Fabrication of carbon nanotube lateral field emitters

We report on the fabrication and field emission of carbon nanotube lateral field emitters. Due to its high aspect ratio and mechanical strength, we use vertically aligned multi-wall carbon nanotubes prepared by plasma-enhanced chemical vapour deposition as cathodes, which makes the fabrication of cantilever type lateral field emitters possible. The emission characteristics show that the field emission initiates at 11-17 V. The device has high geometrical enhancement factors (9.3 × 106 cm-1) compared to standard Spindt tips, which may be due to increased field concentration at the nanotube tip and the close proximity of the anode (<1 μm). The relative ease of fabrication compared to vertical field emitters and enhanced field emission characteristics observed makes the carbon nanotube lateral field emitter a good candidate for future integrated nano-electronic devices.

Fabrication of self-aligned side gates to carbon nanotubes

We have fabricated self-aligned, side-gated suspended multi-walled carbon nanotubes (MWCNTs), with nanotube-to-gate spacing of less than 10 nm. Evaporated metal forms an island on a suspended MWCNT, the island and the nanotube act as a mask shielding the substrate, and lift-off then removes the metal island, leaving a set of self-aligned side gates. Al, Cr, Au, and Ti were investigated and the best results were obtained with Cr, at a yield of over 90%.

Cruise Report: Summer 2008 Ecological Assessment of Stellwagen Bank National Marine Sanctuary NOAA Ship NANCY FOSTER NF-08-09-CCEHBR (June 14-June 21, 2008)

Summary: This cruise report is a summary of a field survey conducted within the Stellwagen Bank National Marine Sanctuary (SBNMS), located between Cape Cod and Cape Ann at the mouth of Massachusetts Bay. The survey was conducted June 14 – June 21, 2008 on NOAA Ship NANCY FOSTER Cruise NF-08-09-CCEHBR. Multiple indicators of ecological condition and human dimensions were sampled synoptically at each of 30 stations throughout SBNMS using a random probabilistic sampling design. Samples were collected for the analysis of benthic community structure and composition; concentrations of chemical contaminants (metals, pesticides, PAHs, PCBs, PBDEs) in sediments and target demersal biota; nutrient and chlorophyll levels in the water column; and other basic habitat characteristics such as depth, salinity, temperature, dissolved oxygen, turbidity, pH, sediment grain size, and organic carbon content. In addition to the fish samples that were collected for analysis of chemical contaminants relative to human-health consumption limits, other human-dimension indicators were sampled as well including presence or absence of fishing gear, vessels, surface trash, marine mammals, and noxious sediment odors. The overall purpose of the survey was to collect data to assess the status of ecosystem condition and potential stressor impacts throughout SBNMS, based on these various indicators and corresponding management thresholds, and to provide this information as a baseline for determining how such conditions may be changing with time. While sample analysis is still ongoing a few preliminary results and observations are reported here. A final report will be completed once all data have been processed. The results are anticipated to be of value in supporting goals of the SBNMS and National Marine Sanctuary Program aimed at the characterization, protection, and management of sanctuary resources (pursuant to the National Marine Sanctuary Reauthorization Act) as well as a new priority of NCCOS and NOAA to apply Ecosystem Based approaches to the Management of coastal resources (EBM) through Integrated Ecosystem Assessments (IEAs) conducted in various coastal regions of the U.S. including the Northeast Atlantic continental shelf. This was a multi-disciplinary partnership effort made possible by scientists from the following organizations:  NOAA, National Ocean Service (NOS), National Centers for Coastal Ocean Science (NCCOS), Center for Coastal Environmental Health and Biomolecular Research (CCEHBR), Charleston, SC.  U.S. Environmental Protection Agency (EPA), National Health and Environmental Effects Research Laboratory (NHEERL), Atlantic Ecology Division (GED), Narragansett, RI.  U.S. Environmental Protection Agency (EPA), National Health and Environmental Effects Research Laboratory (NHEERL), Gulf Ecology Division (GED), Gulf Breeze, FL.  U.S. Geological Survey (USGS), National Wetlands Research Center, Gulf Breeze Project Office, Gulf Breeze, FL.  NOAA, Office of Marine and Aviation Operations (OMAO), NOAA ship Nancy Foster. (31pp) (PDF contains 58 pages)

Oceanographic Profiling and Spectroradiometer Observations from the MOCE-2 Cruise: 28 March to 14 April 1993

This report contains results from the second cruise of the Modis Optical Characterization Experiment (MOCE). Data presented here were obtained on the Mexican Research Vessel El Puma between 29 March and 13 April along the Pacific coast of Baja California and in the Gulf of California. Three types of data are reported: high spectral resolution radiometry at three depths for 13 stations; salinity, temperature beam attenuation and chlorophyll-a fluorescence, profiles at the same stations; and total suspended matter and suspended organic carbon and nitrogen.(PDF is 90 pages.)

