Direct Electrochemistry and Electrocatalysis of Microperoxidase-11 Immobilized on Porous

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Direct Electrochemistry and Electrocatalysis of Microperoxidase-11 Immobilized on Porous

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A study on the direct electrochemistry and electrocatalysis of microperoxidase-11 immobilized

on a porous network-like gold film: Sensing of hydrogen peroxide

Qian-Li Zhang,a,b Ai-Jun Wang,a Zi-Yan-Meng,a Ya-Hui Lu,c Hong-Jun Lin,a Jiu-Ju Fenga* aCollege of Chemistry and Life Science, College of Geography and Environmental Science, Zhejiang

Normal University, Jinhua 321004, China bSchool of Chemistry and Biological Engineering, Suzhou University of Science and Technology,

Suzhou, 215009, China cSchool of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007,

China

*Corresponding author: [email protected], Tel./Fax: +86 579 82282269

B 350 ) A  (

t 0 n

e r r u C -350

-700 0.0 0.5 1.0 1.5 Potential(V)

Fig. S1. The CVs of the porous network-like Au film modified electrode in 0.5 M H2SO4 solution.

Scan rate: 100 mV·s–1.

1

A h -4 A

 -2 /

a t n e

r 0 r u

C 2

4

-0.8 -0.6 -0.4 -0.2 0.0 Potential / V

1.6 B ) A

μ 0.8 (

t n

e r

r 0.0 u C -0.8

28 56 84 112 -1 Scan rate ( mV s )

Fig. S2 (A): Typical CVs on the MP-11/cysteamine/Cu@Au/GCE at different scan rates (curve a-h):

10, 20, 30, 40, 50, 60, 70, and 100 mV·s–1 in 20 mM phosphate solution (pH 7.0). (B): The oxidation and reduction currents vs. scan rates.

20 h 15

A 10 

/

t 5 n a e

r r 0 u C -5

-10

-15 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 Potential / V

Fig. S3 Typical CVs on the MP-11/cysteamine/Cu/GCE electrode with different scan rates (curve a-

2 h): 10, 20, 30, 40, 50, 60, 70, and 100 mV·s–1 in 20 mM phosphate solution (pH 7.0).

3

6 A

3 ) A μ

( t

n 0

e r r u C -3

-6 3 4 5 6 7 8 9 pH

-0.18 B Oxidation potential Reduction potential -0.24 ) V (

l a

i -0.30 t n

e t o

P -0.36

-0.42

3.0 4.5 6.0 7.5 9.0 pH

Fig. S4 (A) The oxidation and reduction currents vs. pH. (B) The oxidation and reduction potentials vs. pH.

4

6

3 ) A

μ 0 (

t

n a e r r -3 u C

-6 f -0.8 -0.6 -0.4 -0.2 0.0 Potential (V)

Fig. S5 Typical CVs towards the catalytic reduction of H2O2 on the MP-

11/cysteamine/Cu@Au/GCE in 20 mM N2 saturated phosphate solution with different

concentrations of H2O2 (curve a-f): 0, 0.010, 0.019, 0.039, 0.058, and 0.078 mM. Scan rate: 100

mV·s–1.

45 without H2O2 with 0.039 mM H O 30 2 2 )

A 15  (

t

n e

r 0 r u C -15

-30 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 potential (v)

Fig. S6 Typical CVs of the catalysis of H2O2 on the MP-11/cysteamine/Cu/GCE in 20 mM N2 saturated phosphate solution (pH 7.0) in the absence and presence of 0.039 mM H2O2. Scan rate: 100 mV·s-1.

5 Table S1 Examples of heme proteins based mediator-free H2O2 biosensors.

Materials Stability Linear ranges Detection Refs.

limit

MP-11/Au film 94% (2 weeks) 10 µM ~ 14 mM 0.4 μM Our work

−4 Fe3O4@ SiO2@hemin 85% (4 weeks) 1.0 µM ~ 0.16 mM 2.2×10 [1]

HRP/AuNPs 83 % (12 weeks) 8.0 µM ~ 3.0 mM 2.0 μM [2]

Cyt c/Ag nanocorals 95% (2 weeks) 1.8 μM ~ 23 mM 1.8 μM [3]

Hb/WO3 94% (2 weeks) 3.7µM ~ 0.56 mM 1.5 μM [4]

HRP/GNPs-TNTs 90% (3 days) 5.0 µM ~1.0 mM 2.1 μM [5]

Mb/ZrO2/chitosan 90% (2 weeks) 10.0 µM ~ 1.5 mM 4.0 μM [6]

{Hb/CMK-3}n no change (30 days) 1.2 ~ 57 µM 0.6 μM [7]

Mb/CDA-[bmim]BF4 95% (2 weeks) 5.0~100 μM 2.0 μM [8]

HRP/PTBA PBCs > 90% (1 month) 1 ~ 300 μM 1 μM [9]

References

1. Feng J-J, Li Z-H, Li Y-F, Wang A-J, Zhang P-P (2012) Electrochemical determination of dioxygen

and hydrogen peroxide using Fe3O4@SiO2@hemin microparticles. Microchim. Acta 176: 201.

2. Wang J, Wang L, Di J, Tu Y (2009) Electrodeposition of gold nanoparticles on indium/tin oxide electrode for fabrication of a disposable hydrogen peroxide biosensor. Talanta 77: 1454.

3. Feng J, Hildebrandt P, Murgida D (2008) Silver nanocoral structures on electrodes: A suitable platform for protein-based bioelectronic devices. Langmuir 24: 1583.

4. Feng J, Xu J, Chen H (2006) Direct electron transfer and electrocatalysis of hemoglobin adsorbed onto electrodeposited mesoporous tungsten oxide. Electrochem Commun 8: 77.

5. Liu X, Feng H, Zhao R, Wang Y, Liu X (2012) A novel approach to construct a horseradish peroxidase|hydrophilic ionic liquids|Au nanoparticles dotted titanate nanotubes biosensor for

6 amperometric sensing of hydrogen peroxide. Biosens Bioelectron 31: 101.

6. Zhao G, Feng J, Xu J, Chen H (2005) Direct electrochemistry and electrocatalysis of heme

proteins immobilized on self-assembled ZrO2 film. Electrochem Commun 7: 724.

7. Feng J, Xu J, Chen H (2007) Direct electron transfer and electrocatalysis of hemoglobin adsorbed on mesoporous carbon through layer-by-layer assembly. Biosens Bioelectron: 22: 1618.

8. Dong S-Y, Gu G-Z, Yu Z-Q, Zhou Y-Z, Tang H-S, Zheng J-B (2011) Hydrogen peroxide biosensor based on cellulose diacetate-ionic liquid film immobilizing myoglobin. Chin J Anal Chem 39: 1358.

9. Huang Y, Wang W, Li Z, Qin X, Bu L, Tang Z, Fu Y, Ma M, Xie Q, Yao S, Hu J (2013)

Horseradish peroxidase-catalyzed synthesis of poly(thiophene-3-boronic acid) biocomposites for mono-/bi-enzyme immobilization and amperometric biosensing. Biosens Bioelectron: ASAP.

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