Physical science Division

Richland, Washington, United States

Physical science Division

Richland, Washington, United States

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El-Khoury P.Z.,Physical science Division | Gong Y.,Physical science Division | Abellan P.,Physical science Division | Arey B.W.,Pacific Northwest National Laboratory | And 5 more authors.
Nano Letters | Year: 2015

We report tip-enhanced Raman imaging experiments in which information on sample topography and local electric fields is simultaneously obtained using an all-optical detection scheme. We demonstrate how a Raman-active 4,4′-dimercaptostilbene (DMS)-coated gold tip of an atomic force microscope can be used to simultaneously map the topography and image the electric fields localized at nanometric (20 and 5 nm wide) slits lithographically etched in silver, all using optical signals. Bimodal imaging is feasible by virtue of the frequency-resolved optical response of the functionalized metal probe. Namely, the probe position-dependent signals can be subdivided into two components. The first is a 500-2250 cm-1 Raman-shifted signal, characteristic of the tip-bound DMS molecules. The molecules report on topography through the intensity contrast observed as the tip scans across the nanoscale features. The variation in molecular Raman activity arises from the absence/formation of a plasmonic junction between the scanning probe and patterned silver surface, which translates into dimmed/enhanced Raman signatures of DMS. Using these molecular signals, we demonstrate that sub-15 nm spatial resolution is attainable using a 30 nm DMS-coated gold tip. The second response consists of two correlated sub-500 cm-1 signals arising from mirror-like reflections of (i) the incident laser field and (ii) the Raman scattered response of an underlying glass support (at 100-500 cm-1) off the gold tip. We show that both the reflected low-wavenumber signals trace the local electric fields in the vicinity of the nanometric slits. (Figure Presented) © 2015 American Chemical Society.


Tao S.,Fudan University | Lu X.,Fudan University | Levac N.,University of California at Irvine | Bateman A.P.,University of California at Irvine | And 6 more authors.
Environmental Science and Technology | Year: 2014

Fine aerosol particles in the urban areas of Shanghai and Los Angeles were collected on days that were characterized by their stagnant air and high organic aerosol concentrations. They were analyzed by nanospray-desorption electrospray ionization mass spectrometry with high mass resolution (m/Δm = 100,000). Solvent mixtures of acetonitrile and water and acetonitrile and toluene were used to extract and ionize polar and nonpolar compounds, respectively. A diverse mixture of oxygenated hydrocarbons, organosulfates, organonitrates, and organics with reduced nitrogen were detected in the Los Angeles sample. A majority of the organics in the Shanghai sample were detected as organosulfates. The dominant organosulfates that were detected at two locations have distinctly different molecular characteristics. Specifically, the organosulfates in the Los Angeles sample were dominated by biogenic products, while the organosulfates of a yet unknown origin found in the Shanghai sample had distinctive characteristics of long aliphatic carbon chains and low degrees of oxidation and unsaturation. The use of the acetonitrile and toluene solvent facilitated the observation of this type of organosulfates, which suggests that they could have been missed in previous studies that relied on sample extraction using common polar solvents. The high molecular weight and low degree of unsaturation and oxidization of the uncommon organosulfates suggest that they may act as surfactants and plausibly affect the surface tension and hygroscopicity of atmospheric particles. We propose that direct esterification of carbonyl or hydroxyl compounds by sulfates or sulfuric acid in the liquid phase could be the formation pathway of these special organosulfates. Long-chain alkanes from vehicle emissions might be their precursors. © 2014 American Chemical Society.

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