Oxidation at a solâgel composite electrode doped with a dirhodium-substituted polyoxometalate for amperometric detection of peptides separated by HPLC

Cox, James A.; Holmstrom, Scott D.; Tess, Mark E.

doi:10.1016/s0039-9140(00)00477-x

Cited by 15 publications

(17 citation statements)

References 18 publications

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“…Such cases are typified in the analysis of thiols (4,22,55,120,121,147) and nitric oxide (78 -83) (81)) are routinely used to improve the electrode performance. The basic mechanism through which these systems operate is detailed in Fig.…”

Section: Modified Surfacesmentioning

confidence: 99%

Advances in the Voltammetric Analysis of Small Biologically Relevant Compounds

Lawrence

Beckett

Davis

et al. 2002

Analytical Biochemistry

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Section: Modified Surfacesmentioning

confidence: 99%

Advances in the Voltammetric Analysis of Small Biologically Relevant Compounds

Lawrence

Beckett

Davis

et al. 2002

Analytical Biochemistry

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“…Because they are known to catalyze the electrochemical oxidation of biological compounds [37,38,43–45], this study employed RuOx and AuNP-Rh 2 PMo 11 as catalysts. The former is deposited from components with sizes at are well-below 10-nm, so it was anticipated that is can be used with both of the modified electrodes, whereas the size of the latter is on the 10-nm scale, making its incorporation into the pores formed by G4-PAMAM problematic.…”

Section: Resultsmentioning

confidence: 99%

“…The second factor, incorporation of electrochemical catalysts for the oxidation of phospholipids in GC | ormosil (10 nm) and GC | ormosil (50 nm) electrodes, was tested using AuNP-Rh 2 PMo 11 [37,38] and RuOx [43–45], as discussed in the previous section. The test compounds were PC and cardiolipin, CL.…”

Section: Resultsmentioning

confidence: 99%

“…In this study, dirhodium-substituted phosphomolybdic acid that was adsorbed to gold nanoparticles, AuNP-Rh 2 PMo 11 , was the test catalyst [37]. The Rh II,III couple mediates the oxidation of such species as phosphatidylcholine and biological compounds with thiol or disulfide functionalities [20,38]. When Rh 2 PMo 11 was used as a protecting group on AuNPs, there was evidence of synergism in the mediation of the oxidation of compounds such as methionine [37].…”

Section: Introductionmentioning

confidence: 99%

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Electrochemically assisted fabrication of size-exclusion films of organically modified silica and application to the voltammetry of phospholipids

Mehdi

Rutkowska

Kulesza

et al. 2013

J Solid State Electrochem

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Modification of electrodes with nm-scale organically modified silica films with pores diameters controlled at 10- and 50-nm is described. An oxidation catalyst, mixed-valence ruthenium oxide with cyano crosslinks or gold nanoparticles protected by dirhodium-substituted phosophomolybdate (AuNP-Rh2PMo11), was immobilized in the pores. These systems comprise size-exclusion films at which the biological compounds, phosphatidylcholine and cardiolipin, were electrocatalytically oxidized without interference from surface-active concomitants such as bovine serum albumin. 10-nm pores were obtained by adding generation-4 poly(amidoamine) dendrimer, G4-PAMAM, to a (CH3)3SiOCH3 sol. 50-nm pores were obtained by modifying a glassy carbon electrode (GC) with a sub-monolayer film of aminopropyltriethoxylsilane, attaching 50-nm diameter poly(styrene sulfonate), PSS, spheres to the protonated amine, transferring this electrode to a (CH3)3SiOCH3 sol, and electrochemically generating hydronium at uncoated GC sites, which catalyzed ormosil growth around the PSS. Voltammetry of Fe(CN)63− and Ru(NH3)63+ demonstrated the absence of residual charge after removal of the templating agents. With the 50-nm system, the pore structure was sufficiently defined to use layer-by-layer electrostatic assembly of AuNP-Rh2PMo11 therein. Flow injection amperometry of phosphatidylcholine and cardiolipin demonstrated analytical utility of these electrodes.

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“…The synthesis of Rh II -substituted polyoxometalates by first forming the lacunary structure by removing a metal and its terminal oxygen from phosphotungstic acid and then substituting dirhodium acetate to yield [(PO 4 )W 11 O 35 {Rh 2 (OAc) 2 }] 5- , Rh 2 PW 11 , has been described [18]. The Rh 2 PW 11 formed from this Keggin anion or the analogous molybdenum compound, Rh 2 PMo 11 , was demonstrated to catalyze the electrochemical oxidation of methionine and cystine [19], phosphatidylcholine [20], and various peptides [21]. …”

Section: Introductionmentioning

confidence: 99%

Preparation and electrocatalytic application of composites containing gold nanoparticles protected with rhodium-substituted polyoxometalates

Wiaderek¹,

Cox²

2011

Electrochimica Acta

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Substitution of a metal center of phosphomolybdate, PMo 12 O 40 3-(PMo 12 ), or its tungsten analogue with dirhodium(II) and subsequent stabilization of gold nanoparticles, AuNPs, with Rh 2 PMo 11 is demonstrated. The AuNP-Rh 2 PMo 11 mediates oxidations but adsorbs too weakly for direct modification of electrode materials. Stability in quiescent solution was achieved by modifying glassy carbon (GC) with 3-aminopropyltriethoxysilane (APTES) and then electrostatically assembling AuNP-Rh 2 PMo 11 . At GC|APTES|AuNP-Rh 2 PMo 11 , cyclic voltammetry showed the expected set of three reversible peak-pairs for PMo 11 in the range -0.2 to 0.6 vs (Ag/AgCl)/V and the reversible Rh II,III couple at 1.0 vs (Ag/AgCl)/V. The presence of AuNPs increased the current for the reduction of bromate by a factor of 2.5 relative to that at GC| Rh 2 PMo 11 , and the electrocatalytic oxidation of methionine displayed characteristics of synergism between the AuNP and Rh II . To stabilize AuNP-Rh 2 PMo 11 on a surface in a flow system, GC was modified by electrochemically assisted deposition of a sol-gel with templated 10-nm pores prior to immobilizing the catalyst in the pores. The resulting electrode permitted determination of bromate by flow-injection amperometry with a detection limit of 4.0 × 10 -8 mol dm -3 .

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Oxidation at a solâgel composite electrode doped with a dirhodium-substituted polyoxometalate for amperometric detection of peptides separated by HPLC

Cited by 15 publications

References 18 publications

Advances in the Voltammetric Analysis of Small Biologically Relevant Compounds

Advances in the Voltammetric Analysis of Small Biologically Relevant Compounds

Electrochemically assisted fabrication of size-exclusion films of organically modified silica and application to the voltammetry of phospholipids

Preparation and electrocatalytic application of composites containing gold nanoparticles protected with rhodium-substituted polyoxometalates

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Oxidation at a solâgel composite electrode doped with a dirhodium-substituted polyoxometalate for amperometric detection of peptides separated by HPLC

Cited by 15 publications

References 18 publications

Advances in the Voltammetric Analysis of Small Biologically Relevant Compounds

Advances in the Voltammetric Analysis of Small Biologically Relevant Compounds

Electrochemically assisted fabrication of size-exclusion films of organically modified silica and application to the voltammetry of phospholipids

Preparation and electrocatalytic application of composites containing gold nanoparticles protected with rhodium-substituted polyoxometalates

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Oxidation at a solâgel composite electrode doped with a dirhodium-substituted polyoxometalate for amperometric detection of peptides separated by HPLC