Ultrahigh nanostructured drug payloads from degradable mesoporous silicon aerocrystals.

Porous silicon has found increased attention as a drug delivery system due to its unique features such as high drug payloads, surface area and biodegradation. In this study supercritical fluid (SCF) assisted drying of ultrahigh porosity (>90%) silicon particles and flakes was shown to result in much higher mesopore volumes (~4.66 cm3/g) and surface areas (~680 m2/g) than with air-drying. The loading and physical state of the model drug (S)-(+)-Ibuprofen in SCF dried matrices was quantified and assessed using thermogravimetric analysis, differential scanning calorimetry, UV-Vis spectrophotometry, gravimetric analysis, gas adsorption and electron microscopy. Internal drug payloads of up to 72% were achieved which was substantially higher than values published for both conventionally dried porous silicon (17-51%) and other mesoporous materials (7-45%). In-vitro degradability kinetics of SCF-dried matrices in simulated media was also found to be faster than air-dried controls. The in-vitro release studies provided improved but sustained drug dissolution at both pH 2.0 and pH 7.4.

Enhancement of Peroxidase Stability Against Oxidative Self-Inactivation by Co-immobilization with a Redox-Active Protein in Mesoporous Silicon and Silica Microparticles.

The study of the stability enhancement of a peroxidase immobilized onto mesoporous silicon/silica microparticles is presented. Peroxidases tend to get inactivated in the presence of hydrogen peroxide, their essential co-substrate, following an auto-inactivation mechanism. In order to minimize this inactivation, a second protein was co-immobilized to act as an electron acceptor and thus increase the stability against self-oxidation of peroxidase. Two heme proteins were immobilized into the microparticles: a fungal commercial peroxidase and cytochrome c from equine heart. Two types of biocatalysts were prepared: one with only covalently immobilized peroxidase (one-protein system) and another based on covalent co-immobilization of peroxidase and cytochrome c (two-protein system), both immobilized by using carbodiimide chemistry. The amount of immobilized protein was estimated spectrophotometrically, and the characterization of the biocatalyst support matrix was performed using Brunauer-Emmett-Teller (BET), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX), and Fourier transform infrared (FTIR) analyses. Stability studies show that co-immobilization with the two-protein system enhances the oxidative stability of peroxidase almost four times with respect to the one-protein system. Thermal stability analysis shows that the immobilization of peroxidase in derivatized porous silicon microparticles does not protect the protein from thermal denaturation, whereas biogenic silica microparticles confer significant thermal stabilization.

Silicon: the evolution of its use in biomaterials.

In the 1970s, several studies revealed the requirement for silicon in bone development, while bioactive silicate glasses simultaneously pioneered the current era of bioactive materials. Considerable research has subsequently focused on the chemistry and biological function of silicon in bone, demonstrating that the element has at least two separate effects in the extracellular matrix: (i) interacting with glycosaminoglycans and proteoglycans during their synthesis, and (ii) forming ionic substitutions in the crystal lattice structure of hydroxyapatite. In addition, the dissolution products of bioactive glass (predominantly silicic acids) have significant effects on the molecular biology of osteoblasts in vitro, regulating the expression of several genes including key osteoblastic markers, cell cycle regulators and extracellular matrix proteins. Researchers have sought to capitalize on these effects and have generated a diverse array of biomaterials, which include bioactive glasses, silicon-substituted hydroxyapatites and pure, porosified silicon, but all these materials share similarities in the mechanisms that result in their bioactivity. This review discusses the current data obtained from original research in biochemistry and biomaterials science supporting the role of silicon in bone, comparing both the biological function of the element and analysing the evolution of silicon-containing biomaterials.

Porous silicon confers bioactivity to polycaprolactone composites in vitro.

Silicon is an essential element for healthy bone development and supplementation with its bioavailable form (silicic acid) leads to enhancement of osteogenesis both in vivo and in vitro. Porous silicon (pSi) is a novel material with emerging applications in opto-electronics and drug delivery which dissolves to yield silicic acid as the sole degradation product, allowing the specific importance of soluble silicates for biomaterials to be investigated in isolation without the elution of other ionic species. Using polycaprolactone as a bioresorbable carrier for porous silicon microparticles, we found that composites containing pSi yielded more than twice the amount of bioavailable silicic acid than composites containing the same mass of 45S5 Bioglass. When incubated in a simulated body fluid, the addition of pSi to polycaprolactone significantly increased the deposition of calcium phosphate. Interestingly, the apatites formed had a Ca:P ratio directly proportional to the silicic acid concentration, indicating that silicon-substituted hydroxyapatites were being spontaneously formed as a first order reaction. Primary human osteoblasts cultured on the surface of the composite exhibited peak alkaline phosphatase activity at day 14, with a proportional relationship between pSi content and both osteoblast proliferation and collagen production over 4 weeks. Culturing the composite with J744A.1 murine macrophages demonstrated that porous silicon does not elicit an immune response and may even inhibit it. Porous silicon may therefore be an important next generation biomaterial with unique properties for applications in orthopaedic tissue engineering.

Morphological changes (including filamentation) in Escherichia coli grown under starvation conditions on silicon wafers and other surfaces.

Using a scanning electron microscope, pleomorphism (notably filamentation) was seen when Escherichia coli was grown under starvation conditions for 14 d on microporous silicon wafers, titanium, glass and plastic discs. Under these conditions, the 'standard', rod shaped cell (1-3 microns) failed to separate after division and filaments developed, some as long as 50 microns, with many showing bulbous tips. Filamentation began to occur 5 d after the imposition of starvation conditions. Dumbbell shaped cells were also observed, although apparent 'Y' and 'V'-shaped cells proved to be artefacts, caused by overlapping rods. The implications of the appearance of pleomorphism in E. coli, when grown under starvation conditions, is discussed in relation to its pathogenicity and growth in the environment.