Daniel Andreescu

Paper bioassay based on ceria nanoparticles as colorimetric probes.

We report the first use of redox nanoparticles of cerium oxide as colorimetric probes in bioanalysis. The method is based on changes in the physicochemical properties of ceria nanoparticles, used here as chromogenic indicators, in response to the analyte. We show that these particles can be fully integrated in a paper-based bioassay. To construct the sensor, ceria nanoparticles and glucose oxidase were coimmobilized onto filter paper using a silanization procedure. In the presence of glucose, the enzymatically generated hydrogen peroxide induces a visual color change of the ceria nanoparticles immobilized onto the bioactive sensing paper, from white-yellowish to dark orange, in a concentration-dependent manner. A detection limit of 0.5 mM glucose with a linear range up to 100 mM and a reproducibility of 4.3% for n = 11 ceria paper strips were obtained. The assay is fully reversible and can be reused for at least 10 consecutive measurement cycles, without significant loss of activity. Another unique feature is that it does not require external reagents, as all the sensing components are fixed onto the paper platform. The bioassay can be stored for at least 79 days at room temperature while maintaining the same analytical performance. An example of analytical application was demonstrated for the detection of glucose in human serum. The results demonstrate the potential of this type of nanoparticles as novel components in the development of robust colorimetric bioassays.

A new electrocatalytic mechanism for the oxidation of phenols at platinum electrodes

Electrochemical oxidation of phenolic compounds generally produces unstable phenoxy radicals that readily polymerize to passivate the surface of solid electrodes. In this study, the electrocatalytic oxidation of phenol in the presence and absence of methanol was investigated by cyclic voltammetry on a platinum electrode. The cyclic voltammogram of phenol in a mixture of phosphate buffer/methanol solution showed well-defined peaks at ∼600 mV vs. Ag/AgCl reference electrode, which surprising, gradually increased with repetitive scanning, stabilizing after 50 cycles. This unexpected behavior is in contrast to previous studies involving phenolic compounds, which always show a decrease in intensity during continuous potential scanning. Scanning electrochemical spectroscopy (SEM) was further used to investigate the changes in the surface morphology of the Pt electrode after electrodeposition. A new electrocatalytic mechanism for phenol oxidation on the surface of a Pt electrode is suggested in the presence of methanol. The proposed mechanism is based on the formation of a film of Pt oxide/hydroxides onto which the phenol and the products of its electrochemical oxidation are further deposited. The mechanism was also studied using more complex phenolic compounds including resveratrol, quercetin and bisphenol A. The results emphasized the effect of aryl substituents on the electrochemistry of this particular class of compounds.

Electroanalytical evaluation of antioxidant activity of cerium oxide nanoparticles by nanoparticle collisions at microelectrodes.

We describe a simple, cost-effective and rapid electrochemical screening approach to evaluate antioxidant activity of cerium oxide nanoparticles (CeO2 NPs) by single nanoparticle collision at microelectrodes. The method is based on direct monitoring of the interaction between a Pt microelectrode and surface bound superoxo and peroxo anions of CeO2 NPs (Ce-O2(-)/O2(2-)) formed upon exposure to H2O2, selected here as a model reactive oxygen species. We observe an increase in spike current frequency for CeO2 NPs exposed to H2O2, which we attribute to the reduction of surface bound oxygen species when the particles collide with the microelectrode. The results were confirmed with spectroscopic techniques that demonstrate changes in surface reactivity and composition. The spike frequency was found to correlate well with the superoxide dismutase activity of these particles. This approach could enable routine screening of antioxidant NPs using a rapid and inexpensive assay.

Applications and implications of nanoceria reactivity: measurement tools and environmental impact

Cerium oxide nanoparticles or nanoceria have a unique structure and interesting and unusual redox and catalytic properties that vary with the size, shape, charge, surface coating and chemical reactivity. This paper highlights applications and environmental implications of nanoceria, and describes methodologies for the assessment of the reactivity and potential toxicological effects of these particles. The physical and chemical properties in the particle design that are responsible for their reactivity and transformation in environmental and biological conditions are described. Processes such as surface oxidation, formation of surface complexes and potential interaction with redox active components of the environment are discussed. An overview of analytical characterization methods for study of nanoceria properties, reactivity and impact, highlighting methodological challenges and limitations is presented. Examples discussed include strategies to determine physicochemical properties, cytotoxicity and antioxidant or pro-oxidant activity in various exposure environments. Development of new measurement tools to facilitate rapid assessment and accelerate screening of these particles for their reactivity and effects is discussed. Future research needs for environmental assessment of benefits and potential risks associated with the use of nanoceria are also provided.

Redox reactivity of cerium oxide nanoparticles against dopamine

The interaction between dopamine and the redox active cerium oxide nanoparticles, or nanoceria was studied using a suite of spectroscopic and surface characterization methods. Changes in the chemical reactivity and concentration of dopamine upon exposure to nanoceria was assessed in aqueous solutions and a human physiological fluid--human serum. The results indicate strong attachment of dopamine to the nanoparticle surface through oxidation followed by chemisorption of the oxidative product with formation of a charge transfer complex. Such oxidation/surface adsorption processes between nanoceria and dopamine lead to a reduction of the concentration of free dopamine in aqueous environments. These findings suggest that the redox reactivity of nanoceria may alter dopamine levels in biological systems exposed to these particles and indicate the need for a comprehensive assessment of the potential neurological consequences that might result from intended or unintended exposure to these particles.

Chapter 7 New materials for biosensors, biochips and molecular bioelectronics

Publisher Summary This chapter reviews the state-of-the-art biosensing materials and addresses the limitations of existing biosensing materials. Biosensor devices are fabricated from a large variety of materials for simplifying assay as well as for ensuring the requirements of reproducibility, biocompatibility, cost, and suitability for mass production. Novel materials are thus needed to improve the mechanical and chemical stability of the sensor for practical applications in various conditions and to improve the immobilization scheme to ensure sensor stability and the spatial control of biomolecules. The most important materials for chemical and biochemical sensors include organic polymers, sol–gel systems, semiconductors, and various other conducting composites. The chapter discusses various requirements for selecting an electrode material for the construction of biosensors: (1) biocompatibility with the biological element, (2) absence of diffusion barriers, (3) stability with changes in temperature, pH, ionic strength, or macroenvironment, (4) sufficient sensitivity and selectivity for the analyte of interest, and (5) low cost and ease of mass production.

Functional Paper-Based Platform for Rapid Capture and Detection of CeO2 Nanoparticles

Development of systems for capture, sequestration, and tracking of nanoparticles (NPs) is becoming a significant focus in many aspects of nanotechnology and environmental research. These systems enable a broad range of applications for evaluating concentration, distribution, and effects of NPs for environmental, clinical, epidemiological, and occupational exposure studies. Herein, we describe the first example of a ligand-graft multifunctional platform for capture and detection of cerium oxide (CeO2 or ceria) NPs. The approach involves the use of redox-active ligands containing o-dihydroxy functionality, enabling multivalent binding, surface retention, and formation of charge transfer complexes between the grafted ligand and the NPs. Using this strategy, paper-based and microarray-printed platforms with NP-capture ability involving either catechol or ascorbic acid as ligands were successfully fabricated. Surface modification was determined by infrared spectroscopy, electron microscopy, X-ray spectroscopy, and thermogravimetric analysis. Functionality was demonstrated for the rapid assessment of NPs in chemical mechanical planarization (CMP) slurries and CMP wastewaters. This novel approach can enable further development of devices and separation technologies including platforms for retention and separation of NPs and measurement tools for detection of NPs in various environments.