We have prepared electrodes modified with either carbon nanoparticles or vertically aligned carbon nanotubes for AA oxidation. We show that by connecting the CNP anode to a Prussian blue electrochromic display we can create a truly self-powered sensor that does not require any external power source for determining the concentration of AA in a sample.

1. 1
Self-Powered Biosensor for Ascorbic Acid with a
Prussian Blue Electrochromic Display
Adrianna Zloczewska
Anna Celebanska
Katarzyna Szot
Dorota Tomaszewska
Marcin Opallo
Martin Jönsson-Niedziółka
Institute of Physical Chemistry
Polish Academy of Sciences
Warsaw, Poland
Martin Jönsson-Niedziólka, martinj@ichf.edu.pl Twitter: @ekorrhjulet
Mikrosympozjum sprawozdawcze, IPS PAS.
Institute of Physical Chemistry PAS, Warsaw Poland

2. 2
Outline
- Self-powered sensors
- CNP electrodes
- Ascorbic acid sensing
- Biocathode
- Ascorbic acid biofuel cell
- Self-powered sensor
Photo: Gabriel Hess
Institute of Physical Chemistry PAS, Warsaw Poland

3. 3
Photo: Caleb Charland, http://calebcharland.com/

4. 4
Self-powered sensor
Fuel cell where output is determined by concentration of analyte
E. Katz, A. F. Bückmann, and I. Willner, J. Am. Chem. Soc. 123, 10752 (2001).
Institute of Physical Chemistry PAS, Warsaw Poland

5. 5
Truly self-powered sensors
Foto: Jessica Bender
T. Hanashi, T. Yamazaki, W. Tsugawa, S. Ferri, D. Nakayama, M.
Tomiyama, K. Ikebukuro, and K. Sode, Biosensors & Bioelectronics 24, 1837
(2009).
BioCapacitor
0.1 mM glucose
1.1 mM glucose
Institute of Physical Chemistry PAS, Warsaw Poland

6. 6
Modification of ITO electrodes with carbon nanoparticles
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CNP-
solutionaq
CNP+
solutionaq
+ carbon nanoparticle modified with
positively charged ammonium functionalities
S
O
O
NH
NH3+
SO3 carbon nanoparticle modified
with phenylsulfonate
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J.D. Watkins et al. Phys.Chem.Chem.Phys., 12 4872 (2010).
K. Szot, et al., Electrochem. Commun. 12, 737 (2010).
1 layer
3 layers
Institute of Physical Chemistry PAS, Warsaw Poland

7. 7
Ascorbic acid oxidation
CNP+
-CNP
-
electrode
ITO
M. Kundys et al., Anal. Methods 6 (2014) 7532.
Institute of Physical Chemistry PAS, Warsaw Poland

8. 8
Ascorbic acid sensing
Cyclic voltammetry on CNP film electrode in phosphate buffer, pH =
4.8 (dashed line) and in AA solutions of different concentrations: 0.5,
1.0, 1.5, 2.0, 2.5, 3.0, 4.0 and 6.0 mM; v = 10 mVs-1
A. Zloczewska et al., Biosens. Bioelectron. 54 (2014) 455.
CNP+
-CNP
-
electrode
Institute of Physical Chemistry PAS, Warsaw Poland

9. 9
A. Zloczewska, M Jönsson-Niedziolka, J. Power Sources 228, 104-111 (2013).
RE
CE
WE
Cu tape
silicone
spacer
UV-Vis cuvettes
with holes
electrolyte
H2O
H+
O2
ē
RE – reference electrode
CE - counter electrode
SWCNT – single-walled CNTs
Bilirubin
oxidase
Functionalised
SWCNT
Silicate matrix
Biocathode
Institute of Physical Chemistry PAS, Warsaw Poland

10. 10
A. Zloczewska, M Jönsson-Niedziolka, J. Power Sources 228, 104-111 (2013).
H2O
H+
O2
ē
RE – reference electrode
CE - counter electrode
SWCNT – single-walled CNTs
Bilirubin
oxidase
Functionalised
SWCNT
Silicate matrix
Biocathode
Gas-side filled with: argon a) & b), air c) and
dioxygen d). a) the electrolyte was also deaerated.
a)
b)
c)
d)
Institute of Physical Chemistry PAS, Warsaw Poland

11. 11
Ascorbic acid BFC
AA-anode and the biocathode working in 1 mM AA,
A. Zloczewska et al., Biosens. Bioelectron. 54 (2014) 455.
Institute of Physical Chemistry PAS, Warsaw Poland

12. 12
Ascorbic acid BFC
AA concentrations: 1, 2, 4 and 6 mM.
CNP+
-CNP
-
anode - Air-breathing CNT cathode
A. Zloczewska et al., Biosens. Bioelectron. 54 (2014) 455.
Institute of Physical Chemistry PAS, Warsaw Poland

13. 13
Ascorbic acid BFC
CNP+
-CNP
-
anode - Air-breathing CNT cathode
AA-BFC working as a Willner-Katz type self-powered sensor.
CNP anode | CNT air-breathing cathode
Current measured at constant E = 0.3V.
A. Zloczewska et al., Biosens. Bioelectron. 54 (2014) 455.
Institute of Physical Chemistry PAS, Warsaw Poland

14. 14
Electrochromic display
Prussian Blue display as
sensor output. Display prepared
by electro-deposition of PB on
ITO.
J. J. García-Jareño, D. Benito, J.
Navarro-Laboulais, F. Vicente,
and J. Garcia-Jareno, J. Chem.
Educ. 75, 881 (1998).
Institute of Physical Chemistry PAS, Warsaw Poland
https://crystallography365.wordpress.com/2014/02/02/are-you-feeling-blue-the-structure-of-prussian-blue/

15. 15
Truly self-powered sensor
H. Liu and R. M. Crooks, Analytical Chemistry 84, 2528 (2012).
A. Zloczewska et al., Biosens. Bioelectron. 54 (2014) 455.
Institute of Physical Chemistry PAS, Warsaw Poland

16. 16
Higher accuracy using image analysis
J. L. Delaney, C. F. Hogan, J. Tian, and W. Shen,
Analytical Chemistry 83, 1300 (2011).
Automated analysis of colour of photos taken
each 5 s.
Transparency values fitted to find colour after
60 s
A. Zloczewska et al., Biosens. Bioelectron. 54 (2014) 455.
Institute of Physical Chemistry PAS, Warsaw Poland

17. 17
Conclusions
We have used carbon nanoparticle electrodes for AA oxidation a
low potential.
We can connect these anode to a biocathode to made an AA
biofuel cell
The AA BFC can be used a self-powered sensor
It can also be connected to a PB display to make a truly self-
powered sensor.
Institute of Physical Chemistry PAS, Warsaw Poland

18. 18
Acknowledgements
This work was partially financed by:
The European Union 7.FP under the grant REGPOT-CT-2011- 285949-
NOBLESSE
The Polish Ministry of Science and Higher Education under the contract
IP2011 020771.
The work of AZ was realized within the International PhD Projects
Programme of the Foundation for Polish Science, co-financed from the
European Regional Development Fund within the Innovative Economy
Operational Programme "Grants for innovation"
Thank you for your attention
NanOtechnology, Biomaterials and
aLternative Energy Source for ERA integration
FP7–REGPOT–CT–2011–285949-NOBLESSE
Institute of Physical Chemistry PAS, Warsaw Poland