Coated Cerium Oxide Nanoparticles Research Articles

Ordered hierarchical superlattice amplifies coated-CeO2 nanoparticles luminescence

Achieving a controlled preparation of nanoparticle superstructures with spatially periodic arrangement, also called superlattices, is one of the most intriguing and open questions in soft matter science. The interest in such regular superlattices originates from the potentialities in tailoring the physicochemical properties of the individual constituent nanoparticles, eventually leading to emerging behaviors and/or functionalities that are not exhibited by the initial building blocks. Despite progress, it is currently difficult to obtain such ordered structures; the influence of parameters, such as size, softness, interaction potentials, and entropy, are neither fully understood yet and not sufficiently studied for 3D systems. In this work, we describe the synthesis and characterization of spatially ordered hierarchical structures of coated cerium oxide nanoparticles in water suspension prepared by a bottom-up approach. Covering the CeO2 surface with amphiphilic molecules having chains of appropriate length makes it possible to form ordered structures in which the particles occupy well-defined positions. In the present case superlattice arrangement is accompanied by an improvement in photoluminescence (PL) efficiency, as an increase in PL intensity of the superlattice structure of up to 400 % compared with that of randomly dispersed nanoparticles was observed. To the best of our knowledge, this is one of the first works in the literature in which the coexistence of 3D structures in solution, such as face-centered cubic (FCC) and Frank-Kasper (FK) phases, of semiconductor nanoparticles have been related to their optical properties.

Deep Eutectic Solvent Coated Cerium Oxide Nanoparticles Based Polysulfone Membrane to Mitigate Environmental Toxicology.

In this study, ceria nanoparticles (NPs) and deep eutectic solvent (DES) were synthesized, and the ceria-NP's surfaces were modified by DES to form DES-ceria NP filler to develop mixed matrix membranes (MMMs). For the sake of interface engineering, MMMs of 2%, 4%, 6% and 8% filler loadings were fabricated using solution casting technique. The characterizations of SEM, FTIR and TGA of synthesized membranes were performed. SEM represented the surface and cross-sectional morphology of membranes, which indicated that the filler is uniformly dispersed in the polysulfone. FTIR was used to analyze the interaction between the filler and support, which showed there was no reaction between the polymer and DES-ceria NPs as all the peaks were consistent, and TGA provided the variation in the membrane materials with respect to temperature, which categorized all of the membranes as very stable and showed that the trend of stability increases with respect to DES-ceria NPs filler loading. For the evaluation of efficiency of the MMMs, the gas permeation was tested. The permeability of CO2 was improved in comparison with the pristine Polysulfone (PSF) membrane and enhanced selectivities of 35.43 (αCO2/CH4) and 39.3 (αCO2/N2) were found. Hence, the DES-ceria NP-based MMMs proved useful in mitigating CO2 from a gaseous mixture.

Synthesis of Stable Cerium Oxide Nanoparticles Coated with Phosphonic Acid-Based Functional Polymers.

Functional polymers, such as poly(ethylene glycol) (PEG), terminated with a single phosphonic acid, hereafter PEGik-Ph are often applied to coat metal oxide surfaces during post-synthesis steps but are not sufficient to stabilize sub-10 nm particles in protein-rich biofluids. The instability is attributed to the weak binding affinity of post-grafted phosphonic acid groups, resulting in a gradual detachment of the polymers from the surface. Here, we assess these polymers as coating agents using an alternative route, namely, the one-step wet-chemical synthesis, where PEGik-Ph is introduced with cerium precursors during the synthesis. Characterization of the coated cerium oxide nanoparticles (CNPs) indicates a core-shell structure, where the cores are 3 nm cerium oxide and the shell consists of functionalized PEG polymers in a brush configuration. Results show that CNPs coated with PEG1k-Ph and PEG2k-Ph are of potential interest for applications as nanomedicines due to their high Ce(III) content and increased colloidal stability in cell culture media. We further demonstrate that the CNPs in the presence of hydrogen peroxide show an additional absorbance band in the UV-vis spectrum, which is attributed to Ce-O22- peroxo-complexes and could be used in the evaluation of their catalytic activity for scavenging reactive oxygen species.

