Enhanced Photoluminescence in Acetylene-Treated ZnO Nanorods.

Zinc oxide (ZnO) nanorods were manufactured using the aqueous chemical growth (ACG) method, and the effect of thermal acetylene treatment on their morphology, chemical composition, and optical properties was investigated. Changes in the elemental content of the treated rods were found to be different than in previous reports, possibly due to the different defect concentrations in the samples, highlighting the importance of synthesis method selection for the process. Acetylene treatment resulted in a significant improvement of the ultraviolet photoluminescence of the rods. The greatest increase in emission intensity was recorded on ZnO rods treated at the temperature of 825 °C. The findings imply that the changes brought on by the treatment are limited to the surface of the ZnO rods.

Candida albicans aspects of novel silane system-coated titanium and zirconia implant surfaces.

OBJECTIVES: The aim of the present study was to evaluate the effect of novel silane system coatings on zirconia and titanium implant surfaces and the attachment of the fungal pathogen Candida albicans. MATERIALS AND METHODS: Titanium and zirconia specimens were silica-coated and silanized either with a commercial silane primer (RelyX Ceramic Primer™, 3M ESPE) or a novel silane system primer. The novel silane system primer was a blend of 1.0 vol% 3-acryloxypropyltrimethoxysilane and 0.3 vol% bis-1,2-(triethoxysilyl)ethane diluted in acidified ethanol-water solvent. The surface roughness (Ra ), the surface free energy and the chemical composition of substrate surfaces after treatments were evaluated. C. albcans biofilms were developed on silica-coated + silanized surfaces during 48 h of incubation time. Colony forming units (CFU) and real-time PCR (RT-PCR) quantified the cells on the material surfaces. Statistical analyses were carried out by 1-way ANOVA, Tukey post hoc and Games Howell post hoc test at 5% significance level (p). RESULTS: On zirconia and titanium surfaces, the Ra and the chemical composition of the specimens were equal (P < 0.05). The surface free energy was decreased on titanium specimens and increased on zirconia specimen after silanization. CFU of C. albicans was significantly lower on zirconia coated with RelyX Ceramic Primer™, (P < 0.001) and on titanium coated with both silanes (P = 0.002). RT-PCR revealed no differences between the mean quantities of C. albicans (P ≥ 0.067). CONCLUSION: Silica-coating and silanization had modified the titanium and zirconia surfaces significantly. Both the control and experimental silane primers might inhibit the biofilm formation of C. albicans.

Amine modification of thermally carbonized porous silicon with silane coupling chemistry.

Thermally carbonized porous silicon (TCPSi) microparticles were chemically modified with organofunctional alkoxysilane molecules using a silanization process. Before the silane coupling, the TCPSi surface was activated by immersion in hydrofluoric acid (HF). Instead of regeneration of the silicon hydride species, the HF immersion of silicon carbide structure forms a silanol termination (Si-OH) on the surface required for silanization. Subsequent functionalization with 3-aminopropyltriethoxysilane provides the surface with an amine (-NH(2)) termination, while the SiC-type layer significantly stabilizes the functionalized structure both mechanically and chemically. The presence of terminal amine groups was verified with FTIR, XPS, CHN analysis, and electrophoretic mobility measurements. The overall effects of the silanization to the morphological properties of the initial TCPSi were analyzed and they were found to be very limited, making the treatment effects highly predictable. The maximum obtained number of amine groups on the surface was calculated to be 1.6 groups/nm(2), corresponding to 79% surface coverage. The availability of the amine groups for further biofunctionalization was confirmed by successful biotinylation. The isoelectric point (IEP) of amine-terminated TCPSi was measured to be at pH 7.7, as opposed to pH 2.6 for untreated TCPSi. The effects of the surface amine termination on the cell viability of Caco-2 and HT-29 cells and on the in vitro fenofibrate release profiles were also assessed. The results indicated that the surface modification did not alter the loading of the drug inside the pores and also retained the beneficial enhanced dissolution characteristics similar to TCPSi. Cellular viability studies also showed that the surface modification had only a limited effect on the biocompatibility of the PSi.

Resin zirconia bonding promotion with some novel coupling agents.

OBJECTIVES: To evaluate and compare three novel coupling agents: 2-hydroxyethyl methacrylate, itaconic acid and oleic acid to two silane coupling agents, one commercial silane product and 3-acryloxypropyltrimethoxysilane on the bond durability of resin composite to zirconia. METHODS: Zirconia samples were silica-coated by air abrasion and each of the five coupling agents was then applied to give five test groups. Resin composite stubs were bonded onto the conditioned zirconia surfaces. The samples were stored: dry storage, 30 days in water and thermocycled to give a total of fifteen test groups. The shear bond strengths were determined using a universal testing machine and data analyzed by two-way ANOVA and Tukey HSD (p<0.05) with shear bond strength as dependent variable and storage condition and primers as independent variables. The bond formation of the five coupling agents to zirconia was examined by X-ray photoelectron spectroscopy (XPS). RESULTS: Two-way ANOVA analysis showed that there was a significant difference for different primers (p<0.05) and different storage conditions (p<0.05) on the shear bond strength values measured. XPS analysis showed a shift in binding energy for O(1s) after priming with the five coupling agents which revealed different bond formations related to the functional groups of the coupling agents. SIGNIFICANCE: The shear bond strength values measured for all coupling agents after water storage and thermocycling exceed the minimum shear bond strength value of 5MPa set by ISO. The silane coupling agent, 3-acryloxypropyltrimethoxysilane, showed the highest bond strength of the three storage conditions.

