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Full-Text Articles in Physical Sciences and Mathematics

Inverse Velocity Dependence Of Vibrationally Promoted Electron Emission From A Metal Surface, N. H. Nahler, J. D. White, Jerry L. Larue, Daniel J. Auerbach, Alec M. Wodtke Aug 2008

Inverse Velocity Dependence Of Vibrationally Promoted Electron Emission From A Metal Surface, N. H. Nahler, J. D. White, Jerry L. Larue, Daniel J. Auerbach, Alec M. Wodtke

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

All previous experimental and theoretical studies of molecular interactions at metal surfaces show that electronically nonadiabatic influences increase with molecular velocity. We report the observation of a nonadiabatic electronic effect that follows the opposite trend: The probability of electron emission from a low–work function surface—Au(111) capped by half a monolayer of Cs—increases as the velocity of the incident NO molecule decreases during collisions with highly vibrationally excited NO(X2π½, V = 18; V is the vibrational quantum number of NO), reaching 0.1 at the lowest velocity studied. We show that these results are consistent with a vibrational …


The Work Function Of Submonolayer Cesium-Covered Gold: A Photoelectron Spectroscopy Study, Jerry L. Larue, J. D. White, N. H. Nahler, Z. Liu, Y. Sun, P. A. Pianetta, Daniel J. Auerbach, Alec M. Wodtke Jul 2008

The Work Function Of Submonolayer Cesium-Covered Gold: A Photoelectron Spectroscopy Study, Jerry L. Larue, J. D. White, N. H. Nahler, Z. Liu, Y. Sun, P. A. Pianetta, Daniel J. Auerbach, Alec M. Wodtke

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Using visible and x-ray photoelectron spectroscopy, we measured the work function of a Au(111) surface at a well-defined submonolayer coverage of Cs. For a Cs coverage producing a photoemission maximum with a He–Ne laser, the work function is , consistent with previous assumptions used to analyze vibrationally promoted electron emission. A discussion of possible Cs layer structures is also presented.


Synthesis Of Multifunctional Nanogels Using A Protected Macromonomer Approach, Neetu Singh, L. Andrew Lyon Jan 2008

Synthesis Of Multifunctional Nanogels Using A Protected Macromonomer Approach, Neetu Singh, L. Andrew Lyon

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Nanoparticles possessing multiple functionalities provide synthetic handles for varied surface chemistries, making them useful for a range of applications such as biotargeting and drug delivery. However, the combination of interfering functionalities on the same particle is often challenging. We have employed a synthetic scheme involving chemical protection/deprotection to combine interfering functional groups on the same hydrogel nanoparticle. The synthesis of amine-containing poly(N-isopropylacrylamide) nanogels was carried out via free radical precipitation polymerization by incorporating a Fmoc-protected amine poly(ethylene glycol) (PEG) macromonomer. The Fmoc group was then removed to obtain free amines, which were shown to be available for conjugation. We further …


Size-Controlled Synthesis Of Monodisperse Core/Shell Nanogels, William H. Blackburn, L. Andrew Lyon Jan 2008

Size-Controlled Synthesis Of Monodisperse Core/Shell Nanogels, William H. Blackburn, L. Andrew Lyon

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Small, monodisperse nanogels (similar to 50-nm radius) were synthesized by free-radical precipitation polymerization and were characterized using a suite of light scattering and chromatography methods. Nanogels were synthesized with either N-isopropylacrylamide or N-isopropylmethacrylamide as the main monomer, with acrylic acid or 4-acrylamidofluorescein as a comonomer and N,N'-methylenebis(acrylamide) as a cross-linker. By varying the surfactant and initiator concentrations, particle size was controlled while maintaining excellent monodispersity. An amine-containing shell was added to these core particles to facilitate subsequent bioconjugation. Successful conjugation of folic acid to the particles was demonstrated as an example of how such materials might be employed in a …


Reduced Acute Inflammatory Responses To Microgel Conformal Coatings, Amanda W. Bridges, Neetu Singh, Kellie L. Burns, Julia E. Babensee, L. Andrew Lyon, Andrés J. García Jan 2008

Reduced Acute Inflammatory Responses To Microgel Conformal Coatings, Amanda W. Bridges, Neetu Singh, Kellie L. Burns, Julia E. Babensee, L. Andrew Lyon, Andrés J. García

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Implantation of synthetic materials into the body elicits inflammatory host responses that limit medical device integration and biological performance. This inflammatory cascade involves protein adsorption, leukocyte recruitment and activation, cytokine release, and fibrous encapsulation of the implant. We present a coating strategy based on thin films of poly(N-isopropylacrylamide) hydrogel microparticles (i.e. microgels) cross-linked with poly(ethylene glycol) diacrylate. These particles were grafted onto a clinically relevant polymeric material to generate conformal coatings that significantly reduced in vitro fibrinogen adsorption and primary human monocyte/macrophage adhesion and spreading. These microgel coatings also reduced leukocyte adhesion and expression of pro-inflammatory cytokines (TNF-alpha, IL-1 beta, …


Salt Marshes As A Source Of Chromophoric Dissolved Organic Matter (Cdom) To Southern California Coastal Waters, Catherine D. Clark, Liannea P. Litz, Stanley B. Grant Jan 2008

Salt Marshes As A Source Of Chromophoric Dissolved Organic Matter (Cdom) To Southern California Coastal Waters, Catherine D. Clark, Liannea P. Litz, Stanley B. Grant

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

To determine chromophoric dissolved organic matter (CDOM) sources in Southern California coastal waters, optical properties of a river outlet and adjacent tidally flushed salt marshes were monitored (dry season; June July 2001). Average absorption coefficients doubled at ebb vs. flood tides (4.8 +/- 1.5 vs. 2.1 +/- 0.9 m(-1); 300 nm), suggesting significant salt marsh CDOM inputs into coastal waters. Average spectral slopes were not statistically different for any sites or tides (0.010 +/- 0.002 nm(-1)), consistent with salt marsh CDOM dominating coastal waters. Three-dimensional fluorescence excitation-emission matrices (EEMs) at ebb tide showed contributions from terrestrial, protein, and marine humic-like …


Dms Air/Sea Flux And Gas Transfer Coefficients From The North Atlantic Summertime Coccolithophore Bloom, Christa Marandino, Warren J. De Bruyn, Scott Miller, Eric S. Saltzman Jan 2008

Dms Air/Sea Flux And Gas Transfer Coefficients From The North Atlantic Summertime Coccolithophore Bloom, Christa Marandino, Warren J. De Bruyn, Scott Miller, Eric S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Dimethylsulfide (DMS) atmospheric and oceanic concentrations and eddy covariance air/sea fluxes were measured over the N. Atlantic Ocean during July 2007 from Iceland to Woods Hole, MA, USA. Seawater DMS levels north of 55 degrees N ranged from 3 to 17 nM, with variability related to the satellite-derived distributions of coccoliths and to a lesser extent, chlorophyll. For the most intense bloom region southwest of Iceland, DMS air/sea fluxes were as high as 300 mu mol m(-2) d(-1), larger than current model estimates. The observations imply that gas exchange coefficients in this region are significantly greater than those estimated using …