Analytical Applications of Silica-Modified Electrodes -A Comprehensive Review

This article aims to review the electroanalytical applications of chemically modified electrodes involving silica and silica-containing matrices. After a brief introduction to silica chemistry, the implication of pure and grafted silicas in electrochemistry, as well as that of the silica-based materials originating from the sol-gel technology, will be discussed. The interest of silica-modified electrodes (SiO2-MEs) with respect to electroanalysis will be pointed out by means of several examples. In the last five years, successful applications of SiO2-MEs have been achieved. Among them, silica grafted with inorganic films or organic moieties was successfully applied to the selective preconcentration or the electrocatalytic detection of various analytes. Also, the ability of the sol-gel chemistry to encapsulate enzymes within a silica matrix without preventing its activity was exploited in the development of new amperometric biosensors. These promising fields are thought to lead to significant advances in the near future, because of the explosive growth in both the synthesis of novel mesoporous organically-modified silica-based materials and the huge development of sol-gel chemistry in tailoring and construction of new modified electrodes.

[1]  A. Gautier,et al.  Possible analytical application of laponite clay modified electrodes , 1994 .

[2]  M. Reetz,et al.  Efficient Heterogeneous Biocatalysts by Entrapment of Lipases in Hydrophobic Sol–Gel Materials , 1995 .

[3]  J. Besse,et al.  Anion-exchanging clay-modified electrodes: synthetic layered double hydroxides intercalated with electroactive organic anions , 1994 .

[4]  J. Hart,et al.  Sensing with chemically and biologically modified carbon electrodes. A review. , 1995, The Analyst.

[5]  A. Vlessidis,et al.  Effect of treatment of synthetic zeolite-polymer membranes on their electrochemical-potential response characteristics , 1991 .

[6]  J Gilby Electrochemical sensors a modern success story for an old idea , 1994 .

[7]  O. Lev,et al.  Wiring of Glucose Oxidase to Carbon Matrices VIA Sol-Gel Derived Redox Modified Silicate , 1996 .

[8]  W. Hertl,et al.  Adsorption on hydroxylated silica surfaces , 1969 .

[9]  A. Walcarius,et al.  In situ monitoring of copper(II) fixation on silica gel in aqueous ammonia by means of dielectric measurements and quantitative analysis of adsorbed species , 1998 .

[10]  M. A. R. Barrio,et al.  Voltammetric determination of pentachlorophenol with a silica gel-modified carbon paste electrode , 1992 .

[11]  J S Valentine,et al.  Encapsulation of proteins in transparent porous silicate glasses prepared by the sol-gel method. , 1992, Science.

[12]  D. Arrigan Tutorial review. Voltammetric determination of trace metals and organics after accumulation at modified electrodes , 1994 .

[13]  J. Pereira‐Ramos,et al.  Electrochemical behaviour of a silver-exchanged “mordenite”-type zeolite , 1983 .

[14]  V. Stará,et al.  Silica gel modified carbon composite electrodes , 1991 .

[15]  Joseph Wang,et al.  Metal-dispersed carbon paste electrodes , 1992 .

[16]  M. Yokoyama,et al.  Chemical modification of sol-gel-derived glass by a neutral carrier for ion sensors , 1996 .

[17]  J. Cox,et al.  Humidity-independent solid-state amperometric sensor for carbon monoxide based on an electrolyte prepared by sol-gel chemistry. , 1998, Analytical chemistry.

[18]  P. Ugo,et al.  Ion-exchange voltammetry at polymer-coated electrodes: Principles and analytical prospects , 1995 .

[19]  L. Kubota,et al.  A new sensor for perchlorate ion , 1993 .

[20]  P. Kulesza,et al.  Preparation and characterization of composite films of cobalt tetra(p-tolyl) porphyrin immobilized in zeolitic ruthenium oxide/cyanoruthenate microstructures for anodic electrocatalysis , 1988 .

[21]  D. Levy,et al.  Sol-gel processing of optical and electrooptical materials , 1995 .

[22]  W. Schuhmann,et al.  Carbon-Paste Electrodes with Incorporated Lactate Oxidase and Mediators , 1992 .

[23]  M. Chicharro,et al.  Ephedrine Determination in Human Urine Using a Carbon Paste Electrode Modified with C18 Bonded Silica Gel , 1994 .

[24]  T. Mallouk,et al.  Inorganic analogues of Langmuir-Blodgett films: adsorption of ordered zirconium 1,10-decanebisphosphonate multilayers on silicon surfaces , 1988 .

[25]  T. Titova,et al.  IR spectroscopic study of silica—triethylamine interaction , 1992 .

[26]  Deepak N. Kumar,et al.  Novel, Organically Doped, Sol–Gel‐Derived Materials for Photonics: Multiphasic Nanostructured Composite Monoliths and Optical Fibers , 1997 .