Self-assembled carbon nanotubes on gold: polarization-modulated infrared reflection-absorption spectroscopy, high-resolution X-ray photoemission spectroscopy, and near-edge X-ray absorption fine structure spectroscopy study.

Recently we reported noncovalent functionalization of nanotubes in an aqueous medium with ionic liquid-based surfactants, 1-dodecyl-3-methylimidazolium bromide (1) and 1-(12-mercaptododecyl)-3-methylimidazolium bromide (2), resulting in positively charged single-wall carbon nanotube (SWNT)-1,2 composites. Thiolation of SWNTs with 2 provides their self-assembly on gold as well as templating gold nanoparticles on SWNT sidewalls via a covalent -S-Au bond. In this investigation, we studied the electronic structure, intermolecular interactions, and packing within noncovalently thiolated SWNTs and also nanotube alignment in the bulk of SWNT-2 dried droplets and self-assembled submonolayers (SAMs) on gold by high-resolution X-ray photoemission spectroscopy (HRXPS), C K-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS). HRXPS data confirmed the noncovalent nature of interactions within the nanocomposite of thiolated nanotubes. In PM-IRRAS spectra of SWNT SAMs on gold, the IR-active vibrational SWNT modes have been observed and identified. According to PM-IRRAS data, the hydrocarbon chains of 2 are oriented with less tilt angle to the bare gold normal in a SAM deposited from an SWNT-2 dispersion than those of 1 deposited from an SWNT-1 dispersion on the mercaptoethanesulfonic acid-primed gold. For both the dried SWNT-2 bulk and the SWNT-2 SAM on gold, the C K-edge NEXAFS spectra revealed the presence of CH-pi interactions between hydrocarbon chains of 2 and the pi electronic nanotube structure due to the highly resolved vibronic fine structure of carbon 1s --> R*/sigma*C-H series of states in the alkyl chain of 2. For the SWNT-2 bulk, the observed splitting and upshift of the SWNT pi* orbitals in the NEXAFS spectrum indicated the presence of pi-pi interactions. In the NEXAFS spectrum of the SWNT-2 SAM on gold, the upshifted values of the photon energy for R*/sigma*C-H transitions indicated close contact of 2 with nanotubes and with a gold surface. The angle-dependent NEXAFS for the SWNT-2 bulk showed that most of the molecules of 2 are aligned along the nanotubes, which are self-organized with orientation parallel to the substrate plane, whereas the NEXAFS for the SWNT-2 SAM revealed a more normal orientation of functionality 2 on gold compared with that in the SWNT-2 bulk.

Layer-by-layer electrostatic self-assembly of single-wall carbon nanotube polyelectrolytes.

We have used anionic and cationic single-wall carbon nanotube polyelectrolytes (SWNT-PEs), prepared by the noncovalent adsorption of ionic naphthalene or pyrene derivatives on nanotube sidewalls, for the layer-by-layer self-assembly to prepare multilayers from carbon nanotubes with polycations, such as poly(diallyldimethylammonium) or poly(allylamine hydrochloride) (PDADMA or PAH, respectively), and polyanions (poly(styrenesulfonate), PSS). This is a general and powerful technique for the fabrication of thin carbon nanotube films of arbitrary composition and architecture and allows also an easy preparation of all-SWNT (SWNT/SWNT) multilayers. The multilayers were characterized with vis-near-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), surface plasmon resonance (SPR) measurements, atomic force microscopy (AFM), and imaging ellipsometry. The charge compensation in multilayers is mainly intrinsic, which shows the electrostatic nature of the self-assembly process. The multilayer growth is linear after the initial layers, and in SWNT/polyelectrolyte films it can be greatly accelerated by increasing the ionic strength in the SWNT solution. However, SWNT/SWNT multilayers are much more inert to the effect of added electrolyte. In SWNT/SWNT multilayers, the adsorption results in the deposition of 1-3 theoretical nanotube monolayers per adsorbed layer, whereas the nominal SWNT layer thickness is 2-3 times higher in SWNT/polyelectrolyte films prepared with added electrolyte. AFM images show that the multilayers contain a random network of nanotube bundles lying on the surface. Flexible polyelectrolytes (e.g., PDADMA, PSS) probably surround the nanotubes and bind them together. On macroscopic scale, the surface roughness of the multilayers depends on the components and increases with the film thickness.