ABSTRACT
High-throughput computational materials discovery has promised significant acceleration of the design and discovery of new materials for many years. Despite a surge in interest and activity, the constraints imposed by large-scale computational resources present a significant bottleneck. Furthermore, examples of very large-scale computational discovery carried out through experimental validation remain scarce, especially for materials with product applicability. Here, we demonstrate how this vision became reality by combining state-of-the-art machine learning (ML) models and traditional physics-based models on cloud high-performance computing (HPC) resources to quickly navigate through more than 32 million candidates and predict around half a million potentially stable materials. By focusing on solid-state electrolytes for battery applications, our discovery pipeline further identified 18 promising candidates with new compositions and rediscovered a decade's worth of collective knowledge in the field as a byproduct. We then synthesized and experimentally characterized the structures and conductivities of our top candidates, the NaxLi3-xYCl6 (0≤ x≤ 3) series, demonstrating the potential of these compounds to serve as solid electrolytes. Additional candidate materials that are currently under experimental investigation could offer more examples of the computational discovery of new phases of Li- and Na-conducting solid electrolytes. The showcased screening of millions of materials candidates highlights the transformative potential of advanced ML and HPC methodologies, propelling materials discovery into a new era of efficiency and innovation.
ABSTRACT
Research on cerium oxide nanoparticles (nanoceria) has captivated the scientific community due to their unique physical and chemical properties, such as redox activity and oxygen buffering capacity, which made them available for many technical applications, including biomedical applications. The redox mimetic antioxidant properties of nanoceria have been effective in the treatment of many diseases caused by reactive oxygen species (ROS) and reactive nitrogen species. The mechanism of ROS scavenging activity of nanoceria is still elusive, and its redox activity is controversial due to mixed reports in the literature showing pro-oxidant and antioxidant activity. In light of its current research interest, it is critical to understand the behavior of nanoceria in the biological environment and provide answers to some of the critical and open issues. This review critically analyzes the status of research on the application of nanoceria to treat diseases caused by ROS. It reviews the proposed mechanism of action and shows the effect of surface coatings on its redox activity. It also discusses some of the crucial issues in deciphering the mechanism and redox activity of nanoceria and suggests areas of future research.
Subject(s)
Cerium , Nanoparticles , Oxidation-Reduction , Reactive Oxygen SpeciesABSTRACT
Cerium oxide Nanoparticles (CNPs) are of significant interest to the scientific community due to their wide spread applications in a variety of fields. It is proposed that size dependent variations in the extent of Ce3+ and Ce4+ oxidation states of cerium in CNPs determines the performance of CNPs in application environments. To obtain greater molecular and structural understanding of chemical state transformations previously reported for ceria ≈ 3 nm nanoparticles (CNPs) in response to changing ambient conditions, microXRD and Raman measurements were carried out for various solution conditions. The particles were observed to undergo a reversible transformation from a defective ceria structure to a non-ceria amorphous oxy-hydroxide/peroxide phase in response to the addition of 30% hydrogen peroxide. For CNPs made up of ~8 nm crystallites, a partial transformation was observed and no transformation was observed for CNPs made up of ~ 40 nm crystallites. This observation of differences in size dependent transition behavior may help explain the benefits of using smaller CNPs in applications requiring regenerative behavior.
