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Applied Potential (applied + potential)
Selected AbstractsA Contribution to the Study of the Adsorption of s -Triazine Herbicides on Glassy Carbon Electrodes by Differential-Capacity MeasurementsELECTROANALYSIS, Issue 6 2010S. Pintado Abstract Measurements of differential capacity vs. potential have been made for a series of s -triazine herbicides at different concentrations. In all cases the decrease in capacity was independent of the applied potential, so the adsorption is also independent of the potential. From the measurements it can be established that the adsorption follows Langmuir type isotherms. Adsorption constants were obtained for the different herbicides at 25,°C (simetryn, simazine, terburyn and prometon) as well as those to simetryn at different temperatures, from which the adsorption enthalpy of this herbicide was calculated being its value of 17.5,kJ mol,1. [source] Electrocatalytic Oxidation of Glucose by the Glucose Oxidase Immobilized in Graphene-Au-Nafion BiocompositeELECTROANALYSIS, Issue 3 2010Kangfu Zhou Abstract Graphene was successfully prepared and well separated to individual sheets by introducing SO3,. XRD and TEM were employed to characterize the graphene. UV-visible absorption spectra indicated that glucose oxidase (GOx) could keep bioactivity well in the graphene-Au biocomposite. To construct a novel glucose biosensor, graphene, Au and GOx were co-immobilized in Nafion to further modify a glassy carbon electrode (GCE). Electrochemical measurements were carried out to investigate the catalytic performance of the proposed biosensor. Cyclic voltammograms (CV) showed the biosensor had a typical catalytic oxidation response to glucose. At the applied potential +0.4,V, the biosensor responded rapidly upon the addition of glucose and reached the steady state current in 5,s, with the present of hydroquinone. The linear range is from 15,,M to 5.8,mM, with a detection limit 5,,M (based on the S/N=3). The Michaelis-Menten constant was calculated to be 4.4,mM according to Lineweaver,Burk equation. In addition, the biosensor exhibits good reproducibility and long-term stability. Such impressive properties could be ascribed to the synergistic effect of graphene-Au integration and good biocompatibility of the hybrid material. [source] Construction of L -Lysine Sensor by Layer-by-Layer Adsorption of L -Lysine 6-Dehydrogenase and Ferrocene-Labeled High Molecular Weight Coenzyme Derivative on Gold ElectrodeELECTROANALYSIS, Issue 24 2008Haitao Zheng Abstract A ferrocene-labeled high molecular weight coenzyme derivative (PEI-Fc-NAD) and a thermostable NAD-dependent L -lysine 6-dehydrogenase (LysDH) from thermophile Geobacillus stearothermophilus were used to fabricate a reagentless L -lysine sensor. Both LysDH and PEI-Fc-NAD were immobilized on the surface of a gold electrode by consecutive layer-by-layer adsorption (LBL) technique. By the simple LBL method, the reagentless L -lysine sensor, with co-immobilization of the mediator, coenzyme, and enzyme was obtained, which exhibited current response to L -lysine without the addition of native coenzyme to the analysis system. The amperometric response of the sensor was dependent on the applied potential, bilayer number of PEI-Fc-NAD/LysDH, and substrate concentration. A linear current response, proportional to L -lysine concentration in the range of 1,120,mM was observed. The response of the sensor to L -lysine was decreased by 30% from the original activity after one month storage. [source] Photoelectrocatalytic Oxidation of NADH with Electropolymerized Toluidine Blue OELECTROANALYSIS, Issue 2-3 2007Yusuf Dilgin Abstract A poly(Toluidine Blue O) (poly-TBO) modified electrode was successfully prepared by repeated sweeping the applied potential from ,0.6 to +0.8,V (vs. SCE) on a glassy carbon electrode (GCE) in borate buffer solution at pH,9.1,containing 0.1,M NaNO3 and 0.4,mM Toluidine Blue O (TBO). The poly-TBO modified GCE shows electrocatalytic activity toward NADH oxidation in phosphate buffer solution at pH,7.0, with an overpotential of ca. 350,mV lower than that at the bare electrode. The photoelectrocatalytic oxidation of NADH at this electrode was also successfully investigated by using cyclic voltammetry and amperometry at constant potential. When the modified electrode surface was irradiated with a 250,W halogen lamp, a photoelectrocatalytic effect was observed for NADH oxidation and the current was increased about 2.2 times. The applied potential was selected at +100,mV for amperometric and photoamperometric detection of NADH. A linear calibration graph for NADH was obtained in the range between 1.0×10,5 and 1.0×10,3 M and between 5.0×10,6 and 1.0×10,3 M for amperometric and photoamperometric studies, respectively. The effect of some interfering compounds, such as