Performance evaluation of phosphonium based deep eutectic solvents coated cerium oxide nanoparticles for CO2 capture

The critical challenge being faced by our current modern society on a global scale is to reduce the surging effects of climate change and global warming, being caused by anthropogenic emissions of CO2 in the environment. Present study reports the surface driven adsorption potential of deep eutectic solvents (DESs) surface functionalized cerium oxide nanoparticles (CeNPs) for low pressure CO2 separation. The phosphonium based DESs were prepared using tetra butyl phosphoniumbromide as hydrogen bond acceptor (HBA) and 6 acids as hydrogen bond donors (HBDs). The as-developed DESs were characterized and employed for the surface functionalization of CeNPs with their subsequent utilization in adsorption-based CO2 adsorption. The synthesis of as-prepared DESs was confirmed through FTIR measurements and absence of precipitates, revealed through visual observations. It was found that DES6 surface functionalized CeNPs demonstrated 27% higher adsorption performance for CO2 capturing. On the contrary, DES3 coated CeNPs exhibited the least adsorption progress for CO2 separation. The higher adsorption performance associated with DES6 coated CeNPs was due to enhanced surface affinity with CO2 molecules that must have facilitated the mass transport characteristics and resulted an enhancement in CO2 adsorption performance. Carboxylic groups could have generated an electric field inside the pores to attract more polarizable adsorbates including CO2, are responsible for the relatively high values of CO2 adsorption. The quadruple movement of the CO2 molecules with the electron-deficient and pluralizable nature led to the enhancement of the interactive forces between the CO2 molecules and the CeNPs decorated with the carboxylic group hydrogen bond donor rich DES. The current findings may disclose the new research horizons and theoretical guidance for reduction in the environmental effects associated with uncontrolled CO2 emission via employing DES surface coated potential CeNPs.

Screening of semi-volatile compounds in plants treated with coated cerium oxide nanoparticles by comprehensive two-dimensional gas chromatography.

Literature data about semi-volatile organic compounds in plants and the effect of cerium oxide nanoparticles on them are scarce. Surface modification of nanoparticles may change nanoparticle-environment interaction, and therefore affects compounds in plants. In this research, uncoated and glucose-, levan-, and pullulan-coated cerium oxide nanoparticles were used for wheat and pea treatment during the growth. The aim was the screening of semi-volatile organic compounds from plants' shoots using comprehensive two-dimensional gas chromatography-mass spectrometry, a powerful separation technique allowing to reach unique separation resolution, and investigation of qualitative changes after the treatment with coated cerium oxide nanoparticles. The results were analyzed by the identification of individual peaks and fingerprint analysis by image processing. Wheat samples contained a higher number of semi-volatile organic compounds (108) compared to pea (77) but were less affected by the treatments with coated nanoparticles. The highest number of compounds was detected in wheat after the treatment with levan- and pullulan-coated nanoparticles, and in pea after treatment with levan-coated nanoparticles. This article reports a successful application of a semi-volatile organic compounds profile presented only as categorical variables and unique fingerprint images for the inter-cultivar recognition. This method may be useful in screening nanoparticles' effects on different plants.

Polymer-Coated Cerium Oxide Nanoparticles as Oxidoreductase-like Catalysts.

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.

Interaction of Carbohydrate Coated Cerium-Oxide Nanoparticles with Wheat and Pea: Stress Induction Potential and Effect on Development.