ABSTRACT
Cerium oxide nanoparticles (CeNPs) have gathered much attention in the biomedical field due to its unique antioxidant property. It can protect cells and tissues from oxidative stress induced damage due to its autoregenerative redox cycle. Our study explores the antioxidant and antigenotoxic behavior of PEGylated CeNPs toward oxidative insult produced by buthionine sulfoximine (BSO) in human keratinocytes (HaCaT cells). BSO inhibits the γ-glutamylcysteinesynthetase (γ-GCS) enzyme and thus acts as a glutathione (GSH) depleting agent to modulate the cellular redox potential. GSH is a natural ROS scavenger present in the mammalian cells, and its depletion causes generation of reactive oxygen species (ROS). In this study, we challenged HaCaT cells (keratinocytes) with BSO to alter the redox potential within the cell and monitored toxicity, ROS generation, and nuclear fragmentation. We also followed changes in expressions of related proteins and genes. We found that PEGylated CeNPs can protect HaCaT cells from BSO-induced oxidative damage. BSO-exposed cells, preincubated with PEGylated CeNPs, showed better cell survival and significant decrease in the intracellular levels of ROS. We also observed decrease in lactate dehydrogenase (LDH) release and nuclear fragmentation in CeNP-treated cells that were challenged with BSO as compared to treatment with BSO alone. Exposure of HaCaT cells with BSO leads to altered expression of antioxidant genes and proteins, i.e., thioredoxin reductase (TrxR) and peroxiredoxin 6 (Prx6) whereas, in our study, pretreatment of PEGylated CeNPs reduces the need for induction of genes that produce enzymes involved in the defense against oxidative stress. Since, growing evidence argued the involvement of ROS in mediating death of mammalian cells in several ailments, our finding reinforces the use of PEGylated CeNPs as a potent pharmacological agent under the lower cellular GSH/GSSG ratios for the treatment of diseases mediated by free radicals.
Subject(s)
Cerium/chemistry , Glutamate-Cysteine Ligase/antagonists & inhibitors , Keratinocytes/cytology , Oxidative Stress , Buthionine Sulfoximine/pharmacology , Cells, Cultured , Glutathione , Humans , Keratinocytes/drug effects , Nanoparticles , Oxidation-Reduction , Reactive Oxygen Species/analysisABSTRACT
We studied the interactions between the carboxylate anchoring group from trimethylacetic acid (TMAA) and CeO2(111) surfaces as a function of oxygen stoichiometry using in situ X-ray photoelectron spectroscopy (XPS). The stoichiometric CeO2(111) surface was obtained by annealing the thin film under 2.0 × 10(-5) Torr of oxygen at â¼550 °C for 30 min. In order to reduce the CeO2(111) surface, the thin film was annealed under â¼5.0 × 10(-10) Torr vacuum conditions at 550 °C, 650 °C, 750 °C and 850 °C for 30 min to progressively increase the oxygen defect concentration on the surface. The saturated TMAA coverage on the CeO2(111) surface determined from XPS elemental composition is found to increase with increasing oxygen defect concentration. This is attributed to the increase of under-coordinated cerium sites on the surface with the increase in the oxygen defect concentrations. XPS results were in agreement with periodic density functional theory (DFT) calculations and indicate a stronger binding between the carboxylate group from TMAA and the oxygen deficient CeO2-δ(111) surface through dissociative adsorption.
ABSTRACT
Experimental and theoretical investigations were performed to investigate the effect of water on optical properties of nanoceria as a function of Ce(3+) concentration. Theoretical studies based on density functional plane-wave calculations reveal that the indirect optical transitions in bare ceria nanoparticles are red-shifted with an increase in the concentration of Ce(3+). However, ceria nanoparticles model with adsorbed water molecules show a blue shift in the indirect optical spectra under identical conditions. Direct optical transitions are almost independent of Ce(3+) concentration but show a pronounced blue shift in the aqueous environment relative to the bare nanoparticles. The theoretical study is consistent with our experimental observation in difference of shift behaviour in bare and aqueous suspended ceria nanoparticles. This change from red- to blue-shift in indirect optical transitions is associated with the polarization effect of water molecules on f-electron states.
Subject(s)
Cerium/chemistry , Metal Nanoparticles , Optics and Photonics , Water/chemistry , Models, ChemicalABSTRACT
With the threat of increasing SARS-CoV-2 cases looming in front of us and no effective and safest vaccine available to curb this pandemic disease due to its sprouting variants, many countries have undergone a lockdown 2.0 or planning a lockdown 3.0. This has upstretched an unprecedented demand to develop rapid, sensitive, and highly selective diagnostic devices that can quickly detect coronavirus (COVID-19). Traditional techniques like polymerase chain reaction have proven to be time-inefficient, expensive, labor intensive, and impracticable in remote settings. This shifts the attention to alternative biosensing devices that can be successfully used to sense the COVID-19 infection and curb the spread of coronavirus cases. Among these, nanomaterial-based biosensors hold immense potential for rapid coronavirus detection because of their noninvasive and susceptible, as well as selective properties that have the potential to give real-time results at an economical cost. These diagnostic devices can be used for mass COVID-19 detection to understand the rapid progression of the infection and give better-suited therapies. This review provides an overview of existing and potential nanomaterial-based biosensors that can be used for rapid SARS-CoV-2 diagnostics. Novel biosensors employing different detection mechanisms are also highlighted in different sections of this review. Practical tools and techniques required to develop such biosensors to make them reliable and portable have also been discussed in the article. Finally, the review is concluded by presenting the current challenges and future perspectives of nanomaterial-based biosensors in SARS-CoV-2 diagnostics.
