Association of electroactive counterions with polyelectrolytes. 2. Comparison of electrostatic and coordinative bonding to a mixed polycation-polypyridine

Kobayashi, Junya; Anson, Fred C.

doi:10.1021/j100159a089

Cited by 17 publications

(20 citation statements)

References 3 publications

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“…[1 -3] The chlorine atom in c position to silicon is readily displaced by many nucleophiles, such as ammonia, and amines, [4,5] nitrile, [6] thiols and sulfides, [7 -9] azide, [10] carboxylates, [11] phosphines and phosphites [12] and others. Siloxane polymers bearing 3-chloropropyl substituents are used for the synthesis of interesting organofunctional polymers via transformation of the reactive haloalkyl group.…”

Section: Introductionmentioning

confidence: 99%

Controlled Synthesis of Siloxane Polymers and Siloxane-Siloxane Block Copolymers with 3-Chloropropyl Groups Pendant to the Siloxane Chain

Fortuniak

Chojnowski²,

Sauvet³

2001

Macromol. Chem. Phys.

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Linear polysiloxanes bearing 3‐chloropropyl groups pendant to the polymer chain and containing a vinyl functional group at one chain end were synthesized by anionic ring polymerizations of 2,4,6‐tri(3‐chloropropyl)‐2,4,6‐trimethylcyclotrisiloxane, 1, and 2‐(3‐chloropropyl)‐2,4,4,6,6‐pentamethylcyclotrisiloxane, 2, initiated with butyl lithium or lithium silanolate in tetrahydrofuran. The polymerizations led to high yields of polymers with narrow molecular weight distributions. The precise functionalizations of the polymers were performed by a termination method quenching the polymerization by dimethylvinylchlorosilane. Diblock copolymers AB of narrow molecular weight distribution and a high topological purity were obtained by the sequential anionic copolymerization of hexamethylcyclotrisiloxane, D3, with monomers 1 and 2.

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Section: Introductionmentioning

confidence: 99%

Controlled Synthesis of Siloxane Polymers and Siloxane-Siloxane Block Copolymers with 3-Chloropropyl Groups Pendant to the Siloxane Chain

Fortuniak

Chojnowski²,

Sauvet³

2001

Macromol. Chem. Phys.

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“…octane to propylsilsesquioxane framework was confirmed by 13 C NMR and IR spectroscopy. The solid-state 13 C NMR spectrum and the respective assignments are shown in Figure 1, in which the peaks observed at 10, 16 and 68 ppm were attributed to C 1 , C 2 and C 3 carbon atoms of the n-propyl group. However, the peaks at 53 and 45 ppm were assigned to the C 4 and C 5 DABCO atoms, respectively.…”

Section: Synthesis and Characterization Of Al 2 O 3 /Sidbclmentioning

confidence: 85%

“…A solidstate 13 C NMR spectrum was obtained on a Bruker AC 300/P spectrometer at 75.4 MHz in the CP-MAS mode. Elemental analysis was also performed with a PerkinElmer 2400 series II elemental analyzer.…”

Section: Equipmentsmentioning

confidence: 99%

“…11,12 Besides, polycations prepared by attaching quaternized pyridine groups to a polysiloxane chain have proven to be reliable supporting material for immobilization of negatively charged electro active species. 13,14 Since this approach has provided effective attachments for electro active molecules the scope of this paper is to describe the immobilization of cobalt(II) tetrasulfonated phthalocyanine on alumina coated with 3-n-propyl-1-azonia-4-azabicyclo[2.2.2]octanechloride silsesquioxane polymer and its electrochemical behavior as modifier for a carbon paste electrode in electrocatalytic application. The coating of 3-n-propyl-1-azonia-4-azabicyclo[2.2.2] octane silsesquioxane chloride on alumina surface can be easily accomplished by mixing alumina particles with the polymer aqueous solution for a period of time, followed by solvent evaporation.…”

Section: Introductionmentioning

confidence: 99%

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Al2O3 coated with 3-n-propyl-1-azonia-4-azabicyclo[2.2.2]octane silsesquioxane chloride and its use for immobilization of cobalt(II) tetrasulfonated phthalocyanine in oxalic acid electrooxidation

Ramos

Arguello

Magosso

et al. 2008

J. Braz. Chem. Soc.

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Um polímero solúvel em água, preparado pelo método sol-gel e designado cloreto de 3-n-propil-1-azonia-4-azabiciclo[2.2.2]octano silsesquioxano, foi adsorvido sobre a superfície da alumina. Essa alumina recoberta com o polímero foi capaz de imobilizar efetivamente complexos de ftalocianina tetrassulfonada metalada com Co(II) como contra-íons. A ftalocianina de cobalto imobilizada dessa forma fica fortemente aderida sobre a superfície do cloreto de Al 2 O 3 /3-n-propil-1-azonia-4-azabiciclo[2.2.2]octano silsesquioxano. Além disso, quando incorporada a um eletrodo de pasta de carbono mostra uma boa resposta eletrocatalítica para a oxidação de ácido oxálico. Foi obtida uma relação linear (r = 0,998) para o gráfico de correntes de resposta obtidas por cronoamperometria e a concentração de ácido oxálico na faixa de 7.4 × 10 -5 a 9.1 × 10 -4 mol L A water-soluble polymer prepared by sol-gel process, 3-n-propyl-1-azonia-4-azabicyclo[2.2.2] octane silsesquioxane chloride, was adsorbed on alumina surface. This polymer-coated alumina was able to effectively immobilize cobalt(II) tetrasulfonated phthalocyanine complexes as counter ions. Cobalt phthalocyanine immobilized in this way is well and tightly adsorbed on Al 2 O 3 /3-npropyl-1-azonia-4-azabicyclo[2.2.2]octane silsesquioxane chloride surface. Furthermore, when incorporated to a carbon paste electrode showed a good electrocatalytic response toward the acid oxalic oxidation, making it a suitable electrode material. A linear relationship (r = 0.998) between the current responses obtained by chronoamperometric measurements and the oxalic acid concentration in the range of 7.4 × 10 -5 -9.1 × 10 -4 mol L -1 was observed. A detection limit of 18 µmol L -1 was also determined.

