Timothy B. Tighe

Solid-State Water Electrolysis with an Alkaline Membrane

We report high-performance, durable alkaline membrane water electrolysis in a solid-state cell. An anion exchange membrane (AEM) and catalyst layer ionomer for hydroxide ion conduction were used without the addition of liquid electrolyte. At 50 °C, an AEM electrolysis cell using iridium oxide as the anode catalyst and Pt black as the cathode catalyst exhibited a current density of 399 mA/cm(2) at 1.80 V. We found that the durability of the AEM-based electrolysis cell could be improved by incorporating a highly durable ionomer in the catalyst layer and optimizing the water feed configuration. We demonstrated an AEM-based electrolysis cell with a lifetime of >535 h. These first-time results of water electrolysis in a solid-state membrane cell are promising for low-cost, scalable hydrogen production.

Interaction of vapor-deposited Ti and Au with molecular wires

We have investigated the interaction of vapor-deposited titanium and gold with a self-assembled monolayer (SAM) of 4-[4′-(phenylethynyl)-phenylethynyl]-benzenthiol, an unsubstituted oligo(phenylene-ethynylene), chemisorbed on a gold substrate, a typical SAM of interest for molecular electronics. Deposited titanium atoms are observed to react in a top-down fashion with the SAM molecules to form Ti–C bonds, destroying the monolayer structure. In contrast, deposited Au atoms undergo continuous penetration through the monolayer, even at high coverages, leaving the SAM “floating” on the Au substrate surface.

Solvation of zero-valent metals in organic thin films

Aluminum, copper and silver atoms are found to form a weakly solvated quasi-isotropic layer when vapor-deposited onto methoxy groups exposed at the surface of a hexadecanethiolate self-assembled monolayer on Au {1 1 1}. The nature of the interactions was revealed using SIMS, XPS and IRS, and supported by DFT calculations. This method complements 3D gas-phase cluster experiments by providing an approach for controlling solvation geometry and bonding via the molecular parameters of the monolayer. The results are discussed in terms of their applicability to the design of controlled interfaces, particularly metal contacts in molecular electronic devices.

Fabrication and characterization of cell sheets using methylcellulose and PNIPAAm thermoresponsive polymers: A comparison Study: CELL SHEETS USING MC AND PNIPAAm THERMORESPONSIVE POLYMERS

Culturing cells on thermoresponsive polymers enables cells to be harvested as an intact cell sheet without disrupting the extracellular matrix or compromising cell-cell junctions. Previously, cell sheet fabrication methods using methylcellulose (MC) gel and PNIPAAm were independently demonstrated. In this study, MC and PNIPAAm fabrication methods are detailed and the resulting cell sheets characterized in parallel studies for direct comparison of human adipose derived stromal/stem cell (hASCs) sheet formation, cell morphology, viability, proliferation, and osteogenic potential over 21 days. A cell viability study revealed that hASCs in MC and PNIPAAm cell sheets remained viable for 21 days and proliferated until confluency. Osteogenic cell sheets exhibited upregulation of alkaline phosphatase (ALP) at day 7, as well as calcium deposition at 21 days. Additionally, expression of osteocalcin (OCN), a late-stage marker of osteogenesis, was quantified at days 14 and 21 using RT-PCR. OCN was upregulated in MC cell sheets at day 14 and PNIPAAm cell sheets at days 14 and 21. These results indicate that hASCs formed into cell sheets commit to an osteogenic lineage when cultured in osteogenic conditions. Cell sheets composed of hASCs may be used for further studies of hASC differentiation or surgical delivery of undifferentiated cells to defect sites.

Assessing the hierarchical structure of titanium implant surfaces

The physical texture of implant surfaces are known to be one important factor in creating a stable bone-implant interface. Simple roughness parameters (for e.g., Sa or Sz) are not entirely adequate when characterizing surfaces possessing hierarchical structure (macro, micro, and nano scales). The aim of this study was to develop an analytical approach to quantify hierarchical surface structure of implant surfaces possessing nearly identical simple roughness. Titanium alloys with macro/micro texture (MM) and macro/micro/nano texture (MMN) were chosen as model surfaces to be evaluated. There was no statistical difference (p > 0.05) in either Sa (13.56 vs. 13.43 µm) or Sz (91.74 vs. 92.39 µm) for the MM and MMN surfaces, respectively. However, when advanced filtering algorithms were applied to these datasets, a statistical difference in roughness was found between MM (Sa = 0.54 µm) and MMN (Sa = 1.06 µm; p < 0.05). Additionally, a method was developed to specifically quantify the density of surface features appearing similar in geometry to natural osteoclastic pits. This analysis revealed a significantly greater numbers of these features (i.e., valleys) on the MMN surface as compared to the MM surface. Finally, atomic force microscopy showed a rougher nano-texture on the MMN surface compared with the MM surface (p < 0.05). The results support recent published studies that show a combination of appropriate micron and nano surface results in a more robust cellular response and increased osteoblast differentiation.

Nucleation and Growth of Vapor-Deposited Metal Films on Self-Assembled Monolayers Studied by Multiple Characterization Probes

The underlying chemistry of the interaction of metal atoms with organic thin films and polymer surfaces has important implications in many areas of science and technology but uncovering critical details of the mechanisms has been difficult, primarily because of the lack of well-defined organic surfaces. Self-assembled monolayers (SAMs)1–3 can now provide an approach to overcoming this problem.4–15 However, in order to fully utilize these precision surfaces it is also necessary to utilize combinations of surface science techniques that can reveal information about both the nature of the metal atoms and the organic surface chemistry and structure.