Determination of surface pK(a) of HS(CH2)(10)COOH SAMs using an electrochemical titration method

The self-assembled monolayer(SAM) of 11-mercaptoundecanoic acid [HS(CH2)(10)COOH] was formed on a gold electrode and the effect of the charge of end group on the electrochemical response of Fe(CN)(6)(3-) at the SAM modified electrode was studied by cyclic voltammetry. At high pH, when the -COOH groups are dissociated, the current of Fe(CN)(6)(3-) is suppressed; as the solution pH is lowered, the current of Fe(CN)(6)(3-) increases. The electrochemical titration curve was obtained by correlating the currents of Fe(CN)(6)(3-) to the different pH values of electrolyte, from which the surface pK(a) was obtained to be 3. 0+/-0. 2. Furthermore, the reason of small pK(a) value was explained using SAMs of different surface coverage.

Electrochemical behavior and electrocatalytic properties of ultrathin films containing silicotungstic heteropolyanion SiW12O404-

We describe here a controlled fabrication of ultrathin monolayer and multilayer films consisting of silicotungstic heteropolyanion SiW12O404- and a cationic polymer of quaternized poly(4-vinylpyridine) partially complexed with osmium bis(2,2'-bipyridine) on Au electrodes previously self-assembled with cysteamine monolayers based on layer-by-layer electrostatic interaction. The thus-forming monolayer and multilayer chemically modified electrodes are investigated by cyclic voltammetry on their electrochemical behavior and electrocatalytic properties. The composite ultrathin films exhibit remarkable electrocatalytic effects on the reduction of BrO3-, H2O2, and HNO2. The electrocatalytic effects on HNO2 reduction are enhanced with increasing layer number from 1 to 3 but level off with much thicker multilayers. The stability of the monolayer and multilayer films is also examined. (C) 2000 The Electrochemical Society. S0013-4651(99)04-057-4. All rights reserved.

A novel method for preparing ordered SnO2/TiO2 alternate nanoparticulate films

A novel method using LB films as precursors to prepare pure inorganic ordered film with periodic structure was developed. Surfactant-stabilized SnO2 nanoparticulate organosols and TiO2 nanoparticulate organosols were prepared and used as spreading solutions. Using LB technique, the good film-forming ability of the surfactant-stabilized SnO2 nanoparticles and TiO2 nanoparticles was confirmed by the determination of the pi -A isotherms. The surfactant-stabilized SnO2 and TiO2 nanoparticulate monolayers were fabricated on the water surface and then were transferred to solid substrates (CaF2, quartz, silicon, and so on) alternately, layer-by-layer. Then the as-deposited alternate LB film was treated at different temperatures. The as-deposited alternate LB film and the treated film were characterized by Fourier transform infrared spectroscopy, UV visible spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The results indicate that our method was successful. The as-deposited alternate LB film formed a periodic structure with a long spacing of 6.5 nm that was composed of SnO2 nanoparticles, TiO2 nanoparticles, and arachidic acid. The treated film composed of SnO2 nanoparticles and TiO2 nanoparticles formed a pure inorganic periodic structure with an ordered distance of 5.4 nm. (C) 2001 Academic Press.

Amplification of antigen-antibody interactions based on biotin labeled protein-streptavidin network complex using impedance spectroscopy

Antibody was covalently immobilized by amine coupling method to gold surfaces modified with a self-assembled monolayer of thioctic acid. The electrochemical measurements of cyclic voltammetry and impedance spectroscopy showed that the hexacyanoferrate redox reactions on the gold surface were blocked due to the procedures of self-assembly of thioctic acid and antibody immobilization. The binding of a specific antigen to antibody recognition layer could be detected by measurements of the impedance change. A new amplification strategy was introduced for improving the sensitivity of impedance measurements using biotin labeled protein- streptavidin network complex. This amplification strategy is based on the construction of a molecular complex between streptavidin and biotin labeled protein. This complex can be formed in a cross-linking network of molecules so that the amplification of response signal will be realized due to the big molecular size of complex. The results show that this amplification strategy causes dramatic improvement of the detection sensitivity of hIgG and has good correlation for detection of hIgG in the range of 2-10 mug/ml. (C) 2001 Elsevier Science B.V. All rights reserved.