[27]  W. Stöber,et al.  Controlled growth of monodisperse silica spheres in the micron size range , 1968 .

[28]  R. Murray,et al.  CHEMICALLY MODIFIED ELECTRODES , 1977 .

[29]  Paras N. Prasad,et al.  Chemical Sensor Based on an Artificial Receptor Element Trapped in a Porous Sol-Gel Glass Matrix , 1993 .

[30]  L. Kubota,et al.  Preparation and characterization of Ti (IV) oxide grafted onto silica on a silica gel surface , 1991 .

[31]  D. Avnir,et al.  Properties of trypsin and of acid phosphatase immobilized in sol‐gel glass matrices , 1992, Biotechnology and applied biochemistry.

[32]  M. Smyth,et al.  Sol-gel based amperometric biosensor incorporating an osmium redox polymer as mediator for detection of L-lactate. , 1997, Talanta.

[33]  B. P. Sullivan,et al.  Electrocatalytic reduction of carbon dioxide by thin polymeric films containing metallic rhodium , 1989 .

[34]  R. D. Hamilton,et al.  Chemical methods of analysis for crystalline silica: A critical literature review , 1994 .

[35]  S. Dong,et al.  The application of chemically modified electrodes in analytical chemistry , 1989 .

[36]  N. L. Filho,et al.  Sorption and preconcentration of metal ions on silica gel modified with 2,5-dimercapto-1,3,4-thiadiazole , 1996 .

[37]  P. Hernández,et al.  Cyclic voltammetry of Tifluadom at a C18-modified carbon-paste electrode , 1990 .

[38]  Salvador Alegret,et al.  Determination of organophosphorus and carbamate pesticides using a biosensor based on a polishable, 7,7,8,8-tetracyanoquino-dimethane-modified, graphite—epoxy biocomposite , 1997 .

[39]  Hybrid Mesoporous Materials with Functionalized Monolayers , 1998 .

[40]  P. Audebert,et al.  Modified electrodes from hydrophobic alkoxide silica gels—Insertion of electroactive compounds and glucose oxidase , 1994 .

[41]  T. Mallouk,et al.  Structural characterization of multilayer metal phosphonate film on silicon using angular‐dependent x‐ray photoelectron spectroscopy , 1989 .

[42]  David Avnir,et al.  Biocatalysis by sol-gel entrapped enzymes , 1992 .

[43]  Joseph Wang,et al.  Dimethylglyoxime doped sol-gel carbon composite voltammetric sensor for trace nickel , 1997 .

[44]  H. Böttcher,et al.  Biosensor properties of glucose oxidase immobilized within SiO2 gels , 1997 .

[45]  M. Goicolea,et al.  Utilization of a silica-modified carbon paste electrode for the direct determination of todralazine in biological fluids , 1993 .

[46]  J. F. Arranz,et al.  Preconcentration and voltammetric determination of the herbicide metamitron with a silica-modified carbon paste electrode , 1997 .

[47]  Joseph Wang,et al.  Improved performance of carbon paste amperometric biosensors through the incorporation of fumed silica , 1994 .

[48]  Elizabeth Fátima Perez,et al.  Electrochemical Sensor for Hydrazine Based on Silica Modified with Nickel Tetrasulfonated Phthalocyanine , 1998 .

[49]  Chulhee Kim,et al.  Sol−Gel Method for the Matrix of Chloride-Selective Membranes Doped with Tridodecylmethylammonium Chloride , 1997 .

[50]  K. Shea,et al.  Aryl-bridged polysilsesquioxanes - New microporous materials , 1989 .

[51]  I. Uchida,et al.  Electrochemistry of polynuclear transition metal cyanides: Prussian blue and its analogues , 1986 .

[52]  Maria Fernanda Pimentel,et al.  Application of factorial design to improve a FIA system for penicillin determination , 1997 .

[53]  James N. Miller,et al.  Highlight. Sol–gel systems for biosensors , 1996 .

[54]  L. Kubota,et al.  Potentiometric study using chemically modified silica gel with pyridinium as membrane for ClO4− ions , 1995 .

[55]  Modeeparampil N. Kamalasanan,et al.  Electrochemical growth of polyaniline in porous sol-gel films , 1996 .

[56]  D. Brunel,et al.  MCM-41 type silicas as supports for immobilized catalysts , 1995 .

[57]  P. Kulesza,et al.  Solid-State Voltammetry — Analytical Prospects , 1998 .

[58]  T. Pinnavaia,et al.  Access in mesoporous materials: Advantages of a uniform pore structure in the design of a heavy metal ion adsorbent for environmental remediation , 1997 .

[59]  U. Narang,et al.  Removal of ribonucleases from solution using an inhibitor-based sol-gel-derived Biogel , 1995 .

[60]  Susumu Yoshikawa,et al.  Entrapment of Glucose Oxidase in Silica Gel by the Sol-Gel Method and Its Application to Glucose Sensor , 1992 .

