EMSL: Scott Lea's Publications

Baer DR, MH Engelhard, AR Felmy, JJ Ford, JZ Hu, AS Lea, P Nachimuthu, LV Saraf, JA Sears, and S Thevuthasan. 2009. "New Approaches for Characterizing Sensor and Other Modern Complex Materials." ECS Transactions 19(6):137-148. doi:10.1149/1.3118546 Abstract Advances in understanding of sensor and other modern complex materials are often enabled by new research tools. This paper highlights three capability development themes used to identify new research tools to be provided to users of the U. S. Department of Energy’s Environmental Molecular Sciences Laboratory. These capability development directions address the importance of dynamic measurements in realistic environments, the need for increased resolution in three dimensional analyses as well as the importance of linking theory and experiment. Capability development involves expanding the range of operation for a number of important techniques, developing and applying new capabilities, and advancing methods of data processing. Examples of current developments are provided including those related to magnetic resonance, x-ray diffraction, application of a focused beam capability to fuel cell aging, and near real time analysis of XPS spectra.

Tarasevich BJ, AS Lea, W Bernt, MH Engelhard, and WJ Shaw. 2009. "Adsorption of Amelogenin onto Self-Assembled and Fluoroapatite Surfaces." Journal of Physical Chemistry B 113(7):1833-1842. Abstract Abstract. The interactions of proteins at surfaces are of great importance to biomineralizaton processes and to the development and function of biomaterials. Amelogenin is a unique biomineralization protein because it self-assembles to form supramolecular structures called “nanospheres,” spherical aggregates of monomers that are 20-60 nm in diameter. Although the nanosphere quaternary structure has been observed in solution, the quaternary structure of amelogenin adsorbed onto surfaces is also of great interest because the surface structure is critical to its function. We report studies of the adsorption of the amelogenin onto self-assembled monolayers (SAMs) with COOH and CH3 end group functionality and single crystal fluoroapatite (FAP). Dynamic light scattering (DLS) experiments showed that the solutions contained nanospheres and aggregates of nanospheres. Protein adsorption onto the various substrates was evidenced by null ellipsometry, x-ray photoelectron spectroscopy (XPS), and external reflectance Fourier transform infrared spectroscopy (ERFTIR). Although only nanospheres were observed in solution, ellipsometry and atomic force microscopy (AFM) indicated that the protein adsorbates were much smaller structures than the original nanospheres, from monomers to small oligomers in size. Monomer adsorption was promoted onto the CH3 surfaces and small oligomer adsorption was promoted onto the COOH and FAP substrates. In some cases, remnants of the original nanospheres adsorbed as multilayers on top of the underlying subnanosphere layers. This work suggests that amelogenin can adsorb by the “shedding” or disassembling of substructures from the nanospheres onto substrates and indicates that amelogenin may have a range of possible quaternary structures depending on whether it is in solution or interacting with surfaces.

Tarasevich BJ, AS Lea, W Bernt, MH Engelhard, and WJ Shaw. 2009. "Changes in the quaternary structure of amelogenin when adsorbed onto surfaces." Biopolymers 91(2):103-107. doi:10.1002/bip.21095 Abstract The amelogenin protein is involved in the formation of highly controlled and anisotropic hydroxyapatite crystals in tooth enamel. Amelogenin is unique in that it self assembles to form supramolecular quaternary structures called “nanospheres,” spherical aggregates of amelogenin monomers typically 20-60 nm in diameter. Although nanospheres have been observed in solution, the quaternary structure of amelogenin adsorbed onto surfaces is not well known. A better understanding of the surface structure is of great importance, however, because the function of amelogenin depends on it. We report studies of the adsorption of amelogenin onto self-assembled monolayers (SAMs) containing COOH and CH3 end group functionality as well as single crystal fluoroapatite (FAP), a biologically relevant surface. The supramolecular structures of the protein in solution as determined by dynamic light scattering (DLS) were compared with the supramolecular structures of the protein physisorbed onto surfaces as studied by atomic force microscopy (AFM). We found that although our solutions contained only nanospheres of narrow size distribution, smaller structures such as monomers and dimers were observed onto both hydrophilic and hydrophobic surfaces. This suggests that amelogenin can adsorb onto surfaces as small structures that peel away or “shed” from the nanospheres that are present in solution.