ascorbic acid and dopamine on the electrocatalytic and photoelectrocatalytic oxidation of NADH was tested. [source] Organically Modified Sol-Gel/Chitosan Composite Based Glucose BiosensorELECTROANALYSIS, Issue 7 2003Xu Chen Abstract A new type of organically modified sol-gel/chitosan composite material was developed and used for the construction of glucose biosensor. This material provided good biocompatibility and the stabilizing microenvironment around the enzyme. Ferrocene was immobilized on the surface of glassy carbon electrode as a mediator. The characteristics of the biosensor were studied by cyclic voltammetry and chronoamperometry. The effects of enzyme-loading, buffer pH, applied potential and several interferences on the response of the enzyme electrode were investigated. The simple and low-cost glucose biosensor exhibited high sensitivity and good stability. [source] Investigation of the Effect of Different Glassy Carbon Materials on the Performance of Prussian Blue Based Sensors for Hydrogen PeroxideELECTROANALYSIS, Issue 3 2003Francesco Ricci Abstract Three different kinds of glassy carbon (GC-R, GC-K, GC-G) were equally pretreated, further modified with electrochemically deposited Prussian Blue and used as sensors for hydrogen peroxide at an applied potential of ,50,mV (vs. Ag|AgCl). Their performance was evaluated with respect to the following parameters: the coverage and electrochemistry of the electrodeposited Prussian Blue, the sensitivity and the lower limit of detection for hydrogen peroxide, and the operational stability of the sensors. GC-R showed the best behavior concerning the surface coverage and the operational stability of the electrodeposited Prussian Blue. For this electrode the sensitivity for hydrogen peroxide (10,,M) was 0.25,A/M cm2 and the detection limit was 0.1,,M. Scanning electron microscopy was used to study the surfaces of the three electrodes before and after the electrodeposition of Prussian Blue and to search for the reason for the three different behaviors between the different glassy carbon materials. The Prussian Blue modified GC-R was also used for the construction of a glucose biosensor based on immobilizing glucose oxidase in Nafion membranes on top of electrodeposited Prussian Blue layer. The operational stability of the glucose biosensors was studied in the flow injection mode at an applied potential of ,50,mV (vs. Ag|AgCl) and alternatively injecting standard solutions of hydrogen peroxide (10,,M) and glucose (1,mM) for 3,h. For the GC-R based biosensor a 2.8% decrease of the initial glucose response was observed. [source] Study on the enhancement of Ru(bpy)32+ electrochemiluminescence by nanogold and its application for pentoxyverine detectionELECTROPHORESIS, Issue 23 2005Yingju Liu Abstract In this work, CE separation with end-column Ru(bpy)32+ ECL detection for the quantitative determination of pentoxyverine was firstly performed. The experimental conditions, such as the applied potential, injection voltage, injection time, and the pH of separation buffer, were discussed in detail. Gold nanoparticles were found to enhance the ECL intensity at an appropriate volume ratio of nanogold with Ru(bpy)32+ but without changing their nanoproperties proved by transmission electron microscopy (TEM) and UV-vis spectra. The detection limits with or without nanogold were 6,nM and 0.6,,M, respectively. Successful separation of pentoxyverine, chlorpheniramine, and lidocaine was achieved. This method was also applied to monitor drug binding with HSA, and the binding constant for pentoxyverine was estimated as 1.8×103/M. [source] Tuning Specific Biomolecular Interactions Using Electro-Switchable Oligopeptide SurfacesADVANCED FUNCTIONAL MATERIALS, Issue 16 2010Chun L. Yeung Abstract The ability to regulate biomolecular interactions on surfaces driven by an external stimuli is of great theoretical interest and practical impact in the biomedical and biotechnology fields. Herein, a new class of responsive surfaces that rely on electro-switchable peptides to control biomolecular interactions on gold surfaces is presented. This system is based upon the conformational switching of positively charged oligolysine peptides that are tethered to a gold surface, such that bioactive molecular moieties (biotin) incorporated on the oligolysines can be reversibly exposed (bio-active state) or concealed (bio-inactive state) on demand, as a function of surface potential. The dynamics of switching the biological properties is studied by observing the binding events between biotin and fluorescently labeled NeutrAvidin. Fluorescence microscope images and surface plasmon resonance spectral data clearly reveal opposite binding behaviors when +0.3 V or ,0.4 V vs. SCE are applied to the surface. High fluorescence intensities are observed for an applied positive potential, while