[61]  Helmut K. Schmidt,et al.  New materials for contact lenses prepared from Si- and Ti-alkoxides by the sol-gel process , 1984 .

[62]  P. Audebert,et al.  Electrochemical probing of the activity of glucose oxidase embedded sol-gel matrixes , 1993 .

[63]  P. Audebert,et al.  Electrochemical probing of the sol–gel–xerogel evolution , 1991 .

[64]  O. Lev,et al.  Sol-gel derived, ferrocenyl-modified silicate-graphite composite electrode: Wiring of glucose oxidase , 1996 .

[65]  L. Hench,et al.  The sol-gel process , 1990 .

[66]  S. Cosnier,et al.  Sol-gel derived composite materials for the construction of oxidase/peroxidase mediatorless biosensors , 1997 .

[67]  Gunther A. P. Zaldivar,et al.  Structure and electrochemical property of the cobalt(II) hexacyanoferrate complex immobilized on Sn(IV) oxide coated on silica gel surface , 1994 .

[68]  P. Voort,et al.  Silylation of the silica surface a review , 1996 .

[69]  J. Wang,et al.  Sol-gel-derived gold composite electrodes. , 1997, Analytical chemistry.

[70]  S. Sampath,et al.  Renewable, reagentless glucose sensor based on a redox modified enzyme and carbon‐silica composite , 1996 .

[71]  N. Oyama,et al.  Catalysis of the electroreduction of hydrogen peroxide by montmorillonite clay coatings on graphite electrodes , 1986 .

[72]  P. Kulesza,et al.  Electrocatalysis at a novel electrode coating of nonstoichiometric tungsten (VI,V) oxide aggregates , 1988 .

[73]  P. Hernández,et al.  Voltammetric determination of methyl parathion, ortho, meta and para nitrophenol with a carbon paste electrode modified with C18 , 1993 .

[74]  S. Sampath,et al.  Sol-gel derived ceramic-carbon enzyme electrodes: Glucose oxidase as a test case , 1996 .

[75]  I. Uchida,et al.  Anion-exchanged clay (hydrotalcite-like compounds) modified electrodes , 1987 .

[76]  J. Leckie,et al.  Cation Binding Predictions of Surface Complexation Models: Effects of pH, Ionic Strength, Cation Loading, Surface Complex, and Model Fit , 1997 .

[77]  Elizabeth Fátima Perez,et al.  Anodic oxidation of cysteine catalysed by nickel tetrasulphonated phthalocyanine immobilized on silica gel modified with titanium (IV) oxide , 1998 .

[78]  John P. Hart,et al.  Chemically modified, carbon-based electrodes and their application as electrochemical sensors for the analysis of biologically important compounds. A review , 1992 .

[79]  D. Avnir,et al.  Design and Properties of Enzymes Immobilized in Sol-Gel Glass Matrices , 1991 .

[80]  S. Bharathi Sol-gel-derived nanocrystalline gold-silicate composite biosensor , 1998 .

[81]  J. Lère-Porte,et al.  Trialkoxysilyl Mono-, Bi-, and Terthiophenes as Molecular Precursors of Hybrid Organic-Inorganic Materials , 1994 .

[82]  V. Stará,et al.  Chemically modified carbon paste and carbon composite electrodes , 1989 .

[83]  N. Tsubokawa,et al.  Preparation of a silica gel–carbon black composite by the sol–gel process in the presence of polymer-grafted carbon black , 1998 .

[84]  T. Spiro,et al.  Oxidative electrochemistry of electropolymerized metalloprotoporphyrin films , 1984 .

[85]  Y. Gushikem,et al.  Development of a chemically modified electrode based on carbon paste and functionalized silica gel for preconcentration and voltammetric determination of mercury(II) , 1993 .

[86]  J. E. Mark The Sol–Gel Route to Inorganic‐Organic Composites , 1996 .

[87]  Avelino Corma,et al.  From Microporous to Mesoporous Molecular Sieve Materials and Their Use in Catalysis. , 1997, Chemical reviews.

[88]  J. Li,et al.  Silica sol-gel immobilized amperometric enzyme electrode for peroxide determination in the organic phase , 1998 .

[89]  S. Alegret Rigid carbon–polymer biocomposites for electrochemical sensing. A review , 1996 .

[90]  M. Mahmoud Comparison of Metal Uptake Properties of Silica Gel-Bound Ion Exchangers and Some Amine Derivatives , 1996 .

[91]  David Avnir,et al.  Organic Chemistry within Ceramic Matrixes: Doped Sol-Gel Materials , 1995 .

[92]  Björn Persson,et al.  Selective detection in flow analysis based on the combination of immobilized enzymes and chemically modified electrodes , 1991 .

