Functionalized surfaces and surface functionalization of nanomaterials

Nature leads, we follow. But nanotechnologists are in hot pursuit, in designing controllable structures that can mimic naturally occurring and artificially synthesized materials on a common platform. The supramolecular chemistry concerns the investigation of nature principles to produce fascinating complexed and functional molecular assemblies, as well as the utilization of these principles to generate novel devices and materials, potentially useful for sensing, catalysis, transport and other applications in medical or engineering science. The work presented in this thesis is a compilation of different synthetic methods to achieve inorganic-organic hybrid nanomaterials. Silicatein, a protein enzyme, which acts both as a catalyst and template for the formation of silica needles in marine sponges, has been used for the biosynthesis of semiconductor metal oxides on surfaces. Silicatein was immobilized on gold (111) surfaces using alkane thiol, as well as on a novel self-assembly of NTA on top of a “cushion” of reactive ester polymer has been successfully employed to make functionalised surfaces. The immobilization of silicatein on surfaces was monitored by surface plasmon spectroscopy, atomic force microscopy and confocal laser scanning microscopy. Surface bound silicatein retains its biocatalytic activity, which was demonstrated by monitoring its hydrocatalytic activity to catalyse the synthesis of biosilica, biotitania, and biozirconia. The synthesis of semiconductor metal oxides was characterized using scanning electron microscopy. This hydrolytic biocatalyst is used to synthesize the gold nanoparticles. The gold nanoparticles are formed by reduction of tetrachloroaurate, AuCl4-, by the action of sulfhydryl groups hidden below the surface groups of the protein. The resulting gold nanoparticles which are stabilized by surface bound silicatein further aggregate to form Au nanocrystals. The shape of the nanocrystals obtained by using recombinant silicatein is controlled through chiral induction by the protein during the nucleation of the nanocrystals. As an extension of this work, TiO2 nanowires were functionalized using polymeric ligand which incorporates the nitrilotriacetic acid (NTA) linker in the back bone to immobilize His-tagged silicatein onto the TiO2 nanowires. The surface bound protein not only retains its original hydrolytic properties, but also acts as a reductant for AuCl4- in the synthesis of hybrid TiO2/silicatein/Au nanocomposites. Functionalized, monocrystalline rutile TiO2 nanorods were prepared from TiCl4 in aqueous solution in the presence of dopamine. The surface bound organic ligand controls the morphology as well as the crystallinity and the phase selection of TiO2. The surface amine groups can be tailored further with functional molecules such as dyes. As an example, this surface functionality is used for the covalent binding of a fluorescent dye,4-chloro-7- nitrobenzylurazene (NBD) to the TiO2 nanorods. The polymeric ligands have been used successfully for the in-situ and post-functionalization of TiO2 nanoparticles. Besides to chelating dopamine anchor group the multifunctional ligand system presented here incorporates a modifier molecule which allows the binding of functional molecules (here the dyes pyrene, NBD, and Texas Red) as well as additional entities which allow tailoring the solubility of inorganic nanocrystals in different solvents. A novel method for the surface functionalization of fullerene-type MoS2 nanoparticles and subsequently binding these nanoparticles onto TiO2 nanowires has been reported using polymeric ligands. The procedure involves the complexation of IF-MoS2 with a combination of Ni2+ via an umbrella-type nitrilotriacetic acid (NTA) and anchoring them to the sidewalls of TiO2 nanowires utilizing the hydroxyl groups of dopamine present in the main contents of polymeric ligand. A convenient method for the synthesis of Au/CdS nanocomposites has been presented, which were achieved through the novel method of thiol functionalization of gold colloids. The thermodynamically most stable phase of ZrO2 (cubic) has been obtained at much lower temperature (180°C). These nanoparticles are highly blue fluorescent, with a high surface area.

