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.
A hybrid sol-gel/polyurethane glucose biosensor that releases nitric oxide is developed and characterized. The biosensor consists of a platinum electrode coated with four polymeric membranes including the following: (1) sol-gel with immobilized glucose oxidase (GOx); (2) polyurethane to protect the enzyme; (3) NO donor-modified sol-gel particle-doped polyurethane; and (4) polyurethane. This configuration was developed due to the drastic reduction in sensitivity observed for NO donor-modified sol-gel film-based glucose sensors. For the hybrid sol-gel/polyurethane biosensor, sol-gel particles are first modified with the NO donor and then incorporated into a polyurethane layer that is coated onto the preimmobilized GOx electrode. In this manner, the GOx layer is not exposed to the harsh conditions necessary to impart NO release ability to the biosensor, and only a minimal decrease in sensitivity due to the NO release is observed. The glucose response of the NO-releasing glucose biosensor and its NO generation profiles are reported. In addition, the stability of the sol-gel particles in the supporting polyurethane membrane is discussed.
An amperometric sol-gel derived sensor that both releases nitric oxide (NO) and measures physiologically relevant concentrations of oxygen (PO2) is described. The sensor consists of a platinum electrode coated with an aminosilane/ethyltrimethoxysilane hybrid xerogel film. Hydrophilic polyurethane (HPU) is doped into the hybrid film to reduce sensor hydration time and increase oxygen permeability. Diazeniumdiolate NO donors are formed within the polymer matrix by exposing the cured film to high pressures of NO. These coatings release up to 7.2 pmol s(-1) cm(-2) of NO over the first 12 h and maintain detectable levels of NO release through 48 h. Sensors modified with HPU-doped, NO-releasing xerogels exhibit a linear response to O2 within 30 min of polarization at -0.65 V vs. Ag/AgCl, and have a sensitivity of approximately 6 nA/mmHg O2. The xerogel coating is stable in buffer solution with minimal fragmentation over 48 h. In vitro biocompatibility studies indicate that these materials effectively reduce platelet adhesion.
A potentiometric sol-gel derived (xerogel) pH sensor based on covalently attached amine groups is described. The sensor consists of a Ag/AgCl electrode coated with a hybrid aminosilane/alkylsilane xerogel film. Various combinations of aminosilanes and alkylsilanes are evaluated for their potentiometric response to pH. The optimal sensor design is composed of (aminoethylaminomethyl)phenethyltrimethoxysilane and methyltrimethoxysilane. This sensor exhibits near-Nerstian response (-55 mV.decade(-)(1)), responds rapidly (< or =3 s) to changes in pH, and has H(+) selectivity coefficients (log K(pot)(H)()+ (, )(j)()) of -13 and -11 for interfering j cations Na(+) and K(+), respectively. In vitro platelet adhesion tests indicate that the xerogel coatings are more blood compatible than conventional poly(vinyl chloride) and poly(urethane) ion-selective electrode coatings.
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