Inclusion complexation of tetrathiafulvalene in cyclodextrins and bioelectroanalysis of the glucose-glucose oxidase reaction

Peter M. Schmidt; R. Stephen Brown; John H.T. Luong

doi:10.1016/0009-2509(95)00046-8

Inclusion complexation of tetrathiafulvalene in cyclodextrins and bioelectroanalysis of the glucose-glucose oxidase reaction

Peter M. Schmidt
, R. Stephen Brown
, John H.T. Luong

National Research Council of Canada

Research output: Contribution to journal › Article › peer-review

Abstract

Tetrathiafulvalene (TTF) forms water-soluble inclusion complexes with α-, hp-β- and γ-cyclodextrin (CD). Cyclic voltammetry (CV) has been performed at a stationary electrode to characterize these TTF:CD inclusion complexes. The CV analysis yielded average peak separations of 63 mV and diffusion limited currents, indicating completely reversible electron transfer. The half-wave potential (E_{1 2}) of the complex shifted to more positive values with increasing CD concentration, permitting use of a modified Nernst equation to estimate the complexation ratio and the equilibrium formation constant (K_form) of the complexes. The complexation ratio was determined as 1:2, 1:1 and 1:1 for TTF with α-CD, hp-β-CD and γ-CD, respectively. The K_form for these complexes was then estimated to be 5.44 × 10³ m⁶/kmol², 5.40 × 10³ m³/kmol and 0.141 × 10³ m³/kmol. The diffusion coefficients (D_o) for 1 mol/m³ TTF in α-CD varied from 4.44 × 10^-11 to 0.76 × 10^-11 m²/s as the α-CD concentration increased from 3 to 50 mol/m³. The D_o values for hp-β-CD varied from 12.9 × 10^-11 to 4.03 × 10^-11 m²/s over the same cyclodextrin range whereas those of γ-CD ranged from 2.20 × 10^-12 to 1.75 × 10^-12 m²/s. CV curves for TTF: hp-β-CD in the presence of glucose and GOx showed a large anodic current with no discernible peaks, indicating bioelectrocatalysis. The ratio of this current to the diffusion limited current was used to determine the second-order homogeneous rate constant k_s for the reaction with GOx, which demonstrated the efficiency of the inclusion complex as a mediator. The k_s value for 1 mol/m³ TTF decreased from 3.84 × 10⁵ to 1.04 × 10⁵ m³/kmol s with an increase in hp-β-CD concentration from 3 to 15 mol/m³. Extremely high diffusion and kinetic parameters in 3 mol/m³ CD solutions were due to insolubility of TTF at low CD concentrations, and indicated that the CD concentration must be maintained above this level.

Original language	English
Pages (from-to)	1867-1876
Number of pages	10
Journal	Chemical Engineering Science
Volume	50
Issue number	12
DOIs	https://doi.org/10.1016/0009-2509(95)00046-8
Publication status	Published - Jun 1995
Externally published	Yes

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@article{3f69e55baa9c4c66ac55c1d2fd20cc7e,

title = "Inclusion complexation of tetrathiafulvalene in cyclodextrins and bioelectroanalysis of the glucose-glucose oxidase reaction",

abstract = "Tetrathiafulvalene (TTF) forms water-soluble inclusion complexes with α-, hp-β- and γ-cyclodextrin (CD). Cyclic voltammetry (CV) has been performed at a stationary electrode to characterize these TTF:CD inclusion complexes. The CV analysis yielded average peak separations of 63 mV and diffusion limited currents, indicating completely reversible electron transfer. The half-wave potential (E 1 2) of the complex shifted to more positive values with increasing CD concentration, permitting use of a modified Nernst equation to estimate the complexation ratio and the equilibrium formation constant (Kform) of the complexes. The complexation ratio was determined as 1:2, 1:1 and 1:1 for TTF with α-CD, hp-β-CD and γ-CD, respectively. The Kform for these complexes was then estimated to be 5.44 × 103 m6/kmol2, 5.40 × 103 m3/kmol and 0.141 × 103 m3/kmol. The diffusion coefficients (Do) for 1 mol/m3 TTF in α-CD varied from 4.44 × 10-11 to 0.76 × 10-11 m2/s as the α-CD concentration increased from 3 to 50 mol/m3. The Do values for hp-β-CD varied from 12.9 × 10-11 to 4.03 × 10-11 m2/s over the same cyclodextrin range whereas those of γ-CD ranged from 2.20 × 10-12 to 1.75 × 10-12 m2/s. CV curves for TTF: hp-β-CD in the presence of glucose and GOx showed a large anodic current with no discernible peaks, indicating bioelectrocatalysis. The ratio of this current to the diffusion limited current was used to determine the second-order homogeneous rate constant ks for the reaction with GOx, which demonstrated the efficiency of the inclusion complex as a mediator. The ks value for 1 mol/m3 TTF decreased from 3.84 × 105 to 1.04 × 105 m3/kmol s with an increase in hp-β-CD concentration from 3 to 15 mol/m3. Extremely high diffusion and kinetic parameters in 3 mol/m3 CD solutions were due to insolubility of TTF at low CD concentrations, and indicated that the CD concentration must be maintained above this level.",

author = "Schmidt, \{Peter M.\} and Brown, \{R. Stephen\} and Luong, \{John H.T.\}",

year = "1995",

month = jun,

doi = "10.1016/0009-2509(95)00046-8",

language = "English",

volume = "50",

pages = "1867--1876",

journal = "Chemical Engineering Science",

issn = "0009-2509",

publisher = "Elsevier B.V.",

number = "12",

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TY - JOUR

T1 - Inclusion complexation of tetrathiafulvalene in cyclodextrins and bioelectroanalysis of the glucose-glucose oxidase reaction

AU - Schmidt, Peter M.

