title: A Nanostructured Bifunctional platform for Sensing of Glucose Biomarker in Artificial Saliva: Synergy in hybrid Pt/Au surfaces.
abstract: We report on a bimetallic, bifunctional electrode where a platinum (Pt) surface was patterned with nanostructured gold (Au) fingers with different film thicknesses, which was functionalized with glucose oxidase (GOx) to yield a highly sensitive glucose biosensor. This was achieved by using selective adsorption of a self-assembled monolayer (SAM) onto Au fingers, which allowed GOx immobilization only onto the Au-SAM surface. This modified electrode was termed bifunctional because it allowed to simultaneously immobilize the biomolecule (GOx) on gold to catalyze glucose, and detect hydrogen peroxide on Pt sites. Optimized electrocatalytic activity was reached for the architecture Pt/Au-SAM/GOx with 50nm thickness of Au, where synergy between Pt and Au allowed for detection of hydrogen peroxide (H2O2) at a low applied potential (0V vs. Ag/AgCl). Detection was performed for H2O2 in the range between 4.7 and 102.7 nmol L(-1), with detection limit of 3.4×10(-9) mol L(-1) (3.4 nmol L(-1)) and an apparent Michaelis-Menten rate constant of 3.2×10(-6)molL(-1), which is considerably smaller than similar devices with monometallic electrodes. The methodology was validated by measuring glucose in artificial saliva, including in the presence of interferents. The synergy between Pt and Au was confirmed in electrochemical impedance spectroscopy measurements with an increased electron transfer, compared to bare Pt and Au electrodes. The approach for fabricating the reproducible bimetallic Pt/Au electrodes is entirely generic and may be explored for other types of biosensors and biodevices where advantage can be taken of the combination of the two metals.
authors.affiliation: São Carlos Institute of Chemistry, University of São Paulo, CP 380, CEP 13566-590, São Carlos, São Paulo, Brazil. Electronic address: pauloaugustoraymundopereira@gmail.com.
authors.forename: Paulo A
authors.initials: PA
authors.lastname: Raymundo-Pereira
authors.affiliation: São Carlos Institute of Physics, University of São Paulo, CP 369, CEP 13560-970, São Carlos, São Paulo, Brazil.
authors.forename: Flávio M
authors.initials: FM
authors.lastname: Shimizu
authors.affiliation: São Carlos Institute of Chemistry, University of São Paulo, CP 380, CEP 13566-590, São Carlos, São Paulo, Brazil.
authors.forename: Dyovani
authors.initials: D
authors.lastname: Coelho
authors.affiliation: Laboratório de Microfabricação, Laboratório Nacional de Nanotecnologia, Centro Nacional de Pesquisa em Energia e Materiais/CNPEM, Campinas, SP, Brazil.
authors.forename: Maria H O
authors.initials: MHO
authors.lastname: Piazzeta
authors.affiliation: Laboratório de Microfabricação, Laboratório Nacional de Nanotecnologia, Centro Nacional de Pesquisa em Energia e Materiais/CNPEM, Campinas, SP, Brazil.
authors.forename: Angelo L
authors.initials: AL
authors.lastname: Gobbi
authors.affiliation: São Carlos Institute of Chemistry, University of São Paulo, CP 380, CEP 13566-590, São Carlos, São Paulo, Brazil.
authors.forename: Sergio A S
authors.initials: SAS
authors.lastname: Machado
authors.affiliation: São Carlos Institute of Physics, University of São Paulo, CP 369, CEP 13560-970, São Carlos, São Paulo, Brazil.
authors.forename: Osvaldo N
authors.initials: ON
authors.lastname: Oliveira
mesh_terms: D040761:Biomimetic Materials / Q000032:analysis / Q000737:chemistry; D003217:Conductometry / Q000295:instrumentation*; D004867:Equipment Design; D019544:Equipment Failure Analysis; D005947:Glucose / Q000032:analysis* / Q000737:chemistry; D005949:Glucose Oxidase / Q000737:chemistry*; D006046:Gold / Q000737:chemistry; D006801:Humans; D006861:Hydrogen Peroxide / Q000032:analysis*; D053768:Metal Nanoparticles / Q000737:chemistry*; D010984:Platinum / Q000737:chemistry; D015203:Reproducibility of Results; D012463:Saliva / Q000737:chemistry*; D012680:Sensitivity and Specificity
chemical_list: D010984:Platinum; D006046:Gold; D006861:Hydrogen Peroxide; D005949:Glucose Oxidase; D005947:Glucose
keywords: Bifunctional Surface; Bimetallic; Biosensing; Hybrid Surface; Nanostructured platform