ABSTRACT
Nanoceria has evolved as a promising nanomaterial due to its unique enzyme-like properties, including excellent oxidase mimetic activity, which significantly increases in the presence of fluoride ions. However, this significant increase in oxidase activity has never been utilised as a signal enhancer for the detection of biological analytes partly because of the lack of understanding of the mechanism involved in this process. In this study, we show that the surface oxidation state of cerium ions plays a very crucial role in different enzymatic activities, especially the oxidase mimetic activity by engineering nanoceria with three different surface Ce4+/Ce3+ compositions. Using DFT calculations combined with Bader charge analysis, it is demonstrated that stoichiometric ceria registers a higher oxidase mimetic activity than oxygen-deficient ceria with a low Ce4+/Ce3+ ratio due to a higher charge transfer from a substrate, 3,3',5,5' tetramethylbenzidine (TMB), to the ceria surface. We also show that the fluoride ions can significantly increase the charge transfer from the TMB surface to ceria irrespective of the surface Ce4+/Ce3+ ratio. Using this knowledge, we first compare the fluoride sensing properties of nanoceria with high Ce4+ and mixed Ce4+/Ce3+ oxidation states and further demonstrate that the linear detection range of fluoride ions can be extended to 1-10 ppm for nanoceria with mixed oxidation states. Then, we also demonstrate an assay for fluoride assisted detection of glutathione, an antioxidant with elevated levels during cancer, using nanoceria with a high surface Ce4+/Ce3+ ratio. The addition of fluoride ions in this assay allows the detection of glutathione in the linear range of 2.5-50 ppm with a limit of detection (LOD) of 3.8 ppm. These studies not only underpin the role of the surface Ce4+/Ce3+ ratio in tuning the fluoride assisted boost in the oxidase mimetic activity of nanoceria but also its strategic application in designing better colourimetric assays.
Subject(s)
Fluorides , Glutathione , Density Functional Theory , OxidoreductasesABSTRACT
Cerium oxide nanoparticles, nanoceria, are inorganic antioxidants that have catalytic activities which mimic those of the neuroprotective enzymes superoxide dismutase and catalase. We have previously shown that nanoceria preserve retinal morphology and prevent loss of retinal function in a rat light damage model. In this study, the homozygous tubby mutant mouse, which exhibits inherited early progressive cochlear and retinal degeneration, was used as a model to test the ability of nanoceria to slow the progression of retinal degeneration. Tubby mice were injected systemically, intracardially, with 20 µl of 1mM nanoceria in saline, at postnatal day 10 and subsequently at P20 and P30 whereas saline injected and uninjected wild type (or heterozygous tubby) served as injected and uninjected controls, respectively. Assays for retinal function, morphology and signaling pathway gene expression were performed on P34 mice. Our data demonstrate that nanoceria protect the retina by decreasing Reactive Oxygen Species (ROS), up-regulating the expression of neuroprotection-associated genes; down-regulating apoptosis signaling pathways and/or up-regulating survival signaling pathways to slow photoreceptor degeneration. These data suggest that nanoceria have significant potential as global agents for therapeutic treatment of inherited retinal degeneration and most types of ocular diseases.
