Science.gov

Sample records for surface chemistry investigation

  1. Investigating the surface chemistry of Mars

    SciTech Connect

    Grunthaner, F.J.; Ricco, A.J.; Butler, A.M.; Lane, A.L.; McKay, C.P.; Zent, A.P.; Quinn, R.C.; Murray, B.; Klein, H.P.; Levin, G.V.; Terhune, R.W.; Homer, M.L.; Ksendzov, A.; Niedermann, P.

    1995-10-01

    One of the primary objectives of the Viking missions to Mars in the 1970s was to search for life. Numerous theories were put forth to explain the Viking data, most of which involved an oxidizing species in the Martian surface material. In December 1992, the Mars Oxidant Experiment (MOx) was selected as the U.S. contribution to the Russian Mars 96 mission. Two landers are scheduled for launch in November 1996 and should arrive at Mars in September 1997. The MOx instrument on the Russian lander is designed to investigate the chemical nature of the Martian surface material, with particular emphasis on its oxidative character. The instrument uses fiber-optic technology to monitor real-time physicochemical changes in a suite of chemically sensitive thin-film materials. This report describes the scientific rationale and basis for the MOx instrument, along with the details of its design and construction. 15 refs., 4 figs., 1 tab.

  2. Laboratory investigations: Low Earth orbit environment chemistry with spacecraft surfaces

    NASA Technical Reports Server (NTRS)

    Cross, Jon B.

    1990-01-01

    Long-term space operations that require exposure of material to the low earth orbit (LEO) environment must take into account the effects of this highly oxidative atmosphere on material properties and the possible contamination of the spacecraft surroundings. Ground-based laboratory experiments at Los Alamos using a newly developed hyperthermal atomic oxygen (AO) source have shown that not only are hydrocarbon based materials effected but that inorganic materials such as MoS2 are also oxidized and that thin protective coatings such as Al2O3 can be breached, producing oxidation of the underlying substrate material. Gas-phase reaction products, such as SO2 from oxidation of MoS2 and CO and CO2 from hydrocarbon materials, have been detected and have consequences in terms of spacecraft contamination. Energy loss through gas-surface collisions causing spacecraft drag has been measured for a few select surfaces and has been found to be highly dependent on the surface reactivity.

  3. Investigating playa surface textures: The impact of chemistry and environment on surface morphology and dust

    NASA Astrophysics Data System (ADS)

    Tollerud, H. J.; Fantle, M. S.

    2010-12-01

    Mineral dust is an important component of geochemical cycles, but its impact on those cycles is not thoroughly understood. For instance, dust inputs to the ocean have been suggested to affect the iron cycle by stimulating natural iron fertilization, which then could modify climate. The influence of dust on geochemical cycles is determined by the chemical and mineralogical composition of dust inputs, which is governed in turn by the composition of dust source regions. A loose, unconsolidated surface texture is more easily ablated by wind, and so a location where composition and environmental characteristics encourage this type of surface is more likely to produce dust and influence geochemical cycles. Also, if evaporation concentrates evaporites such as calcite at the surface of a dust producing region, dust Ca concentrations are likely to be higher. Playas can be regionally significant dust source regions, and they are amenable to study as their surface textures often vary significantly across small areas. This study investigates surface processes experimentally, and compares the results to observations of surface texture in a natural playa system (the Black Rock Desert, Nevada). We dry surfaces with 25% to 75% clay and quartz at 40°C for approximately a day, wet the surface to simulate rain, and then repeat the cycle multiple times. We estimate surface roughness, measure surface strength with a penetrometer, and investigate thermal characteristics with an IR camera (wavelength range 8-12μm). We find that textures similar to those in playas can be reproduced with cycles of wetting and drying, such as might occur in an arid environment with intermittent rain. We investigate the addition of calcite and halite, since their precipitation potentially can disrupt the clay surfaces through the formation and expansion of crystals, thereby linking the chemical composition with the disruption of a strong surface texture and an increased chance of dust production. In the

  4. In-Depth Electrochemical Investigation of Surface Attachment Chemistry via Carbodiimide Coupling.

    PubMed

    Booth, Marsilea Adela; Kannappan, Karthik; Hosseini, Ali; Partridge, Ashton

    2015-07-28

    Aminoferrocene is used as an electroactive indicator to investigate carbodiimide coupling reactions on a carboxylic acid-functionalized self-assembled monolayer. The commonly used attachment chemistry with 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) is used for surface activation. A number of conditions are investigated, including EDC and NHS concentration, buffer solutions, incubation timing, and aminoferrocene concentration. Ferrocene is a well-documented electroactive species, and the number of surface-bound ferrocene species can be calculated using electrochemical methods. This capability allows determination of optimal conditions, as well as providing a method for comparing and investigating novel carboxylated surfaces. An EDC-mediated procedure with ∼5 mM EDC and NHS (1:1) made in water, with a full acid monolayer, with 250 μM aminoferrocene for 40 min was found to give the highest ferrocene attachment. An application of this is demonstrated for preparing a probe-DNA-coated surface for DNA sensing. By backfilling with aminoferrocene, a differential quantification of the amount of probe DNA available for sensing can be obtained. This provides an elegant method to monitor an important aspect, namely, probe surface characterization, which will be highly useful for biosensing purposes. PMID:26107592

  5. Investigating thiol-modification on hyaluronan via carbodiimide chemistry using response surface methodology.

    PubMed

    Santhanam, Sruthi; Liang, Jue; Baid, Rinku; Ravi, Nathan

    2015-07-01

    Hyaluronan (HA) is a naturally occurring glycosaminoglycan widely researched for its use as a biomaterial in tissue engineering, drug delivery, angiogenesis, and ophthalmic surgeries. The mechanical properties of this biomaterial can be altered to a required extent by chemically modifying the pendant reactive groups. However, derivatizing these polymers to a predetermined extent has been the Achilles heel for this process. In this study, we have investigated the factors controlling the derivatization of the carboxyl moieties of HA with amine containing thiol, cystamine dihydrochloride (Cys), via carbodiimide crosslinking chemistry. We used fractional factorial design to screen and identify the significant factor(s) affecting the reaction, and response surface methodology (RSM) to develop a model equation for predicting the degree of thiolation of HA. Also, we analyzed the reaction mechanism for potential side reactions. We observed that N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC) (mole ratio with repeat unit of HA) is the significant factor controlling the degree of amidation. The quadratic equations developed from RSM predict the formulation for a desired degree of amidation of HA and percentage of potential side product. Hence, derivatizing HA to a predetermined extent with minimal side product can be achieved using the statistical design of experiments. PMID:25369214

  6. Impact of surface chemistry

    PubMed Central

    Somorjai, Gabor A.; Li, Yimin

    2011-01-01

    The applications of molecular surface chemistry in heterogeneous catalyst technology, semiconductor-based technology, medical technology, anticorrosion and lubricant technology, and nanotechnology are highlighted in this perspective. The evolution of surface chemistry at the molecular level is reviewed, and the key roles of surface instrumentation developments for in situ studies of the gas–solid, liquid–solid, and solid–solid interfaces under reaction conditions are emphasized. PMID:20880833

  7. Getting Physical with Your Chemistry: Mechanically Investigating Local Structure and Properties of Surfaces with the Atomic Force Microscope

    ERIC Educational Resources Information Center

    Heinz, William F.; Hoh, Jan H.

