Surface modification of surface sol-gel derived titanium oxide films by self-assembled monolayers (SAMs) and non-specific protein adsorption studies

Biological events occurring at the implant-host interface, including protein adsorption are mainly influenced by surface properties of the implant. Titanium alloys, one of the most widely used implants, has shown good biocompatibility primarily through its surface oxide. In this study, a surface sol-gel process based on the surface reaction of metal alkoxides with a hydroxylated surface was used to prepare ultrathin titanium oxide (TiOx) coatings on silicon wafers. The oxide deposited on the surface was then modified by self-assembled monolayers (SAMs) of silanes with different functional groups. Interesting surface morphology trends and protein adhesion properties of the modified titanium oxide surfaces were observed as studied by non-specific protein binding of serum albumin. The surface properties were investigated systematically using water contact angle, ellipsometry, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) measurements. Results showed that the surface sol-gel process predominantly formed homogeneous, but rough and porous titanium oxide layers. The protein adsorption was dependent primarily on the silane chemistry, packing of the alkyl chains (extent of van der Waals interaction), morphology (porosity and roughness), and wettability of the sol-gel oxide. Comparison was made with a thermally evaporated TiOx-Ti/Si-wafer substrate (control). This method further extends the functionalization of surface sol-gel derived TiOx layers for possible titanium alloy bioimplant surface modification.     

A first synthesis of thiophene dendrimers

[structure: see text] Thiophene dendrons and dendrimers were designed and synthesized using a convergent approach. Metal-mediated coupling reactions were used in the synthesis. A rational approach allowed the formation of alphaalpha, betabeta, and alphabeta linkages between the dendrons and thiophene units.     

A linearization technique for multi-species transport problems

We study a one-dimensional multi-species system of dispersive-advective contaminant transport equations coupled by nonlinear biological (kinetic reactions) and physical (adsorption) processes. To deal with the nonlinearities and the coupling, and to avoid additional computational costs, we propose a linearization technique based on first-order Taylor’s series expansions. A stabilized finite element in space, combined with an Euler implicit finite difference discretization in time, is used to approximate the dispersive-advective transport problem. Three computational tests are performed with different boundary conditions, retardation factors and kinetic parameters for a nonlinear reactive multi-species transport model. The proposed methodology is shown to be accurate and decrease computational costs in the numerical implementation of nonlinear reactive transport problems.     

Hybrid gold-nanoparticle-cored conjugated thiophene dendrimers: synthesis, characterization, and energy-transfer studies

A series of hybrid Au-nanoparticle-dendrimer materials: nanoparticle-cored thiophene dendrimers (NCTDs) were synthesized, characterized, and investigated for their energy-transfer properties. These hybrid nanoparticles were obtained by the simultaneous and in situ reduction of gold(III) chloride and self-assembly of the thiol-containing thiophene dendritic ligands. The dendron ligands were radially attached to the gold nanoparticles and were analyzed by TEM, UV/Vis, (1)H NMR, and FTIR spectroscopies. The solution fluorescence of the attached thiophene dendrons are quenched progressively. Both alkyl-chain length and dendron size have significant influence on the energy-transfer efficiency, as well as on core sizes and size distribution of the Au nanoparticles. In spite of the phenomenon's dependence on nanoparticle size, the energy transfer generally follows the 1/d(2) distance dependence. Single NCTD nanoparticles were also adsorbed on highly ordered pyrolytic graphite (HOPG) and uniform aggregates were observed on mica flat substrates.     

Antimicrobial graphene polymer (PVK-GO) nanocomposite films

The first report on the fabrication and application of a nanocomposite containing poly-N-vinyl carbazole (PVK) polymer and graphene oxide (GO) as an antimicrobial film was demonstrated. The antimicrobial film was 90% more effective in preventing bacterial colonization relative to the unmodified surface. More importantly, the nanocomposite thin film showed higher bacterial toxicity than pure GO-modified surface.     

Modular peripheral functionalization of thiophene dendrons and dendrimers

A series of thiophene dendrons and dendrimers with peripheral functional groups were designed and synthesized. Two methodologies using thiophene dendrons and dendrons as synthetic building blocks, namely, (1) periphery functionalization; (2) a combination of focal and periphery functionalization have been demonstrated.     

Polymer catenanes via a supramolecularly templated ATRP initiator

Synthesis of polymer catenanes via a living radical polymerization and supramolecular template approach are demonstrated. The ring closure was performed via atom transfer radical cross coupling (ATRC) to obtain polymer catenanes from the linear polymer metal complex precursor.     

Dissipating the Langevin equation in the presence of an external stochastic potential

In the Langevin formalism, the delicate balance maintained between the fluctuations in the system and their corresponding dissipation may be upset by the presence of a secondary, space-dependent stochastic force, particularly in the low-friction regime. In prior work, the latter was dissipated self-consistently through an additional uniform (mean-field) friction [T. Shepherd and R. Hernandez, J. Chem. Phys. 115, 2430 (2001).] An alternative approach to ensure that equipartition is satisfied relies on the use of a space-dependent friction while ignoring nonlocal correlations. The approach is evaluated with respect to its ability to maintain constant temperature for two simple one-dimensional, stochastic potentials of mean force wherein the friction can be evaluated explicitly when there is no memory in the barriers. The use of a space-dependent friction is capable of providing qualitatively similar results to those obtained previously, but in extreme cases deviations from equipartition may be observed due to the neglect of the memory effects present in the stochastic potentials.     

Ultrathin conjugated polymer network films of carbazole functionalized poly(p-phenylenes) via electropolymerization

Ultrathin films of a cross-linked and chemically distinct conjugated poly(p-phenylene) network via electropolymerization are described. The amphiphilic network precursor was synthesized by incorporating the alkoxy carbazole group (-O(CH2)5Cb) to a poly(p-phenylene) (C6PPPOH) backbone. In order to investigate the combined thin film electrochemical and photophysical properties of poly(p-phenylene)s and polycarbazole conjugated polymers, C6PPPC5Cb was deposited on substrates using the Langmuir Blodgett Kuhn (LBK) method. The monolayer isotherm of the polymer, C6PPPC5Cb, showed a liquid expanded region slightly different from the parent polymer C6PPPOH. Multilayers (up to 30 layers) were transferred to different substrates such as quartz, gold coated LaSFN9 and ITO substrates for analysis. For conversion to a conjugated polymer network (CPN) film, the electroactive carbazole group was electropolymerized using cyclic voltammetry (CV) resulting in polycarbazole linking units. The differences in the film properties and corresponding changes in the electrochemical behavior indicate the importance of film thickness and electron/ion transport process in cross linked network films. From the electrochemical studies, the scan rate was found to have a considerable effect on electropolymerization with higher oxidation and reduction peak values found for the rigid network polymer compared to the uncrosslinked polymers.