Reports about the influence of cerium-oxide nanoparticles (nCeO2) on plants are contradictory due to their positive and negative effects on plants. Surface modification may affect the interaction of nCeO2 with the environment, and hence its availability to plants. In this study, the uncoated and glucose-, levan-, and pullulan-coated nCeO2 were synthesized and characterized. The aim was to determine whether nontoxic carbohydrates alter the effect of nCeO2 on the seed germination, plant growth, and metabolism of wheat and pea. We applied 200 mgL−1 of nCeO2 on plants during germination (Ger treatment) or three week-growth (Gro treatment) in hydroponics. The plant response to nCeO2 was studied by measuring changes in Ce concentration, total antioxidative activity (TAA), total phenolic content (TPC), and phenolic profile. Our results generally revealed higher Ce concentration in plants after the treatment with coated nanoparticles compared to uncoated ones. Considering all obtained results, Ger treatment had a stronger impact on the later stages of plant development than Gro treatment. The Ger treatment had a stronger impact on TPC and plant elongation, whereas Gro treatment affected more TAA and phenolic profile. Among nanoparticles, levan-coated nCeO2 had the strongest and positive impact on tested plants. Wheat showed higher sensitivity to all treatments.

Light-induced Nrf2\u2212/\u2212 mice as atrophic age-related macular degeneration model and treatment with nanoceria laden injectable hydrogel

Elevated oxidative stress and associated reactive oxygen species (ROS) accumulation are hallmarks in the induction and progression of age-related macular degeneration (AMD). By exposing nuclear factor erythroid 2-related factor (Nrf2) knockout (Nrf2−/−) mice to mild white light, we were able to generate a new dry-AMD like murine model to the study. This animal model developed phenotypes of photoreceptor degeneration, retinal function impairment, ROS accumulation, and inflammation reaction in a relatively shorter time. In the treatment of this animal model we utilized an antioxidative and water soluble nanoparticle known as glycol chitosan coated cerium oxide nanoparticles (GCCNP). The delivery of GCCNP protected retina against progressive retinal oxidative damage. Further combination of GCCNP with alginate-gelatin based injectable hydrogel provided synergistic antioxidant effects and achieved a more rapid recovery of the retinal pigment epithelium and photoreceptor cells. This combined treatment technique has the potential to translate into a clinical intervention for the treatment of AMD.

Nanoceria-loaded injectable hydrogels for potential age-related macular degeneration treatment.

The major purpose of this article is to evaluate oligochitosan coated cerium oxide nanoparticles (OCCNPs) alginate laden injectable hydrogels and their potential treatment for age-related macular degeneration (AMD). The water soluble OCCNPs were loaded within injectable hydrogels as antioxidative agents. The release of OCCNPs from hydrogel, radical scavenging properties, and biocompatibility were evaluated and calculated in vitro. The effects of OCCNP laden hydrogel downregulating expression of angiogenic proteins and proinflammatory cytokines were quantified in human retinal pigment epithlium-19 (ARPE-19) and umbilical endothelium cell lines. The hydrogels behaved with moderate swelling and controllable degradation. The laden OCCNPs were released in a controlled manner in vitro during two months of testing. The OCCNP loaded hydrogels exhibited robust antioxidative properties in oxygen radical absorbance capacity tests and reduced apoptosis in H2 O2 -induced ARPE-19 cells. Furthermore, OCCNP loaded injectable hydrogels are biocompatible and suppressed the ipopolysaccharides-induced inflammation response in ARPE-19 cells, and inhibited expression of vascular endothelium growth factor in human ARPE-19 and umbilical endothelium cell lines. The alginate-gelatin injectable hydrogel loaded OCCNPs are biocompatible and have high potential in protecting cells from apoptosis, angiogenesis, and production of proinflammatory cytokines in AMD cellular models. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 2795-2804, 2018.

Combination Therapy of NSCLC Using Hsp90 Inhibitor and Doxorubicin Carrying Functional Nanoceria.