    2005-01-01

    Atomic force microscope (AFM) investigates mechanically the chemical properties of individual molecules, surfaces, and materials using suitably designed probes. The current state of the art of AFM in terms of imaging, force measurement, and sample manipulation and its application to physical chemistry is discussed.

  8. Chemistry of SOFC Cathode Surfaces: Fundamental Investigation and Tailoring of Electronic Behavior

    SciTech Connect

    Yildiz, Bilge; Heski, Clemens

    2013-08-31

    1) Electron tunneling characteristics on La0.7Sr0.3MnO3 (LSM) thin-film surfaces were studied up to 580oC in 10-3mbar oxygen pressure, using scanning tunneling microscopy/ spectroscopy (STM/STS). A threshold-like drop in the tunneling current was observed at positive bias in STS, which is interpreted as a unique indicator for the activation polarization in cation oxygen bonding on LSM cathodes. Sr-enrichment was found on the surface at high temperature using Auger electron spectroscopy, and was accompanied by a decrease in tunneling conductance in STS. This suggests that Sr-terminated surfaces are less active for electron transfer in oxygen reduction compared to Mn-terminated surfaces on LSM. 2) Effects of strain on the surface cation chemistry and the electronic structure are important to understand and control for attaining fast oxygen reduction kinetics on transition metal oxides. Here, we demonstrate and mechanistically interpret the strain coupling to Sr segregation, oxygen vacancy formation, and electronic structure on the surface of La0.7Sr0.3MnO3 (LSM) thin films as a model system. Our experimental results from x-ray photoelectron spectroscopy and scanning tunneling spectroscopy are discussed in light of our first principles-based calculations. A stronger Sr enrichment tendency and a more facile oxygen vacancy formation prevail for the tensile strained LSM surface. The electronic structure of the tensile strained LSM surface exhibits a larger band gap at room temperature, however, a higher tunneling conductance near the Fermi level than the compressively strained LSM at elevated temperatures in oxygen. Our findings suggest lattice strain as a key parameter to tune the reactivity of perovskite transition metal oxides with oxygen in solid oxide fuel cell cathodes. 3) Cation segregation on perovskite oxide surfaces affects vastly the oxygen reduction activity and stability of solid oxide fuel cell (SOFC) cathodes. A unified theory that explains the physical

  9. A solid phase extraction based non-disruptive sampling technique to investigate the surface chemistry of macroalgae.

    PubMed

    Cirri, Emilio; Grosser, Katharina; Pohnert, Georg

    2016-01-01

    The surface chemistry of aquatic organisms determines their biotic interactions. Metabolites in the spatially limited laminar boundary layer mediate processes, such as antifouling, allelopathy and chemical defense against herbivores. However, very few methods are available for the investigation of such surface metabolites. An approach is described in which surfaces are extracted by means of C18 solid phase material. By powdering wet algal surfaces with this material, organic compounds are adsorbed and can be easily recovered for subsequent liquid chromatography/mass spectrometry (LC/MS) and gas chromatography/mass spectrometry (GC/MS) investigations. The method is robust, picks up metabolites of a broad polarity range and is easy to handle. It is more universal compared to established solvent dipping protocols and it does not cause damage to the test organisms. A protocol is introduced for the macroalgae Fucus vesiculosus, Caulerpa taxifolia and Gracilaria vermiculophylla, but it can be easily transferred to other aquatic organisms. PMID:26795737

  10. Interstellar Grain Surface Chemistry

    NASA Technical Reports Server (NTRS)

    Tielens, Alexander G. G. M.; Cuzzi, Jeffrey N. (Technical Monitor)

    1995-01-01

    Chemistry on grain surfaces plays an Important role in the formation of interstellar Ices, It can also influence the composition of the gas phase through outgassing near luminous, newly formed stars. This paper reviews the chemical processes taking place on Interstellar grain surfaces with the emphasis on those transforming CO into other hydrocarbons. At low, molecular cloud temperatures (approximately equal to 10K), physisorption processes dominate interstellar grain surface chemistry and GO is largely hydrogenated through reactions with atomic H and oxidized through reactions with atomic O. The former will lead to the formation of H2CO and CH3OH ices, while the latter results in CO2 ice. The observational evidence for these ices in molecular clouds will be discussed. Very close to protostars, the gas and grain temperatures are much higher (approximately equal to 500K) and chemisorption processes, including catalytic surface reactions, becomes important. This will be illustrated based upon our studies of the Fischer-Tropsch Synthesis of CH4 from CO on metallic surfaces. Likely, this process has played an important role in the early solar nebula. Observational consequences will be pointed out.

  11. Contributions of gas-phase plasma chemistry to surface modifications and gas-surface interactions: investigations of fluorocarbon rf plasmas

    NASA Astrophysics Data System (ADS)

    Cuddy, Michael F., II

    The fundamental aspects of inductively coupled fluorocarbon (FC) plasma chemistry were examined, with special emphasis on the contributions of gas-phase species to surface modifications. Characterization of the gas-phase constituents of single-source CF4-, C2F6-, C3F 8-, and C3F6-based plasmas was performed using spectroscopic and mass spectrometric techniques. The effects of varying plasma parameters, including applied rf power (P) and system pressure (p) were examined. Optical emission spectroscopy (OES) and laser-induced fluorescence (LIF) spectroscopy were employed to monitor the behavior of excited and ground CFx (x = 1,2) radicals, respectively. Mass spectrometric techniques, including ion energy analyses, elucidated behaviors of nascent ions in the FC plasmas. These gas-phase data were correlated with the net effect of substrate processing for Si and ZrO2 surfaces. Surface-specific analyses were performed for post-processed substrates via x-ray photoelectron spectroscopy (XPS) and contact angle goniometry. Generally, precursors with lower F/C ratios tended to deposit robust FC films of high surface energy. Precursors of higher F/C ratio, such as CF4, were associated with etching or removal of material from surfaces. Nonetheless, a net balance between deposition of FC moieties and etching of material exists for each plasma system. The imaging of radicals interacting with surfaces (IRIS) technique provided insight into the phenomena occurring at the interface of the plasma gas-phase and substrate of interest. IRIS results demonstrate that CFx radicals scatter copiously, with surface scatter coefficients, S, generally greater than unity under most experimental conditions. Such considerable S values imply surface-mediated production of the CFx radicals at FC-passivated sites. It is inferred that the primary route to surface production of CFx arises from energetic ion bombardment and ablation of surface FC films. Other factors which may influence the observed CFx

  12. Investigation of IAQ-Relevant Surface Chemistry and Emissions on HVAC Filter Materials

    SciTech Connect

    Destaillats, Hugo; Fisk, William J.

