Nanoparticle-based electrochemical sensors for the detection of lactate and hydrogen peroxide

In the present study, electrochemical sensors for the detection of lactate and hydrogen peroxide were constructed by exploiting the physicochemical properties of metal ad metal oxide nanoparticles. This study can be divided into two main sections. While chapter 2, 3, and 4 report on the construction of electrochemical lactate biosensors using CeO2 and CeO2-based mixed metal oxide nanoparticles, chapter 5 and 6 show the development of electrochemical hydrogen peroxide sensors by the decoration of the electrode surface with palladium-based nanoparticles. First generation oxidase enzyme-based sensors suffer from oxygen dependency which results in errors in the response current of the sensors in O2-lean environments. To address this challenge, the surface of the sensors must be modified with oxygen rich materials. In this regard, we developed a novel electrochemical lactate biosensor design by exploiting the oxygen storage capacity of CeO2 and CeO 2-CuO nanoparticles. By the introduction of CeO2 nanoparticles into the enzyme layer of the sensors, negative interference effect of ascorbate which resulted from the formation of oxygen-lean regions was eliminated successfully. When CeO2-based design was exposed to higher degree of O2 -depleted environments, however, the response current of the biosensors experienced an almost 21 % decrease, showing that the OSC of CeO2 was not high enough to sustain the enzymatic reactions. When CeO2-CuO nanoparticles, which have 5 times higher OSC than pristine CeO2, were used as an oxygen supply in the enzyme layer, the biosensors did not show any drop in the performance when moving from oxygen-rich to oxygen-lean conditions. In the second part of the study, PdCu/SPCE and PdAg/rGO-based electrochemical H2O2 sensors were designed and their performances were evaluated to determine their sensitivity, linear range, detection limit, and storage stability. In addition, practical applicability of the sensors was studied in human serum. The chronoamperometry results showed that the PdCu/SPCE sensors yielded a high sensitivity (396.7 µA mM -1 cm-2), a wide linear range (0.5 -11 mM), and a low limit of detection (0.7 µM) at the applied potential of -0.3 V. For PdAg/rGO sensors, a high sensitivity of 247.6 ± 2.7 µA˙mM -1˙cm-2 was obtained towards H2O 2 in a linear range of 0.05 mM to 28 mM

The Role of Metal Oxide Layers in the Sensitivity of Lactate Biosensors Subjected to Oxygen-Limited Conditions

Amperometric lactate biosensors are used to detect lactate concentration in blood and tissues, which is integral in identifying cyanide poisoning, septic shock, and athletic condition. The construction of lactate biosensors with high sensitivity, selectivity, and stability is imperative to diagnose and determine these medical conditions. Lactate detection is currently limited to oxygen-rich environments due to the fact that oxygen is a limiting factor in the lactate reaction. To circumvent this problem, researchers have developed mediators or alternate, oxygen-free enzymes to improve sensitivity. In our study, ceria (CeO2) with high oxygen storage capacity (OSC) was introduced to the enzyme layer to eliminate the effects of oxygen depletion. Fluctuation in oxygen concentration was combatted by use of ceria metal oxide nanopowders, which absorb and release oxygen under oxygen rich and lean conditions respectively. These nanopowders were deposited on the electrode surface in a polyelectrolyte solution. The lactate biosensors were then constructed using layer-by-layer assembly to take advantage of electrostatic interaction between the positively charged polyelectrolyte and negatively charged lactate oxidase (LOx). Polyethylenimine (PEI), a positively charged polymer, was used to immobilize the enzymes on the Pt surface via alternating electrostatic adsorption. It was observed that the introduction of ceria in the enzyme layer reduced oxygen dependency. The results showed that lactate biosensors with high selectivity, sensitivity, and wide detection limit were constructed

Investigation of the Interaction between Nafion Ionomer and Surface Functionalized Carbon Black Using Both Ultrasmall Angle X-ray Scattering and Cryo-TEM