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“…[1][2][3][4][5][6] The present study is an extension of a previous one on poly-(acrylic acid) homopolymers. 6 A random copolymer of acrylic acid and acrylonitirle was synthesized and characterized.…”

mentioning

confidence: 83%

Association of Electroactive Counterions with Polyelectrolytes. 6. Electrostatic and Coordinative Binding of Ru^3+/2+ Centers to a Copolymer of Acrylic Acid and Acrylonitrile

Yasukawa

Anson

1996

J. Phys. Chem.

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A random copolymer of acrylic acid and acrylonitrile was prepared in which the functionality on the polymer chain consisted of 93% carboxylic acid groups, 4.1% nitrile groups, and 2.9% acid anhydride groups. The nitrile groups were used to coordinate Ru(NH 3 ) 5 2+ centers to the copolymer. The anionic carboxylate groups produced at pH values above ∼3.5 were used to bind Ru(NH 3 ) 6 3+ counterions to the resulting polyanionic copolymer. The electrochemical oxidation or reduction of the two redox centers bound to the copolymer were used to estimate diffusion coefficients for the copolymer. Reasonable agreement was obtained between the values obtained from both electroactive redox groups. The diffusion coefficient exhibited a strong dependence on pH that reflected changes in the structure of the copolymer as it was converted from its neutral to its polyanionic form. The rate of the reaction between the Ru(NH 3 ) 5 OH 2 2+ complex and the nitrile groups of the copolymer increased significantly with pH because electrostatic binding of the cation to the polyanionic copolymer increased the concentration of the complex in the vicinity of the nitrile groups. Adsorption of the copolymer on the surface of the electrodes interfered with the oxidation of Ru(NH 3 ) 5 2+ groups coordinated to the dissolved copolymer but not with Ru(NH 3 ) 6 3+ counterions electrostatically bound to the polyanion. A possible explanation for the contrasting behavior is suggested.In recent reports from this laboratory, the electrochemical behavior of electroactive counterions in aqueous solutions of a variety of water soluble polyelectrolytes has been described. [1][2][3][4][5][6] The present study is an extension of a previous one on poly-(acrylic acid) homopolymers. 6 A random copolymer of acrylic acid and acrylonitirle was synthesized and characterized. The copolymer contained a few nitrile groups interspersed along chains of poly(acrylic acid). The two functional groups (-COO -and -CN) available in this copolymer made it possible to obtain both electrostatic and coordinative binding of suitable metal complexes to the polyelectrolyte. When electroactive metal complexes were used, the resulting copolymer-metal complex molecules exhibited electrochemical responses which offered a simple and convenient means to estimate diffusion coefficients for polymers that are otherwise much more tedious to measure. Quantitative comparisons of the magnitude and pH dependence of the responses obtained from both electrostatically and coordinatively bound redox groups provided information about the diffusion coefficients and structures of the copolymer molecule in solution. One objective was to verify that polymer diffusion coefficients evaluated from the electrochemical responses of electrostatic or covalently attached redox groups were self-consistent. In addition, a kinetic study of the rate of the reaction between Ru(NH 3 ) 5 OH 2 2+ cations and nitrile groups of the copolymer revealed a significant rate enhancement when the reaction proceeds within the poly...

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Association of electroactive counterions with polyelectrolytes. 2. Comparison of electrostatic and coordinative bonding to a mixed polycation-polypyridine

Cited by 17 publications

References 3 publications

Controlled Synthesis of Siloxane Polymers and Siloxane-Siloxane Block Copolymers with 3-Chloropropyl Groups Pendant to the Siloxane Chain

Controlled Synthesis of Siloxane Polymers and Siloxane-Siloxane Block Copolymers with 3-Chloropropyl Groups Pendant to the Siloxane Chain

Al2O3 coated with 3-n-propyl-1-azonia-4-azabicyclo[2.2.2]octane silsesquioxane chloride and its use for immobilization of cobalt(II) tetrasulfonated phthalocyanine in oxalic acid electrooxidation

Association of Electroactive Counterions with Polyelectrolytes. 6. Electrostatic and Coordinative Binding of Ru^3+/2+ Centers to a Copolymer of Acrylic Acid and Acrylonitrile

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Association of electroactive counterions with polyelectrolytes. 2. Comparison of electrostatic and coordinative bonding to a mixed polycation-polypyridine

Cited by 17 publications

References 3 publications

Controlled Synthesis of Siloxane Polymers and Siloxane-Siloxane Block Copolymers with 3-Chloropropyl Groups Pendant to the Siloxane Chain

Controlled Synthesis of Siloxane Polymers and Siloxane-Siloxane Block Copolymers with 3-Chloropropyl Groups Pendant to the Siloxane Chain

Al2O3 coated with 3-n-propyl-1-azonia-4-azabicyclo[2.2.2]octane silsesquioxane chloride and its use for immobilization of cobalt(II) tetrasulfonated phthalocyanine in oxalic acid electrooxidation

Association of Electroactive Counterions with Polyelectrolytes. 6. Electrostatic and Coordinative Binding of Ru3+/2+ Centers to a Copolymer of Acrylic Acid and Acrylonitrile

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Association of Electroactive Counterions with Polyelectrolytes. 6. Electrostatic and Coordinative Binding of Ru^3+/2+ Centers to a Copolymer of Acrylic Acid and Acrylonitrile