University of North Florida
Browse the Citations
-OR-

Contact Info

Stuart Chalk, Ph.D.
Department of Chemistry
University of North Florida
Phone: 1-904-620-1938
Fax: 1-904-620-3535
Email: schalk@unf.edu
Website: @unf

View Stuart Chalk's profile on LinkedIn

Arkady A. Karyakin

Abbrev:
Karyakin, A.A.
Other Names:
Address:
Faculty of Chemistry, M. V. Lomonosov Moscow State University, 119899, Moscow, Russia
Phone:
NA
Fax:
+7-095-939-27-42

Citations 7

"Electroanalytical Applications Of Prussian Blue And Its Analogs"
Russian Chem. Bull. 2001 Volume 50, Issue 10 Pages 1811-1817
A. A. Karyakin, E. E. Karyakina

Abstract: The applications of transition metal hexacyanoferrates in electroanalysis are surveyed. Prussian Blue (ferric hexacyanoferrate) is recognized as the most promising low-potential transducer for hydrogen peroxide reduction among all known systems. The advantages of Prussian Blue over platinum or peroxidase electrodes for hydrogen peroxide detection are discussed. Various types of biosensors based on transition metal hexacyanoferrates and oxidase enzymes are considered. Amperometric biosensors based on Prussian Blue-modified electrodes allow the detection of glucose and glutamate down to 10^-7 mol L-1 in the flow injection mode. The future prospects of Prussian Blue-modified electrodes in analytical chemistry for the monitoring of chemical toxic agents, in clinical diagnostics, and in food control are outlined.
Glucose

"Flow-Injection Analysis Of Residual Glucose In Wines Using A Semiautomatic Analyzer Equipped With A Prussian Blue-Based Biosensor"
Electroanalysis 2003 Volume 15, Issue 5-6 Pages 447-451
E. A. Ulasova, L. Micheli, L. Vasii, D. Moscone, G. Palleschi, S. V. Vdovichev, A. V. Zorin, S. A. Krutovertsev, E. E. Karyakina, A. A. Karyakin*

Abstract: The Prussian Blue modified glassy-carbon (GC) electrode assembled with glucose oxidase (GOD) immobilized in Nafion on the top of the electrode surface area has been inserted in a wall-jet cell connected to a semiautomatic analyzer, which controls all the operations for carrier buffer, flow and sample injection. The Prussian Blue based glucose biosensor inserted in the FIA analyzer has shown linear response to glucose at an applied potential of 0.0 V (Ag/AgCl) in the range of 10^-6-10-3 M. Residual glucose has been detected in red and white wines. A dilution of 1 : 1000 has been used for all the wines tested. Neither matrix effect, nor electrochemical interferences were observed. A comparison with a spectrophotometric glucose kit gave excellent correlation for levels of glucose detected. FIA analyzer compared with the standard analytical kit resulted in simplified procedures and a reduced time for the analysis.

"Prussian Blue And Its Analogues: Electrochemistry And Analytical Applications"
Electroanalysis 2001 Volume 13, Issue 10 Pages 813-819
Arkady A. Karyakin

Abstract: This article reviews fundamental aspects of deposition, structure and electrochemistry of Prussian Blue and its analogues. Special attention is given to the metal hexacyanoferrates with potential analytical applications. Prussian Blue and its analogues as advanced sensing materials for nonelectroactive ions are discussed. In contrast to common smart materials, the sensitivity and selectivity of metal hexacyanoferrates to such ions is provided by thermodynamic background. Prussian Blue itself is recognized as the most advantageous low-potential transducer for hydrogen peroxide over all known systems. Both high sensitivity (ca. 1 A M-1 cm-2) and selectivity in relation to oxygen reduction are more than three orders of magnitude higher, than for platinum electrodes. Biosensors based on different transducing principles containing enzymes oxidases are compared, and the devices operated due to hydrogen peroxide detection with the Prussian Blue based transducer are shown to be the most advantageous ones. The future prospects of chemical and biological sensors based on metal hexacyanoferrates are outlined.

"Electropolymerized Flavin Adenine Dinucleotide As An Advanced NADH Transducer"
Anal. Chem. 2004 Volume 76, Issue 7 Pages 2004-2009
Arkady A. Karyakin, Yulia N. Ivanova, Ksenia V. Revunova and Elena E. Karyakina

Abstract: Electropolymerizing the prosthetic group (flavin adenine dinucleotide, FAD) responsible in the active sites of dehydrogenases for NAD+[verbar]NADH regeneration, we succeeded in mimicking enzyme activity. Poly(FAD) characterized by an additional polymer-type redox reaction has been discovered as a highly effective electrocatalyst for NADH oxidation: operating at the lowest potentials reported for NADH transducers (0.00 V, pH 7.4), poly(FAD) is characterized by the electrochemical rate constant of 1.8 ± 0.6 x 10^-3 cm s-1, which is at the level of the NADH mass-transfer constant. Flow injection analysis of NADH with the poly(FAD)-modified wall-jet electrode as a detector has been characterized by a linear calibration range prolonged down to 5 x 10^-7 M and a sensitivity of 0.08 A M-1 cm-2, which taking into account the dispersion coefficient (~3), is at the diffusion-limiting value. In contrast to the low molecular weight mediators able to exhibit similar electrocatalytic properties, poly(FAD)-modified electrodes are characterized by the dramatically improved stability and, thus, can be considered as the most advantageous NADH transducers for analytical chemistry.