    2010-02-01

    Chemical reactions involving ozone of outdoor origin and indoor materials are known to be significant sources of formaldehyde and other irritant gas-phase oxidation products in the indoor environment. HVAC filters are exposed to particularly high ozone concentrations--close to outdoor levels. In this study, we investigated chemical processes taking place on the surface of filters that included fiberglass, polyester, cotton/polyester blend and synthetic (e.g., polyolefin) filter media. Ozone reactions were studied on unused filter media, and on filters that were deployed for 3 months in two different locations: at the Lawrence Berkeley National Laboratory and at the Port of Oakland. Specimens from each filter were exposed to ozone under controlled conditions in a laboratory flow tube at a constant flow of dry or humidified air (50percent relative humidity). Ozone was generated with a UV source upstream of the flow tube, and monitored using a photometric detector. Ozone breakthrough curves were recorded for each sample exposed to ~;;150 ppbv O3 for periods of ~;;1000 min, from which we estimated their uptake rate. Most experiments were performed at 1.3 L/min (corresponding to a face velocity of 0.013 m/s), except for a few tests performed at a higher airflow rate, to obtain a face velocity of 0.093 m/s, slightly closer to HVAC operation conditions. Formaldehyde and acetaldehyde, two oxidation byproducts, were collected downstream of the filter and quantified. Emissions of these volatile aldehydes were consistently higher under humidified air than under dry conditions, at which levels were near the limit of detection. Our results confirm that there are significant reactions of ozone as air containing ozone flows through HVAC filters, particularly when the filters are loaded with particles and the air is humidified. The amount of ozone reacted was not clearly related to the types of filter media, e.g., fiberglass versus synthetic. Specific fiberglass filters that were

  13. The investigation of the viscoelastic properties of silica/PMMA nanocomposites as a function of silica surface chemistry

    NASA Astrophysics Data System (ADS)

    Conway, Heather; Rende, Deniz; Ozisik, Rahmi

    2013-03-01

    Poly(methyl methacrylate), PMMA, has been used as an economic alternative to glass and polycarbonate in differing situations because of its lightweight, shatter resistance, and ease of processability. The uses of PMMA can be expanded if its weakness to impact force and its scratch resistance are improved. In the current study, viscoelastic properties of silica nanoparticle filled PMMA were investigated via nanoindentation experiments. Silica nanoparticles are known to increase the toughness of PMMA. In the current study, silica nanoparticles were chemically modified with fluorinated alkanes to alter nanofiller-polymer interactions. Results show that viscoelastic properties are strongly affected by silica surface chemistry and silica concentration. This work was partially supported by NSF CMMI-1200270 and DUE-1003574

  14. A two-dimensional atmospheric chemistry modeling investigation of Earth's Phanerozoic O3 and near-surface ultraviolet radiation history

    NASA Astrophysics Data System (ADS)

    Harfoot, Michael B. J.; Beerling, David J.; Lomax, Barry H.; Pyle, John A.

    2007-04-01

    We use the Cambridge two-dimensional (2-D) chemistry-radiation transport model to investigate the implications for column O3 and near-surface ultraviolet radiation (UV), of variations in atmospheric O2 content over the Phanerozoic (last 540 Myr). Model results confirm some earlier 1-D model investigations showing that global annual mean O3 column increases monotonically with atmospheric O2. Sensitivity studies indicate that changes in temperature and N2O exert a minor influence on O3 relative to O2. We reconstructed Earth's O3 history by interpolating the modeled relationship between O3 and O2 onto two Phanerozoic O2 histories. Our results indicate that the largest variation in Phanerozoic column O3 occurred between 400 and 200 Myr ago, corresponding to a rise in atmospheric O2 to ˜1.5 times the present atmospheric level (PAL) and subsequent fall to ˜0.5 PAL. The O3 response to this O2 decline shows latitudinal differences, thinning most at high latitudes (30-40 Dobson units (1 DU = 0.001 atm cm) at 66°N) and least at low latitudes (5-10 DU at 9°N) where a "self-healing" effect is evident. This O3 depletion coincides with significant increases in the near-surface biologically active UV radiation at high latitudes, +28% as weighted by the Thimijan spectral weighting function. O3 and UV changes were exacerbated when we incorporated a direct feedback of the terrestrial biosphere on atmospheric chemistry, through enhanced N2O production as the climate switched from an icehouse to a greenhouse mode. On the basis of a summary of field and laboratory experimental evidence, we suggest that these UV radiation increases may have exerted subtle rather than catastrophic effects on ecosystem processes.

  15. Surface chemistry investigation of colloid transport in packed beds. Final report, August 1, 1989--July 31, 1996

    SciTech Connect

    Olson, T.M.

    1996-12-31

    The importance of colloids as co-transport agents for pollutants in subsurface systems hinges on the extent to which electrostatic or other sources of repulsive colloid-collector interactions inhibit their filtration. When electrostatic interactions are favorable, for example when the colloid and groundwater media have opposite charge, colloids may be expected to travel only a few centimeters in saturated porous media. Repulsive electrostatic interactions between colloids and aquifer media with the same charge sign are postulated to significantly mobilize particles. As it happens, however, theories describing particle filtration from first principles, i.e., DLVO (Derjagin and Landau, Verwey and Overbeek) theory, dramatically underestimate filtration rates when colloid-collector interactions are electrostatically repulsive. One of the primary objectives of the project was to experimentally investigate potential reasons for the historical lack of agreement between particle filtration models based on DLVO theory and observed particle deposition rates. An important hypothesis of the study was to test the validity of the assumption of surface homogeneity, as required by these models. The approach was to focus on collector surfaces that were commonly used as model systems, e.g., glass beads and quartz sand. Laboratory-scale column filtration experiments were conducted with colloidal polystyrene latex spheres. Collector surface preparation and cleaning approaches were examined, as well as the effects of solution chemistry.

  16. Fracture mechanics and surface chemistry investigations of environment-assisted crack growth

    NASA Technical Reports Server (NTRS)

    Wei, R. P.; Klier, K.; Simmons, G. W.; Chou, Y. T.

    1984-01-01

    It is pointed out that environment-assisted subcritical crack growth in high-strength steels and other high-strength alloys (particularly in hydrogen and in hydrogenous environments) is an important technological problem of long standing. This problem is directly related to issues of structural integrity, durability, and reliability. The terms 'hydrogen embrittlement' and 'stress corrosion cracking' have been employed to describe the considered phenomenon. This paper provides a summary of contributions made during the past ten years toward the understanding of environmentally assisted crack growth. The processes involved in crack growth are examined, and details regarding crack growth and chemical reactions are discussed, taking into account crack growth in steels exposed to water/water vapor, the effect of hydrogen, reactions involving hydrogen sulfide, and aspects of fracture surface morphology and composition. Attention is also given to the modeling of crack growth response, crack growth in gas mixtures, and the interaction of solute atoms with the crack-tip stress field.