K-RAS driven non-small-cell lung cancer (NSCLC) represents a major cause of death among smokers. Recently, nanotechnology has introduced novel avenues for the diagnosis and personalized treatment options for cancer. Herein, we report a novel, multifunctional nanoceria platform loaded with a unique combination of two therapeutic drugs, doxorubicin (Doxo) and Hsp90 inhibitor ganetespib (GT), for the diagnosis and effective treatment of NSCLC. We hypothesize that the use of ganetespib synergizes and accelerates the therapeutic efficacy of Doxo via ROS production, while minimizing the potential cardiotoxicity of doxorubicin drug. Polyacrylic acid (PAA)-coated cerium oxide nanoparticles (PNC) were fabricated for the targeted combination therapy of lung cancers. Using "click" chemistry, the surface carboxylic acid groups of nanoceria were decorated with folic acid to target folate-receptor-overexpressing NSCLC. As a result of combination therapy, results showed more than 80% of NSCLC death within 48 h of incubation. These synergistic therapeutic effects were assessed via enhanced ROS, cytotoxicity, apoptosis, and migration assays. Overall, these results indicated that the targeted codelivery of Doxo and GT using nanoceria may offer an alternative combination therapy option for the treatment of undruggable NSCLC.

Improving endothelialization by the combined application of polyethylene glycol coated cerium oxide nanoparticles and VEGF in electrospun polyurethane scaffolds.

Synthetic small-diameter vascular grafts are of limited use mainly due to the lack of endothelial cells (ECs), which inhibit intraluminal thrombosis and intimal hyperplasia. Grafts loaded with homing factors for circulating endothelial progenitor cells (EPCs) have the potential to achieve in situ endothelialization. In view of the important role that EPCs play in the construction of small-diameter artificial blood vessels, antioxidant therapy aiming to inhibit oxidative stress-induced EPC apoptosis should be the focus of clinical interest. In this study, polyethylene glycol coated cerium oxide nanoparticles (CNPs-PEG) with antioxidant properties were successfully synthesized and characterized. The effects of CNPs-PEG on EPC viability and EPC apoptosis induced by oxidative stress were examined. Then, CNPs-PEG together with a potent angiogenesis cytokine vascular endothelial growth factor (VEGF) were encapsulated into polyurethane (PU) scaffolds via electrospinning. The morphology, mechanical properties and CNPs-PEG/VEGF release profiles of the scaffolds were investigated. The growth of EPCs on the scaffolds, and the effects of the released CNPs-PEG and VEGF on anti-EPC apoptosis and endothelialization in vitro were studied. The results showed that CNPs-PEG had favorable stability and cytocompatibility. They could effectively inhibit H2O2-induced EPC apoptosis. The scaffolds showed sustained release behavior of CNPs-PEG/VEGF and favorable cytocompatibility. The released CNPs-PEG retained the anti-apoptosis properties and, moreover, enhanced the effects of VEGF on the mobilization and differentiation of EPCs. It is concluded that the combined application of CNPs-PEG and VEGF in electrospun PU scaffolds facilitated endothelialization in vitro, and thus should be promising for the construction of small-diameter artificial blood vessels.

Antioxidant activity of levan coated cerium oxide nanoparticles

Levan coated cerium oxide nanoparticles (LCNPs) with the enhanced antioxidant activity were successfully synthesized and characterized. Levan and their derivatives are attractive for biomedical applications attributable to their antioxidant, anti-inflammation and anti-tumor properties. LCNPs were synthesized using the one-pot and green synthesis system with levan. For production of nanoparticles, levan plays a role as a stabilizing and reducing agent. Fourier transform infrared spectroscopy (FT-IR) analysis showed that LCNPs successfully synthesized. The morphology and size of nanoparticles were confirmed by transmission electron microscopy (TEM) and dynamic light scattering (DLS). LCNPs have good water solubility and stability. The conjugation of levan with cerium oxide nanoparticles improved antioxidant activity. Moreover the level of ROS was reduced after treatment of LCNPs to H2O2 stimulated NIH3T3 cells. These results demonstrate that the LCNPs are useful for applying of treatment of ROS induced diseases.

