Nanomaterials have allowed significant breakthroughs in bio-engineering and medical fields. In the present paper a holistic assessment on diverse biocompatible nanocomposites are studied. Their compatibility with advanced fabrication methods such as additive manufacturing for the design of functional medical implants is also critically reviewed. The significance of nanocomposites and processing techniques is also envisaged comprehensively in regard with the needs and futures of implantable medical device industries.
DNA immobilization on surfaces is crucial to a number of applications. However, detailed understanding of DNA/surface chemistry remains poorly documented, especially on oxide surfaces, due to the complexity of such large molecules. This work focuses on a simpler molecule, 2-deoxythymidine-5-monophosphate (dTMP), which contains all the chemical elements of DNA. It confirms that adsorption of dTMP onto OH-terminated SiO 2 surfaces does not result in a chemical bond (dTMP readily washes off) and instead shows that dTMP chemically adsorbs on Al 2 O 3 surfaces. We combine first-principles calculations, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy to determine the bonding configuration of dTMP onto alumina surfaces controllably grown by atomic layer deposition. We demonstrate that dTMP covalently reacts with alumina. Calculations indicate that covalent bonding of all dTMP polar groups (sugar ring, phosphate group, and thymine) is thermodynamically favored. Spectroscopic data and theory-based assignments of vibrational modes show that the bonding takes place primarily through both the thymine and phosphate groups. The reactivity and the tendency for dTMP to lie flat on the surface lead to an irreversible and disorganized dTMP layering. Studies of dTMP adsorption as a function of Al 2 O 3 thickness show that the density of grafted dTMP can be controlled, with measurable amounts even above the Al 2 O 3 monolayer coverage. These findings provide technological directions for DNA-based nanotechnologies to graft DNA on surfaces that would otherwise be unreactive.
DNA-directed assembly of nano-objects as a means to manufacture advanced nanomaterial architectures has been the subject of many studies. However, most applications have dealt with noble metals as there are fundamental difficulties to work with other materials. In this work, we propose a generic and systematic approach for functionalizing and characterizing oxide surfaces with single-stranded DNA oligonucleotides. This protocol is applied to aluminum and copper oxide nanoparticles due to their great interest for the fabrication of highly energetic heterogeneous nanocomposites. The surface densities of streptavidin and biotinylated DNA oligonucleotides are precisely quantified combining atomic absorption spectroscopy with conventional dynamic light scattering and fluorometry and maximized to provide a basis for understanding the grafting mechanism. First, the streptavidin coverage is consistently below 20% of the total surface for both nanoparticles. Second, direct and unspecific grafting of DNA single strands onto Al and CuO nanoparticles largely dominates the overall functionalization process: ∼95% and 90% of all grafted DNA strands are chemisorbed on the CuO and Al nanoparticle surfaces, respectively. Measurements of hybridization efficiency indicate that only ∼5 and ∼10% of single-stranded oligonucleotides grafted onto the CuO and Al surfaces are involved in the hybridization process, corresponding precisely to the streptavidin coverage, as evidenced by the occupancy of 0.9 and 1.2 oligonucleotides per protein. The hybridization efficiency of single-stranded oligonucleotides chemisorbed on CuO and Al without streptavidin coating decreases to only ∼2%, justifying the use of streptavidin despite its poor surface occupancy. Finally, the structure of directly chemisorbed DNA strands onto oxide surfaces is examined and discussed.
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