Subject(s)
Apoptosis/drug effects , Cell Survival/drug effects , Cerium/administration & dosage , Nanoparticles/administration & dosage , Photoreceptor Cells, Vertebrate/drug effects , Retinal Degeneration/prevention & control , Signal Transduction/drug effects , Adaptor Proteins, Signal Transducing , Analysis of Variance , Animals , Apoptosis/physiology , Blotting, Western , Cell Survival/physiology , Electroretinography , Mice , Mice, Knockout , Photoreceptor Cells, Vertebrate/physiology , Proteins/genetics , Reactive Oxygen Species , Retinal Degeneration/genetics , Retinal Degeneration/physiopathology , Reverse Transcriptase Polymerase Chain Reaction , Signal Transduction/physiologyABSTRACT
Application of inorganic nanoparticles in diagnosis and therapy has become a critical component in the targeted treatment of diseases. The surface modification of inorganic oxides is important for providing diversity in size, shape, solubility, long-term stability, and attachment of selective functional groups. This Minireview describes the role of polyethylene glycol (PEG) in the surface modification of oxides and focuses on their biomedical applications. Such a PEGylation of surfaces provides "stealth" characteristics to nanomaterials otherwise identified as foreign materials by human body. The role of PEG as structure-directing agent in synthesis of oxides is also presented.
Subject(s)
Nanoparticles/chemistry , Polyethylene Glycols/chemistry , Drug Carriers/chemistry , Humans , Metals/chemistry , Nanoparticles/toxicity , Nanoparticles/ultrastructure , Oxides/chemistryABSTRACT
Long-term stability and surface properties of colloidal nanoparticles have significance in many applications. Here, surface charge modified hydrated cerium oxide nanoparticles (CNPs, also known as nanoceria) are synthesized, and their dynamic ion exchange interactions with the surrounding medium are investigated in detail. Time-dependent zeta (zeta) potential (ZP) variations of CNPs are demonstrated as a useful characteristic for optimizing their surface properties. The surface charge reversal of CNPs observed with respect to time, concentration, temperature, and doping is correlated to the surface modification of CNPs in aqueous solution and the ion exchange reaction between the surface protons (H(+)) and the neighboring hydroxyls ions (OH(-)). Using density functional theory (DFT) calculations, we have demonstrated that the adsorption of H(+) ions on the CNP surface is kinetically more favorable while the adsorption of OH(-) ions on CNPs is thermodynamically more favorable. The importance of selecting CNPs with appropriate surface charges and the implications of dynamic surface charge variations are exemplified with applications in microelectronics and biomedical.
Subject(s)
Cerium/chemistry , Computer Simulation , Models, Chemical , Nanoparticles/chemistry , Adsorption , Colloids/chemical synthesis , Colloids/chemistry , Hydroxides/chemistry , Ions/chemistry , Protons , Surface Properties , Thermodynamics , Water/chemistryABSTRACT
The series of breakthroughs that have occurred within the realm of nanotechnology have been the source of several new products and technological interventions. One of the most salient examples in this regard is the widespread employment of titanium dioxide (TiO2) nanoparticles across a range of consumer goods. Given that waste is generated at every stage of the consumer-product cycle (from production to disposal), many items with TiO2 nanoparticles are likely to end up being discarded into water bodies. In order to understand the interaction of TiO2 NPs with aquatic ecosystem, the ecological fate and toxicity of TiO2 NPs was studied by exposing zebrafish embryos to a combination of abiotic factors (humic acid and clay) to assess its effect on the development of zebrafish embryos. The physiological changes were correlated with genetic marker analysis to holistically understand the effect on embryos development. Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was used to analyze the interaction energy between TiO2 NPs and natural organic matter (NOM) for understanding the aggregation behavior of engineered nanoparticles (ENPs) in media. The study revealed that combination of HA and clay stabilized TiO2 NPs, compared to bare TiO2 and HA or clay alone. TiO2 NPs and TiO2 NPsâ¯+â¯Clay significantly altered the expression of genes involved in development of dorsoventral axis and neural network of zebrafish embryos. However, the presence of HA and HAâ¯+â¯clay showed protective effect on zebrafish embryo development. The complete system analysis demonstrated the possible ameliorating effects of abiotic factors on the ecotoxicity of ENPs.
