Correlation between Permselectivity and Chemical Structure of Overoxidized Polypyrrole Membranes Used in Electroproduced Enzyme Biosensors

Palmisano, Francesco; Malitesta, Cosimino; Centonze, Diego; Zambonin, P. G.

doi:10.1021/ac00109a046

Cited by 143 publications

(81 citation statements)

References 29 publications

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“…This suggests that the mechanism of oxidation and polymerization processes at the initial step(s) of synthesis (formation of the Ppy onto the metal) is di †erent compared with the mechanism of polymer Ðlm growth onto the Ppy Ðlm itself. The imine-type nitrogen in overoxidized Ppy has also been observed by Palmisano et al 45 The theoretical studies of the oligomers of the oxidized pyrrole (1-dehydropyrrole) indicate strong dependence of the properties (conductivity) of the oligomer on the oxidative modiÐcation.46,47…”

Section: Chemical Composition Of the Polymer ðLmsmentioning

confidence: 60%

“…Furthermore, the selectivity and sensitivity of Ppy can be changed through electrochemical overoxidation of the polymer. 44,45 This also leads to a decrease in conductivity and electroactivity, which, as a rule, is considered to be highly undesirable. On the contrary, such a modiÐcation of Ppy Ðlms seems to be providing good corrosion protection.…”

Section: Chemical Composition Of the Polymer ðLmsmentioning

confidence: 99%

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An XPS and AFM study of polypyrrole coating on mild steel

Idla

Talo

Niemi

et al. 1997

Surf. Interface Anal.

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We have characterized electrically conductive polymer, polypyrrole (Ppy), films on mild steel with atomic force microscopy (AFM) and x‐ray photoelectron spectroscopy (XPS). The Ppy films were polymerized electrochemically from sodium p‐toluene sulphonate (ToS) water–ethanol solution. A very good corrosion protective effect of those films on mild steel has been observed previously. After drying in air, thin Ppy films (∽200 nm) were highly adhesive, whereas thicker films (∽7.5 μm) could easily be peeled off from the metal. All films had a nodular surface structure. Thin films were very smooth and their roughness increased with their thickness. The AFM study of the interface between the metal and the polymer showed areas of different morphology, which suggests that adhesive and cohesive failure of the polymer film occurs. A strong variation of the chemical composition at the interfacial layer was observed. A sulphur‐rich layer was formed at the interface, indicating that the counter‐anions (ToS) were accumulated on the surface of the metal. High‐binding energy iron and imine‐type nitrogen were detected in a thin Ppy film. Moreover, thin films were substantially overoxidized. The number of anions incorporated into the Ppy matrix varied as a function of film thickness: the ‘doping level’ was about 30% for thicker films and only 12% for thin ones. Nitrate counter‐anion‐containing Ppy films were also studied in some cases for comparison. © 1997 John Wiley & Sons, Ltd.

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Section: Chemical Composition Of the Polymer ðLmsmentioning

confidence: 60%

Section: Chemical Composition Of the Polymer ðLmsmentioning

confidence: 99%

An XPS and AFM study of polypyrrole coating on mild steel

Idla

Talo

Niemi

et al. 1997

Surf. Interface Anal.

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“…30 As a result, the two anodic peak potentials of DA and AA are well-separated, indicating high selectivity and sensitivity of the DNA-SWNT electrode.…”

Section: Resultsmentioning

confidence: 93%

DNA Functionalized Single-Walled Carbon Nanotubes for Electrochemical Detection

et al. 2005

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Single-walled carbon nanotubes (SWNTs) were effectively dispersed and functionalized by wrapping with single-stranded DNA (ssDNA). The ssDNA-SWNTs attach strongly on glass substrate and easily form a uniform film, making it possible for electrochemical analysis and sensing. The film was fabricated into a working electrode, which exhibited good electrochemical voltammetric properties, such as flat and wide potential window, well-defined quasi-reversible voltammetric responses, and quick electron transfer for a Fe(CN) 6 3-/Fe(CN) 6 4 system, indicating that the ssDNA-SWNTs film should be a good analytical electrode for electrochemical detection or sensing. This was demonstrated by highly selective and sensitive detection of a low concentration of dopamine in the presence of excess ascorbic acid.

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“…34 Details on the strategy adopted for optimization have been previously reported. 35 Quantification was performed by using peak areas; comparison between data from different elements was possible after correction (division) by empirically derived atomic sensitivity factors (uncertainty for atomic ratios of ¾10%).…”

Section: Measurements By Xpsmentioning

confidence: 99%

Surface (XPS, SIMS) chemical investigation on poly(pyrrole-3-acetic acid) films electrosynthesized on Ti and TiAlV substrates for the development of new bioactive substrates

Giglio

Calvano

Losito

et al. 2005

Surf. Interface Anal.

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Electropolymerization of pyrrole-3-acetic acid was performed by cyclic voltammetry on titanium and Ti90Al6V4 substrates with the aim of developing a multilayer structure for applications in advanced biomaterials. The polymeric films obtained were characterized by both XPS and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Information on the poly(pyrrole-3-acetic acid) (PPy-3-acetic) surface structure was achieved by a detailed XPS analysis of C 1s and N 1s signals. The number of COOH groups was quantified by XPS coupled to a chemical derivatization reaction in which esterification with trifluoroethanol was exploited so that the presence of fluorine (or the CF 3 component in C 1s spectra) could be used as a marker for COOH groups. As a result, it was found that more than 90% of the monomer units along PPy-3-acetic chains bear carboxylic functionalities, of which 60% are protonated and 40% are present as carboxylate groups. Some decarboxylation occurs with film ageing.The PPy-3-acetic films were also investigated by ToF-SIMS in the negative ion mode, thus obtaining, for the first time, interesting information on the structure of the top surface layers of a polymer belonging to the polypyrrole family. In particular, clusters of peaks related to PPy-3-acetic oligomers were detected and the decarboxylation phenomenon on top of the polymer surface was confirmed.

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Correlation between Permselectivity and Chemical Structure of Overoxidized Polypyrrole Membranes Used in Electroproduced Enzyme Biosensors

Cited by 143 publications

References 29 publications

An XPS and AFM study of polypyrrole coating on mild steel

An XPS and AFM study of polypyrrole coating on mild steel

DNA Functionalized Single-Walled Carbon Nanotubes for Electrochemical Detection

Surface (XPS, SIMS) chemical investigation on poly(pyrrole-3-acetic acid) films electrosynthesized on Ti and TiAlV substrates for the development of new bioactive substrates

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