  17. Surface chemistry of palladium

    SciTech Connect

    Gentle, T.M.

    1984-05-01

    Several classes of catalytically important molecules on Pd single crystals were studied. Influence of surface structure and composition on reactions involving formation and scission of carbon-carbon and carbon-hydrogen bonds was investigated under uhv conditions on single crystals and higher pressures on polycrystalline films. Reactions of acetylene on Pd(111), Pd(100), and Pd(110) were studied using thermal desorption spectroscopy, chemical displacement reactions, and isotopic labeling techniques. Pd single crystals catalyzes trimerization to benzene, hydrogenation to ethylene, and hydrosilation with trimethylsilane. Several atoms such as Si, P, S, and Cl have a profound influence on the catalysis. Single-crystal Pd surfaces catalyzes the dehydrogenation of organosilanes; silacyclohexane chemisorbed on Pd(110) underwent dehydrogenation upon thermal desorption to form silabenzene. Desulfurization products were observed in the thermal desorption spectra chemisorbed thiophene, 3-methylthiophene, and 2,5-dimethylthiophene. Mechanisms of carbon-hydrogen bond scission were investigated for a variety of methyl-substituted benzenes, revealing some degree of regiospecificity in C-H bond scission. Several reactions of unsaturated hydrocarbons were also investigated at higher pressures (10/sup -2/ torr) on polycrystalline Pd films.

  18. Investigations of the structure and "interfacial" surface chemistry of Bioglass (RTM) materials by solid-state multinuclear NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Sarkar, Gautam

    formation of surface silica species and follow the formation of phosphate species, respectively, while cross-polarization magic-angle spinning (CP/MAS) 29Si and 31P NMR have provided information about low intensity NMR peaks due to various silicon- and phosphorus-species present in the vicinity of associated protons on the surface of in vitro reacted BioglassRTM materials. The solid-state NMR investigations of the "interfacial" surface reactions of BioglassRTM materials are discussed in the context of the structure of these materials and the influence of this structure on the kinetics and the mechanism of their "interfacial" surface chemistry. (Abstract shortened by UMI.) BioglassRTM, trademark, University of Florida, Gainesville, FL, 32611.

  19. Cavity ring-down spectroscopy with an automated control feedback system for investigating nitrate radical surface chemistry reactions

    NASA Astrophysics Data System (ADS)

    Flemmer, Michael M.; Ham, Jason E.

    2012-08-01

    Nitrate radical (NO3•) surface chemistry of indoor environments has not been well studied due to the difficulty in generating and maintaining NO3• at low concentrations for long term exposures. This article presents the Surface Chemistry Reactant Air Delivery and Experiment System (SCRADES), a novel feedback controlled system developed to deliver nitrate radicals at specified concentrations (50-500 ppt, ±30 ppt) and flow rates (500-2000 ml min-1) to a variety of indoor surfaces to initiate reaction chemistry for periods of up to 72 h. The system uses a cavity ring-down spectrometer (CRDS), with a detection limit of 1.7 ppt, to measure the concentration of NO3• supplied to a 24 l experiment chamber. Nitrate radicals are introduced via thermal decomposition of N2O5 and diluted with clean dry air until the desired concentration is achieved. Additionally, this article addresses details concerning NO3• loss through the system, consistency of the NO3• concentration delivered, and stability of the CRDS cavity over long exposure durations (72 h).

  20. Visualizing Chemistry: Investigations for Teachers.

    ERIC Educational Resources Information Center

    Ealy, Julie B.; Ealy, James L., Jr.

    This book contains 101 investigations for chemistry classrooms. Topics include: (1) Physical Properties; (2) Reactions of Some Elements; (3) Reactions Involving Gases; (4) Energy Changes; (5) Solutions and Solubility; (6) Transition Metals and Complex Ions; (7) Kinetics and Equilibrium; (8) Acids and Bases; (9) Oxidation-Reduction; (10)…

  1. Experimental and computational investigation of acetic acid deoxygenation over oxophilic molybdenum carbide: Surface chemistry and active site identity

    DOE PAGESBeta

    Schaidle, Joshua A.; Blackburn, Jeffrey; Farberow, Carrie A.; Nash, Connor; Steirer, K. Xerxes; Clark, Jared; Robichaud, David J.; Ruddy, Daniel A.

    2016-01-21

    Ex situ catalytic fast pyrolysis (CFP) is a promising route for producing fungible biofuels; however, this process requires bifunctional catalysts that favor C–O bond cleavage, activate hydrogen at near atmospheric pressure and high temperature (350–500 °C), and are stable under high-steam, low hydrogen-to-carbon environments. Recently, early transition-metal carbides have been reported to selectively cleave C–O bonds of alcohols, aldehydes, and oxygenated aromatics, yet there is limited understanding of the metal carbide surface chemistry under reaction conditions and the identity of the active sites for deoxygenation. In this study, we evaluated molybdenum carbide (Mo2C) for the deoxygenation of acetic acid, anmore » abundant component of biomass pyrolysis vapors, under ex situ CFP conditions, and we probed the Mo2C surface chemistry, identity of the active sites, and deoxygenation pathways using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations.« less

  2. Surface chemistry in photodissociation regions

    NASA Astrophysics Data System (ADS)

    Esplugues, G. B.; Cazaux, S.; Meijerink, R.; Spaans, M.; Caselli, P.

    2016-06-01

    Context. The presence of dust can strongly affect the chemical composition of the interstellar medium. We model the chemistry in photodissociation regions (PDRs) using both gas-phase and dust-phase chemical reactions. Aims: Our aim is to determine the chemical compositions of the interstellar medium (gas/dust/ice) in regions with distinct (molecular) gas densities that are exposed to radiation fields with different intensities. Methods: We have significantly improved the Meijerink PDR code by including 3050 new gas-phase chemical reactions and also by implementing surface chemistry. In particular, we have included 117 chemical reactions occurring on grain surfaces covering different processes, such as adsorption, thermal desorption, chemical desorption, two-body reactions, photo processes, and cosmic-ray processes on dust grains. Results: We obtain abundances for different gas and solid species as a function of visual extinction, depending on the density and radiation field. We also analyse the rates of the formation of CO2 and H2O ices in different environments. In addition, we study how chemistry is affected by the presence/absence of ice mantles (bare dust or icy dust) and the impact of considering different desorption probabilities. Conclusions: The type of substrate (bare dust or icy dust) and the probability of desorption can significantly alter the chemistry occurring on grain surfaces, leading to differences of several orders of magnitude in the abundances of gas-phase species, such as CO, H2CO, and CH3OH. The type of substrate, together with the density and intensity of the radiation field, also determine the threshold extinction to form ices of CO2 and H2O. We also conclude that H2CO and CH3OH are mainly released into the gas phase of low, far-ultraviolet illuminated PDRs through chemical desorption upon two-body surface reactions, rather than through photodesorption.

