Development of a low cost Hemin based dissolved oxygen sensor with anti-biofouling coating for water monitoring

Conventional electrochemical dissolved oxygen (DO) sensors are expensive as they use Platinum in their construction. In addition, these sensors bio-foul when used in natural or wastewater, which leads to reduced sensitivity and variable performance. Here, we address these problems by i) replacing Platinum with Hemin as a low cost alternative for electrocatalysing the oxygen reduction reaction and ii) using silicone rubber (PDMS) functionalized with polyethyleneglycol (PEG) as the anti biofouling gas permeable membrane to provide selectivity with an increased lifetime. Our DO sensor has a sensitivity of 20.7 (μA/cm2)/(mg/L) over a DO concentration range of 7-2 mg/L. Also, the common interferences such as phosphate and nitrate show minor influence in DO detection. Furthermore, the PEG grafting PDMS membranes protects the sensor from biofouling for 20 days in accelerated bio-fouling condition, while the unfunctionalized sensor loses its sensitivity in less than one day.

[1]  P. Ravi Selvaganapathy,et al.  Microfluidic Reference Electrode with Free-Diffusion Liquid Junction , 2013 .

[2]  Xueji Zhang,et al.  Metallo Protoporphyrin Functionalized Microelectrodes for Electrocatalytic Sensing of Nitric Oxide. , 2009, American journal of biomedical sciences.

[3]  A. Wiȩckowski,et al.  Synthesis and characterization of carbon-supported transition metal oxide nanoparticles — Cobalt porphyrin as catalysts for electroreduction of oxygen in acids , 2010 .

[4]  Guann-Pyng Li,et al.  Electroosmotic properties of microfluidic channels composed of poly(dimethylsiloxane). , 2001, Journal of chromatography. B, Biomedical sciences and applications.

[5]  A. Jannakoudakis,et al.  Electrocatalytic reactions on carbon fibre electrodes modified by hemine II. Electro-oxidation of hydrazine , 1989 .

[6]  Ya-Pu Zhao,et al.  Influence of different amount of Au on the wetting behavior of PDMS membrane , 2008, Biomedical microdevices.

[7]  Qin Zhou,et al.  Template-synthesized cobalt porphyrin/polypyrrole nanocomposite and its electrocatalysis for oxygen reduction in neutral medium , 2007 .

[8]  A. Wiȩckowski,et al.  Enhanced ORR activity of cobalt porphyrin co-deposited with transition metal oxides on Au and C electrodes. The ORR threshold data , 2013 .

[9]  J. Genzer,et al.  Surface modification of Sylgard-184 poly(dimethyl siloxane) networks by ultraviolet and ultraviolet/ozone treatment. , 2002, Journal of colloid and interface science.

[10]  N. Voelcker,et al.  Recent developments in PDMS surface modification for microfluidic devices , 2010, Electrophoresis.

[11]  M. Deen,et al.  Electrochemical growth of high-aspect ratio nanostructured silver chloride on silver and its application to miniaturized reference electrodes , 2011, Nanotechnology.

[12]  A. Jannakoudakis,et al.  Electrocatalytic reactions on carbon fibre electrodes modified by hemine I. Electroreduction of oxygen , 1989 .

[13]  H.J. Kadim,et al.  An optical fiber sensor for biofilm measurement using intensity modulation and image analysis , 2000, IEEE Journal of Selected Topics in Quantum Electronics.

[14]  Fwu-Shan Sheu,et al.  Application of multi-walled carbon nanotubes functionalized with hemin for oxygen detection in neutral solution , 2004 .

[15]  Lauro T Kubota,et al.  Dissolved oxygen amperometric sensor based on layer-by-layer assembly using host-guest supramolecular interactions. , 2010, Analytica chimica acta.

[16]  M. Jamal Deen,et al.  Microfabricated Reference Electrodes and their Biosensing Applications , 2010, Sensors.

[17]  H. Flemming,et al.  Biofouling in water systems – cases, causes and countermeasures , 2002, Applied Microbiology and Biotechnology.

[18]  L. C. Clark,et al.  ELECTRODE SYSTEMS FOR CONTINUOUS MONITORING IN CARDIOVASCULAR SURGERY , 1962 .

[19]  J. Zhao,et al.  Fabrication of a multilayer film electrode containing porphyrin and its application as a potentiometric sensor of iodide ion. , 1998, Talanta.

[20]  B. MacCraith,et al.  Tailoring of sol-gel films for optical sensing of oxygen in gas and aqueous phase. , 1998, Analytical chemistry.

[21]  Pierre Gros,et al.  Use of polypyrrole film containing Fe(CN)63− as pseudo-reference electrode: application for amperometric biosensors , 2001 .

[22]  J. Prakash,et al.  Electrocatalytic activity of ruthenium for oxygen reduction in alkaline solution , 2000 .

[23]  Chaojie Song,et al.  Electrocatalytic Oxygen Reduction Reaction , 2008 .

[24]  M. C. Blanco-López,et al.  Preparation and Characterization of a Molecularly Imprinted Microgel for Electrochemical Sensing of 2,4,6-Trichlorophenol , 2011 .

[25]  Rongrong Chen,et al.  CoPc- and CoPcF16-Modified Ag Nanoparticles as Novel Catalysts with Tunable Oxygen Reduction Activity in Alkaline Media , 2011 .

[26]  L. Kubota,et al.  A highly sensitive amperometric sensor for oxygen based on iron(II) tetrasulfonated phthalocyanine and iron(III) tetra-(N-methyl-pyridyl)-porphyrin multilayers. , 2008, Analytica chimica acta.

[27]  M. Brook,et al.  Protein repellant silicone surfaces by covalent immobilization of poly(ethylene oxide). , 2005, Biomaterials.

[28]  Bin Wang,et al.  Recent development of non-platinum catalysts for oxygen reduction reaction , 2005 .

[29]  Jing Fan,et al.  Covalent modified hydrophilic polymer brushes onto poly(dimethylsiloxane) microchannel surface for electrophoresis separation of amino acids. , 2008, Journal of chromatography. A.

[30]  S. Liao,et al.  Hemin: A Highly Effective Electrocatalyst Mediating the Oxygen Reduction Reaction , 2011 .