Ceria nanotubes with extended cavities can be obtained by a facile oxidation−coordination-assisted dissolution process of the partially oxidized one-dimensional Ce(OH)3. Moreover, the ceria nanotubes with large cavities and thin walls exhibit excellent reducibility and high oxygen storage capacity, indicating they are potential novel catalytic materials.
The Birch reduction (lithium in liquid ammonia) of graphite gives a highly reduced, exfoliated product that is free of lithium. Edge and interior hydrogenation were demonstrated by solid-state (13)C NMR spectroscopy. Elemental analysis of a carefully purified sample allows the chemical composition to be expressed as (C(1.3)H)(n). Atomic force microscopy images showed that the reduced graphene was highly exfoliated. Hydrogen mapping by electron energy loss spectroscopy showed that the entire surface of the reduced sample was covered by hydrogen, consistent with the NMR studies also indicating that hydrogen was added in interior positions of the graphene lattice as well as along the edge. A large band gap (4 eV) further establishes the high level of hydrogenation.
Sensors based upon surface-enhanced Raman spectroscopy (SERS) are attractive because they have narrow, vibrationally specific spectral peaks that can be excited using red and near-infrared light which avoids photobleaching, penetrates tissue, and reduces autofluorescence. Several groups have fabricated pH nanosensors by functionalizing silver or gold nanoparticle surfaces with an acidic molecule and measuring the ratio of protonated to deprotonated Raman bands. However, a limitation of these sensors is that macromolecules in biological systems can adsorb onto the nanoparticle surface and interfere with measurements. To overcome this interference, we encapsulated pH SERS sensors in a 30 nm thick silica layer with small pores which prevented bovine serum albumin (BSA) molecules from interacting with the pH-indicating 4-mercaptobenzoic acid (4-MBA) on the silver surfaces but preserved the pH-sensitivity. Encapsulation also improved colloidal stability and sensor reliability. The noise level corresponded to less than 0.1 pH units from pH 3 to 6. The silica-encapsulated functionalized silver nanoparticles (Ag-MBA@SiO(2)) were taken up by J774A.1 macrophage cells and measured a decrease in local pH during endocytosis. This strategy could be extended for detecting other small molecules in situ.
A class of zinc reagents (RXZnCH(2)Y) generated with an appropriate organozinc is very effective for the cyclopropanation of olefins. The reactivity and selectivity of these reagents can be regulated by tuning the electronic and steric nature of the RX group on Zn. A reasonable level of enantioselectivity was obtained for the cyclopropanation of unfunctionalized olefins when a chiral (iodomethyl)zinc species was used, providing a valuable approach for the asymmetric cyclopropanation of unfunctionalized olefins.
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