  3. Surface chemistry of deuterated molecules

    NASA Astrophysics Data System (ADS)

    Tielens, A. G. G. M.

    1983-03-01

    The chemical composition of grain mantles is calculated in order to determine the concentration of deuterated molecules relative to their hydrogenated counterparts in grain mantles. The computation takes into account reactions involving deuterium in the gas phase and on grain surfaces. The results show that the abundance of deuterium molecules in grain mantles is much higher than expected on the basis of the cosmic abundance ratio of D to H. HDCO has a relatively high abundance in grain mantles as compared to other deuterated molecules, due to the fact that H abstraction from HDCO has a lower activation barrier than D abstraction. The infrared characteristics of the calculated grain mantles are discussed and observational tests of the model calcultions are suggested. The contribution of grain surface chemistry to the concentration of molecules in the gas phase is briefly considered.

  4. Surface chemistry of liquid metals

    NASA Technical Reports Server (NTRS)

    Mann, J. Adin, Jr.; Peebles, Henry; Peebles, Diamond; Rye, Robert; Yost, Fred

    1993-01-01

    The fundamental surface chemistry of the behavior of liquid metals spreading on a solid substrate is not at all well understood. Each of these questions involves knowing the details of the structure of interfaces and their dynamics. For example the structure of a monolayer of tin oxide on pure liquid tin is unknown. This is in contrast to the relatively large amount of data available on the structure of copper oxide monolayers on solid, pure copper. However, since liquid tin has a vapor pressure below 10(exp -10)torr for a reasonable temperature range above its melting point, it is possible to use the techniques of surface science to study the geometric, electronic and vibrational structures of these monolayers. In addition, certain techniques developed by surface chemists for the study of liquid systems can be applied to the ultra-high vacuum environment. In particular we have shown that light scattering spectroscopy can be used to study the surface tension tensor of these interfaces. The tin oxide layer in particular is very interesting in that the monolayer is rigid but admits of bending. Ellipsometric microscopy allows the visualization of monolayer thick films and show whether island formation occurs at various levels of dosing.

  5. Influence of pH and Surface Chemistry on Poly(L-lysine) Adsorption onto Solid Supports Investigated by Quartz Crystal Microbalance with Dissipation Monitoring.

    PubMed

    Choi, Jae-Hyeok; Kim, Seong-Oh; Linardy, Eric; Dreaden, Erik C; Zhdanov, Vladimir P; Hammond, Paula T; Cho, Nam-Joon

    2015-08-20

    Poly(L-lysine) (PLL) adsorption onto various materials has been widely applied as a surface modification strategy and layer-by-layer fabrication method. Considering the role of electrostatic charges, a detailed understanding of the influence of solution pH on PLL adsorption process is important for optimization of PLL coating protocols. Herein, PLL adsorption onto different polar and hydrophilic substrates—silica, an amine-terminated self-assembled monolayer (SAM) on gold, and a carboxyl-terminated SAM on gold—across a range of pH conditions was investigated using the quartz crystal microbalance with dissipation. The adsorption kinetics consisted of an initial rapid phase, followed by a second phase where adsorption rate gradually decelerated. These features were interpreted by applying a mean-field kinetic model implying diffusion-limited adsorption in the first phase and reconfiguration of adsorbed PLL molecules in the second phase. The adsorption kinetics and uptake were found to be sensitive to the pH condition, surface chemistry, and flow rate. The strongest PLL adsorption occurred at pH 11 on all three surfaces while weak PLL adsorption generally occurred under acidic conditions. The surface morphology and roughness of adsorbed PLL layers were investigated using atomic force microscopy, and strong PLL adsorption is found to produce a uniform and smooth adlayer while weak adsorption formed a nonuniform and rough adlayer. PMID:26061703

  6. Chemistry. Teacher's Guide. Investigations in Natural Science.

    ERIC Educational Resources Information Center

    Renner, John W.; And Others

    Investigations in Natural Science is a program in secondary school biology, chemistry, and physics based upon the description of science as a quest for knowledge, not the knowledge itself. This teaching guide is designed for use with the 19 chemistry investigations found in the student manual. These investigations focus on concepts related to:…

  7. Surface Chemistry Enhanced Microbial Bioelectrocatalysis

    PubMed Central

    Santoro, Carlo; Babanova, Sofia; Artyushkova, Kateryna; Cornejo, Jose’ A.; Ista, Linnea; Bretschger, Orianna; Marsili, Enrico; Atanassov, Plamen; Schuler, Andrew J.

    2016-01-01

    Self-assembled monolayers (SAMs) modified gold anodes are used in single chamber microbial fuel cells (SCMFC) for organics removal and electricity generation. Hydrophilic (−N(CH3)3+, −OH, −COOH) and hydrophobic (−CH3) SAMs are examined for their effect on bacterial attachment, current and power output. The different substratum chemistry affects both the current and power output and the community composition of the electrochemically active biofilm formed. Of the four SAM-modified anode tested, −N(CH3)3+ results in shortest start up time, highest single electrode polarization and power density, followed by −OH and –COOH SAMs. Hydrophobic SAM decreases bacteria attachment and anodes performance in comparison to hydrophilic SAMs. Electron transfer rate is faster on the N(CH3)3+-surface than on other surfaces, and correlates with a high abundance of δ-Proteobacteria, including electrochemically active species. A consortium of Clostridia and δ-Proteobacteria is found on all the anode surfaces, suggesting a synergistic cooperation under anodic conditions. PMID:26025340

  8. Unexpected surface chemistry in capillaries for electrophoresis.

    PubMed

    Kaupp, S; Bubert, H; Baur, L; Nelson, G; Wätzig, H

    2000-10-13

    Good and reproducible capillary quality is needed to develop robust methods and to facilitate method transfer in CE. Physical surface defects no longer play a major role in variability of fused-silica capillaries. Nevertheless, problems are frequently being reported when buffers in the pH range between 4 and 7 are used. Thus the surface chemistry has been studied by X-ray photoelectron spectroscopy. Silicon-carbon bindings have been found on inner capillary surfaces for electrophoresis. This binding type is not completely removed by pre-conditioning with 1 M NaOH for 30 min. This corresponds to the result, that capillaries provide more stable migration times, especially in the pH range 4-7, when they are pre-conditioned for longer than 1 h. The origin of this Si-C bond is still not quite clear. They could be caused by graphite which is used during the fabrication of the raw cylinders prior to capillary drawing. Further investigations are intended in order to understand if there are any differences in surface carbon content from batch to batch and if this can influence experimental results in CE. A better understanding of the surface chemistry should not only improve robustness in CE, but also help to facilitate and accelerate capillary pre-conditioning and rinsing procedures to remove strongly adsorbed analytes or matrices. PMID:11100849

  9. Chemistry. Student Investigations and Readings. Investigations in Natural Science.

    ERIC Educational Resources Information Center

    Renner, John W.; And Others

    Investigations in Natural Science is a program in secondary school biology, chemistry, and physics based upon the description of science as a quest for knowledge, not the knowledge itself. This student manual contains the 19 chemistry investigations. These investigations focus on concepts related to: interactions with water; salt and calcium;…