Investigation of the model compounds at 4-aminobenzoic acid modified glassy carbon electrode by scanning electrochemical microscopy

In this paper, we studied the reactions of both potassium ferricyanide and hexaammineruthenium(III) chloride at a 4-aminobenzoic acid (4-ABA) modified glassy carbon electrode (GCE) by scanning electrochemical microscopy (SECM) in different pH solutions. The surface of the modified electrode has carboxyl groups, the dissociation of which are strongly dependent upon the solution pH values. The rate constant kb of the oxidation of ferrocyanide on the modified electrode can be obtained by fitting the experimental tip current-distance (I-T-d) curves with the theoretical values. The surface pK(a) of the 4-ABA modified GCE was estimated from the plot of standard rate constant k(o) versus the solution pH and is equal to 3.2, which is in good agreement with the reported result. The SECM approach curves for Ru(NH3)(6)(3+) both on the bare and the modified electrodes show similar diffusion control processes. These results can be explained by the electrostatic interactions between the modified electrode surface and the model compounds with different charges. (C) 2001 Elsevier Science BN. All rights reserved.

Controlled nucleation and growth of surface-confined gold nanoparticles on a (3-aminopropyl)trimethoxysilane-modified class slide: A strategy for SPR substrates

The thickness of the gold film and its morphology, including the surface roughness, are very important for getting a good, reproducible response in the SPR technique. Here, we report a novel alternative approach for preparing SPR-active substrates that is completely solution-based. Our strategy is based on self-assembly of the gold colloid monolayer on a (3-aminopropyl)trimethoxysilane-modified glass slide, followed by electroless gold plating. Using this method, the thickness of films can be easily controlled at the nanometer scale by setting the plating time in the same conditions. Surface roughness and morphology of gold films can be modified by both tuning the size of gold nanoparticles and agitation during the plating. Surface evolution of the Au film was followed in real time by UV-vis spectroscopy and in situ SPRS. To assess the surface roughness and electrochemical stability of the Au films, atomic force microscopy and cyclic voltammetry were used. In addition, the stability of the gold adhesion is demonstrated by three methods. The as-prepared Au films on substrates are reproducible and stable, which allows them to be used as electrodes for electrochemical experiments and as platforms for studying SAMs.

Mixed ion transfer analysis in redox processes of electroactive thin films

Electrochemical quartz crystal microbalance (EQCM) technique was used to measure the ion transfer in redox processes in electroactive organic thin films, such as self-assembled monolayer (SAM) (4-pyridyl hydroquinone, abbr. 4PHQ), multilayer based on SAM and conducting polymer film (here poly-(3,4-ethylenedioxythiophene), abbr. PEDOT). A mechanism of mixed ion transfer is developed and presented. Analysis of mixed ion transfer during redox processes successfully elucidates the deviation of oscillation frequency of the quartz crystal from theoretical expectation.

A new kind of potassium sensor based on capacitance measurement of mimic membrane

A novel type of potassium sensor based on the capacitance change of valinomycin-incorporated bilayer supported on a gold electrode has been developed and characterized. The lipid membrane was Formed by painted method and monitored simultaneously by capacitance variation. The capacitance of the electrode-supported membrane was found to be modulated by different concentrations of K+. Investigating the capacitance change allows a simple and specific technique for the measurement of potassium ion in solution. Especially, the homemade capacitance meter is, to our knowledge, used to monitor the bilayer membrane formation and detect K+ for the first time. It has been proved that this capacitance measurement is a very useful technique because it is simple and sensitive compared to the other methods.

Electrochemical behavior of heteropoly acid anions adsorbed in electrodes modified with mesoporous molecular sieve silica

Heteropoly acid H4SiW12O48 (denoted as SiW12) was assembled with the mesoporous materials MCM-41 modified with 3-aminopropyltriethoxysilane (APTES) (denote MCM-41((m))). The electrochemical behavior of SiW12/MCM-41((m)) complexes-based electrode indicated SiW12 anion was adsorbed by MCM-41((m)). In MCM-41((m)) electrode, large voltammetric waves, showing that the electrostatic bound ions adsorbed in MCM-41((m)) were electrochemically active. The potential application as amperometric sensors for nitrite is anticipated.

Technique for determination of gold electrode area and its application of characterization in self-assembling process

Underpotential deposition(UPD) of copper at polycrystal gold surface under different concentrations has been studied, and its reversibility and stability in high concentration (0.2M CuSO4+0.IM H2SO4) have been demonstrated by cyclic voltermmetry and EQCM. A Valid approach to determine the gold electrode area in presence of adsorbed species has been provided by using Cu UPD method. Further, the growth kinetics of decane thiol on gold has also been investigated based on such a Cu UPD technique.

