Photoelectrochemical oxidation of DNA by ruthenium tris(bipyridine) on a tin oxide nanoparticle electrode

Selective photoelectrochemical oxidation of DNA was achieved by ruthenium tris(bipyridine) immobilized on a tin oxide nanoparticle electrode. The metal complex was covalently attached to a protein, avidin, which adsorbed strongly on the tin oxide electrode by electrostatic interaction. Upon irradiation with 473-nm light, anodic photocurrent was generated in a blank electrolyte and was enhanced significantly after addition of poly(guanadylic acid) (poly-G) into the electrolyte. The current increased progressively with the nucleotide concentration, suggesting the enhancement effect was related to poly-G. The action spectrum indicates that the photocurrent was initiated by light absorption of the ruthenium compound immobilized on the electrode. Among the various polynucleotides examined, poly-G produced the largest photocurrent increase, followed by poly-A, single-stranded DNA, chemically damaged DNA, and double-stranded DNA, whereas poly-C and poly-U showed little effect. The combined experimental data support the hypothesis that the photoexcited Ru2+ species injects an electron into the semiconductor and produces Ru3+, which is then reduced back to Ru2+ by guanine and adenine bases in DNA, resulting in the recycling of the metal complex and enhanced photocurrent. The photoelectrochemical reaction can be employed as a new method for the detection of DNA damage.     

二氧化锡电极的研究及其发展

随着玻璃电熔技术的快速发展,玻璃电熔炉对二氧化锡电极的电极要求越来越高,从早期的致密度到后来的电学性能,近期,随着陶瓷增韧方面的发展,对其力学性能特别是强韧性提出了新的要求.通过对二氧化锡电极研究的全面介绍,指出其最新发展及今后的发展方向.     

Synthesis and analysis of an indium tin oxide nanoparticle dispersion

Interest in inkjet printing of indium tin oxide (ITO) has created the need for a dispersible and highly crystalline nanoparticle form that displays no agglomeration in solution. We have developed a synthesis route to the production of a colloidal ITO nanoparticle system which meets these requirements. The 5 nm diameter ITO particles are highly crystalline and display intrinsic properties similar to those observed in thin-film samples. Most importantly, the organic compounds that initiate the reaction cascade also act as stabilizers against agglomeration and allow the particles to be dispersed in solution for months and potentially years. The colloidal form also provides an additional material with which to probe the fundamental physics of ITO.     

Synthesis of tin oxide nanoparticle film by cathodic electrodeposition

Three-dimensional SnO2 nanoparticle films were deposited onto a copper substrate by cathodic electrodeposition in a nitric acid solution. A new formation mechanism for SnO2 films is proposed based on the oxidation of Sn2+ ion to Sn4+ ion by NO+ ion and the hydrolysis of Sn4+. The particle size of SnO2 was controlled by deposition potential. The SnO2 showed excellent charge capacity (729 mAh/g) at a 0.2 C rate and high rate capability (460 mAh/g) at a 5 C rate.     

Water vapor detection with individual tin oxide nanowires

Individual tin oxide nanowires (NWs), contacted to platinum electrodes using focused ion beam assisted nanolithography, were used for detecting water vapor (1500-32?000?ppm) in different gaseous environments. Responses obtained in synthetic air (SA) and nitrogen atmospheres suggested differences in the sensing mechanism, which were related to changes in surface density of the adsorbed oxygen species in the two cases. A model describing the different behaviors has been proposed together with comparative evaluation of NW responses against sensors based on bulk tin oxide. The results obtained on ten?individual devices (tested >6 times) revealed the interfering effect of water in the detection of carbon monoxide and illustrated the intrinsic potential of nanowire-based devices as humidity sensors. Investigations were made on sensitivity, recovery time and device stability as well as surface-humidity interactions. This is the first step towards fundamental understanding of single-crystalline one-dimensional (1D) tin oxide nanostructures for sensor applications, which could lead to integration in real devices.     

掺锑二氧化锡纳米涂层电极制备及电催化氧化性能

采用改进的热氧化工艺制备了掺锑二氧化锡纳米涂层电极,对电极的成分、结构和形貌进行了表征,并进行了电化学性能测试.以自制电极为阳极,钛板为阴极,进行了对硝基苯酚溶液的电催化氧化降解实验;以紫外可见分光光度计和高效液相色谱等为检测手段,对对硝基苯酚的降解途径进行了初步分析.     