AU - Brown, R. Stephen

AU - Luong, John H.T.

PY - 1995/6

Y1 - 1995/6

N2 - Tetrathiafulvalene (TTF) forms water-soluble inclusion complexes with α-, hp-β- and γ-cyclodextrin (CD). Cyclic voltammetry (CV) has been performed at a stationary electrode to characterize these TTF:CD inclusion complexes. The CV analysis yielded average peak separations of 63 mV and diffusion limited currents, indicating completely reversible electron transfer. The half-wave potential (E 1 2) of the complex shifted to more positive values with increasing CD concentration, permitting use of a modified Nernst equation to estimate the complexation ratio and the equilibrium formation constant (Kform) of the complexes. The complexation ratio was determined as 1:2, 1:1 and 1:1 for TTF with α-CD, hp-β-CD and γ-CD, respectively. The Kform for these complexes was then estimated to be 5.44 × 103 m6/kmol2, 5.40 × 103 m3/kmol and 0.141 × 103 m3/kmol. The diffusion coefficients (Do) for 1 mol/m3 TTF in α-CD varied from 4.44 × 10-11 to 0.76 × 10-11 m2/s as the α-CD concentration increased from 3 to 50 mol/m3. The Do values for hp-β-CD varied from 12.9 × 10-11 to 4.03 × 10-11 m2/s over the same cyclodextrin range whereas those of γ-CD ranged from 2.20 × 10-12 to 1.75 × 10-12 m2/s. CV curves for TTF: hp-β-CD in the presence of glucose and GOx showed a large anodic current with no discernible peaks, indicating bioelectrocatalysis. The ratio of this current to the diffusion limited current was used to determine the second-order homogeneous rate constant ks for the reaction with GOx, which demonstrated the efficiency of the inclusion complex as a mediator. The ks value for 1 mol/m3 TTF decreased from 3.84 × 105 to 1.04 × 105 m3/kmol s with an increase in hp-β-CD concentration from 3 to 15 mol/m3. Extremely high diffusion and kinetic parameters in 3 mol/m3 CD solutions were due to insolubility of TTF at low CD concentrations, and indicated that the CD concentration must be maintained above this level.

AB - Tetrathiafulvalene (TTF) forms water-soluble inclusion complexes with α-, hp-β- and γ-cyclodextrin (CD). Cyclic voltammetry (CV) has been performed at a stationary electrode to characterize these TTF:CD inclusion complexes. The CV analysis yielded average peak separations of 63 mV and diffusion limited currents, indicating completely reversible electron transfer. The half-wave potential (E 1 2) of the complex shifted to more positive values with increasing CD concentration, permitting use of a modified Nernst equation to estimate the complexation ratio and the equilibrium formation constant (Kform) of the complexes. The complexation ratio was determined as 1:2, 1:1 and 1:1 for TTF with α-CD, hp-β-CD and γ-CD, respectively. The Kform for these complexes was then estimated to be 5.44 × 103 m6/kmol2, 5.40 × 103 m3/kmol and 0.141 × 103 m3/kmol. The diffusion coefficients (Do) for 1 mol/m3 TTF in α-CD varied from 4.44 × 10-11 to 0.76 × 10-11 m2/s as the α-CD concentration increased from 3 to 50 mol/m3. The Do values for hp-β-CD varied from 12.9 × 10-11 to 4.03 × 10-11 m2/s over the same cyclodextrin range whereas those of γ-CD ranged from 2.20 × 10-12 to 1.75 × 10-12 m2/s. CV curves for TTF: hp-β-CD in the presence of glucose and GOx showed a large anodic current with no discernible peaks, indicating bioelectrocatalysis. The ratio of this current to the diffusion limited current was used to determine the second-order homogeneous rate constant ks for the reaction with GOx, which demonstrated the efficiency of the inclusion complex as a mediator. The ks value for 1 mol/m3 TTF decreased from 3.84 × 105 to 1.04 × 105 m3/kmol s with an increase in hp-β-CD concentration from 3 to 15 mol/m3. Extremely high diffusion and kinetic parameters in 3 mol/m3 CD solutions were due to insolubility of TTF at low CD concentrations, and indicated that the CD concentration must be maintained above this level.

UR - https://www.scopus.com/pages/publications/0029311318

U2 - 10.1016/0009-2509(95)00046-8

DO - 10.1016/0009-2509(95)00046-8

M3 - Article

AN - SCOPUS:0029311318

SN - 0009-2509

VL - 50

SP - 1867

EP - 1876

JO - Chemical Engineering Science

JF - Chemical Engineering Science

IS - 12

ER -

Inclusion complexation of tetrathiafulvalene in cyclodextrins and bioelectroanalysis of the glucose-glucose oxidase reaction

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