  10. The Surface Chemistry of Metal Chalcogenide Nanocrystals

    NASA Astrophysics Data System (ADS)

    Anderson, Nicholas Charles

    The surface chemistry of metal chalcogenide nanocrystals is explored through several interrelated analytical investigations. After a brief discussion of the nanocrystal history and applications, molecular orbital theory is used to describe the electronic properties of semiconductors, and how these materials behave on the nanoscale. Quantum confinement plays a major role in dictating the optical properties of metal chalcogenide nanocrystals, however surface states also have an equally significant contribution to the electronic properties of nanocrystals due to the high surface area to volume ratio of nanoscale semiconductors. Controlling surface chemistry is essential to functionalizing these materials for biological imaging and photovoltaic device applications. To better understand the surface chemistry of semiconducting nanocrystals, three competing surface chemistry models are presented: 1.) The TOPO model, 2.) the Non-stoichiometric model, and 3.) the Neutral Fragment model. Both the non-stoichiometric and neutral fragment models accurately describe the behavior of metal chalcogenide nanocrystals. These models rely on the covalent bond classification system, which divides ligands into three classes: 1.) X-type, 1-electron donating ligands that balance charge with excess metal at the nanocrystal surface, 2.) L-type, 2-electron donors that bind metal sites, and 3.) Z-type, 2-electron acceptors that bind chalcogenide sites. Each of these ligand classes is explored in detail to better understand the surface chemistry of metal chalcogenide nanocrystals. First, chloride-terminated, tri-n-butylphosphine (Bu 3P) bound CdSe nanocrystals were prepared by cleaving carboxylate ligands from CdSe nanocrystals with chlorotrimethylsilane in Bu3P solution. 1H and 31P{1H} nuclear magnetic resonance spectra of the isolated nanocrystals allowed assignment of distinct signals from several free and bound species, including surface-bound Bu3P and [Bu3P-H]+[Cl]- ligands as well as a Bu

  11. The EDM surface: Topography, chemistry, and metallurgy

    SciTech Connect

    Fuller, J.E.

    1991-01-01

    The surface created by the electric discharge machining (EDM) process is of special interest because it has been shown to have a negative effect on the fatigue properties of many alloys. An understanding of the surface metallurgy and chemistry is important in predicting those alloys which are most susceptible to failure. Remedial actions, including thickness minimization, alteration, or removal of the surface layer are addressed.

  12. Laboratory Investigations of Stratospheric Halogen Chemistry

    NASA Technical Reports Server (NTRS)

    Wine, Paul H.; Nicovich, J. Michael; Stickel, Robert E.; Hynes, Anthony J.

    1997-01-01

    A final report for the NASA-supported project on laboratory investigations of stratospheric halogen chemistry is presented. In recent years, this project has focused on three areas of research: (1) kinetic, mechanistic, and thermochemical studies of reactions which produce weakly bound chemical species of atmospheric interest; (2) development of flash photolysis schemes for studying radical-radical reactions of stratospheric interest; and (3) photochemistry studies of interest for understanding stratospheric chemistry. The first section of this paper contains a discussion of work which has not yet been published. All subsequent chapters contain reprints of published papers that acknowledge support from this grant.

  13. Surface chemistry driven actuation in nanoporous gold

    SciTech Connect

    Biener, J; Wittstock, A; Zepeda-Ruiz, L; Biener, M M; Zielasek, V; Kramer, D; Viswanath, R N; Weissmuller, J; Baumer, M; Hamza, A V

    2008-04-14

    Although actuation in biological systems is exclusively powered by chemical energy, this concept has not been realized in man-made actuator technologies, as these rely on generating heat or electricity first. Here, we demonstrate that surface-chemistry driven actuation can be realized in high surface area materials such as nanoporous gold. For example, we achieve reversible strain amplitudes in the order of a few tenths of a percent by alternating exposure of nanoporous Au to ozone and carbon monoxide. The effect can be explained by adsorbate-induced changes of the surface stress, and can be used to convert chemical energy directly into a mechanical response thus opening the door to surface-chemistry driven actuator and sensor technologies.

  14. Multifunctional Surface Manipulation Using Orthogonal Click Chemistry.

    PubMed

    Brooks, Karson; Yatvin, Jeremy; McNitt, Christopher D; Reese, R Alexander; Jung, Calvin; Popik, Vladimir V; Locklin, Jason

    2016-07-01

    Polymer brushes are excellent substrates for the covalent immobilization of a wide variety of molecules due to their unique physicochemical properties and high functional group density. By using reactive microcapillary printing, poly(pentafluorophenyl acrylate) brushes with rapid kinetic rates toward aminolysis can be partially patterned with other click functionalities such as strained cyclooctyne derivatives and sulfonyl fluorides. This trireactive surface can then react locally and selectively in a one pot reaction via three orthogonal chemistries at room temperature: activated ester aminolysis, strain promoted azide-alkyne cycloaddition, and sulfur(VI) fluoride exchange, all of which are tolerant of ambient moisture and oxygen. Furthermore, we demonstrate that these reactions can also be used to create areas of morphologically distinct surface features on the nanoscale, by inducing buckling instabilities in the films and the grafting of nanoparticles. This approach is modular, and allows for the development of highly complex surface motifs patterned with different chemistry and morphology. PMID:27280689

  15. THE COORDINATION CHEMISTRY OF METAL SURFACES

    SciTech Connect

    Muetterties, Earl L.

    1980-10-01

    In coordinately unsaturated molecular metal complexes, carbon-hydrogen bonds of the peripheral ligands may, if the stereochemistry allows, closely approach a metal center so as to develop a three-center two-electron bond between the carbon, the hydrogen, and the metal atoms, C-H-M. In some instances, the interaction .is followed by a scission of the C-H bond whereby the metal is effectively oxidized and discrete M-H and M-C {sigma} bonds are forrned. This class of metal-hydrogen-carbon interactions and reactions is shown to be a common phenomenon in metal surface chemistry. Ultra high vacuum studies of nickel and platinum with simple organic molecules like olefins, and arenes are described. These surface chemistry studies were done as a function of surface crystallography and surface composition. The discussion is largely limited to the chemistry of methyl isocyanide, acetonitrile, benzene and toluene. Molecular orbital calculations are presented that support the experimental identification of the importance of C-H-M metal bonding for metal surfaces.

  16. Surface chemistry of porphyrins and phthalocyanines

    NASA Astrophysics Data System (ADS)

    Gottfried, J. Michael

    2015-11-01

    This review covers the surface chemistry of porphyrins, phthalocyanines, their metal complexes, and related compounds, with particular focus on chemical reactions at solid/vacuum interfaces. Porphyrins are not only important biomolecules, they also find, together with the artificial phthalocyanines, numerous technological and scientific applications, which often involve surface and interface related aspects. After a brief summary of fundamental properties of these molecules in the context of surface science, the following topics will be discussed: (1) Aspects of geometric structure, including self-assembly, conformation, mobility and manipulation of the adsorbed molecules. (2) Surface-related changes of the electronic structure and the magnetic properties. (3) The role of the metal center in the surface chemical bond. (4) On-surface coordination reactions, such as direct metalation and coordination of axial ligands. (5) The influence of axial ligands on the surface chemical bond and the magnetic properties.