minimal fluorescence is detected for an applied negative potential. Surface plasmon resonance spectroscopy (SPR) results provided further evidence that NeutrAvidin binding to the surface is controlled by the applied potential. A large SPR response is observed when a positive potential is applied on the surface, while a negative applied potential induces over 90% reduction in NeutrAvidin binding. [source] Optical Measurements of Platinum Based Electrocatalysts for the Electrooxidation of Methanol,FUEL CELLS, Issue 1-2 2003K. Gruber Abstract In a combinatorial electrochemistry experiment quinine was used as a pH sensitive fluorescing indicator to detect the catalytic activity of methanol oxidation catalysts. During electrochemical experiments the surface of the electrode array was monitored with a CCD camera. The dependence of the intensity of the fluorescence on the applied potential was used as an analytical tool; to investigate the electrochemical performance of Pt based electrocatalysts, for the electrooxidation of methanol, in both short and long term tests. [source] Experimental Approaches for Controlling Current Flowing through Metal,Molecule,Metal Junctions,ADVANCED MATERIALS, Issue 10 2006E. Tran Abstract Two experimental approaches that enable control of current flow through metal,molecules,metal junctions are described. A number of studies using two-electrode metal,molecules,metal junctions have shown that the current between the electrodes depends on the structures of the incorporated molecules. When a tunneling mechanism dominates electron transport through organic molecules, the molecules behave similar to resistors with resistivities that can be controlled by changing the structure. Incorporation of molecules with increasing conjugation into Hg-based junctions increases the current flow dramatically. Alternatively, by using four-electrode electrochemical junctions that allow the potential of the electrodes to be controlled with respect to the energy levels of the incorporated molecules, it is possible to change the mechanism of electron transfer and produce abrupt increases in the current flow. These signals, analogous to solid-state diodes, are particularly significant for molecular electronics. Electrochemical junctions also permit prediction of the value of the applied potential at which the current will start taking off and to identify the mechanism of charge transport. New and recently published results obtained using junctions based on Hg electrodes in an "electrochemical" mode show that two junctions incorporating redox centers by different interactions behave as current switches, with the current flow dominated by different charge-transport mechanisms. [source] Removal of cadmium from dilute aqueous solutions with a rotating cylinder electrode of expanded metalJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 10 2003Javier M Grau Abstract The removal of cadmium from dilute solutions using a continuous undivided electrochemical reactor with a rotating cylinder cathode of expanded metal is analysed. The effects of cathodic applied potential, size and orientation of expanded metal meshes and inlet cadmium concentration were ascertained. The results show that cadmium can be removed from dilute solutions (inlet concentration range 5,50 mg dm,3) with a high fractional conversion of between 35 and 40% depending on the operating conditions. Thus a minimal residual cadmium concentration of 3 mg dm,3 was achieved. The specific energy consumption increases from 0.6 to 2 kWh mol,1 as the cadmium concentration decreases. Copyright © 2003 Society of Chemical Industry [source] Several basic and practical aspects related to electrochemical deionization of waterAICHE JOURNAL, Issue 3 2010Yaniv Bouhadana Abstract We examine water desalination processes based on the electrosorption of ions onto activated carbon electrodes (capacitive deionization, CDI). A flow-by operation mode was used (solutions flows within channels in the separator, parallel to the electrodes) in both continuous and stopped flow experiments. The different response of solutions containing more than 5000 ppm NaCl and dilute solutions (e.g., 1000 ppm NaCl) to the applied potential is discussed. The electrical current transients on potential steps were faster by two orders of magnitude than the resulting concentration transients due to the dynamics of these deionization processes and the properties of the cells used herein. Guidelines for the practical development of capacitive water deionization processes are discussed herein. It is assumed that for brackish water containing several thousands ppms of NaCl, CDI may be advantageous over competitive methods (e.g., reverse osmosis). © 2009 American Institute of Chemical Engineers AIChE J, 2010 [source] In situ Raman spectra of an NAD+ -modified silver electrode