Abstract:Polymer thin films of poly(4-vinylpyridine), and copolymer of methyl methacrylate and methacrylic acid were prepared by electrolysis of an aqueous solution containing a surfactant with ferrocenyl moiety and corresponding polymer. The film thickness increased linearly with the amount of electricity. The morphology of the films was investigated by scanning electron microscopy.
“…The sharp break at 0.012 mM is indicative of the cmc of FPEG in the aqueous solution. The cmc value approximately coincides with the cmc (7 μM) in 0.2 M Li 2 SO 4 aqueous solution determined by the dye solubilization method 1h and with the cmc (13 and 15 μM) in pure water determined by surface tension and dye solubilization methods,1k respectively. 1 Surface tension vs the logarithm of the concentration of FPEG in +0.16 M NaCl aqueous solution.…”
Section: Resultssupporting
confidence: 77%
“…Γ FPEG and Γ FPEG + ). In the FPEG + structure, the hydrophilic ferrocenium ion is generated from the hydrophobic moiety (the ferrocenylalkyl group), and thus, the hydrophilic−lipophilic balance of FPEG greatly changes. 1f-i, The surface activity of FPEG + is much lower than that of FPEG. The lowered surface activity can be seen in the lowered free energy stabilization by adsorption (see Δ G ° ads , FPEG and Δ G ° ads , FPEG + in Table ).…”
Section: Resultsmentioning
confidence: 99%
“…Much attention has been focused on “redox-switched surfactants”. − The redox-switched surfactants form supramolecular assemblies like micelles and vesicles, as is seen in conventional surfactants. Supramolecular assemblies of the redox surfactants can be reversibly formed and disrupted, depending on the redox states of the redox moieties.…”
Section: Introductionmentioning
confidence: 99%
“…There have been numerous electrochemical attempts to study micelles. ,− ,15a Those studies include the micelles of electroinactive 4-11,13 and electroactive 1,3,4,12,15a surfactants. Kuwana et al have estimated the diffusion coefficient of the micelles of an electroinactive surfactant, Tween 20, by using a probe molecule, ferrocene, which is solubilized in the micelles.…”
Section: Introductionmentioning
confidence: 99%
“…Facci et al have reported changes of the adsorption states with composition of the electrolyte solutions. Saji et al1a have analyzed the specific diffusion process for diffusion-controlled electrochemical reactions of micelles consisting of a redox-active surfactant in terms of micelle/monomer disruption at the critical micelle concentration (cmc) in diffusion layers.…”
Electrochemical studies of a nonionic surfactant, R-(ferrocenylundecyl)-ω-hydroxy-oligo(ethylene oxide) (FPEG), have been conducted in 0.16 M NaCl aqueous solution at a glassy carbon electrode. The correlation between electrochemical responses and dissolved states has been examined in detail. Cyclic voltammograms (v ) 10 mV/s) of the FPEG solutions change with the concentration; below the critical micelle concentration (cmc), the voltammetric shape is of a typical surface-confined species, while above the cmc the diffusioncontrolled waves are superimposed at the cathodic side of the surface waves, and far above the cmc the voltammetric shape is of a typical diffusion-controlled species. FPEG in the aqueous solutions adsorbs onto the glassy carbon electrode surface to form a monolayer because of its surface activity. The adsorption isotherm has been represented by the Frumkin isotherm, which includes the repulsive interaction between the adsorbed FPEG molecules. Above the cmc, FPEG forms micelles. Chronoamperometrically determined apparent diffusion coefficients of the micellar solutions decrease with increasing concentrations. This has been interpreted in terms of the change in the diffusion species by disruption of the micelles into monomers at the cmc in the concentration gradient in diffusion layers. Cyclic voltammetric peak potentials of the micellar solutions shift toward the anodic side with the concentration. This behavior has been explained as the electrochemical reaction coupled with a preceding disassembled reaction of the micelles.
“…The sharp break at 0.012 mM is indicative of the cmc of FPEG in the aqueous solution. The cmc value approximately coincides with the cmc (7 μM) in 0.2 M Li 2 SO 4 aqueous solution determined by the dye solubilization method 1h and with the cmc (13 and 15 μM) in pure water determined by surface tension and dye solubilization methods,1k respectively. 1 Surface tension vs the logarithm of the concentration of FPEG in +0.16 M NaCl aqueous solution.…”
Section: Resultssupporting
confidence: 77%
“…Γ FPEG and Γ FPEG + ). In the FPEG + structure, the hydrophilic ferrocenium ion is generated from the hydrophobic moiety (the ferrocenylalkyl group), and thus, the hydrophilic−lipophilic balance of FPEG greatly changes. 1f-i, The surface activity of FPEG + is much lower than that of FPEG. The lowered surface activity can be seen in the lowered free energy stabilization by adsorption (see Δ G ° ads , FPEG and Δ G ° ads , FPEG + in Table ).…”
Section: Resultsmentioning
confidence: 99%
“…Much attention has been focused on “redox-switched surfactants”. − The redox-switched surfactants form supramolecular assemblies like micelles and vesicles, as is seen in conventional surfactants. Supramolecular assemblies of the redox surfactants can be reversibly formed and disrupted, depending on the redox states of the redox moieties.…”
Section: Introductionmentioning
confidence: 99%
“…There have been numerous electrochemical attempts to study micelles. ,− ,15a Those studies include the micelles of electroinactive 4-11,13 and electroactive 1,3,4,12,15a surfactants. Kuwana et al have estimated the diffusion coefficient of the micelles of an electroinactive surfactant, Tween 20, by using a probe molecule, ferrocene, which is solubilized in the micelles.…”
Section: Introductionmentioning
confidence: 99%
“…Facci et al have reported changes of the adsorption states with composition of the electrolyte solutions. Saji et al1a have analyzed the specific diffusion process for diffusion-controlled electrochemical reactions of micelles consisting of a redox-active surfactant in terms of micelle/monomer disruption at the critical micelle concentration (cmc) in diffusion layers.…”
Electrochemical studies of a nonionic surfactant, R-(ferrocenylundecyl)-ω-hydroxy-oligo(ethylene oxide) (FPEG), have been conducted in 0.16 M NaCl aqueous solution at a glassy carbon electrode. The correlation between electrochemical responses and dissolved states has been examined in detail. Cyclic voltammograms (v ) 10 mV/s) of the FPEG solutions change with the concentration; below the critical micelle concentration (cmc), the voltammetric shape is of a typical surface-confined species, while above the cmc the diffusioncontrolled waves are superimposed at the cathodic side of the surface waves, and far above the cmc the voltammetric shape is of a typical diffusion-controlled species. FPEG in the aqueous solutions adsorbs onto the glassy carbon electrode surface to form a monolayer because of its surface activity. The adsorption isotherm has been represented by the Frumkin isotherm, which includes the repulsive interaction between the adsorbed FPEG molecules. Above the cmc, FPEG forms micelles. Chronoamperometrically determined apparent diffusion coefficients of the micellar solutions decrease with increasing concentrations. This has been interpreted in terms of the change in the diffusion species by disruption of the micelles into monomers at the cmc in the concentration gradient in diffusion layers. Cyclic voltammetric peak potentials of the micellar solutions shift toward the anodic side with the concentration. This behavior has been explained as the electrochemical reaction coupled with a preceding disassembled reaction of the micelles.
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