Chapter 3
Fundamentals of DET-Type
Bioelectrocatalysis
Abstract This chapter starts by introducing the history of DET-type non-catalytic
and bioelectrocatalytic reactions with much attention to the distinction between
DET- and MET-type bioelectrocatalytic reactions. Theoretical features of DETtype bioelectrocatalysis are detailed with emphasis of orientation effect of redox
enzymes and curvature effect of mesoporous electrodes. One of analytical methods
for steady-state catalytic waves of DET-type bioelectrocatalysis is also introduced.
Keywords Metal-containing redox enzymes · Flavoproteins · Steady-state
current · Long-range electron transfer · Random orientation · Mesoporous
electrodes · Data analysis
3.1 History of DET-Type Bioelectrocatalysis
Interfacial electrochemistry, i.e. non-catalytic direct electron transfer (DET), of redox
proteins has been energetically studied in 1970s–1980s especially by Hill group, as
reviewed in the literature [1–4]. During the studies of Hill group, the significance
of use of edge-oriented pyrolytic graphite electrode (EPGE) [5] as well as redox
inactive promoters were pointed out to facilitate DET-type reactions.
In 1978, an important event has been reported as a DET-type bioelectrocatalysis:
catalytic reduction of O 2 by a multi-copper oxidase (MCO) laccase (Lac) adsorbed
on carbon electrodes [6], and the event was well followed by Lee et al. [7]. The reports
inspired researchers in this field, and clear DET-type bioelectrocatalytic voltammograms of redox enzymes with multi-redox sites have been reported one after another
especially by Hill and Ikeda groups in 1988–1992: p-cresolmethylhydroxylase from
Pseudomonas putida at EPGE [8], methylamine dehydrogenase from bacterium
W3A1 at EPGE [9], d-gluconate dehydrogenase (GADH) from Pseudomonas fluorescence FM-1 at carbon paste electrode (CPE) [10], d-fructose dehydrogenase
(FDH) from Gluconobacter sp. at CPE [11], and PQQ-dependent alcohol dehydrogenase (ADH) type III from Gluconobacter suboxydans at gold electrode (AuE)
[12]. Note here that GADH, FDH, and ADH are generated in acetic bacteria. This
time of period is the beginning of the research field of DET-type bioelectrocatalysis.
© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2021
K. Kano et al., Enzymatic Bioelectrocatalysis,
https://doi.org/10.1007/978-981-15-8960-7_3
57
Fundamentals of DET-Type
Bioelectrocatalysis
Abstract This chapter starts by introducing the history of DET-type non-catalytic
and bioelectrocatalytic reactions with much attention to the distinction between
DET- and MET-type bioelectrocatalytic reactions. Theoretical features of DETtype bioelectrocatalysis are detailed with emphasis of orientation effect of redox
enzymes and curvature effect of mesoporous electrodes. One of analytical methods
for steady-state catalytic waves of DET-type bioelectrocatalysis is also introduced.
Keywords Metal-containing redox enzymes · Flavoproteins · Steady-state
current · Long-range electron transfer · Random orientation · Mesoporous
electrodes · Data analysis
3.1 History of DET-Type Bioelectrocatalysis
Interfacial electrochemistry, i.e. non-catalytic direct electron transfer (DET), of redox
proteins has been energetically studied in 1970s–1980s especially by Hill group, as
reviewed in the literature [1–4]. During the studies of Hill group, the significance
of use of edge-oriented pyrolytic graphite electrode (EPGE) [5] as well as redox
inactive promoters were pointed out to facilitate DET-type reactions.
In 1978, an important event has been reported as a DET-type bioelectrocatalysis:
catalytic reduction of O 2 by a multi-copper oxidase (MCO) laccase (Lac) adsorbed
on carbon electrodes [6], and the event was well followed by Lee et al. [7]. The reports
inspired researchers in this field, and clear DET-type bioelectrocatalytic voltammograms of redox enzymes with multi-redox sites have been reported one after another
especially by Hill and Ikeda groups in 1988–1992: p-cresolmethylhydroxylase from
Pseudomonas putida at EPGE [8], methylamine dehydrogenase from bacterium
W3A1 at EPGE [9], d-gluconate dehydrogenase (GADH) from Pseudomonas fluorescence FM-1 at carbon paste electrode (CPE) [10], d-fructose dehydrogenase
(FDH) from Gluconobacter sp. at CPE [11], and PQQ-dependent alcohol dehydrogenase (ADH) type III from Gluconobacter suboxydans at gold electrode (AuE)
[12]. Note here that GADH, FDH, and ADH are generated in acetic bacteria. This
time of period is the beginning of the research field of DET-type bioelectrocatalysis.
© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2021
K. Kano et al., Enzymatic Bioelectrocatalysis,
https://doi.org/10.1007/978-981-15-8960-7_3
57