Tandem Hydroperoxyl-Alkylperoxyl Radical Quenching by an Engineered Nanoporous Cerium Oxide Nanoparticle Macrostructure (NCeONP): Toward Efficient Solid-State Autoxidation Inhibitors.

The use of nanomaterials as inhibitors of the autoxidation of organic materials is attracting tremendous interest in petrochemistry, food storage, and biomedical applications. Metal oxide materials and CeO2 in particular represent one of the most investigated inorganic materials with promising radical trapping and antioxidant abilities. However, despite the importance, examples of the CeO2 material's ability to retard the autoxidation of organic substrates are still lacking, together with a plausible chemical mechanism for radical trapping. Herein, we report the synthesis of a new CeO2-derived nanoporous material (NCeONP) with excellent autoxidation inhibiting properties due to its ability to catalyze the cross-dismutation of alkyl peroxyl (ROO•) and hydroperoxyl (HOO•) radicals, generated in the system by the addition of the pro-aromatic hydrocarbon γ-terpinene. The antioxidant ability of NCeONP is superior to that of other nanosized metal oxides, including TiO2, ZnO, ZrO2, and pristine CeO2 nanoparticles. Studies of the reaction with a sacrificial reductant allowed us to propose a mechanism of inhibition consisting of H atom transfer from HOO• to the metal oxides (MOx + HOO• → MOx-H• + O2), followed by the release of the H atom to an ROO• radical (MOx-H• + ROO• → MOx + ROOH). Besides identifying NCeONP as a promising material for developing effective antioxidants, our study provides the first evidence of a radical mechanism that can be exploited to develop novel solid-state autoxidation inhibitors.

Gold nanorods or nanospheres? Role of particle shape on tuning the shape memory effect of semicrystalline poly(ε-caprolactone) networks.

In this study, modified poly(ε-caprolactone) (PCL) tri-block copolymers were successfully synthesized through ring opening polymerization. The nanocomposite films containing either colloidal gold nanorods (AuNRs) or gold nanospheres (AuNSs) in the polymer matrix were fabricated without chemical modification to realize light-responsive shape memory behaviors. The localized surface plasmon resonance of AuNPs was utilized by irradiating the selective wavelength of light to create a photothermal effect. The polymer microstructures were investigated by NMR, and the thermal properties of the polymer networks were studied by TGA and DSC. The addition of AuNPs did not change the melting temperature, (T m) of the SMP. The AuNRs were fairly well dispersed within the PCL matrix as observed using SEM-EDAX analysis and as indicated from the uniform shape memory transitions of the SMP/AuNR nanocomposites. The shape memory behavior was quantitatively analyzed by cyclic thermomechanical tests using DMA. The laser-triggered shape memory properties of the nanocomposites were analyzed and the shape recovery process from a rectangular shaped film to a helical coil was demonstrated. The speed of SMP recovery was found to be dependent on the geometry and concentration of the AuNPs in the nanocomposite, as well as on the laser wavelength and intensity.