Nutritional quality assessment of tomato fruits after exposure to uncoated and citric acid coated cerium oxide nanoparticles, bulk cerium oxide, cerium acetate and citric acid

Little is known about the effects of surface modification on the interaction of nanoparticles (NPs) with plants. Tomato (Solanum lycopersicum L.) plants were cultivated in potting soil amended with bare and citric acid coated nanoceria (nCeO2, nCeO2+CA), cerium acetate (CeAc), bulk cerium oxide (bCeO2) and citric acid (CA) at 0–500 mg kg−1. Fruits were collected year-round until the harvesting time (210 days). Results showed that nCeO2+CA at 62.5, 250 and 500 mg kg−1 reduced dry weight by 54, 57, and 64% and total sugar by 84, 78, and 81%. At 62.5, 125, and 500 mg kg−1 nCeO2+CA decreased reducing sugar by 63, 75, and 52%, respectively and at 125 mg kg−1 reduced starch by 78%, compared to control. The bCeO2 at 250 and 500 mg kg−1, increased reducing sugar by 67 and 58%. In addition, when compared to controls, nCeO2 at 500 mg kg−1 reduced B (28%), Fe (78%), Mn (33%), and Ca (59%). At 125 mg kg−1 decreased Al by 24%; while nCeO2+CA at 125 and 500 mg kg−1 increased B by 33%. On the other hand, bCeO2 at 62.5 mg kg−1 increased Ca (267%), but at 250 mg kg−1 reduced Cu (52%), Mn (33%), and Mg (58%). Fruit macromolecules were mainly affected by nCeO2+CA, while nutritional elements by nCeO2; however, all Ce treatments altered, in some way, the nutritional quality of tomato fruit. To our knowledge, this is the first study comparing effects of uncoated and coated nanoceria on tomato fruit quality.

Hyaluronan coated cerium oxide nanoparticles modulate CD44 and reactive oxygen species expression in human fibroblasts.

Cerium oxide nanoparticles are being widely explored for cell therapies. In this study, nanoceria was functionalized with hyaluronan (HA) using the organosilane linker, 3-aminopropyltriethoxysilane. HA-nanoceria was found to be cytocompatible and to reduce intracellular reactive oxygen species in human fibroblasts. The HA-nanoceria was found to colocalize with CD44 on the surface of the cells and once internalized traffic to the lysosomes, be degraded and induce markers of autophagy. These particles were also effective in reducing the cell surface expression of CD44. Together these data suggest that HA-nanoceria is a promising drug delivery material to target CD44-expressing cells through a variety of mechanisms. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 1736-1746, 2016.

PH and time dependent antioxidant activity of dextran coated cerium oxide nanoparticles

pH and time dependent antioxidant activity of dextran coated cerium oxide nanoparticles

Effects of uncoated and citric acid coated cerium oxide nanoparticles, bulk cerium oxide, cerium acetate, and citric acid on tomato plants

Little is known about the physiological and biochemical responses of plants exposed to surface modified nanomaterials. In this study, tomato (Solanum lycopersicum L.) plants were cultivated for 210days in potting soil amended with uncoated and citric acid coated cerium oxide nanoparticles (nCeO2, CA+nCeO2) bulk cerium oxide (bCeO2), and cerium acetate (CeAc). Millipore water (MPW), and citric acid (CA) were used as controls. Physiological and biochemical parameters were measured. At 500mg/kg, both the uncoated and CA+nCeO2 increased shoot length by ~9 and ~13%, respectively, while bCeO2 and CeAc decreased shoot length by ~48 and ~26%, respectively, compared with MPW (p≤0.05). Total chlorophyll, chlo-a, and chlo-b were significantly increased by CA+nCeO2 at 250mg/kg, but reduced by bCeO2 at 62.5mg/kg, compared with MPW. At 250 and 500mg/kg, nCeO2 increased Ce in roots by 10 and 7 times, compared to CA+nCeO2, but none of the treatments affected the Ce concentration in above ground tissues. Neither nCeO2 nor CA+nCeO2 affected the homeostasis of nutrient elements in roots, stems, and leaves or catalase and ascorbate peroxidase in leaves. CeAc at 62.5 and 125mg/kg increased B (81%) and Fe (174%) in roots, while at 250 and 500mg/kg, increased Ca in stems (84% and 86%, respectively). On the other hand, bCeO2 at 62.5 increased Zn (152%) but reduced P (80%) in stems. Only nCeO2 at 62.5mg/kg produced higher total number of tomatoes, compared with control and the rest of the treatments. The surface coating reduced Ce uptake by roots but did not affect its translocation to the aboveground organs. In addition, there was no clear effect of surface coating on fruit production. To our knowledge, this is the first study comparing the effects of coated and uncoated nCeO2 on tomato plants.