Subject(s)
Clay/chemistry , Metal Nanoparticles/toxicity , Titanium/toxicity , Animals , Embryo, Nonmammalian , Embryonic Development/drug effects , Humic Substances/analysis , Metal Nanoparticles/chemistry , Titanium/chemistry , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/toxicity , ZebrafishABSTRACT
Cerium oxide nanoparticles have been shown to mimic oxidoreductase enzymes by catalyzing the decomposition of organic substrates and reactive oxygen species. This mimicry can be found in superoxide radicals and hydrogen peroxides, which are harmful molecules produced in oxidative stress-associated diseases. Despite the fact that nanoparticle functionalization is mandatory in the context of nanomedicine, the influence of polymer coatings on their enzyme-like catalytic activity is poorly understood. In this work, six polymer-coated cerium oxide nanoparticles are prepared by the association of 7.8 nm cerium oxide cores with two poly(sodium acrylate) and four poly(ethylene glycol) (PEG)-grafted copolymers with different terminal or anchoring end groups, such as phosphonic acids. The superoxide dismutase-, catalase-, peroxidase-, and oxidase-like catalytic activities of the coated nanoparticles were systematically studied. It is shown that the polymer coatings do not affect the superoxide dismutase-like, impair the catalase-like and oxidase-like, and surprisingly improves peroxidase-like catalytic activities of cerium oxide nanoparticles. It is also demonstrated that the particles coated with the PEG-grafted copolymers perform better than the poly(acrylic acid)-coated ones as oxidoreductase-like enzymes, a result that confirms the benefit of having phosphonic acids as anchoring groups at the particle surface.
Subject(s)
Acrylic Resins/chemistry , Cerium/chemistry , Nanoparticles/chemistry , Polyethylene Glycols/chemistry , Catalase/chemistry , Catalase/metabolism , Catalysis , Oxidoreductases/chemistry , Oxidoreductases/metabolism , Particle Size , Peroxidase/chemistry , Peroxidase/metabolism , Reactive Oxygen Species/chemistry , Reactive Oxygen Species/metabolism , Superoxide Dismutase/chemistry , Superoxide Dismutase/metabolism , Surface PropertiesABSTRACT
Carbon nitride (CN), a 2D material composed of only carbon (C) and nitrogen (N), which are linked by strong covalent bonds, has been used as a metal-devoid and visible-light-active photocatalyst owing to its magnificent optoelectronic and physicochemical properties including suitable bandgap, adjustable energy-band positions, tailor-made surface functionalities, low cost, metal-free nature, and high thermal, chemical, and mechanical stabilities. CN-based materials possess a lot of advantages over conventional metal-based inorganic photocatalysts including ease of synthesis and processing, versatile functionalization or doping, flexibility for surface engineering, low cost, sustainability, and recyclability without any leaching of toxic metals from photocorrosion. Carbon nitrides and their hybrid materials have emerged as attractive candidates for CO2 capture and its reduction into clean and green low-carbon fuels and valuable chemical feedstock by using sustainable and intermittent renewable energy sources of sunlight and electricity through the heterogeneous photo(electro)catalysis. Here, the latest research results in this field are summarized, including implementation of novel functionalized nanostructured CNs and their hybrid heterostructures in meeting the stringent requirements to raise the efficiency of the CO2 reduction process by using state-of-the-art photocatalysis, electrocatalysis, photoelectrocatalysis, and feedstock reactions. The research in this field is primarily focused on advancement in the synthesis of nanostructured and functionalized CN-based hybrid heterostructured materials. More importantly, the recent past has seen a surge in studies focusing significantly on exploring the mechanism of their application perspectives, which include the behavior of the materials for the absorption of light, charge separation, and pathways for the transport of CO2 during the reduction process.
ABSTRACT
We report the direct synthesis of cerium oxide nanoparticles (CNPs) in polyethylene glycol (PEG) based solutions with efficient radical scavenging properties. Synthesis of CNPs in PEG demonstrated a concentration dependent (of PEG) redox activity characterized by UV-visible spectroscopy. PEGylated CNPs acted as efficient radical scavengers, and superoxide dismutase (SOD) activity of CNPs synthesized in various concentration of PEG did not reduce compared to bare nanoceria. In addition to superoxide, PEGylated nanoceria demonstrated quenching of peroxide radicals as well. It was observed that the reaction with hydrogen peroxide leads to the formation of a charge transfer complex governed by the concentration of PEG. The stability of the charge transfer complex provides the tunable oxidation state of CNPs. The stability of this complex influences the regenerative capacity of the active 3+ oxidation state of CNPs. The cell viability as well as SOD activity of PEGylated CNPs is compared to those of bare CNPs, and the differences are outlined.
