonding are the prominent forces during the interaction of chlorophyll with both zinc oxide and copper oxide nanoparticles and that the process is spontaneous and exothermic. The interaction of zinc oxide and copper oxide nanoparticles with chlorophyll occurs through electron transfer mechanism. The obtained results are useful in understanding the sensitization processes involving chlorophyll and zinc oxide and copper oxide nanoparticles.     

Graphene oxide dispersions in organic solvents

The dispersion behavior of graphene oxide in different organic solvents has been investigated. As-prepared graphite oxide could be dispersed in N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetrahydrofuran, and ethylene glycol. In all of these solvents, full exfoliation of the graphite oxide material into individual, single-layer graphene oxide sheets was achieved by sonication. The graphene oxide dispersions exhibited long-term stability and were made of sheets between a few hundred nanometers and a few micrometers large, similar to the case of graphene oxide dispersions in water. These results should facilitate the manipulation and processing of graphene-based materials for different applications.     

Effect of the heterointerface on transport properties of in situ formed MgO/titanate heterostructured nanowires

Heterostructured transition metal oxide nanowires are potential candidates to incorporate rich functionalities into nanowire-based devices. Although the oxide heterointerface plays a crucial role in determining the physical properties, the effects of the heterointerface on the oxide nanowire's properties have not been clarified. Here we investigate for the first time the significant role of the heterointerface in determining the transport properties of well-defined MgO/titanate heterostructured nanowires by combining a technique for in situ formation of a oxide heterointerface and microwave conductivity measurement. Variation of the heterointerface strongly affects the nanowire's transport properties due to the crystallinity and the atomic interdiffusion at the oxide heterointerface. Thus, the precise in situ formation of a well-defined heterointerface is crucial to create oxide heterostructured nanowires with the desired transport properties.     

The Relationship of Glutathione-S-Transferase and Multi-Drug Resistance-Related Protein 1 in Nitric Oxide (NO) Transport and Storage

Nitric oxide is a diatomic gas that has traditionally been viewed, particularly in the context of chemical fields, as a toxic, pungent gas that is the product of ammonia oxidation. However, nitric oxide has been associated with many biological roles including cell signaling, macrophage cytotoxicity, and vasodilation. More recently, a model for nitric oxide trafficking has been proposed where nitric oxide is regulated in the form of dinitrosyl-dithiol-iron-complexes, which are much less toxic and have a significantly greater half-life than free nitric oxide. Our laboratory has previously examined this hypothesis in tumor cells and has demonstrated that dinitrosyl-dithiol-iron-complexes are transported and stored by multi-drug resistance-related protein 1 and glutathione-S-transferase P1. A crystal structure of a dinitrosyl-dithiol-iron complex with glutathione-S-transferase P1 has been solved that demonstrates that a tyrosine residue in glutathione-S-transferase P1 is responsible for binding dinitrosyl-dithiol-iron-complexes. Considering the roles of nitric oxide in vasodilation and many other processes, a physiological model of nitric oxide transport and storage would be valuable in understanding nitric oxide physiology and pathophysiology.     

Increasing the Sensitivity and Single‐Base Mismatch Selectivity of the Molecular Beacon Using Graphene Oxide as the “Nanoquencher”

Here, we report a novel, highly sensitive, selective and economical molecular beacon using graphene oxide as the “nanoquencher”. This novel molecular beacon system contains a hairpin‐structured fluorophore‐labeled oligonucleotide and a graphene oxide sheet. The strong interaction between hairpin‐structured oligonucleotide and graphene oxide keep them in close proximity, facilitating the fluorescence quenching of the fluorophore by graphene oxide. In the presence of a complementary target DNA, the binding between hairpin‐structured oligonucleotide and target DNA will disturb the interaction between hairpin‐structured oligonucleotide and graphene oxide, and release the oligonucleotide from graphene oxide, resulting in restoration of fluorophore fluorescence. In the present study, we show that this novel graphene oxide quenched molecular beacon can be used to detect target DNA with higher sensitivity and single‐base mismatch selectivity compared to the conventional molecular beacon.     

