Ultralight multiwalled carbon nanotube (MWCNT) aerogel is fabricated from a wet gel of well-dispersed pristine MWCNTs. On the basis of a theoretical prediction that increasing interaction potential between CNTs lowers their critical concentration to form an infinite percolation network, poly(3-(trimethoxysilyl) propyl methacrylate) (PTMSPMA) is used to disperse and functionalize MWCNTs where the subsequent hydrolysis and condensation of PTMSPMA introduces strong and permanent chemical bonding between MWCNTs. The interaction is both experimentally and theoretically proven to facilitate the formation of a MWCNT percolation network, which leads to the gelation of MWCNT dispersion at ultralow MWCNT concentration. After removing the liquid component from the MWCNT wet gel, the lightest ever free-standing MWCNT aerogel monolith with a density of 4 mg/cm(3) is obtained. The MWCNT aerogel has an ordered macroporous honeycomb structure with straight and parallel voids in 50-150 μm separated by less than 100 nm thick walls. The entangled MWCNTs generate mesoporous structures on the honeycomb walls, creating aerogels with a surface area of 580 m(2)/g which is much higher than that of pristine MWCNTs (241 m(2)/g). Despite the ultralow density, the MWCNT aerogels have an excellent compression recoverable property as demonstrated by the compression test. The aerogels have an electrical conductivity of 3.2 × 10(-2) S·cm(-1) that can be further increased to 0.67 S·cm(-1) by a high-current pulse method without degrading their structures. The excellent compression recoverable property, hierarchically porous structure with large surface area, and high conductivity grant the MWCNT aerogels exceptional pressure and chemical vapor sensing capabilities.

Cerium oxide nanoparticles (CNPs) have been demonstrated to protect biological tissues against radiation induced damage and scavenging of superoxide anions, prevent laser induced retinal damage, reduce spinal injury, possess pH dependent antioxidant properties, prevent cardiovascular myopathy, and as a tool for immunoassays and other inflammatory diseases.1a-j It is speculated that nanoceria is a regenerative radical scavenger with the ability to regenerate the active Ce 3+ oxidation state for radical scavenging which separates it from other nanomaterials based antioxidant systems such as hydroxylated and water-soluble C-60 and SWCNTs.1k, l Thus far there are no reports on controlling the regeneration of the Ce 3+ oxidation state which is the most important parameter in the application of CNPs as a reliable, regenerative radical scavenger. There is an imminent need to increase the residence time of CNPs in the body and to control the regeneration of the Ce 3+ oxidation state. PEG has been reported to increase the residence time of NPs and proteins inside cells and provide biocom-patibility.2 PEGylated counterparts of the Superoxide Dismutase (SOD) enzymes have shown improved performance over non-PEGylated enzymes. 2 Herein, we report our efforts to synthesize CNPs directly in PEG (600 MW) solution and determine the effect of increasing [PEG] (PEG vol % as 5, 10, 20, 40, 60, and 80) on the SOD mimetic properties exhibited by nanoceria. We also report how the active Ce 3+ oxidation state can be regenerated and demonstrate the role of PEG on the redox chemistry of CNPs catalyzed by H 2 O 2 . Several complexes of PEGs with lanthanides have been reported and characterized.3 To evaluate the effect of [PEG] on the complexation of cerium, UV-vis spectra of the precursor salt of cerium (cerium nitrate hexahydrate) in different solutions of PEG were obtained (SI-1). All PEG solutions show higher absorption relative to the water based solution of cerium nitrate, but the observed nonspecific trend could not be ascribed to a systematic decrease in the solvent polarity or dielectric constant. This observation indicates the complexation of cerium ions with PEG. In contrast to this Uekawa et al.4a, b reported a red shift upon addition of cerium nitrate in PEG and ascribed the red shift to the complexation of PEG with cerium ions. The CNPs were synthesized as described in the experimental details (SI-2). A high resolution transmission electron micrograph (Figure 1a NIH-PA Author ManuscriptNIH-PA Author Manuscript NIH-PA Author Manuscriptdemonstrates that PEG is present as an amorphous layer on CNPs confirmed by an amorphous background around the crystalline CNPs. To confirm further, CNPs synthesized in PEG were dialyzed using a 3500 MWCO cellulose membrane and the FTIR spectrum was collected from the dried powder. Figure 1b confirms the presence of PEG on the nanoceria particles from FTIR of 20% PEG CNPs. Biocompatibility and SOD Mimetic Activity of CNPs in PEGCell viability analysis was performed for CNPs in PEG solution u...

Cerium oxide nanoparticles (CeNPs) have shown promise as catalytic antioxidants in cell culture and animal models as both superoxide dismutase and catalase mimetics. The reactivity of the cerium (Ce) atoms at the surface of its oxide particle is critical to such therapeutic properties, yet little is known about the potential for a protein or small molecule corona to form on these materials in vivo. Moreover Ce atoms in these active sites have the potential to interact with small molecule anions, peptides, or sugars when administered in culture or animal models. Several nanomaterials have been shown to alter or aggregate under these conditions, rendering them less useful for biomedical applications. In this work we have studied the change in catalytic properties of CeNPs when exposed to various biologically relevant conditions in vitro. We have found that CeNPs are resistant to broad changes in pH and also not altered by incubation in cell culture medium. However to our surprise phosphate anions significantly altered the characteristics of these nanomaterials and shifted the catalytic behavior due to the binding of phosphate anions to cerium. Given the abundance of phosphate in biological systems in an inorganic form, it is likely that the action of CeNPs as a catalyst may be strongly influenced by the local concentration of phosphate in the cells and/or tissues in which it has been introduced.

Enhancing the optical emission of cerium oxide nanoparticles is essential for potential biomedical applications. In the present work, we report a simple chemical precipitation technique to synthesize europium-doped cerium oxide nanostructures to enhance the emission properties. Structural and optical properties showed an acute dependence on the concentration of oxygen ion vacancy and trivalent cerium, which, in turn, could be modified by dopant concentration and the annealing temperature. Results from X-ray photoelectron spectroscopy showed an increase in tetravalent cerium concentration to 85% on annealing at 900 degrees C. The concentration of oxygen ion vacancy increased from 1.7x10(20) cm(-3) to 4.1x10(20) cm(-3) with the increase in dopant concentration. Maximum emission at room temperature was obtained for 15 mol % Eu-doped ceria, which improved with annealing temperature. The role of oxygen ion vacancies and trivalent cerium in modifying the emission properties is discussed.