Selective detection of hydrogen sulfide using copper oxide-doped tin oxide based thick film sensor array

In this work, copper oxide-doped (1, 3 and 5 wt%) tin oxide powders have been synthesised by sol–gel method and thick film sensor array has been developed by screen printing technique for the detection of H₂S gas. Powder X-ray diffraction pattern shows that the tin oxide (SnO₂) doped with 3 wt% copper oxide (CuO) has smaller crystallite size in comparison to 0, 1 and 5 wt% CuO-doped SnO₂. Furthermore, field emission scanning electron microscopy manifests the formation of porous film consisting of loosely interconnected small crystallites. The effect of various amounts of CuO dopant has been studied on the sensing properties of sensor array with respect to hydrogen sulfide (H₂S) gas. It is found that the SnO₂ doped with 3 wt% CuO is extremely sensitive (82%) to H₂S gas at 150 °C, while it is almost insensitive to many other gases, i.e., hydrogen (H₂), carbon monoxide (CO), sulphur dioxide (SO₂) and liquefied petroleum gas (LPG). Moreover, at low concentration of gas, it shows fast recovery as compared to response time. Such high performance of 3 wt% CuO-doped SnO₂ thick film sensor is probably due to the diminishing of the p–n junction and the smallest crystallite size (11 nm) along with porous structure.     

Fabrication and photoelectrochemical characteristics of the patterned CdS microarrays on indium tin oxide substrates

In an effort to investigate the extraordinary photoelectrochemical characteristics of nanostructured CdS thin films in promising photovoltaic device applications, the patterned CdS microarrays with different feature sizes (50, 130, and 250 μm in diameter) were successfully fabricated on indium tin oxide (ITO) glass substrates using the chemical bath deposition method. The ultraviolet lithography process was employed for fabricating patterned octadecyltrichlorosilane (OTS) self-assembled monolayers (SAMs) as the functional organic thin layer template. The results show that the regular and compact patterned CdS microarrays had been deposited onto ITO glass surfaces, with clear edges demarcating the boundaries between the patterned CdS region and substrate under an optimal depositing condition. The microarrays consisted of pure nanocrystalline CdS with average crystallite size of about 10.7 nm. The photocurrent response and the optical adsorption of the patterned CdS microarray thin films increased with the decrease of the feature size, which was due to the increased CdS surface area, as well as the increased optical path length within the patterned CdS thin films, resulting from multiple reflection of incident light. The resistivity values increase with the increase of feature size, due to the increase of the relative amount of gaps between CdS microarrays with increasing the feature size of patterned CdS microarrays.     

Direct gravure printing of indium tin oxide nanoparticle patterns on polymer foils

A direct gravure printing process for UV-curable indium tin oxide (ITO) nanoparticle patterns on polyethylene terephthalate and polyethylene naphthalate foils is presented for use as transparent electrodes. Both large-area coatings and patterns of ITO with thicknesses from 0.2 to > 1 μm and feature sizes on the order of 100 μm were realized with a sheet resistance down to 400 Ω_□ and a transmission > 85% in the visible. In order to reach the lowest sheet resistance, a post-treatment under inert or reducing conditions at temperatures of 130 to 180 °C was used. Special requirements regarding the gravure printing of electronic material from nanoparticles and potential applications are discussed.     

Selective detection of a catecholamine against electroactive interferents using an interdigitated heteroarray electrode consisting of a metal oxide electrode and a metal band electrode

We developed an interdigitated array electrode (IDAE) consisting of a metal oxide electrode and a metal band heteroelectrode and employed it for the selective detection of catecholamines. We used an indium-tin oxide (ITO) film as the oxidation electrode of the IDAE because the ITO was able to suppress response currents from L-ascorbic acid (AA) and uric acid (UA), which are major electroactive interferents in biological fluids. However, the ITO film also suppresses the reduction of quinones including oxidized catecholamines. We developed a simple technique for fabricating our hetero IDAE, which also preserves the electrochemical properties of the ITO. When we compared hetero ITO-gold, homo ITO-ITO, and carbon-carbon IDAEs, we found that the hetero IDAE provided both high sensitivity and selectivity for DA detection. We achieved high selectivities for DA against AA and UA. The ratios of the response currents of AA and UA to DA were calculated as 6 and 5%, respectively.     