[93]  Joseph Wang,et al.  Tailoring the macroporosity and performance of sol-gel derived carbon composite glucose sensors , 1997 .

[94]  Jianjun Wei,et al.  Reagentless amperometric biosensor highly sensitive to hydrogen peroxide based on the incorporation of Meldola Blue, fumed-silica and horseradish peroxidase into carbon paste , 1997 .

[95]  L. Kubota,et al.  Adsorption of metal ions from ethanol on an iminosalicyl-modified silica gel , 1989 .

[96]  David Avnir,et al.  Enzymes and Other Proteins Entrapped in Sol-Gel Materials , 1994 .

[97]  Joseph Wang,et al.  Low-potential stable detection of β-NADH at sol–gel derived carbon composite electrodes , 1998 .

[98]  L. Kubota,et al.  A new amperometric biosensor for fructose using a carbon paste electrode modified with silica gel coated with Meldola's Blue and fructose 5-dehydrogenase , 1996 .

[99]  T. Kuwana,et al.  Electrochemical and Spectroscopic Studies of Metal Hexacyanometalate Films I . Cupric Hexacyanoferrate , 1983 .

[100]  M. Eckhoff,et al.  Electrochromism in the mixed-valence hexacyanides. 1. Voltammetric and spectral studies of the oxidation and reduction of thin films of Prussian blue , 1981 .

[101]  L. Gorton,et al.  Preliminary electrochemical study of phenothiazines and phenoxazines immobilized on zirconium phosphate , 1997 .

[102]  S. Lee,et al.  Humidity Dependence of Carbon Monoxide Oxidation Rate in a Nafion‐Based Electrochemical Cell , 1995 .

[103]  O. Lev,et al.  Direct synthesis of gold nanodispersions in sol–gel derived silicate sols, gels and films , 1997 .

[104]  W. Ford,et al.  Surface modification of colloidal silica , 1990 .

[105]  K. Carrado,et al.  Electrochemical Surface Analysis of Nonconducting Solids: Ferricyanide and Phenol as Electrochemical Probes of the Surfaces of Layered Double Hydroxide Anion‐Exchanging Clays , 1990 .

[106]  P. Audebert,et al.  Sol–gel–xerogel evolution investigated by electroactive probes in silica and transition-metal oxide based gels , 1992 .

[107]  L. Kubota,et al.  Factorial design optimization of redox properties of methylene blue adsorbed on a modified silica gel surface , 1997 .

[108]  J. Cox,et al.  ELECTROANALYTICAL METHODS BASED ON MODIFIED ELECTRODES: A REVIEW OF RECENT ADVANCES , 1996 .

[109]  Ovadia Lev,et al.  Sol-gel derived renewable-surface biosensors , 1995 .

[110]  N. Kostić,et al.  Photoinduced electron transfer from zinc cytochrome c to cationic ruthenium(III) complexes within silica glass prepared by the sol-gel method , 1997 .

[111]  Juan Li,et al.  Silica sol–gel immobilized amperometric biosensor for the determination of phenolic compounds , 1998 .

[112]  A. Yasuda,et al.  Mechanism of the Sensitivity of the Planar CO Sensor and Its Dependency on Humidity , 1992 .

[113]  M. Mahmoud,et al.  Metal uptake properties of silica gel-immobilized aminophenol and aminobenzoic acid and their application for heavy metal removal from sugar cane molasses , 1997 .

[114]  Joseph Wang,et al.  Sol-gel-derived cobalt phthalocyanine-dispersed carbon composite electrodes for electrocatalysis and amperometric flow detection , 1997 .

[115]  R. Murray,et al.  Application of a polymer solid electrolyte for the vapor-phase electrocatalysis of dioxygen reduction by some cobalt porphyrins , 1987 .

[116]  K. Shea,et al.  Arylsilsesquioxane gels and related materials. New hybrids of organic and inorganic networks , 1992 .

[117]  R. C. Hughes,et al.  Enzyme Electrodes with Glucose Oxidase Immobilized on Stöber Glass Beads , 1995 .

[118]  Lauro T. Kubota,et al.  Tin(IV) oxide grafted on a silica gel surface as a conducting substrate base for cupric hexacyanoferrate , 1991 .

[119]  J. Navarro-Laboulais,et al.  Temperature dependence of impedance spectra of Prussian Blue films deposited on ITO electrodes , 1998 .

[120]  T. W. Żerda,et al.  Diffusion and Preferential Adsorption of Sol-Gel Glass , 1991 .

[121]  W. Heineman,et al.  Spectroelectrochemical sensing based on multimode selectivity simultaneously achievable in a single device. 2. Demonstration of selectivity in the presence of direct interferences. , 1997, Analytical chemistry.

[122]  P. Audebert,et al.  Modified electrodes from organic-inorganic hybrid gels formed by hydrolysis-polycondensation of some trimethoxysilylferrocenes , 1996 .

