Chad L. Leverette

Aligned Silver Nanorod Arrays as Substrates for Surface-Enhanced Infrared Absorption Spectroscopy

Preferentially aligned silver nanorod arrays prepared by oblique angle vapor deposition were evaluated as substrates for surface-enhanced infrared absorption (SEIRA) spectroscopy. These nanorod arrays have an irregular surface lattice and are composed of tilted, cylindrically shaped nanorods that have an average length of 868 nm ± 95 nm and an average diameter of 99 nm ± 29 nm. The overall enhancement factor for chemisorbed organic films of para-nitrobenzoic acid (PNBA) deposited onto the Ag nanorod arrays analyzed by external reflection SEIRA was calculated to be 31 ± 9 compared to infrared reflection–absorption spectroscopy (IRRAS) obtained from a 500 nm Ag film substrate. This enhancement is attributed to the unique optical properties of the nanorod arrays as well as the increased surface area provided by the nanorod substrate. SEIRA reflection–absorbance intensity was observed with both p- and s-polarized incident radiation with angles of incidence ranging from 25° to 80°. The largest intensity was achieved with p-polarization and incident angles larger than 75°. Polarization-dependent ultraviolet/visible/near-infrared (UV/Vis/NIR) spectra of the nanorod arrays demonstrate that the red-shifted surface plasmon peaks of the elongated nanorods may be partially responsible for the observed SEIRA response. The SEIRA detection limit for the Ag nanorod arrays was estimated to be 0.08 ng/cm2. Surface-enhanced Raman scattering (SERS) and SEIRA analysis of chemisorbed PNBA utilizing the same nanorod substrate is demonstrated.

IN SITU URANIUM STABILIZATION BY MICROBIAL METABOLITES

Microbial melanin production by autochthonous bacteria was explored in this study as a means to increase U immobilization in U contaminated soil. This article demonstrates the application of bacterial physiology and soil ecology for enhanced U immobilization in order to develop an in situ, U bio-immobilization technology. We have demonstrated microbial production of a metal chelating biopolymer, pyomelanin, in U contaminated soil from the Tims Branch area of the Department of Energy (DOE), Savannah River Site (SRS), South Carolina, as a result of tyrosine amendments. Bacterial densities of pyomelanin producers were >10(6) cells per g wet soil. Pyomelanin demonstrated U complexing and mineral binding capacities at pH 4 and 7. In laboratory studies, in the presence of goethite or illite, pyomelanin enhanced U sequestration by these minerals. Tyrosine amended soils in a field test demonstrated increased U sequestration capacity following pyomelanin production up to 13 months after tyrosine treatments.

Dependence of Surface-Enhanced Infrared Absorption (SEIRA) Enhancement and Spectral Quality on the Choice of Underlying Substrate: A Closer Look at Silver (Ag) Films Prepared by Physical Vapor Deposition (PVD)

Silver (Ag) films of varying thickness were simultaneously deposited using physical vapor deposition (PVD) onto six infrared (IR) substrates (BaF2, CaF2, Ge, AMTIR, KRS-5, and ZnSe) in order to correlate the morphology of the deposited film with optimal SEIRA response and spectral band symmetry and quality. Significant differences were observed in the surface morphology of the deposited silver films, the degree of enhancement provided, and the spectral appearance of para-nitrobenzoic acid (PNBA) cast films for each silver-coated substrate. These differences were attributed to each substrates chemical properties, which dictate the morphology of the Ag film and ultimately determine the spectral appearance of the adsorbed analyte and the magnitude of SEIRA enhancement. Routine SEIRA enhancement factors (EFs) for all substrates were between 5 and 150. For single-step Ag depositions, the following ranking identifies the greatest SEIRA enhancement factor and the maximum absorption of the 1345 cm−1 spectral marker of PNBA at the optimal silver thickness for each substrate: BaF2 (EF = 85 ± 19, 0.059 A, 10 nm Ag) > CaF2 (EF = 75 ± 30, 0.052 A, 10 nm Ag) > Ge (EF = 45 ± 8, 0.019 A, 5 nm Ag) > AMTIR (EF = 38 ± 8, 0.024 A, 15 nm Ag) > KRS-5 (EF = 24 ± 1, 0.015 A, 12 nm Ag) > ZnSe (EF = 9 ± 5, 0.008 A, 8 nm Ag). A two-step deposition provides 59% larger EFs than single-step depositions of Ag on CaF2. A maximum EF of 147 was calculated for a cast film of PNBA (surface coverage = 341 ng/cm2) on a 10 nm two-step Ag film on CaF2 (0.102 A, 1345 cm−1 symmetric NO2 stretching band). The morphology of the two-step Ag film has smaller particles and greater particle density than the single-step Ag film.

Spectroscopic Evidence for Atmospheric Stabilization of Aluminum Borohydride in Polydimethylsiloxane Grease

Raman and infrared vibrational spectroscopy were used to confirm the presence of aluminum borohydride dissolved in a commercial polydimethylsiloxane vacuum grease at room temperature. Spectroscopic evidence for an adduct between the aluminum borohydride and polydimethylsiloxane is also presented. Once dissolved in the polydimethylsiloxane grease, the aluminum borohydride was stabilized with respect to its usual pyrophoric reactivity in wet or dry air.

Identification of a consistent polyene component of purple pigment in diseased sclerites of Caribbean corals across region, species, and insult agent

Gorgonians respond to insult (damage and disease) by producing sclerites containing a purple pigment as opposed to the normal white sclerites. Raman microscopy is used to study the purple areas of three species of diseased coral, Gorgonia ventalina, Pseudoplexaura porosa, and Eunicea laciniata obtained from Puerto Rico. These spectra were compared to Gorgonia ventalina samples previously reported that were obtained from San Salvador, Bahamas. Spectra from two samples of G. ventalina that had been infected by different agents, Aspergillus sydowii and a slime mold, were also obtained. The results indicate that the purple compounds (polyenes) generated by the coral in response to infection are similar regardless of region from which the coral were harvested, of species of coral, and of the infective agent. A discussion of the Raman spectra of G. ventalina and the other coral species is presented.