Substitution of transparent conducting oxide thin films for indium tin oxide transparent electrode applications

The present status and prospects for further development of reduced or indium-free transparent conducting oxide (TCO) materials for use in practical thin-film transparent electrode applications such as liquid crystal displays are presented in this paper: reduced-indium TCO materials such as ZnO-In₂O₃, In₂O₃-SnO₂ and Zn-In-Sn-O multicomponent oxides and indium-free materials such as Al- and Ga-doped ZnO (AZO and GZO). In particular, AZO thin films, with source materials that are inexpensive and non-toxic, are the best candidates. The current problems associated with substituting AZO or GZO for ITO, besides their stability in oxidizing environments as well as the non-uniform distribution of resistivity resulting from dc magnetron sputtering deposition, can be resolved. Current developments associated with overcoming the remaining problems are also presented: newly developed AZO thin-film deposition techniques that reduce resistivity as well as improve the resistivity distribution uniformity using high-rate dc magnetron sputtering depositions incorporating radio frequency power. In addition, stability tests of resistivity in TCO thin films evaluated in air at 90% relative humidity and 60 °C have demonstrated that sufficiently moisture-resistant AZO thin films can be produced at a substrate temperature below 200 °C when the film thickness was approximately 200 nm. However, improving the stability of AZO and GZO films with a thickness below 100 nm remains a problem.     

Modification of indium tin oxide electrodes with nucleic acids: detection of attomole quantities of immobilized DNA by electrocatalysis

Indium tin oxide electrodes were modified with DNA, and the guanines in the immobilized nucleic acid were used as a substrate for electrocatalytic oxidation by Ru(bpy)3(3+) (bpy = 2,2'-bipyridine). Nucleic acids were deposited onto 12.6-mm2 electrodes from 9:1 DMF/water mixtures buffered with sodium acetate. The DNA appeared to denature in the presence of DMF, leading to adsorption of single-stranded DNA. The nucleic acid was not removed by vigorous washing or heating the electrodes in water, although incubation in phosphate buffer overnight liberated the adsorbed biomolecule. Acquisition of cyclic voltammograms or chronoamperomograms of Ru(bpy)3(2+) at the modified electrodes produced catalytic signals indicative of oxidation of the immobilized guanine by Ru(III). The electrocatalytic current was a linear function of the extent of modification with a slope of 0.5 microA/pmol of adsorbed guanine; integration of the current-time traces gave 2.2+/-0.4 electrons/guanine molecule. Use of long DNA strands therefore gave steep responses in terms of the quantity of adsorbed DNA strand. For example, electrodes modified with a 1497-bp PCR product from the HER-2 gene produced detectable catalytic currents when as little as 550 amol of strand was adsorbed, giving a sensitivity of 44 amol/mm2.     

Ultrasensitive DNA detection using oligonucleotide-silver nanoparticle conjugates

Oligonucleotide-gold nanoparticle (OGN) conjugates are powerful tools for the detection of target DNA sequences due to the unique properties conferred upon the oligonucleotide by the nanoparticle. Practically all the research and applications of these conjugates have used gold nanoparticles to the exclusion of other noble metal nanoparticles. Here we report the synthesis of oligonucleotide-silver nanoparticle (OSN) conjugates and demonstrate their use in a sandwich assay format. The OSN conjugates have practically identical properties to their gold analogues and due to their vastly greater extinction coefficient both visual and absorption analyses can occur at much lower concentrations. This is the first report of OSN conjugates being successfully used for target DNA detection and offers improved sensitivity which is of interest to a range of scientists.     

Selective release of DNA from the surface of indium-tin oxide thin electrode films using thiol-disulfide exchange chemistry

A new challenge in biointerfacial science is the development of dynamic surfaces with the ability to adjust and tune the chemical functionality at the interface between the biological and nonbiological entities. In this paper we describe fabrication of indium-tin oxide (ITO) electrodes and the design of a ligand that can be switched to enable selectively controlled interactions with DNA. Tailoring the surface composition of the ITO electrode to optimize its optical and electrical properties was also studied. The surface attachment chemistry investigated utilizes thiol-disulfide exchange chemistry. This chemistry involved the covalent attachment of a thiol-functionalized silane anchor to a hydroxyl-activated ITO electrode surface. Subsequent reaction with 2-(2-pyridinyldithio)ethanamine hydrochloride formed the disulfide bridge and provided the terminal amine group, which facilitates addition of a cross-linker. DNA was then covalently bound to the cross-linker, and hybridization with the complementary Cy3-labeled target DNA was achieved. Selective release of the attached DNA was demonstrated by both chemical and electrical reduction of the disulfide bond. The surface chemistry was then recycled, and rehybridization of the target DNA was achieved. The ability to control specific release of biomolecules has applications for the development of novel biosensor platforms and a range of medical devices.     