Cerium Oxide Nanoparticles Decorated Graphene Nanosheets for Selective Detection of Dopamine.

The fabrication of a novel amperometric biosensor based on selective determination of dopamine (DA) using nafion coated cerium oxide nanoparticles (NPs) decorated graphene nanosheets (CeO2-HEG-nafion) as a transducer candidate is reported. Graphene was synthesized by hydrogen exfoliation technique. Decoration of CeO2NPs over graphene nanosheets was done by chemical reduction method. The electrochemical impedance spectroscopy (EIS) study shows the enhanced electron transfer kinetics of the composite compared to HEG modified and bare glassy carbon electrode (GCE). The response of the composite towards dopamine displays a lower oxidation potential of 0.23 V and a high oxidation current. The sensor exhibits linearity from 10 µM to 780 µM with a detection limit of 1 µM. In the presence of nafion, it shows excellent selectivity for coexisting interference species like Ascorbic acid (AA) and Uric acid (UA). The excellent performance of the biosensor can be attributed to large active surface area, enhanced electron transfer kinetics and high catalytic activity of the composite.

Synthesis and Characterization of Polyvinylpyrrolidone Coated Cerium Oxide Nanoparticles

There is a pressing need for the development of standard and reference nanomaterials for environmental nanoscience and nanotoxicology. To that aim, suspensions of polyvinylpyrrolidone (PVP)-coated ceria nanoparticles (NPs) were produced. Four differently sized monodispersed samples were produced by using different PVP chain lengths. The chemical and physical properties of these NPs were characterized as prepared and in different ecotoxicology exposure media. Dynamic light scattering analysis showed that the samples were monodispersed, with an unchanged size when suspended in the different media over a 72 h period. Electron microscopy confirmed this and revealed that the larger (ca. 20 nm) particles were aggregates composed of the smaller individual particles (4-5 nm). Electron energy loss spectroscopy (EELS) showed that the smallest and largest samples were composed almost entirely of cerium(III) oxide, with only small amounts of cerium(IV) present in the largest sample. Dissolved cerium concentrations in media were low and constant, showing that the NPs did not dissolve over time. The simple synthesis of the these NPs and their physical and chemical stability in different environmental conditions make them potentially suitable for use as reference materials for (eco)toxicology and surface water environmental studies.

Antibacterial Activity of Polymer Coated Cerium Oxide Nanoparticles

Cerium oxide nanoparticles have found numerous applications in the biomedical industry due to their strong antioxidant properties. In the current study, we report the influence of nine different physical and chemical parameters: pH, aeration and, concentrations of MgSO4, CaCl2, KCl, natural organic matter, fructose, nanoparticles and Escherichia coli, on the antibacterial activity of dextran coated cerium oxide nanoparticles. A least-squares quadratic regression model was developed to understand the collective influence of the tested parameters on the anti-bacterial activity and subsequently a computer-based, interactive visualization tool was developed. The visualization allows us to elucidate the effect of each of the parameters in combination with other parameters, on the antibacterial activity of nanoparticles. The results indicate that the toxicity of CeO2 NPs depend on the physical and chemical environment; and in a majority of the possible combinations of the nine parameters, non-lethal to the bacteria. In fact, the cerium oxide nanoparticles can decrease the anti-bacterial activity exerted by magnesium and potassium salts.

13C CP/MAS NMR Study of Cross-linked Poly(vinylpyrrolidone) on Surface of Cerium Oxide Nanoparticles

Abstract The highly dispersed property of poly(vinylpyrrolidone) (PVP)-coated cerium oxide nanoparticles can be retained for a long time in polar solvents. In this 13C CP/MAS NMR study, it is revealed that the surface PVP forms cross-linked structures during the synthesis of the nanoparticles.