Subject(s)
Cerium/chemistry , Free Radical Scavengers/chemistry , Nanoparticles/chemistry , Polyethylene Glycols/chemistry , Biocompatible Materials/chemistry , Free Radical Scavengers/chemical synthesis , Hydrogen Peroxide/chemistry , Oxidation-Reduction , Spectrophotometry, Ultraviolet , Superoxide Dismutase/chemistry , Superoxides/chemistryABSTRACT
The valence and oxygen defect properties of cerium oxide nanoparticles (nanoceria) suggest that they may act as auto-regenerative free radical scavengers. Overproduction of the free radical nitric oxide (NO) by the enzyme inducible nitric oxide synthase (iNOS) has been implicated as a critical mediator of inflammation. NO is correlated with disease activity and contributes to tissue destruction. The ability of nanoceria to scavenge free radicals, or reactive oxygen species (ROS), and inhibit inflammatory mediator production in J774A.1 murine macrophages is investigated. Cells internalize nanoceria, the treatment is nontoxic, and oxidative stress and pro-inflammatory iNOS protein expression are abated with stimulation. In vivo studies show nanoceria deposition in mouse tissues with no pathogenicity. Taken together, it is suggested that cerium oxide nanoparticles are well tolerated in mice and are incorporated into cellular tissues. Furthermore, nanoceria may have the potential to reduce ROS production in states of inflammation and therefore serve as a novel therapy for chronic inflammation.
Subject(s)
Cerium/administration & dosage , Cytokines/immunology , Macrophages/drug effects , Macrophages/immunology , Nanoparticles/administration & dosage , Reactive Oxygen Species/immunology , Animals , Anti-Inflammatory Agents/pharmacology , Anti-Inflammatory Agents/toxicity , Cell Line , Cerium/toxicity , Materials Testing , Mice , Nanoparticles/toxicity , Tissue DistributionABSTRACT
Copper oxide nanoparticles (CuO NPs) is one of the most commonly used metal oxide nanoparticles for commercial and industrial products. An increase in the manufacturing and use of the CuO NPs based products has increased the likelihood of their release into the aquatic environment. This has attracted major attention among researchers to explore their impact in human as well as environmental systems. CuO NPs, once released into the environment interact with the biotic and abiotic constituents of the ecosystem. Hence the objective of the study was to provide a holistic understanding of the effect of abiotic factors on the stability and aggregation of CuO NPs and its correlation with their effect on the development of zebrafish embryo. It has been observed that the bioavailability of CuO NPs decrease in presence of humic acid (HA) and heteroagglomeration of CuO NPs occurs with clay minerals. CuO NPs, CuO NPs + HA and CuO NPs + Clay significantly altered the expression of genes involved in development of dorsoventral axis and neural network of zebrafish embryos. However, the presence of HA with clay showed protective effect on zebrafish embryo development. These findings provide new insights into the interaction of NPs with abiotic factors and combined effects of such complexes on developing zebrafish embryos genetic markers.
Subject(s)
Clay/chemistry , Copper/toxicity , Metal Nanoparticles/toxicity , Water Pollutants, Chemical/toxicity , Animals , Bentonite , Copper/chemistry , Ecosystem , Embryo, Nonmammalian/abnormalities , Embryo, Nonmammalian/drug effects , Humic Substances/analysis , Nanoparticles , Oxides , Water Pollutants, Chemical/analysis , Zebrafish/embryologyABSTRACT
The formation of nanorods, driven by the physicochemical phenomena during the freezing and after the aging of frozen ceria nanoparticle suspensions, is reported. During freezing of a dilute aqueous solution of CeO2 nanocrystals, some nuclei remain in solution while others are trapped inside micro- and nanometer voids formed within the growing ice front. Over time (2-3 weeks) the particles trapped within the nanometer-wide voids in the ice combine by an oriented attachment process to form ceria nanorods. The experimental observations are consistent with molecular dynamics simulations of particle aggregation in constrained environments. These observations suggest a possible strategy for the templated formation of nanostructures through self-assembly by exploiting natural phenomena, such as voids formed during freezing of water. This research suggests a very simple, green chemical route to guide the formation of one- and three-dimensional self-assembled nanostructures.