at various potentialsJOURNAL OF RAMAN SPECTROSCOPY, Issue 3 2004Haifeng Yang Abstract At various potentials, the in situ confocal Raman technique was employed to detect SERS signals from a silver electrode surface modified with NAD+ through a self-assembled monolayer (SAM) method. The SERS bands of the NAD+ molecule are much more sensitive to changes in the applied potential compared with experimental results reported previously. It is demonstrated in detail that the NAD+ molecules undergo reorientation at or desorption from the silver electrode surface with a potential shift from ,0.5 to 0.0 V vs a saturated calomel electrode based on a charge-transfer mechanism for explanation of the SERS signals. The effect of buffer electrolytes on the results of the SERS experiment was also investigated. Copyright © 2004 John Wiley & Sons, Ltd. [source] Copper-filled macroporous Si and cavity underneath for microchannel heat sink technologyPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 11 2008F. Zacharatos Abstract Thermal management in ICs becomes essential as integration density and total power consumption increase. The use of microchannels in high power density electronics cooling is a well-known technique for heat transfer. In this work we developed Cu-filled macroporous Si channels with a Cu-filled cavity underneath, which may be used as heat sinks in high power density electronics cooling. Macroporous Si is formed by electrochemical dissolution of bulk Si, while pore filling with copper is achieved by electro-deposition. Using appropriate design, the resulting composite material may be fabricated on selected areas on the silicon substrate for use as heat sink on Si. The surface area is defined by patterning. The macroporous Si structure is composed of either randomly distributed pores or pores arranged in two-dimensional (2-D) arrays, fabricated by pre-patterning the Si surface before anodization so as to form pore initiation pits. The pore size in this work was 5,m, while the porous layer and the cavity underneath had both a thickness of 40 ,m. Copper deposition proceeds first by filling the micro-cavity underneath the porous layer. This is achieved by linearly increasing the applied potential during electro-deposition. After full Cu-filling of the cavity, pore filling starts from the bottom of each pore and proceeds laterally, while no nucleation takes place on pore wall. In this way, homogeneous copper wires within pores may be fabricated. The Cu/Si composite material is appropriate for forming channels with improved heat transfer within the Si wafer. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Microstructure of nanopores in AAO templates favoring the growth of nickel nanowires by electrodepositionPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 12 2007Jong-Hyun Jeong Abstract Morphology of periodical nanoscale pores in AAO templates has been studied in relation with anodizing process, focusing on the growth of nickel nanowires by electrochemical deposition. The AAO templates were prepared by a two-step anodization process. The high purity aluminum plates were anodized in oxalic acid aqueous solution with variation of cell voltage. The pore size and interpore distance both increase with the applied potential. During the post treatment of barrier thinning, small-size pores with split-up structure at the tips are observed due to current-limited anodizing process (decreasing cell potential). The rectifying properties of the barrier layer allow the pores to be filled by nickel by AC electrodeposition. The nickel nanowires array shows the ferromagnetic properties with a preferred magnetic orientation along the wire axis. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Electroreduction of Oxygen by Cytochrome,c Oxidase Immobilized in Electrode-Supported Lipid Bilayer MembranesCHEMISTRY & BIODIVERSITY, Issue 9 2004Lianyong Su Cytochrome c oxidase is the terminal enzyme in mammalian respiration, and one of its main functions is to catalyze the reduction of oxygen under physiological conditions. Direct reduction of oxygen at electrodes requires application of substantial overpotentials. In this work, bovine cytochrome c oxidase has been immobilized in electrode-supported lipid bilayer membranes to investigate the electroreduction of oxygen under flow conditions. The effect that temperature, solution pH, and solution composition have on the reduction of oxygen by this novel enzyme-modified electrode is reported. Results indicate that the electroreduction of oxygen is most pronounced at low pH (6.4) and elevated temperature (38°). At an applied potential of ,350,mV vs. Ag/AgCl (1M KCl), a current density of ca. 7,,A/cm2 was obtained. The current responses obtained at these electrodes are stable over a period of ca. 10,14 days (10,15% decrease in response). The cytochrome c