Carbon-carbon bond forming reactions from bis(carbene)-platinum(II) complexes and olefin polymerization and oligomerization using group 4 post-metallocene complexes

A long-standing challenge in transition metal catalysis is selective C–C bond coupling of simple feedstocks, such as carbon monoxide, ethylene or propylene, to yield value-added products. This work describes efforts toward selective C–C bond formation using early- and late-transition metals, which may have important implications for the production of fuels and plastics, as well as many other commodity chemicals.

The industrial Fischer-Tropsch (F-T) process converts synthesis gas (syngas, a mixture of CO + H₂) into a complex mixture of hydrocarbons and oxygenates. Well-defined homogeneous catalysts for F-T may provide greater product selectivity for fuel-range liquid hydrocarbons compared to traditional heterogeneous catalysts. The first part of this work involved the preparation of late-transition metal complexes for use in syngas conversion. We investigated C–C bond forming reactions via carbene coupling using bis(carbene)platinum(II) compounds, which are models for putative metal–carbene intermediates in F-T chemistry. It was found that C–C bond formation could be induced by either (1) chemical reduction of or (2) exogenous phosphine coordination to the platinum(II) starting complexes. These two mild methods afforded different products, constitutional isomers, suggesting that at least two different mechanisms are possible for C–C bond formation from carbene intermediates. These results are encouraging for the development of a multicomponent homogeneous catalysis system for the generation of higher hydrocarbons.

A second avenue of research focused on the design and synthesis of post-metallocene catalysts for olefin polymerization. The polymerization chemistry of a new class of group 4 complexes supported by asymmetric anilide(pyridine)phenolate (NNO) pincer ligands was explored. Unlike typical early transition metal polymerization catalysts, NNO-ligated catalysts produce nearly regiorandom polypropylene, with as many as 30-40 mol % of insertions being 2,1-inserted (versus 1,2-inserted), compared to <1 mol % in most metallocene systems. A survey of model Ti polymerization catalysts suggests that catalyst modification pathways that could affect regioselectivity, such as C–H activation of the anilide ring, cleavage of the amine R-group, or monomer insertion into metal–ligand bonds are unlikely. A parallel investigation of a Ti–amido(pyridine)phenolate polymerization catalyst, which features a five- rather than a six-membered Ti–N chelate ring, but maintained a dianionic NNO motif, revealed that simply maintaining this motif was not enough to produce regioirregular polypropylene; in fact, these experiments seem to indicate that only an intact anilide(pyridine)phenolate ligated-complex will lead to regioirregular polypropylene. As yet, the underlying causes for the unique regioselectivity of anilide(pyridine)phenolate polymerization catalysts remains unknown. Further exploration of NNO-ligated polymerization catalysts could lead to the controlled synthesis of new types of polymer architectures.

Finally, we investigated the reactivity of a known Ti–phenoxy(imine) (Ti-FI) catalyst that has been shown to be very active for ethylene homotrimerization in an effort to upgrade simple feedstocks to liquid hydrocarbon fuels through co-oligomerization of heavy and light olefins. We demonstrated that the Ti-FI catalyst can homo-oligomerize 1-hexene to C₁₂ and C₁₈ alkenes through olefin dimerization and trimerization, respectively. Future work will include kinetic studies to determine monomer selectivity by investigating the relative rates of insertion of light olefins (e.g., ethylene) vs. higher α-olefins, as well as a more detailed mechanistic study of olefin trimerization. Our ultimate goal is to exploit this catalyst in a multi-catalyst system for conversion of simple alkenes into hydrocarbon fuels.

Competing Ecosystem Services: an Assessment of Carbon and Timber in the Tropical Forests of Central America

29 p.