  17. Surface chemistry and structure of beryllium oxide

    SciTech Connect

    Fuller, E.L. Jr.; Eager, M.H.; Smithwick, R.W. III; Smyrl, N.R.

    1982-02-01

    Detailed examination of nitrogen sorption isotherms related to the surface chemistry and structure of high-purity beryllium oxide and the products of alkali treatment aid in a better understanding of the topochemical problems encountered in the production of ceramic items. Details are corroborated by additional techniques: diffuse reflectance infrared Fourier transform (DRIFT); mercury intrusion porosimetry (MIP); and scanning electron microscopy (SEM). The results correlate well with studies on other oxides when the unique thermophysical properties of this material are considered.

  18. Chemistry in the near-surface atmosphere at Ganymede

    NASA Astrophysics Data System (ADS)

    Shematovich, V. I.

    2013-09-01

    Theoretical predictions of the composition and chemical evolution of near-surface atmospheres of the icy satellites in the Jovian and Kronian systems are of great importance for assessing the biological potential of these satellites. Depending on the satellite mass the formation of the rarefied exosphere with the relatively dense near-surface layer is possible as, for example, in the case of the relatively heavy Galilean satellites Europa and Ganymede in the Jovian system [1-3]. Ganymede is of special interest, because observations indicate that Ganymede has a significant O2 near - surface atmosphere, probably subsurface ocean, and is the only satellite with its own magnetosphere. Processes of formation of the rarefied gaseous envelope of Ganymede and chemical exchange between atmosphere and icy surface will be considered. The water vapour is usually the domin ant parent species in such gaseous envelope because of the ejection from the satellite icy surface due to the thermal outgassing, non-thermal photolysis and radiolysis and other active processes at work on the surface. The photochemis try of water vapour in the near - surface atmospheric layer [4] and the radiolysis of icy regolith [5] result in the supplement of the atmosphere by an admixture of H2, O2, OH and O. Returning molecules have species-dependent behaviour on contact with icy surface of the satellite and non-thermal energy distributions for the chemical radicals. The H2 and O2 molecules stick with very low efficiency and are immediately desorbed thermally, but returning H2O, OH, H and O stick to the grains in the icy regolith with unit efficiency. The suprathermal radicals OH, H, and O entering the regolith can drive the surface chemistry. The numerical kinetic model to investigate on the molecular level the chemistry of the atmosphere - surface interface of the rarefied Н2О-dominant gaseous envelope at Ganymede was developed. Such numerical model simulates the gas-phase and diffusive surface

  19. Chemistry of bimetallic and alloys surfaces

    SciTech Connect

    Koel, B.E.

    1991-10-18

    We have continued our work on elucidating the underlying principles that govern chemical reactions occurring on bimetallic and alloy surfaces. Our goal is to aid in the atomic level explanation of the reactivity and selectivity of alloy and bimetallic cluster catalysts and to provide a fundamental basis for the design of new catalysts with improved performance. Our approach is to use a battery of surface science methods to obtain fundamental data on the thermochemistry and kinetics of the adsorption and reaction of molecules on extensively characterized, single-crystal bimetallic surfaces. We measure changes in chemisorption bond strength, adsorption site distributions, and hydrocarbon fragment stability and reactivity and correlate these results with the geometric and electronic structure of the metal atoms on the surface. Often, our aim is to carefully design experiments that isolate the several factors (e.g., ensemble and ligand effects) that control surface chemistry and catalysis on bimetallic and alloy surfaces in order to better understand the importance of each contribution. In the past 18 months, we have continued to study how alkali promoters strongly affect the reactions of hydrocarbons on Pt and Ni surfaces by altering the electronic structure and inducing significant site-blocking effects. We have shown that bismuth coadsorption provides benchmark data on ensemble sizes required for chemical reactions on Pt and Ni surfaces. Surface alloys of Sn/Pt are being used for detailed probing of ensemble sizes and also reactive site requirements. 22 refs.

  20. Acid-base surface chemistry and sorption of some lanthanides on K{sup +}-saturated Marblehead illite: 1. Results of an experimental investigation

    SciTech Connect

    Sinitsyn, V.A.; Aja, S.U.; Kulik, D.A.; Wood, S.A.

    2000-01-01

    The surface reactivity and sorption of Nd and Eu onto K{sup +}-saturated, Marblehead illite has been investigated in 0.01, 0.1, and 1.0 M KCl solutions at 25 C; the potentiometric titrations were conducted using back-titration techniques. Batch experimental protocols were used in both series of studies. The ionic strength-dependent, proton surface charge density ({sigma}{sub H}) varies from {minus}1500 to {minus}1,700 mC/m{sup 2} in 1.0 M KCl solutions and from {minus}1800 to {minus}2,200 mC/m{sup 2} in 0.01 and 0.1 M KCl solutions. An isoelectric point was not defined by the {sigma}{sub H} vs. pH curves, which reflects the multi-phase nature of natural illitic materials. The functional dependence of REE binding constants (log K{sub e}) on surface coverage (log {Gamma}{sub REE}) indicates the existence of a multiplicity of energetically distinct surface types. These surface site types include amphoteric silanol and aluminol sites, basal planar surfaces, and frayed edges; the frayed edges are observed only in low ionic strength solutions (I {le} 0.1 M KCl).

  1. Magmatic and fragmentation controls on volcanic ash surface chemistry

    NASA Astrophysics Data System (ADS)

    Ayris, Paul M.; Diplas, Spyros; Damby, David E.; Hornby, Adrian J.; Cimarelli, Corrado; Delmelle, Pierre; Scheu, Bettina; Dingwell, Donald B.

    2016-04-01

    The chemical effects of silicate ash ejected by explosive volcanic eruptions on environmental systems are fundamentally mediated by ash particle surfaces. Ash surfaces are a composite product of magmatic properties and fragmentation mechanisms, as well as in-plume and atmospheric alteration processes acting upon those surfaces during and after the eruption. Recent attention has focused on the capacity of alteration processes to shape ash surfaces; most notably, several studies have utilised X-ray photoelectron spectroscopy (XPS), a technique probing the elemental composition and coordination state of atoms within the top 10 nm of ash surfaces, to identify patterns of elemental depletions and enrichments relative to bulk ash chemical composition. Under the presumption of surface and bulk equivalence, any disparities have been previously attributed to surface alteration processes, but the ubiquity of some depletions (e.g., Ca, Fe) across multiple ash studies, irrespective of eruptive origin, could suggest these to be features of the surface produced at the instant of magma fragmentation. To investigate this possibility further, we conducted rapid decompression experiments at different pressure conditions and at ambient and magmatic temperature on porous andesitic rocks. These experiments produced fragmented ash material untouched by secondary alteration, which were compared to particles produced by crushing of large clasts from the same experiments. We investigated a restricted size fraction (63-90 μm) from both fragmented and crushed materials, determining bulk chemistry and mineralogy via XRF, SEM-BSE and EPMA, and investigated the chemical composition of the ash surface by XPS. Analyses suggest that fragmentation under experimental conditions partitioned a greater fraction of plagioclase-rich particles into the selected size fraction, relative to particles produced by crushing. Trends in surface chemical composition in fragmented and crushed particles mirror that

  2. Carbon Dioxide Chemistry on Titan's Surface

    NASA Astrophysics Data System (ADS)

    Hodyss, R. P.; Cable, M. L.; Malaska, M. J.; Vu, T. H.