[123]  R. Murray,et al.  Chemically modified tin oxide electrode , 1975 .

[124]  K. Balkus,et al.  Synthesis and Characterization of Cobalt-Complex Functionalized MCM-41 , 1997 .

[125]  Somnath Chandra,et al.  Glucose biosensor based on a sol-gel-derived platform , 1994 .

[126]  J. F. Arranz,et al.  Study of the electro-adsorptive behaviour of the herbicide nitralin by means of voltammetric techniques. , 1997, Talanta.

[127]  P. Johnson,et al.  On the use of polymerizing silica gel systems for the immobilization of trypsin , 1971 .

[128]  J. Devynck,et al.  Electrochemistry of chemically modified zeolites : discussion and new trends , 1994 .

[129]  Joseph Wang,et al.  Fumed-silica containing carbon-paste dehydrogenase biosensors , 1993 .

[130]  D. Rolison,et al.  Analytical implications of zeolites in overlayers at electrodes. , 1991, Talanta.

[131]  P. Atanasov,et al.  Mathematical modeling of an amperometric enzyme electrode based on a porous matrix of Stöber glass beads , 1996 .

[132]  P. Judeinstein,et al.  Hybrid organic–inorganic materials: a land of multidisciplinarity , 1996 .

[133]  Kingo Itaya,et al.  Spectroelectrochemistry and electrochemical preparation method of Prussian blue modified electrodes , 1982 .

[134]  J. Devynck,et al.  Zeolite-porphyrin modified electrodes , 1985 .

[135]  A. L. Crumbliss,et al.  The Use of Inorganic Materials to Control or Maintain Immobilized Enzyme Activity , 1994 .

[136]  Immobilization of Cobalt Complexes on Mesoporous MCM-41 Support Materials , 1996 .

[137]  K. Terada,et al.  Sorption of copper(II) by some complexing agents loaded on various supports , 1983 .

[138]  A. Walcarius,et al.  Silica-modified carbon paste electrode for copper determination in ammoniacal medium , 1997 .

[139]  Juan Li,et al.  Mediated amperometric glucose sensor modified by the sol-gel method , 1997 .

[140]  J. B. Higgins,et al.  A new family of mesoporous molecular sieves prepared with liquid crystal templates , 1992 .

[141]  P. Voort,et al.  Influence of water in the reaction of γ-aminopropyltriethoxysilane with silica gel. A Fourier-transform infrared and cross-polarisation magic-angle-spinning nuclear magnetic resonance study , 1992 .

[142]  R. Corriu,et al.  Solution Chemistry for the Elaboration of Solids , 1997 .

[143]  Joseph Wang,et al.  Modified electrodes for electrochemical sensors , 1991 .

[144]  O. Lev,et al.  Voltammetric studies of composite ceramic carbon working electrodes , 1994 .

[145]  T. Mallouk,et al.  Adsorption of ordered zirconium phosphonate multilayer films on silicon and gold surfaces , 1988 .

[146]  Alanah Fitch,et al.  Clays as architectural units at modified-electrodes , 1998 .

[147]  Vernon D. Neff,et al.  Electrochemical Oxidation and Reduction of Thin Films of Prussian Blue , 1978 .

[148]  S. Sampath,et al.  Inert metal-modified, composite ceramic-carbon, amperometric biosensors:  renewable, controlled reactive layer. , 1996, Analytical chemistry.

[149]  Jacques Livage,et al.  Optical detection of parasitic protozoa in sol-gel matrices , 1994, Optics & Photonics.

[150]  C. Mello,et al.  Experimental evidence of the chaotic regime in a salicylate biosensor , 1997 .

[151]  Rosanna Toniolo,et al.  Electroanalytical Sensors for Nonconducting Media Based on Electrodes Supported on Perfluorinated Ion-Exchange Membranes , 1997 .

[152]  T. King,et al.  Spectroscopic studies of sol-gel-derived organically modified silicates , 1996 .

[153]  Andreas Stein,et al.  Advanced zeolite materials science , 1989 .

[154]  Long Jiang,et al.  Improvement of enzymatic activity and lifetime of Langmuir-Blodgett films by using submicron SiO2 particles , 1992 .

[155]  J. Uytterhoeven,et al.  Infra-red spectroscopic study of the adsorption of amines on the A-type and B-type hydroxyls of an aerosil silica gel , 1971 .

[156]  S. Pons,et al.  Oxidative voltammetry of some tetraphenylporphyrins in the presence of nucleophiles leading to isoporphyrins , 1987 .

[157]  D. Avnir,et al.  Recent Developments in Organically Doped Sol-Gel Sensors: A Microns-Scale Probe; Successful Trapping of Purified Polyclonal Antibodies; Solutions to the Dopant-Leaching Problem , 1994 .