oxidase-modified electrodes described here could potentially be used for the direct electroreduction of oxygen to water in a biofuel cell. [source] Fast Determination of Clenbuterol and Salbutamol in Feed and Meat Products Based on Miniaturized Capillary Electrophoresis with Amperometric DetectionCHINESE JOURNAL OF CHEMISTRY, Issue 12 2007Qing-Cui CHU Abstract The fast separation capability of a novel miniaturized capillary electrophoresis with an amperometric detection (,CE-AD) system was demonstrated by determining clenbuterol and salbutamol in real samples. The effects of several factors such as the acidity and concentration of the running buffer, the separation voltage, the applied potential and the injection time on CE-AD were examined and optimized. Under the optimum conditions, the two , -agonists could be baseline separated within 60 s at a separation voltage of 2 kV in a 90 mmol/L H3BO3 -Na2B4O7 running buffer (pH 7.4), which was not interfered by ascorbic acid and uric acid. Highly linear response was obtained for above compounds over three orders of magnitude with detection limits ranging from 1.20×10,7 to 6.50×10,8 mol/L (S/N=3). This method was successfully used in the analysis of feed and meat products with relatively simple extraction procedures. [source] Photoelectrochemical Study of Nanostructured ZnO Thin Films for Hydrogen Generation from Water SplittingADVANCED FUNCTIONAL MATERIALS, Issue 12 2009Abraham Wolcott Abstract Photoelectrochemical cells based on traditional and nanostructured ZnO thin films are investigated for hydrogen generation from water splitting. The ZnO thin films are fabricated using three different deposition geometries: normal pulsed laser deposition, pulsed laser oblique-angle deposition, and electron-beam glancing-angle deposition. The nanostructured films are characterized by scanning electron microscopy, X-ray diffraction, UV-vis spectroscopy and photoelectrochemical techniques. Normal pulsed laser deposition produces dense thin films with ca. 200,nm grain sizes, while oblique-angle deposition produces nanoplatelets with a fishscale morphology and individual features measuring ca. 900 by 450,nm on average. In contrast, glancing-angle deposition generates a highly porous, interconnected network of spherical nanoparticles of 15,40,nm diameter. Mott-Schottky plots show the flat band potential of pulsed laser deposition, oblique-angle deposition, and glancing-angle deposition samples to be ,0.29, ,0.28 and +0.20,V, respectively. Generation of photocurrent is observed at anodic potentials and no limiting photocurrents were observed with applied potentials up to 1.3,V for all photoelectrochemical cells. The effective photon-to-hydrogen efficiency is found to be 0.1%, 0.2% and 0.6% for pulsed laser deposition, oblique-angle deposition and glancing-angle deposition samples, respectively. The photoelectrochemical properties of the three types of films are understood to be a function of porosity, crystal defect concentration, charge transport properties and space charge layer characteristics. [source] Spatially Selective Functionalization of Conducting Polymers by "Electroclick" ChemistryADVANCED MATERIALS, Issue 44 2009Thomas Steen Hansen Conducting polymer microelectrodes can electrochemically generate the catalyst required for their own functionalization by "click chemistry" with high spatial resolution. Interdigitated microelectrodes prepared from an azide-containing conducting polymer are selectively functionalized in sequence by two alkyne-modified fluorophores by control of the applied potentials. [source] Highly stable electrochromic polyamides based on N,N -bis(4-aminophenyl)- N,,N,-bis(4- tert -butylphenyl)-1,4-phenylenediamineJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 9 2009Sheng-Huei Hsiao Abstract A new triphenylamine-containing aromatic diamine monomer, N,N -bis(4-aminophenyl)- N,,N,-bis(4- tert -butylphenyl)-1,4-phenylenediamine, was synthesized by an established synthetic procedure from readily available reagents. A novel family of electroactive polyamides with di- tert -butyl-substituted N,N,N,,N,-tetraphenyl-1,4-phenylenediamine units were prepared via the phosphorylation polyamidation reactions of the newly synthesized diamine monomer with various aromatic or aliphatic dicarboxylic acids. All the polymers were amorphous with good solubility in many organic solvents, such as N -methyl-2-pyrrolidinone (NMP) and N,N -dimethylacetamide, and could be solution-cast into tough and flexible polymer films. The polyamides derived from aromatic dicarboxylic acids had useful levels of thermal stability, with glass-transition temperatures of 269,296 °C, 10% weight-loss temperatures in excess of 544 °C, and char yields at 800 °C in nitrogen higher than 62%. The dilute solutions of these polyamides in NMP exhibited strong absorption bands