Zhu Z, P Nachimuthu, and AS Lea. 2009. "Molecular Depth Profiling of Sucrose Films: A Comparative Study of C₆₀n⁺ Ions and Traditional Cs⁺ and O₂⁺ Ions." Analytical Chemistry 81(20):8272-8279. doi:10.1021/ac900553z Abstract Time-of-flight secondary ion mass spectrometry (ToF-SIMS) depth profiling of sucrose thin films were investigated using 10 keV C60+, 20 keV C602+, 30 keV C603+, 250 eV, 500 eV and 1000 eV Cs+ and O2+ as sputtering ions. With C60n+ ions, the molecular ion signal initially decreases, and reaches a steady-state that is about 38-51% of its original intensity, depending on the energy of the C60n+ ions. On the contrary, with Cs+ and O2+ sputtering, molecular ion signals decrease quickly to the noise level, even using low energy (250 eV) sputtering ions. In addition, the sucrose/Si interface by C60+ sputtering is much narrower than that of Cs+ and O2+ sputtering. To understand the mechanisms of sputtering-induced damage by these ions, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) were used to characterize the bottoms of these sputter craters. XPS data show very little chemical change in the C60+ sputter crater, while considerable amorphous carbon was found in the O2+ and Cs+ sputter craters, indicating extensive decomposition of the sucrose molecules. AFM images show a very flat bottom in the C60+ sputter crater, while the Cs+ and O2+ sputter crater bottoms are significantly rougher than that of the C60+ sputter crater. Based on above data, we developed a simple model to explain different damage mechanisms during sputtering process.

Badireddy AR, BR Korpol, S Chellam, PL Gassman, MH Engelhard, AS Lea, and KM Rosso. 2008. "Spectroscopic Characterization of Extracellular Polymeric Substances from Escherichia coli and Serratia marcescens: Suppression using Sub-Inhibitory Concentrations of Bismuth Thiols." Biomacromolecules 9(11):3079-3089. doi:10.1021/bm800600p Abstract Free and capsular EPS produced by Escherichia coli and Serratia marcescens were characterized in detail using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and Auger electron spectroscopy (AES). Total EPS production decreased upon treatment with sub-inhibitory concentrations of lipophilic bismuth thiols (bismuth dimercaptopropanol, BisBAL; bismuth ethanedithiol, BisEDT; and bismuth pyrithione, BisPYR), BisBAL being most effective. Bismuth thiols also influenced acetylation and carboxylation of polysaccharides in EPS from S. marcescens. Extensive homology between EPS samples in the presence and absence of bismuth was observed with proteins, polysaccharides, and nucleic acids varying predominantly only in the total amount expressed. Second derivative analysis of the amide I region of FTIR spectra revealed decreases in protein secondary structures in the presence of bismuth thiols. Hence, anti-fouling properties of bismuth thiols appear to originate in their ability to suppress O-acetylation and protein secondary structures in addition to total EPS secretion.

Karagulian F, AS Lea, CW Dilbeck, and BJ Finlayson-Pitts. 2008. "A New Mechanism for Ozonolysis of Unsaturated Organics on Solids: Phosphocholines on NaCl as A Model for Sea Salt particles." Physical Chemistry Chemical Physics. PCCP 10(4):528-541. doi:10.1039/b712715d Abstract The ozonolysis of an approximately one monolayer film of 1-oleoyl-2-palmitoyl-sn-glycero-3-phosphocholine (OPPC) on NaCl was followed in real time using diffuse reflectance infrared Fourier transform spectrometry (DRIFTS) at 23 °C. Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry and AUGER electron spectroscopy were used as complementary analytical techniques. Ozone concentrations ranged from 1.7  1012 to 7.0  1013 molecules cm-3 (70 ppb to 2.5 ppm). Upon exposure to O3, there was a loss of C=C accompanied by the formation of a strong band at ~1110 cm-1 due to the formation of a stable secondary ozonide (1,3,4-trioxolane, SOZ). The yield of the SOZ was lower when the reaction was carried out in the presence of water vapor at concentrations corresponding to relative humidities between 2 and 25 %. The dependencies of the rate of SOZ formation on the concentrations of ozone and water vapor are consistent with the initial formation of a primary ozonide (1,2,3-trioxolane, POZ) that can react with O3 or H2O in competition with its thermal decomposition to a Criegee intermediate and aldehyde. This interpretation is also consistent with the measured dependence of the SOZ yield on the ozone concentration. Estimates were obtained for the rate constants for the POZ thermal decomposition and for its reactions with O3 and H2O, as well as for the initial reaction of O3 with OPPC. The SOZ decomposed upon photolysis at  > 300 nm, generating aldehydes, carboxylic acids and anhydrides. These studies show that the primary ozonide has a sufficiently long lifetime when formed on a solid substrate that direct reactions with O3 and H2O can compete with its thermal decomposition. In dry polluted atmospheres, ozone-alkene reactions may lead in part to the formation of stable secondary ozonides whose chemistry, photochemistry and toxicity should be taken into account in models of such regions.

