Optical PEBBLE (probes encapsulated by biologically localized embedding) nanosensors have been developed for dissolved oxygen using organically modified silicate (ormosil) nanoparticles as a matrix. The ormosil nanoparticles are prepared via a sol-gel-based process, which includes the formation of core particles with phenyltrimethoxysilane as a precursor followed by the formation of a coating layer with methyltrimethoxysilane as a precursor. The average diameter of the resultant particles is 120 nm. These sensors incorporate the oxygen-sensitive platinum porphyrin dye as an indicator and an oxygen-insensitive dye as a reference for ratiometric intensity measurement. Two pairs of indicator dye and reference dye, respectively, platinum(II) octaethylporphine and 3,3'-dioctadecyloxacarbocyanine perchlorate, and platinum(II) octaethylporphine ketone and octaethylporphine, were used. The sensors have excellent sensitivity with an overall quenching response of 97%, as well as excellent linearity of the Stern-Volmer plot (r(2) = 0.999) over the whole range of dissolved oxygen concentrations (0-43 ppm). In vitro intracellular changes of dissolved oxygen due to cell respiration were monitored, with gene gun injected PEBBLEs, in rat C6 glioma cells. A significant change was observed with a fluorescence ratio increase of up to 500% after 1 h, for nine different sets of cells, which corresponds to a 90% reduction in terms of dissolved oxygen concentration. These results clearly show the validity of the delivery method for intracellular studies of PEBBLE sensors, as well as the high sensitivity, which is needed to achieve real-time measurements of intracellular dissolved oxygen concentration.

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We demonstrate the effectiveness of dual-layer coating of cathode active materials for improving the cycling performance and thermal stability of lithium-ion cells. Layered nickel-rich LiNi0.6Co0.2Mn0.2O2 cathode material was synthesized and double-layer coated with alumina nanoparticles and poly(3,4-ethylenedioxythiophene)-co-poly(ethylene glycol). The lithium-ion cells assembled with a graphite negative electrode and a double-layer-coated LiNi0.6Co0.2Mn0.2O2 positive electrode exhibited high discharge capacity, good cycling stability, and improved rate capability. The protective double layer formed on the surface of LiNi0.6Co0.2Mn0.2O2 materials effectively inhibited the dissolution of Ni, Co, and Mn metals from cathode active materials and improved thermal stability by suppressing direct contact between electrolyte solution and delithiated Li(1-x)Ni0.6Co0.2Mn0.2O2 materials. This effective design strategy can be adopted to enhance the cycling performance and thermal stability of other layered nickel-rich cathode materials used in lithium-ion batteries.

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