In making a catalyst ink, the interactions between Nafion ionomer and catalyst support are the key factors that directly affect both ionic conductivity and electronic conductivity of the catalyst layer in a membrane electrode assembly. One of the major aims of this investigation is to understand the behavior of the catalyst support, Vulcan XC-72 (XC-72) aggregates, in the existence of the Nafion ionomer in a catalyst ink to fill the knowledge gap of the interaction of these components. The dispersion of catalyst ink depends not only on the solvent but also on the interaction of Nafion and carbon particles in the ink. The interaction of Nafion ionomer particles and XC-72 catalyst aggregates in liquid media was studied using ultrasmall-angle X-ray scattering and cryogenic TEM techniques. Carbon black (XC-72) and functionalized carbon black systems were introduced to study the interaction behaviors. A multiple curve fitting was used to extract the particle size and size distribution from scattering data. The results suggest that the particle size and size distribution of each system changed significantly in Nafion + XC-72 system, Nafion + NH2-XC72 system, and Nafion + SO3H-XC-72 system, which indicates that an interaction among these components (i.e., ionomer particles and XC-72 aggregates) exists. The cryogenic TEM, which allows for the observation the size of particles in a liquid, was used to validate the scattering results and shows excellent agreement

Polybenzimidazole (PBI) Functionalized Nanographene as Highly Stable Catalyst Support for Polymer Electrolyte Membrane Fuel Cells (PEMFCs)

Nanoscale graphenes were used as cathode catalyst supports in proton exchange membrane fuel cells (PEMFCs). Surface-initiated polymerization that covalently bonds polybenzimidazole (PBI) polymer on the surface of graphene supports enables the uniform distribution of the Pt nanoparticles, as well as allows the sealing of the unterminated carbon bonds usually present on the edge of graphene from the chemical reduction of graphene oxide. The nanographene effectively shortens the length of channels and pores for O2 diffusion/water dissipation and significantly increases the primary pore volume. Further addition of p-phenyl sulfonic functional graphitic carbon particles as spacers, increases the specific volume of the secondary pores and greatly improves O2 mass transport within the catalyst layers. The developed composite cathode catalyst of Pt/PBI-nanographene (50 wt%) + SO3H-graphitic carbon black demonstrates a higher beginning of life (BOL) PEMFC performance as compared to both Pt/PBI-nanographene (50 wt%) and Pt/PBI-graphene (50 wt%) + SO3H-graphitic carbon black (GCB). Accelerated stress tests show excellent support durability compared to that of traditional Pt/Vulcan XC72 catalysts, when subjected to 10,000 cycles from 1.0 V to 1.5 V. This study suggests the promise of using PBI-nanographene + SO3H-GCB hybrid supports in fuel cells to achieve the 2020 DOE targets for transportation applications

Nanoparticle-based electrochemical sensors for the detection of lactate and hydrogen peroxide

In the present study, electrochemical sensors for the detection of lactate and hydrogen peroxide were constructed by exploiting the physicochemical properties of metal ad metal oxide nanoparticles. This study can be divided into two main sections. While chapter 2, 3, and 4 report on the construction of electrochemical lactate biosensors using CeO2 and CeO2-based mixed metal oxide nanoparticles, chapter 5 and 6 show the development of electrochemical hydrogen peroxide sensors by the decoration of the electrode surface with palladium-based nanoparticles. First generation oxidase enzyme-based sensors suffer from oxygen dependency which results in errors in the response current of the sensors in O2-lean environments. To address this challenge, the surface of the sensors must be modified with oxygen rich materials. In this regard, we developed a novel electrochemical lactate biosensor design by exploiting the oxygen storage capacity of CeO2 and CeO 2-CuO nanoparticles. By the introduction of CeO2 nanoparticles into the enzyme layer of the sensors, negative interference effect of ascorbate which resulted from the formation of oxygen-lean regions was eliminated successfully. When CeO2-based design was exposed to higher degree of O2 -depleted environments, however, the response current of the biosensors experienced an almost 21 % decrease, showing that the OSC of CeO2 was not high enough to sustain the enzymatic reactions. When CeO2-CuO nanoparticles, which have 5 times higher OSC than pristine CeO2, were used as an oxygen supply in the enzyme layer, the biosensors did not show any drop in the performance when moving from oxygen-rich to oxygen-lean conditions. In the second part of the study, PdCu/SPCE and PdAg/rGO-based electrochemical H2O2 sensors were designed and their performances were evaluated to determine their sensitivity, linear range, detection limit, and storage stability. In addition, practical applicability of the sensors was studied in human serum. The chronoamperometry results showed that the PdCu/SPCE sensors yielded a high sensitivity (396.7 µA mM -1 cm-2), a wide linear range (0.5 -11 mM), and a low limit of detection (0.7 µM) at the applied potential of -0.3 V. For PdAg/rGO sensors, a high sensitivity of 247.6 ± 2.7 µA˙mM -1˙cm-2 was obtained towards H2O 2 in a linear range of 0.05 mM to 28 mM