氧化石墨烯吸附亚甲基蓝的分子动力学模拟

采用分子动力学方法研究了亚甲基蓝在不同氧化度的氧化石墨烯表面的吸附行为及其动力学性质, 从微观角度讨论了亚甲基蓝由体相到氧化石墨烯表面的吸附过程及主要作用机制, 并通过亚甲基蓝分子动力学性质解释了氧化石墨烯的氧化度和含氧官能团类型对吸附行为的影响. 结果表明, 吸附过程中, 亚甲基蓝主要受氧化石墨烯表面含氧官能团的静电作用, 以近似垂直氧化石墨烯表面的方向进入, 并以平行的方式吸附于氧化石墨烯表面; 亚甲基蓝不易脱离高氧化度氧化石墨烯的吸附位点; 吸附平衡过程中, 相对于低氧化度的氧化石墨烯, 高氧化度氧化石墨烯对亚甲基蓝的束缚性更强, 同时与亚甲基蓝间相互作用更强; 含氧官能团中的环氧基与亚甲基蓝间的作用势能更强, 且羟基能够与亚甲基蓝间形成氢键结构, 共同保障了亚甲基蓝吸附层的稳定性.     

An investigation of anodic film formation on electrodeposited ruthenium by potential sweep techniques

Potential sweep techniques were used to investigate the anodic behaviour of reduced ruthenium surfaces, prepared by electrodeposition on gold-plated substrates, as a function of sweep rate, temperature and pH. The most important factor appeared to be pH as this strongly influenced the oxide layer thickness and both the number and location of the peaks on the voltammogram. The formation of thin oxide films on ruthenium at intermediate pH values (3.5–9.5) is attributed to the growth of a compact amorphous film with significant metal-oxygen-metal bridging in the structure. Heavier oxide growth in strong acid is attributed to protonation of the oxide lattice resulting in the formation of a more porous anodic film. Thicker oxide growth in strong base is attributed to the growth of a higher (+6) oxide under these conditions. The effects of both sweep rate and temperature on anodic behaviour in strong acid are attributed to activation-controlled rearrangement of the oxide film.     

Kinetics and mechanism of electrochemical reduction of multilayer oxides on a smooth platinum electrode surface in acidic electrolyte

The electrochemical reduction of multilayer oxides which were formed on a smooth Pt electrode surface under severe anodic conditions was investigated using a galvanostatic transient, a linear potential sweep and a potential step technique. Four regions of the surface oxide reduction were distinguished in the galvanostatic E?t curve and four corresponding cathodic current peaks were observed in the potentiodynamic i?E profile. These four regions or peaks are attributed to the reduction of four O-containing layers: an oxygen monolayer adsorbed on the oxide surface, two oxide layers in a first and a second lattice and a multilayer oxide in the deeper lattices having a phase property. The reduction rate of the first lattice oxide layer is determined by a second electron transfer. Under a rapid stripping condition, the reduction of the second oxide layer is considered to be controlled by the place exchange reaction. The extremely large reduction rate of the multilayer oxide compared with the formation rate is explained in terms of the proton-electron model.     

Determination of Lysozyme by Graphene Oxide–Polyethylene Glycol-Based Fluorescence Resonance Energy Transfer

The surface of graphene oxide was modified by bis(3-aminopropyl)-terminated polyethylene glycol to produce a composite graphene–polyethylene glycol. The graphene oxide/polyethylene glycol maximum absorption peak in the ultraviolet–visible spectrum was redshifted, and transmission electron microscope images showed that graphene oxide was cleaved into small nanosheets to form graphene oxide/polyethylene glycol. The dispersibility of graphene oxide/polyethylene glycol in physiological solution was higher than for graphene oxide. The optimum composite of graphene oxide/polyethylene glycol was used as a quencher in a fluorescence resonance energy transfer aptasensor for the determination of lysozyme detection. The results showed that graphene oxide/polyethylene glycol rapidly and efficiently quenched the fluorescence of the dye-labeled aptamer. The fluorescence was recovered by adding lysozyme to the system. The aptamer fluorescence intensity exhibited a strong linear dependence on the lysozyme concentration from 50 to 300?nM, and the lysozyme detection limit was approximately 11?nM. This method was used for the determination of lysozyme in egg whites, demonstrating that this approach is a promising alternative for the determination of lysozyme.     