Influence of polyvinylpyrrolidone on properties of flexible electrically conducting indium tin oxide nanoparticle coatings

The influence of the organic film agent polyvinylpyrrolidone (PVP) on the electrical conductivity of indium tin oxide (ITO) nanoparticle coatings on polyethyleneterephthalate films was investigated. The ITO/PVP nanocomposite coatings show a decrease of the specific resistance with increasing PVP content up to 40 vol.%, whereas for higher PVP contents the specific resistance increases. The lowest specific resistance of 6 Ω cm is almost 20 times lower than that of a pure ITO nanoparticle coating. Annealing at 200 °C leads to a further decrease of the specific resistance for all volume fractions of PVP. Specific resistances of 0.5 Ω cm could be achieved for PVP contents of 33–40 vol.%. In addition, the PVP has a strong influence on the electrical conductivity of ITO/PVP coatings under bending which was investigated using a specially constructed device for the application of various bending loads. The ITO/PVP nanocomposite films show a significant lower increase of the sheet resistance under oscillatory bending compared to pure ITO nanoparticle coatings. However, the transmission in the visible range of ITO/PVP nanocomposites decreases with increasing PVP content up to 40 vol.%.     

Characterization and photocatalytic activity of nanostructured indium tin oxide thin-film electrode for azo-dye degradation

Photocatalytically active indium tin oxide thin film electrodes were prepared by electron beam evaporation technique onto a glass substrate having thickness 120 nm. Degradation of reactive dye yellow direct 42 has been performed using photoeletrocatalysis. A biased potential is applied across indium tin oxide photoelectrode illuminated by UV light. The best experimental conditions were found to be dye concentration 1.0 × 10^− 5 mol L^− 1, pH 5.25 and 0.5 mol L^− 1 NaCl as supporting electrolyte when the photoelectrode was biased at + 0.5 V versus saturated calomel electrode. The effects of other electrolytes, dye concentration, pH solution, electrode annealing temperature and applied potentials have been also investigated and are discussed. Several common inorganic salts Na₂SO₄, Na₂CO₃, NaNO₃ and NaCl were chosen to act as supporting electrolytes, which was added into the dye solution. It is shown that the charge-transfer resistance of photoanode can be calculated by the analysis of its electrochemical impedance spectroscopy, and the photoelectrocatalytic degradation rate of yellow direct 42 was inversely proportional to the value of charge-transfer resistance of photoelectrodes at different pH. The value of charge-transfer resistance is smaller, the higher its photoelectro-activity is.     

All-solid-state reflectance-type electrochromic devices using iridium tin oxide film as counter electrode

We prepared an all-solid-state reflectance-type electrochromic device (ECD), consisting of the following five layers: Al/WO₃/Ta₂O₅/Ir_xSn_1 − xO₂/ITO. Using RF ion plating, we prepared a film containing dispersed iridium oxide in a tin oxide matrix; this film acts as the counter electrode in the all-solid-state ECD. Protons were used as coloration ions in the ECD. The size of the ECD was 150 cm², and the reflectance changed between more than 60% from 15%. The coloration and bleaching response times were less than a few seconds. We analyze the optical characteristics of the ECD, and report the results of a consecutive drive test and a high-temperature heat resistance test.     

Evaluation of the film formation and the charge transport mechanism of indium tin oxide nanoparticle films

The structure formation and charge transfer of thin nanoparticulate indium tin oxide (ITO) films prepared by dip-coating was studied as a function of stabilizer before and after annealing at different temperatures. The analysis of the film structure by optical methods revealed that it is a function of the stability. Suspensions containing an optimum stabilizer concentration of 0.1 mol/l resulted in densely packed films with a peak specific conductivity of 8.3 S cm^− 1 after annealing at 550 °C for 1 h in air and 121 S cm^− 1 after annealing in forming gas at 250 °C for 1 h, respectively. Furthermore, for the densely packed films fluctuation-induced tunnelling was found to be the dominant charge transport mechanism, whereas for the low density films a thermally activated charge transport was observed. That the films of maximum density showed a metallic charge transport behaviour at temperatures above 300 K indicated the optimal contact between ITO particles had been achieved.     

Potentiometric sensing of chemical warfare agents: surface imprinted polymer integrated with an indium tin oxide electrode

Rapid and specific recognition of methylphosphonic acid (MPA), the degradation product of nerve agents sarin, soman, VX, etc., was achieved with potentiometric measurements using a chemical sensor fabricated by a surface imprinting technique coupled with a nanoscale transducer, indium tin oxide (ITO). An octadecylsiloxane thin layer was covalently bound to the ITO-coated glass surface in the presence of MPA. After extraction of MPA, potentiometric measurements showed selective detection of MPA. The selectivity of the sensor has been tested on other alkylphosphonic acids, such as ethylphosphonic acid and propylphosphonic acid, as well as tert-butylphosphonic acid. The viability of the sensor in the presence of other chemical analogues, such as organophosphorus pesticides and herbicides, was investigated.