From polymer precursors to metal oxides

We report on a strategy to prepare metal oxides including binary oxide and mixed metal oxide (MMO) in form of nanometer-sized particles using polymer as precursor. Zinc oxide nanoparticles are prepared as an example. The obtained zinc polyacrylate precursor is amorphous as confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The conversion from polymer precursor to ZnO nanocrystals by thermal pyrolysis was investigated by means of XRD, thermogravimetric analysis (TGA) and electron microscopy. The as-synthesized ZnO consists of many individual particles with a diameter around 40 nm as shown by scanning electron microscopy (SEM). The photoluminescence (PL) and electron paramagnetic (EPR) properties of the material are investigated, too. Employing this method, ZnO nanocrystalline films are fabricated via pyrolysis of a zinc polyacrylate precursor film on solid substrate like silicon and quartz glass. The results of XRD, absorption spectra as well as TEM prove that both the ZnO nanopowder and film undergo same evolution process. Comparing the PL properties of films fabricated in different gas atmosphere, it is assigned that the blue emission of the ZnO films is due to crystal defect of zinc vacancy and green emission from oxygen vacancy. Two kinds of ZnO-based mixed metal oxide (Zn1-xMgxO and Zn1-xCoxO) particles with very precise stoichiometry are prepared by controlled pyrolysis of the corresponding polymer precursor at 550 oC. The MMO crystal particles are typically 20-50 nm in diameter. Doping of Mg in ZnO lattice causes shrinkage of lattice parameter c, while it remains unchanged with Co incorporation. Effects of bandgap engineering are seen in the Mg:ZnO system. The photoluminescence in the visible is enhanced by incorporation of magnesium on zinc lattice sites, while the emission is suppressed in the Co:ZnO system. Magnetic property of cobalt doped-ZnO is checked too and ferromagnetic ordering was not found in our samples. An alternative way to prepare zinc oxide nanoparticles is presented upon calcination of zinc-loaded polymer precursors, which is synthesized via inverse miniemulsion polymerization of the mixture of the acrylic acid and zinc nitrate. The as-prepared ZnO product is compared with that obtained from polymer-salt complex method. The obtained ZnO nanoparticles undergo surface modification via a phosphate modifier applying ultrasonication. The morphology of the modified particles is checked by SEM. And stability of the ZnO nanoparticles in aqueous dispersion is enhanced as indicated by the zeta-potential results.

Inorganic-organic hybrid polymers: Solution-processible coating materials for defined surface functionalization

A new class of inorganic-organic hybrid polymers could successfully been prepared by the combination of different polymerization techniques. The access to a broad range of organic polymers incorporated into the hybrid polymer was realized using two independent approaches.rnIn the first approach a functional poly(silsesquioxane) (PSSQ) network was pre-formed, which was capable to initiate a controlled radical polymerization to graft organic vinyl-type monomers from the PSSQ precursor. As controlled radical polymerization techniques atom transfer radical polymerization (ATRP), as well as reversible addition fragmentation chain transfer (RAFT) polymerization could be used after defined tuning of the PSSQ precursor either toward a PSSQ macro-initiator or to a PSSQ macro-chain-transfer-agent. The polymerization pathway, consisting of polycondensation of trialkoxy-silanes followed by grafting-from polymerization of different monomers, allowed synthesis of various functional hybrid polymers. A controlled synthesis of the PSSQ precursors could successfully be performed using a microreactor setup; the molecular weight could be adjusted easily while the polydispersity index could be decreased well below 2.rnThe second approach aimed to incorporate differently derived organic polymers. As examples, polycarbonate and poly(ethylene glycol) were end-group-modified using trialkoxysilanes. After end-group-functionalization these organic polymers could be incorporated into a PSSQ network.rnThese different hybrid polymers showed extraordinary coating abilities. All polymers could be processed from solution by spin-coating or dip-coating. The high amount of reactive silanol moieties in the PSSQ part could be cross-linked after application by annealing at 130° for 1h. Not only cross-linking of the whole film was achieved, which resulted in mechanical interlocking with the substrate, also chemical bonds to metal or metal oxide surfaces were formed. All coating materials showed high stability and adhesion onto various underlying materials, reaching from metals (like steel or gold) and metal oxides (like glass) to plastics (like polycarbonate or polytetrafluoroethylene).rnAs the material and the synthetic pathway were very tolerant toward different functionalities, various functional monomers could be incorporated in the final coating material. The incorporation of N-isopropylacrylamide yielded in temperature-responsive surface coatings, whereas the incorporation of redox-active monomers allowed the preparation of semi-conductive coatings, capable to produce smooth hole-injection layers on transparent conductive electrodes used in optoelectronic devices.rnThe range of possible applications could be increased tremendously by incorporation of reactive monomers, capable to undergo fast and quantitative conversions by polymer-analogous reactions. For example, grafting active esters from a PSSQ precursor yielded a reactive surface coating after application onto numerous substrates. Just by dipping the coated substrate into a solution of a functionalized amine, the desired function could be immobilized at the interface as well as throughout the whole film. The obtained reactive surface coatings could be used as basis for different functional coatings for various applications. The conversion with specifically tuned amines yielded in surfaces with adjustable wetting behaviors, switchable wetting behaviors or as recognition element for surface-oriented bio-analytical devices. The combination of hybrid materials with orthogonal reactivities allowed for the first time the preparation of multi-reactive surfaces which could be functionalized sequentially with defined fractions of different groups at the interface. rnThe introduced concept to synthesis functional hybrid polymers unifies the main requirements on an ideal coating material. Strong adhesion on a wide range of underlying materials was achieved by secondary condensation of the PSSQ part, whereas the organic part allowed incorporation of various functionalities. Thus, a flexible platform to create functional and reactive surface coatings was achieved, which could be applied to different substrates. rn