Nanostructured latex films from poly(butyl methacrylate) latex cross-linked with poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) triblock macro-cross-linker

Biphasic polymer latexes were synthesized by a seeded swelling and polymerization method. The latexes were composed of a poly(butyl methacrylate) core and a poly(ethylene oxide) rich shell cross-linked with poly(ethylene oxide)-poly (propylene oxide)-poly(ethylene oxide) triblock diol diacrylate macro-cross-linker. Nanostructured films were obtained by annealing the biphasic polymer latexes at a temperature between the glass-transition temperatures of the core latex and the cross-linked poly(ethylene oxide) based shell. Atomic force microscope images of the latex film revealed that the poly(butyl methacrylate) core phase is confined in the poly(ethylene oxide)-rich continuous phase with the form of separate nanosized spheres.     

钙硼对CuO/Al_2O_3催化剂结构及醋酸仲丁酯氢解性能的影响

以经氧化钙和氧化硼改性的氧化铝为载体,采用浸渍法制备了负载型CuO/Al2O3催化剂,采用XRD、BET、TPR和NH3-TPD技术对催化剂CuO/Al2O3进行了表征.结果表明,氧化硼既可以作为结构性助剂提高铜在催化剂表面的分散度,又可以作为电子性助剂有利于催化剂表面氧化铜物种的稳定;氧化钙的引入降低了催化剂表面酸性,有利于催化剂的选择性提高.采用氧化硼和氧化钙改性的Cu10B20Ca30为催化剂,醋酸仲丁酯转化率可达99.5%,生成仲丁醇和乙醇的选择性分别达98.9%和97.8%.     

Study on microarc oxidation of AZ31B magnesium alloy in alkaline metal silicate solution

The effects of pulsating current and voltage sources with different magnitudes on an oxide film formed by microarc oxidation (MAO) of AZ31B magnesium alloy in alkaline metal silicate solution were investigated. The thickness of an oxide film increased with increasing current source but the uniformity of the surface of an oxide film became worse. The unstable oxidation process represented by fluctuating voltage established across an oxide film was discussed and related to the surface roughness and the melting down of magnesium alloy. By comparing the surface of an oxide film a pulsating current source produced more uniform oxide film on magnesium alloy than a pulsating voltage source.     

A Review of Glucose Biosensors Based on Graphene/Metal Oxide Nanomaterials

In recent years, considerable attention has been paid to developing economical yet rapid glucose sensors using graphene and its composites. Recently, the excellent properties of graphene and metal oxide nanoparticles have been combined to provide a new approach for highly sensitive glucose sensors. This review focuses on the development of graphene functionalized with different nanostructured metal oxides (such as copper oxide, zinc oxide, nickel oxide, titanium dioxide, iron oxide, cobalt oxide, and manganese dioxide) for use as glucose biosensors. Additionally, a brief introduction of the electrochemical principles of glucose biosensors (including amperometric, potentiometric, and conductometric) is presented. Finally, the current status and future prospects are outlined for graphene/metal oxide nanomaterials in glucose sensing.     

Nonstoichiometric La(2 - x)GeO(5 - delta) monoclinic oxide as a new fast oxide ion conductor.