"Prussian Blue Based Nanoelectrode Arrays For H2O2 Detection"
Anal. Chem. 2004 Volume 76, Issue 2 Pages 474-478
Arkady A. Karyakin, Elena A. Puganova, Igor A. Budashov, Ilya N. Kurochkin, Elena E. Karyakina, Vladimir A. Levchenko, Vladimir N. Matveyenko and Sergey D. Varfolomeyev

Abstract: We propose to form nanoelectrode arrays by deposition of the electrocatalyst through lyotropic liquid crystalline templates onto inert electrode support. Whereas Prussian Blue is known to be a superior electrocatalyst in hydrogen peroxide reduction, carbon materials used as electrode support demonstrate only a minor activity. We report on the possibility for nanostructuring of Prussian Blue by its electrochemical deposition through lyotropic liquid crystalline templates, which is noticed from atomic force microscopy images of the resulting surfaces. The resulting Prussian Blue based nanoelectrode arrays in flow injection analysis mode demonstrate a sub-part-per-billion detection limit (1 x 10^-8 M) and a linear calibration range starting exactly from the detection limit and extending over 6 orders of magnitude of H2O2 concentrations (1 x 10^-8 to 1 x 10^-2 M), which are the most advantageous analytical performances in hydrogen peroxide electroanalysis.

"Optimal Environment For Glucose Oxidase In Perfluorosulfonated Ionomer Membranes: Improvement Of First-generation Biosensors"
Anal. Chem. 2002 Volume 74, Issue 7 Pages 1597-1603
Arkady A. Karyakin, Elena A. Kotel'nikova, Lilia V. Lukachova, Elena E. Karyakina, and Joseph Wang

Abstract: An optimal environment for glucose oxidase (GOx) in Naflon membranes is achieved using an advanced immobilization protocol based on a nonaqueous immobilization route. Exposure of glucose oxidase to water-organic mixtures with a high (85-95%) content of the organic solvent resulted in stabilization of the enzyme by a membrane-forming polyelectrolyte. Such an optimal environment leads to the highest enzyme specific activity in the resulting membrane, as desired for optimal use of the expensive oxidases. Casting solution containing glucose oxidase and Naflon is completely stable over 5 days in a refrigerator, providing almost absolute reproducibility of GOx-Nafion membranes. A glucose biosensor was prepared by casting the GOx-Nafion membranes over Prussian Blue-modified glassy carbon disk electrodes. The biosensor operated in the FIA mode allows the detection of glucose down to the 0.1 muM level, along with high sensitivity (0.05 A M-1 cm-2), which is only 10 times lower than the sensitivity of the hydrogen peroxide transducer used. A comparison with the recently reported enzyme electrodes based on similar H2O2 transducers (transition metal hexacyanoferrates) shows that the proposed approach displays a dramatic (100-fold) improvement in sensitivity of the resulting biosensor. Combined with the attractive performance of a Prussian Blue-based hydrogen peroxide transducer, the proposed immobilization protocol provides a superior performance for first-generation glucose biosensors in term of sensitivity and detection limits.
Glucose

"Amperometric Biosensor For Glutamate Using Prussian Blue-based Artificial Peroxldase As A Transducer For Hydrogen Peroxide"
Anal. Chem. 2000 Volume 72, Issue 7 Pages 1720-1723
Arkady A. Karyakin, Elena E. Karyakina, and Lo Gorton

Abstract: The specially deposited Prussian Blue denoted as artificial peroxidase was used as a transducer for hydrogen peroxide, The electrocatalyst as stable, highly active, and selective to hydrogen peroxide reduction in the presence of oxygen, which allowed sensing of H2O2 around 0.0 V (Ag/AgCl). Glutamate oxidase was immobilized on the surface of the Prussian Blue-modified electrode in a Nafion layer using a nonaqueous enzymology approach. The calibration range for glutamate in flow injection system was 1 x 10^-7-1 x 10^-4 M. The lowest concentration of glutamate detected (1 x 10^-7 M) and the highest sensitivity in the linear range of 0.21 A M-1 cm-2 were achieved. The influence of reductants was practically avoided using the low potential of an indicator electrode (0.0 V Ag/AgCl). The attractive performance characteristics of the glutamate biosensor illustrate the advantages of Prussian Blue-based artificial peroxidase as transducer for hydrogen peroxide detection.