Determination of surface pK(a) of SAM using an electrochemical titration method

A self-assembled monolayer (SAM) of 3-mercaptopropionic acid (HSCH2CH2COOH) was formed on a gold electrode. The effect of the charge of the end group on the electrochemical response of Fe(CN)(6)(3-) at the SAM modified electrode was studied by using cyclic voltammetry. At high pH, when the -COOH groups are dissociated, Fe(CN)(6)(3-) current is suppressed; as the solution pH is lowered, Fe(CN)(6)(3-) current increases. The electrochemical titration curve was obtained by correlating the currents to the different electrolyte pH values, from which the surface pK(a) was obtained to be 5.2+/-0.1. Furthermore, a calculation equation was presented to simulate the electrochemical titration. As comparison, the surface pK(a) was also measured by contact angle titration as 5.6+/-0.1. The surface pK(a) values determined by the two methods in our work are consistent and accurate.

A novel potentiodynamic method of electrochemical growth for layer-by-layer film formation based on electrostatic interaction

A novel method of electrochemical growth was developed for layer-by-layer film formation and proven more advantageous than the commonly used immersion growth in obtaining more uniform multilayer assemblies, as well as being able to proceed in salt-containing solutions without competitive adsorption from the salt ions. (C) 1999 Elsevier Science S.A. All rights reserved.

Particulate multilayers prepared from surfactant-stabilized SnO2 nanoparticles

Surfactant-stabilized SnO2 nanoparticulate organosol was prepared. The organosol mixed with arachidic acid was spread on water surfaces in a Langmuir-Blodgett (LB) balance. Surface pressure versus surface area isotherms were determined. The surfactant-stabilized SnO2 nanoparticulate monolayers were transferred, layer-by-layer by the LB technique, to solid substrates. Then the multilayers were characterized by Fourier transform IR spectroscopy, UV-visible spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The results indicate that the multilayer is composed of SnO2 nanoparticles and arachidic acid. It forms a Z-type periodic structure with a long spacing of 7.48 nm, i.e. a kind of three-dimensional superlattice. (C) 1999 Elsevier Science S.A. All rights reserved.

The progress in the method of immobilizing biomolecules for piezoelectric immunosensors

The working principle of piezoelectric mass sensor is generally introduced. Tbe recent progress about the method of immobilizing biomolecule, such as antigen, antibody etc. onto piezoelectric crystal surfaces has been reported, including the way of directly immobilizing biomolecules, and immobilizing them using protein A(or protein G), polymer, silianizition agent, SAM technique, LB monolayer technique etc.. At last, some recent trends of the field has been outlined.

Fabrication and characterization of heteropolyanion Langmuir-Blodgett films

The possibility of the formation of Langmuir-Blodgett (LB) films with dimethyldioctadecylammonium (DODA) after the addition of cobalt(II)-substituted Dawson-type tungstodiphosphate anion (briefed as (H2O)(CoP2W17O618-)-P-11) in the subphase has been explored. Marked modifications of the compression isotherms are observed when this anion is dissolved in the subphase, which demonstrates that the polyanions interact with the monolayers. LB films have been readily obtained from this system. The adsorption Fourier transform IR (FT IR) spectroscopy, atomic force microscopy (AFM), X-ray diffraction (XRD) and cyclic voltammetry (CV) have been used to investigate the morphological and molecular structure of the deposited film. The FT IR results showed the presence of the polyanion within the LB films, and the shift for its characteristic bands may be related to the presence of positively charged DODA. AFM measurement reveals that the LB films of DODA/(H2O)(CoP2W17O618)-P-II are regularly and uniformly deposited on the substrate. XRD experiments prove that the lamellar structure of the LB films of DODA/(H2O)(CoP2W17O618-)-P-II is well-defined. The LB films of DODA/(H2O)(CoP2W17O618-)-P-II immobilized onto an indium-oxide (ITO) glass, in aqueous solutions of pH 2.0-5.0, show quite facile redox reactions even for multilayers. All the experiments carried out in the present study suggest that the new materials of heteropolyanions can be formed by LB techniques and beneficial physicochemical properties of heteropolyanions can be maintained/enhanced through molecular-level design. (C) 1999 Elsevier Science S.A. All rights reserved.