Diagnostic Biosensor Polymers - American Chemical Society

Chapter 15

Hydrogen Peroxide Electrodes Based on Electrical Connection of Redox Centers

Downloaded by UNIV OF TENNESSEE KNOXVILLE on November 14, 2016 | http://pubs.acs.org Publication Date: May 5, 1994 | doi: 10.1021/bk-1994-0556.ch015

of Various Peroxidases to Electrodes through a ThreeDimensional Electron-Relaying Polymer Network Mark S. Vreeke and Adam Heller Department of Chemical Engineering, The University of Texas at Austin, Austin, TX 78712 Hydrogen Peroxide has been shown to be efficiently electroreduced at an electrode modified with a hydrophilic, permeable film of horseradish peroxidase covalently bound to a 3-dimensional epoxy network having polyvinyl pyridine (PVP)-complexed [Os(bpy) Cl] redox centers. Four peroxide sensing cathodes based on peroxidases from Arthromyces ramosus, horseradish and bovine milk are compared. Their sensitivity at 0.0V (SCE) ranges from 0.1 - 1.0 A cm M , and their limiting currents relate to the enzyme's ability to complex with the redox epoxy network. +2/+3

1

2

-2

-1

Electrochemical and optical hydrogen peroxide detection forms the basis for several medical diagnostic tests. Electrochemical detection offers the advantages of smaller required sample size and ease of integration into a flow system. A common electrochemical scheme uses an oxidase to catalyze the selective conversion of substrate equivalents to H 2 O 2 equivalents. This conversion is followed by amperometric assay of the H 0 O 2 , e.g. by its oxidation on platinum at700mV (SCE). At 700mV (SCE) electrooxidation of various reducing species in the biological samples can interfere with the assay. Peroxidase enzymes (POD) catalyze the reduction of H 2 O 2 by electron donors (HA) in the following reaction (POD)

2HA

+ H0 2

2

•

2H 0 + 2A 2

(1) Amperometric peroxidase based H 2 O 2 sensors have been made by using fast reversible redox couples (see Tables I and II). In these, the reducing member of the redox couple (essentially species HA in reaction 1) donates electrons to H 2 O 2 and is oxidized (reaction 2) 0097-6156/94/0556-0180$08.00/0 © 1994 American Chemical Society

Usmani and Akmal; Diagnostic Biosensor Polymers ACS Symposium Series; American Chemical Society: Washington, DC, 1994.


Osmium bipyridine

Glassy carbon

ferrocene carboxylic acid

ferrocene^

potassium hexacyanoferrate(II)

Sn02

Carbon paste

Graphite foil

d

None

NMP+TCNQ"

d

Hexacyanoferrate (.01M)

Pt

f

O-phenylenediamine^

Carbon paste

d

None

Spectrographic graphite

c

None

Mediator or Redox Matrix

-0.02

0.05

0.2

0.05

-0.05

-0.15

0.05

0.0

0.0

Electrode Potential

e

0.03

N.A.b

.04

.168

N.A.

N.A.b

0.175

1

2

10"

2

_1

Sensitivity Acm" M

< 600

0.1-10

0.01-1

5-1700

3.1-200

0.1-500

0.1-100

Linear range mM

7

6

5

4

3

2

1

1

Reference

Electrolyte was dioxanc with 15% 8 aqueous buffer Continued on next page

Nafion coating was applied to the electrode to prevent loss of mediator

HRP immobilized with glutaraldehyde

HRP entrapped with dialysis membrane

HRP was immobilized onto a nylon net

Βutanone peroxide was used as the substrate

BSA with glutaraldehyde crosslinking

HRP covalently bound to a hydrophilic redox epoxy network crossinked with PEGDGE

HRP covalently bound to a hydrophilic epoxy network. Polyvinyl pyridine-dcrivcd polyamine crosslinked with PEGDE.

Comments

Amperometric H2O2 Sensors Based on H R P Modified Electrodes

Glassy carbon

Electrode Surface

Table I.



j)

h) i)

a) b) c) d) e) 0 g)

d

d

Notei

0.0

0.0

0.0

Note g

2.0J

N.A.

HRP was free in solution

Albumin, glutaraldehyde, HRP and oxidase (xanthine, unease, glucose) matrix held close to the electrode with a dialysis membrane.

n

0.05-6J

Glycerophosphate oxidase, HRP and BSA were covalently crosslinked on the glassy carbon surface.

n

14

13

12

11

HRP immobilized on arylaminoderivatized controlled-pore glass, packed into a flow through reactor

e

N.A.

N.A.

10

Membrane with albumin and glutaraldehyde

9

n

The biotin/avidin complex was used to obtain a surface layer of HRP

N.A. 0.1-1000

40-5000

potential vs SCE macroporous electrode uncertainty as to whether surface species created during electrode pretreatment are mediating freely diffusing mediator flow system probably mediated by soluble component of organic metal or reaction product of organic metal cyclic voltametry used to provide selective detection of oxygen generated by autocatalytic decomposition of hydrogen peroxide HRP incorporated into a bienzyme system mediators used and redox potential are: [Ru(NH3)5py](C104)3 = +28 CpFeC2B9Hl 1 = -80 aminomethy!ferrocene = +309 (2-aminoethyl)ferrocene = +185 ferrocene monocarboxylic acid = +275 1, Γ dimcthyl-3-(2-aminocthyl) ferrocene = +75 best reported result for ferrocene monocarboxylic acid

1

hexacyanoferrate (II)

Glassy carbon

Several


Amino silylated glassy carbon

Gold or graphite


Spectrographic graphite or Carbon film

d

potassium ferrocyanide

None

Pt, organic metal, or glassy carbon

Carbon fiber

Table I. Continued.



None

None

Edge-oriented pyrolytic graphite

Gold

.0009 3.0

0.0

1.76

0.12

2

_1

Sensitivity Acm' M

0.2

-0.1

Diagnostic Biosensor Polymers - American Chemical Society

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