Surface-Confined Monomers on Electrode Surfaces. 11. Electrochemical and Infrared Spectroscopic Characteristics of Aniline-Terminated Alkanethiol Monolayers on Au Electrochemically Treated in Nonaqueous Media

Schomburg, K. Cory; McCarley, Robin L.

doi:10.1021/la0010222

Cited by 16 publications

(12 citation statements)

References 50 publications

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“…The CV clearly shows oxidation and reduction peaks at +0.65 and +0.52 V (vs Ag/AgCl), respectively. The observed electrochemical behavior is quite similar to that obtained during the polymerization of aniline and ring-substituted anilines dissolved in acidic solutions. ,− The large currents observed at the maximum positive potential are due to the superposition of two distinct processes: one is electron transfer from poly(NDDEAEA), corresponding to the oxidation of the PANI film, and the other is electron transfer from the monomer, NDDEAEA, to the electrode, corresponding to the oxidation of NDDEAEA to produce a precursor of polyaniline formation. In order to investigate the stability of poly(NDDEAEA) films, the electropolymerized electrodes were dipped into a solution of HCl (0.75 M), and the CV was measured.…”

Section: Resultssupporting

confidence: 67%

Conjugated Polymers with Pendant Iniferter Units: Versatile Materials for Grafting

et al. 2011

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A novel compound N-(N 0 ,N 0 -diethyldithiocarbamoylethylamidoethyl)aniline (NDDEAEA) was synthesized and fully characterized. Conjugated poly(NDDEAEA), consisting of N-substituted polyaniline (PANI) backbones with dithiocarbamate ester pendant groups (which can act as iniferters), was synthesized by both chemical and electrochemical polymerization. UV-initiated living polymerization was utilized to graft styrene, methacrylic acid (MAA), lauryl methacrylate, and acrylamido-2-methylpropanesulfonic acid (AMPSA) onto the conjugated macroiniferter which had previously been deposited on various surfaces (glass, polypropylene, polystyrene, and gold electrodes). The resultant polymeric surfaces were characterized by static contact angle measurements, XPS, SEM, and AFM. This versatile new material can be used for creating materials with integrated functionalities (e.g., conductivity, molecular recognition, catalysis and controlled transport properties, etc.) for application in sensors and microfluidic devices and for the construction of patterned surfaces.

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Section: Resultssupporting

confidence: 67%

Conjugated Polymers with Pendant Iniferter Units: Versatile Materials for Grafting

et al. 2011

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“…Furthermore, they have shown that the electrochemical oxidation of 4-ATP at pH ≥ 6 does not yield the redox species giving a reversible redox response, which is distinct from the case of an acidic solution, probably due to the formation of electroinactive products . During the course of the present investigation, two reports appeared discussing the electrochemical oxidation of aniline-terminated alkanethiol monolayers in aqueous acidic and nonaqueous media . According to these reports, the electrochemical oxidation of an aniline-terminated alkanethiol monolayer results in the formation of polymer, dimer, and hydrolyzed dimer …”

Section: Introductionmentioning

confidence: 74%

“…During the course of the present investigation, two reports appeared discussing the electrochemical oxidation of aniline-terminated alkanethiol monolayers in aqueous acidic and nonaqueous media . According to these reports, the electrochemical oxidation of an aniline-terminated alkanethiol monolayer results in the formation of polymer, dimer, and hydrolyzed dimer …”

Section: Introductionmentioning

confidence: 97%

Electrochemical and in Situ FTIR Spectroscopic Investigation on the Electrochemical Transformation of 4-Aminothiophenol on a Gold Electrode in Neutral Solution

