Metal nanoparticles prepared by exsolution at the surface of perovskite oxides have been recently shown to enable new dimensions in catalysis and energy conversion and storage technologies owing to their socketed, well-anchored structure. Here we show that contrary to general belief, exsolved particles do not necessarily re-dissolve back into the underlying perovskite upon oxidation. Instead, they may remain pinned to their initial locations, allowing one to subject them to further chemical transformations to alter their composition, structure and functionality dramatically, while preserving their initial spatial arrangement. We refer to this concept as chemistry at a point and illustrate it by tracking individual nanoparticles throughout various chemical transformations. We demonstrate its remarkable practical utility by preparing a nanostructured earth abundant metal catalyst which rivals platinum on a weight basis over hundreds of hours of operation. Our concept enables the design of compositionally diverse confined oxide particles with superior stability and catalytic reactivity.
Next generation wound care technology capable of diagnosing wound parameters, promoting healthy cell growth and reducing pathogenic infections noninvasively would provide patients with an improved standard of care and an accelerated wound repair mechanism. Temperature is one of the indicating biomarkers specific to chronic wounds. This work reports a hybrid, multifunctional optical material platform -nanodiamond-silk membranes as bioinspired dressings capable of temperature sensing and wound healing. The hybrid structure was fabricated through electrospinning and formed 3D sub-micron fibrous membranes with high porosity. The silk fibres are capable of compensating for the lack of extracellular matrix at the wound site, supporting the wound healing process. The negatively charged nitrogen vacancy (NV -) color centres in nanodiamonds (NDs) exhibit optically detected magnetic resonance (ODMR) properties and act as fluorescent nanoscale thermometers, capable of sensing temperature variations associated to the presence of infection or inflammation in a wound, without physically removing the dressing. Our results show that the presence of NDs in the hybrid ND-silk membranes improve the thermal stability of silk fibres. The NVcolor centres in NDs embedded in silk fibres exhibit well-retained fluorescent and ODMR properties. Using the NVcentres as fluorescent nanoscale thermometers, we achieved temperature sensing at a range of temperatures, including the biologically relevant temperature window, on cellcultured ND-silk membranes. An enhancement in the temperature sensitivity of the NVcentres was observed for the hybrid materials. The hybrid membranes were further tested in vivo in a murine wound healing model and demonstrated biocompatibility and equivalent wound closure rates as the control wounds. Additionally, the hybrid ND-silk membranes showed selective antifouling and biocidal propensity toward Gram-negative Pseudomonas aeruginosa and Escherichia coli, while no effect was observed on Gram-positive Staphylococcus aureus.
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