Yada T, C Floss, FJ Stadermann, E Zinner, T Nakamura, T Noguchi, and AS Lea. 2008. "Stardust in Antarctic Micrometeorites." Meteoritics and Planetary Science 43(8):1287-1298. Abstract We report the discovery of presolar silicate, oxide (hibonite) and (possibly) SiC grains from four Antarctic micrometeorites. The oxygen isotopic compositions of the eighteen presolar silicate (and one oxide) grains found are consistent with those observed previously in primitive meteorites and interplanetary dust particles, and indicate origins in oxygen-rich red giant or asymptotic giant branch stars. Four grains with anomalous C isotopic compositions were also detected. 12C/13C as well as Si ratios are similar to those of mainstream SiC grains; the N isotopic composition of one grain is also consistent with a mainstream SiC classification. Presolar silicate grains were found in three of the seven AMMs studied, and are heterogeneously distributed within these micrometeorites. Fourteen of the 18 presolar silicate grains and 3 of the 4 C-anomalous grains were found within one AMM, T98G8. The presence of magnesiowüstite, which forms mainly through the decomposition of carbonates, in AMMs without presolar silicates, and its absence in the presolar silicate-bearing micrometeorites, suggests that parent body processes (specifically aqueous alteration) may determine the presence or absence of presolar silicates in Antarctic micrometeorites.

Saraf LV, MH Engelhard, and AS Lea. 2007. "Fabrication of SiO2 Microdisk Arrays for Optics and Light Trapping Experiments." Microelectronic Engineering 84(12):2799-2803. doi:10.1016/j.mee.2007.02.001 Abstract We present a simple silicon based microfabrication process that produces an array of SiO2 microdisks using UV lithography. High-resolution SEM images of these structures indicate a smooth outer microdisk cavity surface. Photoemission measurements were performed at different spots on the microdisk and compared with measurements inside the cavity. A silicon to oxygen atomic concentration ratio of 1:2 obtained during depth profiling confirms that the entire microdisk is made up of stoichometric SiO2. In contrast, the inner cavity is mostly silicon with native oxide on top. We discuss the usefulness of SiO2 microdisks in optics for light trapping experiments.

Saraf LV, MH Engelhard, CM Wang, AS Lea, DE McCready, V Shutthanandan, DR Baer, and SA Chambers. 2007. "Metalorganic chemical vapor deposition of carbon-free ZnO using the bis(2,2,6,6 tetramethyl-3,5-heptanedionato)zinc precursor." Journal of Materials Research 22(5):1230-1234. doi:10.1557/JMR.2007.0146 Abstract We report the growth of c-axis oriented ZnO films on silicon (100) single crystal substrates by MOCVD. A relatively uninvestigated precursor, Zn(TMHD)2, was used in a cold-wall MOCVD reactor. XPS and RBS analysis yielded a zinc-to-oxygen atom percent ratio of 0.98 and 1.00 at the surface and in the overall film, respectively indicative of stoichometric ZnO. Due to the presence of carbon at the surface, the excess oxygen at the surface was in the form of C-O bonding. The c-axis orientation was confirmed by HRTEM and XRD. We look at these results from a viewpoint of an ongoing effort to ensure cleaner decompositions using Zn(TMHD)2.

Saraf LV, MH Engelhard, P Nachimuthu, V Shutthanandan, CM Wang, SM Heald, DE McCready, AS Lea, DR Baer, and SA Chambers. 2007. "Nucleation and Growth of MOCVD Grown (Cr, Zn)O Films – Uniform Doping vs. Secondary Phase Formation." Journal of the Electrochemical Society 154(3):D134-D138. doi:10.1149/1.2424422 Abstract We report a detailed study of chromium solubility and secondary phase formation in MOCVD grown (Cr, Zn)O-based films on silicon (100). Simultaneous deposition of 0.15M Cr(TMHD) and 0.025M Zn(TMHD) based precursors in an oxidizing environment with a flow ratio of 1:10 resulted in secondary phase formation rather than uniform Cr doping. Based on several surface and micro-structural techniques, we have identified nano-crystalline ZnCr2O4 and disordered Cr2O3 as the secondary Cr-containing phases that nucleate. Analysis suggests that ZnCr2O4 crystallites are dispersed throughout the film and that disordered Cr2O3 layer may form at the interface. These results reveal a strong tendency for Cr to exist in octahedral, rather than tetrahedral coordination.