2001

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The electrochemical transformation of the self-assembled monolayer of 4-aminothiophenol (4-ATP) has been studied in neutral solution by means of electrochemical and in situ FTIR measurements, and the results are compared with those in acidic solution. The electrochemical transformation in neutral solution results in the formation of a surface-confined aniline dimer, 4‘-mercapto-N-phenylquinone diimine as in the case of acidic solution. The redox peak corresponding to the aniline dimer shifts by −56 mV while increasing the solution pH by 1 unit, suggesting that protons and electrons take part in the redox reaction in the ratio of 1 to 1. The surface coverage of the aniline dimer obtained in the neutral solution is relatively low ((1.3 ± 0.3) × 10-10 mol cm-2) when compared to that in 0.1 M HClO4 solution ((2.4 ± 0.3) × 10-10 mol cm-2). Very similar in situ FTIR spectral features were obtained in both acidic and neutral solutions, indicating that the reaction mechanism follows the same head-to-tail coupling in neutral solution as in the case of acidic solution. The electrochemical and FTIR spectroscopic studies of the model compound, N-phenyl-1,4-phenylene diamine, support the formation of aniline dimer on the electrode surface during the electrochemical transformation of 4-ATP in neutral and acidic solutions. The electroproduced diimine undergoes hydrolysis to yield the monoimine while holding the electrode at high positive potential.

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“…It has been demonstrated with a variety of systems that surface-confined monomers of conductive polymers can serve as nucleation sites for the chemical or electrochemical growth of conductive polymer films. Particular systems investigated include SAMs capped with pyrrole, [14][15][16][17][18][19][20][21][22] aniline, [23][24][25] and thiophene [26][27][28][29][30] monomers, with most of these studies having been done on silicon or gold substrates. The involvement of the surface-confined monomer units in the polymerization results in a strongly adhered, conductive polymer layer compared to what is achieved by electropolymerization from bulk solution onto an unmodified surface.…”

Section: Introductionmentioning

confidence: 99%

Growth and Morphology of Polythiophene on Thiophene-Capped Monolayers: 1. Single Component Monolayers

et al. 2002

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Thin polythiophene films were grown at a variety of oxidizing potentials by electrochemical polymerization on indium tin-oxide surfaces that were modified with a thiophene-capped, self-assembled monolayer (SAM) composed of 11-(3-thienyl)-undecyltrichlorosilane (3TUTS). The evolution of those growing films was tracked via cyclic voltammetry and infrared spectroscopy, and the surface morphology was probed with atomic force microscopy. To allow comparison, similar data were obtained for polythiophene films grown on bare indium tin-oxide (ITO) (no SAM). Our results show that 3TUTS layers can nucleate growth of polythiophene films at potentials below the oxidation potential of monomeric thiophene in solution, and the cyclic voltammetry signature is characteristic of a surface-confined, redox-reversible species; however, at these low potentials no polythiophene growth on the bare ITO electrodes is seen. At higher potentials where polythiophene growth is observed on both types of surfaces, an additional amount of charge corresponding to the amount of thiophene groups along the SAM is transferred across the SAM-modified electrodes. Although spectroscopic data reveal no differences in the films grown on bare and 3TUTS-modified ITO, atomic force microscopy results show that the latter class of films are more homogeneous, have lower roughness, and are denser than the corresponding film grown on bare ITO. We attribute this difference in the morphology of the films to the high nucleation density arising from the pendent thiophene rings of the monolayer.

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Surface-Confined Monomers on Electrode Surfaces. 11. Electrochemical and Infrared Spectroscopic Characteristics of Aniline-Terminated Alkanethiol Monolayers on Au Electrochemically Treated in Nonaqueous Media

Cited by 16 publications

References 50 publications

Conjugated Polymers with Pendant Iniferter Units: Versatile Materials for Grafting

Conjugated Polymers with Pendant Iniferter Units: Versatile Materials for Grafting

Electrochemical and in Situ FTIR Spectroscopic Investigation on the Electrochemical Transformation of 4-Aminothiophenol on a Gold Electrode in Neutral Solution

Growth and Morphology of Polythiophene on Thiophene-Capped Monolayers: 1. Single Component Monolayers

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