[158]  R. Corriu,et al.  Organic-inorganic hybrid materials : hydrolysis and polycondensation of 1,1'-bis-silylated ferrocene derivatives , 1993 .

[159]  Y. Gushikem,et al.  Cyclic Voltammetry Study of Hexacyanoferrate Complex Immobilized on Silica Gel Surface Chemically Modified With Pyridinium Ion , 1993 .

[160]  Y. Gushikem,et al.  Exchange properties of silica gel functionalized with pyridinium ion , 1987 .

[161]  A. Walcarius,et al.  In situ investigation of the ionisation of silica in aqueous ammonia by using a high frequency dielectric method. , 1997, Talanta.

[162]  A. Walcarius,et al.  Voltammetric in situ investigation of an MCM-41-modified carbon paste electrode—a new sensor , 1998 .

[163]  G. Rao,et al.  ELECTRODES MODIFIED WITH COBALT HEXACYANOFERRATE , 1991 .

[164]  K. Kalcher Chemically modified carbon paste electrodes in voltammetric analysis , 1990 .

[165]  M. Majda,et al.  Microporous aluminum oxide films at electrodes , 1985 .

[166]  J. Kauffmann,et al.  Modified Electrodes used to Elucidate Electrochemical Behaviors of Biologically Significant Molecules , 1988 .

[167]  A. N. Andrade,et al.  Electrochemical sensor for NADH based on Meldola's blue immobilized on silica gel modified with titanium phosphate , 1996 .

[168]  L. T. Zhuravlev Surface characterization of amorphous silica—a review of work from the former USSR , 1993 .

[169]  Chris W. Brown,et al.  Sol-gel glass as a matrix for chemical and biochemical sensing , 1997 .

[170]  G. Villemure,et al.  Anionic clay modified electrodes: electron transfer mediated by electroactive nickel, cobalt or manganese sites in layered double hydroxide films , 1997 .

[171]  Juan Li,et al.  Reagentless Amperometric Determination of Hydrogen Peroxide by Silica Sol–Gel Modified Biosensor , 1997 .

[172]  C. H. Rochester,et al.  IR studies of adhesion promoters. Part 2.—Adsorption of an alkyltrimethoxysilane and alkylamino-trimethoxysilane on silica at the solid/liquid interface , 1995 .

[173]  S. Sampath,et al.  3D organized self‐assembled monolayer electrodes: A novel biosensor configuration , 1997 .

[174]  R. Baldwin,et al.  Chemically modified electrodes in liquid chromatography detection: A review. , 1991, Talanta.

[175]  J Wang,et al.  Screen-printable sol-gel enzyme-containing carbon inks. , 1996, Analytical chemistry.

[176]  V. Neff Some Performance Characteristics of a Prussian Blue Battery , 1985 .

[177]  T. Golden,et al.  Metalloporphyrin chemically modified glassy carbon electrodes as catalytic voltammetric sensors , 1989 .

[178]  S. Cosnier,et al.  Mesoporous TiO2 films: New catalytic electrode fabricating amperometric biosensors based on oxidases , 1997 .

[179]  P. Audebert,et al.  Modified electrodes from organic-inorganic hybrid gels containing ferrocene units covalently bonded inside a silica network , 1994 .

[180]  P. Audebert,et al.  Molecular design of hybrid organic-inorganic materials with electronic properties , 1994 .

[181]  James A. Cox,et al.  Solid‐state amperometric sensors for gas phase analytes: A review of recent advances , 1997 .

[182]  L. Kubota,et al.  Electrochemical properties of iron phthalocyanine immobilized on titanium(IV) oxide coated on silica gel surface , 1995 .

[183]  Changzhi Zhao,et al.  Electrochemiluminescence Sensor Having a Pt Electrode Coated with a Ru(bpy)^3^2+-Modified Chitosan/Silica Gel Membrane , 1998 .

[184]  David Avnir,et al.  Biochemically active sol-gel glasses: The trapping of enzymes ☆ , 1990 .

[185]  Swee Ngin Tan,et al.  Silica sol-gel immobilized amperometric biosensor for hydrogen peroxide , 1996 .

[186]  P. Voort,et al.  The role of silanols in the modification of silica gel with aminosilanes , 1995 .

[187]  Y. Gushikem,et al.  Adsorption of metal ions from aqueous and ethanol solutions by silica gel functionalized with pyridinium ions , 1989 .

[188]  C. R. Martin,et al.  Sensors from polymer modified electrodes , 1986 .

[189]  Bruce Dunn,et al.  Bacteriorhodopsin encapsulated in transparent sol-gel glass: a new biomaterial , 1993 .

[190]  M. Berrettoni,et al.  Electrolyte-cation-dependent coloring, electrochromism and thermochromism of cobalt(II) hexacyanoferrate(III, II) films , 1995 .

[191]  H. Yamanaka,et al.  A new amperometric biosensor for salicylate based on salicylate hydroxylase immobilized on polipyrrole film doped with hexacyanoferrate , 1997 .

