The synthesis and characterization of a new nitric oxide (NO)-releasing scaffold prepared from amine-functionalized silica nanoparticles are reported. Inorganic-organic hybrid silica was prepared via cocondensation of tetraethoxy- or tetramethoxysilane (TEOS or TMOS) and aminoalkoxysilane with appropriate amounts of ethanol (or methanol), water, and ammonia. The amine functional groups in the silica were converted to N-diazeniumdiolate NO donors via exposure to high pressures of NO (5 atm) under basic conditions. Control over both the structure and concentration of the silane precursors (i.e., tetraalkoxy- and aminoalkoxysilanes) and specific synthetic conditions allowed for the preparation of NO donor silica particles of widely varying sizes (d = 20-500 nm), NO payloads (50-1780 nmol.mg-1), maximum amounts of NO released (10-5500 ppb.mg-1), half-lives (0.1-12 h), and NO release durations (up to 30 h). The silica nanoparticles were characterized by solid-state 29Si nuclear magnetic resonance (NMR), atomic force microscopy (AFM), elemental analysis, and gas adsorption-desorption isotherms. The advantages of silica-derived NO storage/delivery systems over previously reported macromolecular NO donors include the ability to (1) store large quantities of NO, (2) modulate NO release kinetics, and (3) readily tune particle size based on the composition of the particle. In addition, a one-pot strategy for preparing the NO donor silica allows for straightforward, high-throughput synthesis and purification.

Nitric oxide (NO)-releasing sol-gel materials are synthesized by combining aminefunctionalized alkoxysilanes (aminosilanes) with alkyltrimethoxysilanes (alkylsilanes). Upon hydrolysis and condensation, the amine-functionalized silanes are covalently bound to the alkyltrimethoxysilane backbone and easily converted to diazeniumdiolate NO donors via exposure to high pressures of NO. Immersion of the sol-gel into solution is not required to initiate NO release. The NO-release characteristics of the sol-gels are easily controlled by varying the type and amount of the aminosilane precursor in the sol. The sol-gel coatings release NO for up to 20 d with average fluxes between 8.0 × 10 -12 and 5.6 × 10 -11 mol‚s -1 ‚cm -2 (coating thickness of 50 µm) over the first 10 h. These materials exhibit reduced platelet and bacterial adhesion. The results indicate that sol-gel chemistry may be an effective strategy for preparing coatings that release NO both controllably and locally for a range of applications including blood-and tissue-based devices.

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We report the synthesis of nitric oxide-releasing gold nanoparticles formed by place-exchange reaction of hexanethiol monolayer-protected clusters with diamine nitric oxide donor precursor molecules, which are subsequently converted to N-diazeniumdiolate NO donors. The nitric oxide release from the N-diazeniumdiolate-modified gold nanoparticles is tunable by varying the number and/or the chemical structure of the exchanged amine ligands. The size and stability of NO-releasing nanoparticles may prove useful for a range of biomedical and pharmaceutical applications.

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