Preparation and characterization of a pH- and thermally responsive poly(N-isopropylacrylamide-co-acrylic acid)/porous SiO(2) hybrid.

A multifunctional nanohybrid composed of a pH- and thermoresponsive hydrogel, poly(N-isopropylacrylamide-co-acrylic acid), poly(NIPAM-co-AAc) is synthesized in-situ within the mesopores of an oxidized porous Si template. The hybrid is characterized by electron microscopy and by thin film optical interference spectroscopy. The optical reflectivity spectrum of the hybrid displays Fabry-Pérot fringes characteristic of thin film optical interference, enabling direct, real-time observation of the pH- induced swelling and volume phase transitions associated with the confined poly(NIPAM-co-AAc) hydrogel. The optical response correlates to the percentage of AAc contained within the hydrogel, with a maximum change observed for samples containing 20% AAc. The swelling kinetics of the hydrogel are significantly altered due to the nanoscale confinement; displaying a more rapid response to pH or heating stimuli relative to bulk polymer films. The inclusion of AAc dramatically alters the thermoresponsiveness of the hybrid at pH 7, effectively eliminating the lower critical solution temperature (LCST). The observed changes in the optical reflectivity spectrum are interpreted in terms of changes in the dielectric composition and morphology of the hybrids.

pH-triggered release of vancomycin from protein-capped porous silicon films.

OBJECTIVE: An in vitro model system for pH-triggered release of the antibiotic vancomycin from porous Si films is studied. METHOD: Vancomycin is infused into a mesoporous Si film from a mixed aqueous/acetonitrile solution and trapped by a capping layer containing the protein bovine serum albumin (BSA). The protein effectively traps vancomycin in the porous nanostructure at pH 4.0; the protein dissolves and vancomycin is released into solution when the pH increases to 7.4. The surface chemistry of porous Si exerts a substantial effect on the efficacy of drug loading. The amount of drug loading is larger in freshly-etched (hydrophobic, hydrogen-terminated) porous Si and smaller in methyl-modified, undecylenic acid-modified and thermally oxidized samples. The quantity of drug loaded in a freshly etched porous Si chip is proportional to the thickness of the porous layer, which exhibits a constant volume loading efficiency of 31% (v/v). Flow-cell experiments designed to mimic the transition from pH 4 to 7 that occurs when material moves from the stomach to the upper intestinal tract were performed on the freshly etched films and vancomycin- and BSA-release rates were quantified from the effluent of the flow cell by high-pressure liquid chromatography analysis. RESULTS & CONCLUSION: There is a small, constant rate of vancomycin release at pH 4 that is independent of the amount of drug loaded in the pores. This is attributed to diffusion of vancomycin from the BSA-capping layer. The release rate increases five- to tenfold when the pH of the solution in the flow cell increases to 7.4; 100% of the drug is released within 3 h of this increase.

A simplified biomolecule attachment strategy for biosensing using a porous Si oxide interferometer.

A simple strategy for linking biomolecules to porous Si surfaces and detecting peptide/drug binding is described. Porous Si is prepared using an electrochemical etch and then thermally oxidized by heating in ambient atmosphere. Bovine serum albumin (BSA) is then non-covalently adsorbed to the inner pore walls of the porous Si oxide (PSiO(2)) matrix. The BSA layer is used as a linker for covalent attachment of the peptide Ac-L-Lysine-D-Alanine-D-Alanine (KAA) using published bioconjugation chemistry. BSA-coated surfaces functionalized with KAA display specificity for the glycopeptide vancomycin while resisting adsorption of non-specific reagents. While the biomolecule attachment strategy reported here is used to bind peptides, the scheme can be generalized to the linking of any primary amine-containing molecule to PSiO(2) surfaces.

Engineering the chemistry and nanostructure of porous silicon Fabry-Pérot films for loading and release of a steroid.

A method for engineering the surface chemistry and pore dimensions in porous Si films for the purpose of controlling the loading and release of a hydrophobic drug is described. Loading of the steroid dexamethasone is confirmed by Fourier transform infrared spectroscopy, and the release rates are characterized by observation of the appearance of the drug in solution (UV-vis absorption spectroscopy) and by measurement of the Fabry-Perot fringes in the optical reflectivity spectrum of the porous Si film. Optical reflectivity changes provide a measure of the release rate of the drug that is amenable to in-vivo diagnostic applications. Fresh porous Si films are prepared by electrochemical etch and subsequently modified by hydrosilylation with 1-dodecene. The dodecene-modified samples are more robust in aqueous environments and exhibit slower release rates of the drug relative to freshly etched porous Si. Whereas the relatively large dexamethasone molecule is found to infiltrate the freshly etched samples, it does not enter the chemically modified films, because of steric crowding from the dodecyl species. To achieve a high degree of loading into these modified films, the pores are enlarged before hydrosilylation by treatment with an aqueous solution containing HF and dimethyl sulfoxide. The pore expanded, chemically modified samples admit approximately 70% of the dexamethasone that can be admitted into an unmodified (freshly etched) sample. Diffusion of the steroid from the modified, pore expanded films into phosphate-buffered saline solution is slower than from the unmodified sample by a factor of approximately 20, with 90% of the drug delivered in 3 days for the chemically modified films compared to 3 h for the unmodified films.