centered at 316,342 nm and photoluminescence maxima around 362,465 nm in the violet-blue region. The polyamides derived from aliphatic dicarboxylic acids were optically transparent in the visible region and fluoresced with a higher quantum yield compared with those derived from aromatic dicarboxylic acids. The hole-transporting and electrochromic properties were examined by electrochemical and spectro-electrochemical methods. Cyclic voltammograms of the polyamide films cast onto an indium-tin oxide-coated glass substrate exhibited two reversible oxidation redox couples at 0.57,0.60 V and 0.95,0.98 V versus Ag/AgCl in acetonitrile solution. The polyamide films revealed excellent elcterochemical and electrochromic stability, with a color change from a colorless or pale yellowish neutral form to green and blue oxidized forms at applied potentials ranging from 0.0 to 1.2 V. These anodically coloring polymeric materials showed interesting electrochromic properties, such as high coloration efficiency (CE = 216 cm2/C for the green coloring) and high contrast ratio of optical transmittance change (,T%) up to 64% at 424 nm and 59% at 983 nm for the green coloration, and 90% at 778 nm for the blue coloration. The electroactivity of the polymer remains intact even after cycling 500 times between its neutral and fully oxidized states. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2330,2343, 2009 [source] Synthesis, photoluminescence, and electrochromic properties of wholly aromatic polyamides bearing naphthylamine chromophoresJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 20 2006Guey-Sheng Liou Abstract A series of novel polyamides with pendent naphthylamine units having inherent viscosities of 0.15,1.02 dL/g were prepared via direct phosphorylation polycondensation from various diamines and a naphthylamine-based aromatic dicarboxylic acid, 1-[N,N -di(4-carboxyphenyl)amino]naphthalene. These amorphous polyamides were readily soluble in various organic solvents and could be cast into transparent and tough films. The aromatic polyamides had useful levels of thermal stability associated with high glass-transition temperatures (268,355 °C), 10% weight loss temperatures in excess of 480 °C, and char yields at 800 °C in nitrogen higher than 60%. These polymers showed maximum ultraviolet,visible absorption at 350,358 nm and exhibited fluorescence emission maxima around 435,458 nm in N -methyl-2-pyrrolidinone solutions with fluorescence quantum yields ranging from 0.4 to 15.0%. The hole-transporting and electrochromic properties were examined with electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the polyamide films cast onto an indium tin oxide coated glass substrate exhibited one oxidative redox couple around 1.08,1.16 V (oxidation onset potential) versus Ag/AgCl in an acetonitrile solution and revealed good stability of the electrochromic characteristics, with a color change from colorless to green at applied potentials ranging from 0 to 1.6 V. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6094,6102, 2006 [source] Adsorption of 4,4,-thiobisbenzenethiol on silver surfaces: surface-enhanced Raman scattering studyJOURNAL OF RAMAN SPECTROSCOPY, Issue 3 2008Yuling Wang Abstract Adsorption of 4,4,-thiobisbenzenethiol (4,4,-TBBT) on a colloidal silver surface and a roughened silver electrode surface was investigated by means of surface-enhanced Raman scattering (SERS) for the first time, which indicates that 4,4,-TBBT is chemisorbed on the colloidal silver surface as dithiolates by losing two H-atoms of the SH bond, while as monothiolates on the roughened silver electrode. The different orientations of the molecules on both silver surfaces indicate the different adsorption behaviors of 4,4,-TBBT in the two systems. It is inferred from the SERS signal that the two aromatic rings in 4,4,-TBBT molecule are parallel to the colloidal silver surface as seen from the disappearance of ,CH band (3054 cm,1), which is a vibrational mode to be used to determine the orientation of a molecule on metals according to the surface selection rule, while on the roughened silver electrode surface they are tilted to the surface as seen from the enhanced signal of ,CH. The orientation of the C-S bond is tilted with respect to the silver surface in both cases as inferred from the strong enhancement of the ,CS. SERS spectra of 4,4,-TBBT on the roughened silver electrode with different applied potentials reveal that the enhancement of 4,4,-TBBT on the roughened silver electrode surface may be related to the chemical mechanism (CM). More importantly, the adsorption of 4,4,-TBBT on the silver electrode is expected to be useful to covalently adsorb metal nanoparticles through the free SH bond to form two- or three- dimensional nanostructures. Copyright © 2007 John Wiley & Sons, Ltd. [source] | ||||||||||||||||