[192]  R. J. Barrio,et al.  Electrochemical detection of todralazine in high‐performance liquid chromatography , 1991 .

[193]  J. Moreau,et al.  New mixed organic-inorganic polymers: hydrolysis and polycondensation of bis(trimethoxysilyl)organometallic precursors , 1992 .

[194]  Marco Mascini,et al.  Analytical uses of immobilized biological compounds for detection, medical, and industrial uses , 1988 .

[195]  Bruce Dunn,et al.  Enzymatic activity of glucose oxidase encapsulated in transparent glass by the sol-gel method , 1992 .

[196]  Joseph Wang,et al.  Highly Selective Membrane-Free, Mediator-Free Glucose Biosensor , 1994 .

[197]  P. Searson,et al.  SOL-GEL SYNTHESIS AND CHARACTERIZATION OF CARBON/CERAMIC COMPOSITE ELECTRODES , 1998 .

[198]  R. Rosset,et al.  Determination of the two-phase equilibrium constants of copper(II)-modified silica gels used in liquid chromatography , 1985 .

[199]  I. Rubinstein,et al.  Electrochemical characterization and morphological studies of palladium-modified carbon ceramic electrodes , 1995 .

[200]  Joseph Wang,et al.  Remarkably selective metallized-carbon amperometric biosensors , 1995 .

[201]  M. Smyth,et al.  Sol–gel-based amperometric glucose biosensor incorporating an osmium redox polymer as mediator , 1996 .

[202]  J. Mackenzie Structures and properties of Ormosils , 1994 .

[203]  Paras N. Prasad,et al.  Affinity of antifluorescein antibodies encapsulated within a transparent sol-gel glass , 1993 .

[204]  Lauro T. Kubota,et al.  Electrochemical Properties of [Ru(edta)(H2O)]−Immobilized on a Zirconium(IV) Oxide-Coated Silica Gel Surface , 1996 .

[205]  Y. Mishima,et al.  Determination of hydrogen peroxide using a potassium hexacyanoferrate(III) modified titanium dioxide electrode , 1998 .

[206]  D. A. Russell,et al.  Optical Biosensing of Nitrate Ions Using a Sol–Gel Immobilized Nitrate Reductase , 1997 .

[207]  P. Kulesza,et al.  Electroanalysis with electrodes modified by inorganic films , 1991 .

[208]  C. Rausch,et al.  Electroactivity of Redox Probes Encapsulated within Sol-Gel-Derived Silicate Films , 1997 .

[209]  J. F. Arranz,et al.  Anodic voltammetric assay of the herbicide Metamitron on a carbon paste electrode , 1997, Fresenius' Journal of Analytical Chemistry.

[210]  Y. Lévy,et al.  Thin films of functionalized amorphous silica for immunosensors application , 1994 .

[211]  G. Rao,et al.  Modification of carbon electrodes with zinc hexacyanoferrate , 1997 .

[212]  S. Sjöberg Silica in aqueous environments , 1996 .

[213]  M. Ohtani,et al.  Direct electrochemistry of horse heart cytochrome c at the γ-alumina-coated electrode , 1993 .

[214]  L. Kubota,et al.  Use of ruthenium-(ethylenedinitrito)-tetraacetic acid monohydrate ion immobilized on zirconium(IV) oxide coated silica gel surface as an amperometric sensor for oxygen in water , 1995 .

[215]  F. Bedioui Zeolite-encapsulated and clay-intercalated metal porphyrin, phthalocyanine and Schiff-base complexes as models for biomimetic oxidation catalysts: an overview , 1995 .

[216]  G. Cha,et al.  Chloride-selective membranes prepared with different matrices including polymers obtained by the sol–gel method , 1998 .

[217]  J. Mackenzie Sol-Gel Optics III , 1994 .

[218]  R. Murray,et al.  Microporous glass films as support media for electroactive films on electrodes , 1987 .

[219]  Hongyuan Chen,et al.  The electrochemical characteristics of an inorganic monolayer film modified gold electrode and its molecular recognition of alkali metal cation , 1997 .

[220]  W. Heineman,et al.  Electrochemical Behavior of Graphite Electrodes Modified by Spin-Coating with Sol−Gel-Entrapped Ionomers , 1997 .

[221]  C. Hsueh,et al.  Permselectivities and ion-exchange properties of organically modified sol-gel electrodes , 1997 .

[222]  Kathryn S. Alber,et al.  Electrochemistry in solids prepared by sol-gel processes , 1997 .

[223]  M. Reetz,et al.  Characterization of hydrophobic sol-gel materials containing entrapped lipases , 1996 .

[224]  L. Kubota,et al.  Immobilized ferrocene and glucose oxidase on titanium(IV) oxide grafted onto a silica gel surface and its application as an amperometric glucose biosensor , 1996 .