Oxide ion conductivity in La(2)GeO(5)-based oxide was investigated and it was found that La-deficient La(2)GeO(5) exhibits oxide ion conductivity over a wide range of oxygen partial pressure. The crystal structure of La(2)GeO(5) was estimated to be monoclinic with P2(1)/c space group. Conductivity increased with increasing the amount of La deficiency and the maximum value was attained at x = 0.39 in La(2 - x)GeO(5 - delta). The oxide ion transport number in La(2)GeO(5)-based oxide was estimated to be unity by the electromotive force measurement in H(2)-O(2) and N(2)-O(2) gas concentration cells. At a temperature higher than 1000 K, the oxide ion conductivity of La(1.61)GeO(5 - delta) was almost the same as that of La(0.9)Sr(0.1)Ga(0.8)Mg(0.2)O(3 - delta) or Ce(0.85)Gd(0.15)O(2 - delta), which are well-known fast oxide ion conductors. On the other hand, a change in the activation energy for oxide ion conductivity was observed at 973 K, and at intermediate temperature, the oxide ion conductivity of La(1.61)GeO(5 - delta) became much smaller than that of these well-known fast oxide ion conductors. The change in the activation energy of the oxide ion conductivity seems to be caused by a change in the local oxygen vacancy structure. However, doping a small amount of Sr for La in La(2)GeO(5) was effective to stabilize the high-temperature crystal structure to low temperature. Consequently, doping a small amount of Sr increases the oxide ion conductivity of La(2)GeO(5)-based oxide at low temperature.     

Zerovalent metal polymer composites. III. Metallization of metal oxide surfaces with the aid of metallized functional polymer microdispersions

The adsorption of poly[N-(m- and p-vinylbenzyl)-N,N,N-trimethylammonium tetrachloropal-ladate] complex on inorganic oxide surfaces followed by reduction of the palladium salt to form a catalytically active zerovalent metal polymer composite dispersed on the oxide surface and further deposition of transition metals, e.g., nickel, cobalt, and copper, by “additive” or “subtractive” deposition from electroless plating solutions is described. γ-Ferric oxide was used as a template for such intermetallic replacement reactions, providing materials with controlled amounts of metal. Multimetallic catalysts based on aluminum oxide, zinc oxide, lanthanum oxide, magnesium oxide, and silica were prepared. Iron oxide modified by subtractive deposition of rhodium and iridium on nickel-clad iron oxide were evaluated in Fischer–Tropsch carbonylation reactions leading from synthesis gas to alkanols.     

金属氧化物异质结气体传感器气敏增强机理

金属氧化物异质结由于费米能级效应、不同组分之间的协同作用,常被用来提高电阻型金属氧化物半导体气体传感器的气敏特性。本文简述了近年来国内外金属氧化物异质结材料的类别,主要分为混合氧化物结构、层状结构、第二相粒子修饰结构、一维纳米结构和核-壳结构;重点综述了金属氧化物异质结的气敏增强机理,包括异质结效应、协同效应、催化溢流效应、响应反型、载流子分离及微结构调控六大机理;分析了当前异质结气体传感器面临的瓶颈。最后对纳米异质结气体传感器的发展进行了展望,今后金属氧化物异质结气体传感器可以从明确异质结界面机理展开,这将为自下而上地设计出符合实际需要的气体传感器提供一定参考。     

Electrochemical Properties of Ag@iron Oxide Nanocomposite for Application as Nitrate Sensor

Ag@iron oxide nanocomposite powders were synthesized via a two‐step chemical method. Characterization by UV‐Vis, XRD, SEM‐EDX and TEM revealed they are composed of nanosized crystalline silver particles in strict contact with amorphous iron oxide(s). The electrochemical behavior of the synthesized Ag@iron oxide composite was investigated by cyclic voltammetry. Compared with the single phase‐modified electrodes, the Ag@iron oxide/SPCE electrode exhibits an enhanced cathodic current in response to the target analyte, due to a synergistic effect between Ag crystallites and amorphous iron oxide nanoparticles. An amperometric sensor for detection of nitrate based on Ag@iron oxide modified screen‐printed electrode (Ag@iron oxide/SPCE) has been fabricated, showing a good sensitivity (663 µA mM^?1 cm^?2) and a detection limit of 30 µM.