Subject(s)
Cerium/chemistry , Ice , Nanostructures/chemistry , Computer Simulation , Microscopy, Electron, Transmission , Models, Chemical , Nanostructures/ultrastructure , Nanotubes/chemistry , Nanotubes/ultrastructure , Water/chemistryABSTRACT
Cerium oxide nanoparticles (nanoceria) have recently been shown to protect cells against oxidative stress in both cell culture and animal models. Nanoceria has been shown to exhibit superoxide dismutase (SOD) activity using a ferricytochrome C assay, and this mimetic activity that has been postulated to be responsible for cellular protection by nanoceria. The nature of nanoceria's antioxidant properties, specifically what physical characteristics make nanoceria effective at scavenging superoxide anion, is poorly understood. In this study electron paramagnetic resonance (EPR) analysis confirms the reactivity of nanoceria as an SOD mimetic. X-ray photoelectron spectroscopy (XPS) and UV-visible analyses of nanoceria treated with hydrogen peroxide demonstrate that a decrease in the Ce 3(+)/4(+) ratio correlates directly with a loss of SOD mimetic activity. These results strongly suggest that the surface oxidation state of nanoceria plays an integral role in the SOD mimetic activity of nanoceria and that ability of nanoceria to scavenge superoxide is directly related to cerium(III) concentrations at the surface of the particle.
Subject(s)
Biomimetic Materials/chemistry , Cerium/chemistry , Superoxide Dismutase/metabolism , Biocompatible Materials/chemistry , Biocompatible Materials/metabolism , Biomimetic Materials/metabolism , Cerium/metabolism , Electron Spin Resonance Spectroscopy , Hydrogen Peroxide/chemistry , Nanoparticles/chemistry , Oxidation-ReductionABSTRACT
Catalytically active individual gold (Au) and cerium oxide (CeO2) nanoparticles (NPs) are well known to exhibit specific enzyme-like activities, such as natural catalase, oxidase, superoxide dismutase, and peroxidase enzymes. These activities have been maneuvered to design several biological applications such as immunoassays, glucose detection, radiation and free radical protection and tissue engineering. In biological systems, multienzyme complexes are involved in catalyzing important reactions of essential metabolic processes such as respiration, biomolecule synthesis, and photosynthesis. It is well known that metabolic processes linked with multienzyme complexes offer several advantages over reactions catalyzed by individual enzymes. A functional nanozyme depicting multienzyme like properties has eluded the researchers in the nanoscience community for the past few decades. In the current report, we have designed a functional multienzyme in the form of Gold (core)-CeO2 (shell) nanoparticles (Au/CeO2 CSNPs) exhibiting excellent peroxidase, catalase, and superoxide dismutase enzyme-like activities that are controlled simply by tuning the pH. The reaction kinetic parameters reveal that the peroxidase-like activity of this core-shell nanozyme is comparable to natural horseradish peroxidase (HRP) enzyme. Unlike peroxidase-like activity exhibited by other nanomaterials, Au/CeO2 CSNPs showed a decrease in hydroxyl radical formation, suggesting that the biocatalytic reactions are performed by efficient electron transfers. A significant enzyme-like activity of this core-shell nanoparticle was conserved at extreme pH (2-11) and temperatures (up to 90⯰C), clearly suggesting the superiority over natural enzymes. Further, the utility of peroxidase-like activity of this core-shell nanoparticles was extended for the detection of glucose, which showed a linear range of detection between (100⯵M to 1â¯mM). It is hypothesized that the proximity of the redox potentials of Au+/Au and Ce (III)/Ce (IV) may result in a redox couple promoting the multienzyme activity of core-shell nanoparticles. Au/CeO2 CSNPs may open new directions for development of single platform sensors in multiple biosensing applications.