[225]  Jean-Michel Kauffmann,et al.  Sensors based on carbon paste in electrochemical analysis: A review with particular emphasis on the period 1990–1993 , 1995 .

[226]  Kang Sun,et al.  Biosensing of hydrogen peroxide at carbon paste electrode incorporating N-methyl phenazine methosulphate, fumed-silica and horseradish peroxidase , 1997 .

[227]  C. Lanczycki,et al.  Voltammetric Response of Zeolite‐Modified Electrodes , 1988 .

[228]  D. Rolison Zeolite-modified electrodes and electrode-modified zeolites , 1990 .

[229]  A F Collings,et al.  Biosensors: recent advances , 1997 .

[230]  M. Smyth,et al.  Development of a sol-gel enzyme inhibition-based amperometric biosensor for cyanide , 1997 .

[231]  J. Sonnefeld,et al.  Aminopolysiloxane gels: production and properties , 1996 .

[232]  D. Rolison,et al.  Electrogenerated coatings containing zeolites , 1984 .

[233]  S. Sampath,et al.  Sol−Gel Materials in Electrochemistry , 1997 .

[234]  Lo Gorton,et al.  Carbon paste electrodes modified with enzymes, tissues, and cells , 1995 .

[235]  H. Damme,et al.  Hydroxyls of silica powders , 1990 .

[236]  J. Kulys,et al.  Chemically modified electrodes for the determination of sulphydryl compounds , 1991 .

[237]  Yen Wei,et al.  Large‐Area Electrochromic Coatings Composites of Polyaniline and Polyacrylate‐Silica Hybrid Sol‐Gel Materials , 1996 .

[238]  L. Kubota,et al.  Cyclic voltammetry studies of copper and nickel hexacyanoferrate immobilized on a silica gel surface coated with titanium(IV) oxide , 1993 .

[239]  G. Maciel,et al.  Characterization of silanol reactivity and acidity on octadecyl-bonded chromatographic supports by29Si solidstate nuclear magnetic resonance spectroscopy and surface titration , 1985 .

[240]  D. Rolison The intersection of electrochemistry with zeolite science , 1994 .

[241]  M. Berrettoni,et al.  Spectroelectrochemical characterization of cobalt hexacyanoferrate films in potassium salt electrolyte , 1998 .

[242]  A. Fitch Clay-Modified Electrodes: A Review , 1990 .

[243]  Bruce Dunn,et al.  Sol-gel encapsulation methods for biosensors , 1994 .

[244]  K R Rogers,et al.  Sol-gel-derived thick-film amperometric immunosensors. , 1998, Analytical chemistry.

[245]  Jerzy Zak,et al.  Electrooxidative catalysis using dispersed alumina on glassy carbon surfaces , 1982 .

[246]  Y. Gushikem,et al.  Adsorption of Cu(II), Zn(II), Cd(II), Hg(II) and Pb(II) from aqueous solutions on a 2-mercaptobenzimidazole-modified silica gel , 1990 .

[247]  H. Giesche Synthesis of monodispersed silica powders I. Particle properties and reaction kinetics , 1994 .

[248]  S. Sampath,et al.  Electrochemical oxidation of NADH on sol–gel derived, surface renewable, non-modified and mediator modified composite-carbon electrodes , 1998 .

[249]  L. Kubota,et al.  Cyclic voltammetric study of [Fe(CN)6]3-/4- immobilized on silica gel surface coated with titanium(IV) oxide , 1992 .

[250]  S. Sampath,et al.  Membrane-free, rhodium-modified, methyl silicate-graphite amperometric biosensor , 1997 .

[251]  M. Armond,et al.  Electrode modification by the sol-gel method , 1993 .

[252]  A. Walcarius Zeolite‐modified electrodes: Analytical applications and prospects , 1996 .

[253]  B. Buszewski,et al.  Influence of silica surface chemistry and structure on the properties, structure and coverage of alkyl-bonded phases for high-performance liquid chromatography , 1988 .

[254]  A. Bard,et al.  Clay-modified electrodes , 1983 .

[255]  Ovadia Lev,et al.  Sol-gel vanadium pentaoxide glucose biosensor , 1993 .

[256]  O. Lev,et al.  Sol-Gel-Derived Ceramic-Carbon Composite Electrodes: Introduction and Scope of Applications , 1994 .

[257]  Joseph Wang,et al.  Sol‐gel‐derived metal‐dispersed carbon composite amperometric biosensors , 1997 .

[258]  G. Rao,et al.  Electrochemical characteristics of thin films of nickel hexacyanoferrate formed on carbon substrates , 1991 .

[259]  L. Kubota,et al.  A Modified Carbon Paste Electrode with Silica Gel Coated with Meldola's Blue and Salicylate Hydroxylase as a Biosensor for Salicylate , 1996 .