Graphene-titanium dioxide nanocomposite based hypoxanthine sensor for assessment of meat freshness

We report on the fabrication of a graphene/titanium dioxide nanocomposite (TiO2-G) and its use as an effective electrode material in an amperometric hypoxanthine (Hx) sensor for meat freshness evaluation. The nanocomposite was characterized by TEM, XRD, FTIR, XPS, TGA, BET, and CV using the redox couples [Fe(CN)6]−3/−4 and [Ru(NH3)6]+3/+2 respectively. The TiO2/G nanocomposite offered a favorable microenvironment for direct electrochemistry of xanthine oxidase (XOD). The fabricated Nafion/XOD/TiO2-G/GCE sensor exhibited excellent electro catalytic activity towards Hx with linear range of 20 μM to 512 μM, limit of detection of 9.5 μM, and sensitivity of 4.1 nA/μM. In addition, the biosensor also demonstrated strong anti-interference properties in the presence of uric acid (UA), ascorbic acid (AA) and glucose. Minimal interference of xanthine (Xn) was observed at ~7%. Moreover, the biosensor showed good repeatability (4.3% RSD) and reproducibility (3.8% RSD). The reported biosensor was tested towards the detection of Hx in pork tenderloins stored at room temperature for seven days. There was a good correlation (r=0.9795) between biosensor response and measurements obtained by a standard enzymatic colorimetric method. The TiO2-G nanocomposite is therefore an effective electrode material to be used in electrochemical biosensors to assess the freshness of meat. © 2016 Elsevier B.V

Polybenzimidazole (PBI) Functionalized Nanographene as Highly Stable Catalyst Support for Polymer Electrolyte Membrane Fuel Cells (PEMFCs)

Nanoscale graphenes were used as cathode catalyst supports in proton exchange membrane fuel cells (PEMFCs). Surface-initiated polymerization that covalently bonds polybenzimidazole (PBI) polymer on the surface of graphene supports enables the uniform distribution of the Pt nanoparticles, as well as allows the sealing of the unterminated carbon bonds usually present on the edge of graphene from the chemical reduction of graphene oxide. The nanographene effectively shortens the length of channels and pores for O2 diffusion/water dissipation and significantly increases the primary pore volume. Further addition of p-phenyl sulfonic functional graphitic carbon particles as spacers, increases the specific volume of the secondary pores and greatly improves O2 mass transport within the catalyst layers. The developed composite cathode catalyst of Pt/PBI-nanographene (50 wt%) + SO3H-graphitic carbon black demonstrates a higher beginning of life (BOL) PEMFC performance as compared to both Pt/PBI-nanographene (50 wt%) and Pt/PBI-graphene (50 wt%) + SO3H-graphitic carbon black (GCB). Accelerated stress tests show excellent support durability compared to that of traditional Pt/Vulcan XC72 catalysts, when subjected to 10,000 cycles from 1.0 V to 1.5 V. This study suggests the promise of using PBI-nanographene + SO3H-GCB hybrid supports in fuel cells to achieve the 2020 DOE targets for transportation applications.This article is published as Xin, Le, Fan Yang, Yang Qiu, Aytekin Uzunoglu, Tommy Rockward, Rodney L. Borup, Lia A. Stanciu, Wenzhen Li, and Jian Xie. "Polybenzimidazole (PBI) functionalized nanographene as highly stable catalyst support for polymer electrolyte membrane fuel cells (PEMFCs)." Journal of The Electrochemical Society 163, no. 10 (2016): F1228. DOI: 10.1149/2.0921610jes. Posted with permission.</p