    2015-12-01

    The surfaces of the moons of the outer Solar System are usually considered too cold (30-100 K) for significant chemistry to occur without the input of energy from exogenic sources (such as charged particles or VUV irradiation). In particular, Titan's thick atmosphere prevents significant amounts of high energy radiation from reaching the surface, limiting opportunities for surface chemical reactivity. Recently, we have identified carbamation, the reaction of carbon dioxide with primary amines to form carbamic acids, as a reaction that could occur thermally on Titan's surface. Amines should be present on Titan's surface, formed by photochemical reactions of N2 and CH4 in the upper atmosphere, and amine-containing molecules have been detected as a component of laboratory tholins made in terrestrial laboratories. There is some spectral evidence that CO2 is present on the surface, and CO2 has been definitively identified in the atmosphere. We use a combination of micro-Raman spectroscopy and UHV FTIR spectroscopy to examine the reaction products and kinetics of the carbamation reaction for a variety of primary amines. The reaction occurs readily at Titan surface temperatures (94 K), and leads to both carbamic acids and ammonium carbamate salts. Our kinetic data can be used to estimate the lifetime of CO2 on Titan's surface, and thus constrain the age of possible CO2-bearing cryovolcanic deposits.

  3. Surface modification of Fe2O3 nanoparticles with 3-aminopropyltrimethoxysilane (APTMS): An attempt to investigate surface treatment on surface chemistry and mechanical properties of polyurethane/Fe2O3 nanocomposites

    NASA Astrophysics Data System (ADS)

    Palimi, M. J.; Rostami, M.; Mahdavian, M.; Ramezanzadeh, B.

    2014-11-01

    Fe2O3 nanoparticles were modified with various amounts of 3-amino propyl trimethoxy silane (APTMS). Modified and unmodified nanoparticles were introduced into the polyurethane matrix at different concentrations. Fourier transform infrared radiation (FT-IR) and X-ray photoelectron spectrophotometer (XPS) were employed in order to investigate the APTMS grafting on the nanoparticles field emission-scanning electron microscope (FE-SEM) was utilized in order to investigate nanoparticles dispersion in the polyurethane coating matrix as well as the fracture behavior of the nanocomposites. The mechanical properties of the nanocomposites were investigated by dynamic mechanical thermal analysis (DMTA) and tensile test. The FTIR spectra and XPS analysis clearly showed that APTMS was grafted on the surface of nanoparticles successfully and formed chemical bonds with the surface. Also, surface treatment of the nanoparticles by silane resulted in the significant improvement of the mechanical properties of the polyurethane coating. The improvement was most pronounced when the nanoparticles were modified with 3 gr silane/5 g nanoparticles.

  4. The surface chemistry of iron Fischer-Tropsch catalysts

    SciTech Connect

    Dwyer, D.J.; Hardenburgh, J.H.

    1986-04-01

    The indirect conversion of coal to liquid hydrocarbons via steam gasification followed by synthesis gas (CO/H/sub 2/) chemistry has been the subject of intensive study for a number of decades. A key technological challenge facing researchers in this area is control over the product distribution during the hydrocarbon synthesis step. In the case of iron Fischer-Tropsch catalysts, it has been known that the addition of alkali to the metal catalyst has a significant impact on the product distribution. Iron catalysts treated with alkali produce less methane more alkenes and higher molecular weight products. In spite of numerous investigations, the details of this promotional effect are not understood on a molecular level. To explore the role of alkali in the surface chemistry of iron catalysts, the authors have carried out a combined surface science and catalytic kinetic study of a model iron catalyst with and without surface alkali.

  5. Chemistry of bimetallic and alloy surfaces

    SciTech Connect

    Koel, B.E.

    1991-10-18

    In the first funding period, we continued our work on elucidating the underlying principles that govern chemical reactions occurring on bimetallic and alloy surfaces. Our goal is to aid in the atomic level explanation of the reactivity and selectivity of alloy and bimetallic cluster catalysts and to provide a fundamental basis for the design of new catalysts with improved performance. Our approach is to use a battery of surface science methods to obtain fundamental data on the thermochemistry and kinetics of the adsorption and reaction of molecules on extensively characterized, single-crystal bimetallic surfaces. We measure changes in chemisorption bond strengths, adsorption site distributions, and hydrocarbon fragment stability and reactivity and correlate these results with the geometric and electronic structure of the metal atoms on the surface. Often, our aim is to carefully design experiments that isolate the several factors (e.g., ensemble and ligand effects) that control surface chemistry and catalysis on bimetallic and alloy surfaces in order to better understand the importance of each contribution. Some of the highlights and noteworthy accomplishments made during the first period of this grant are given.

  6. Acidic deposition and surface water chemistry

    NASA Astrophysics Data System (ADS)

    Church, M. R.

    A pair of back-to-back (morning and afternoon) hydrology sessions, held December 10, 1987, at the AGU Fall Meeting in San Francisco, Calif., covered “Predicting the Effects of Acidic Deposition on Surface Water Chemistry.” The combined sessions included four invited papers, 12 contributed papers, and a panel discussion at its conclusion. The gathering dealt with questions on a variety of aspects of modeling the effects of acidic deposition on surface water chemistry.Contributed papers included discussions on the representation of processes in models as well as limiting assumptions in model application (V. S. Tripathi et al., Oak Ridge National Laboratory, Oak Ridge, Tenn., and E. C. Krug, Illinois State Water Survey, Champaign), along with problems in estimating depositional inputs to catchments and thus inputs to be used in the simulation of catchment response (M. M. Reddy et al., U.S. Geological Survey, Lakewood, Colo.; and E. A. McBean, University of Waterloo, Waterloo, Canada). L. A. Baker et al. (University of Minnesota, Minneapolis) dealt with the problem of modeling seepage lake systems, an exceedingly important portion of the aquatic resources in Florida and parts of the upper U.S. Midwest. J. A. Hau and Y. Eckstein (Kent State University, Kent, Ohio) considered equilibrium modeling of two northern Ohio watersheds that receive very different loads of acidic deposition but are highly similar in other respects.

  7. Surface chemistry and mineralogy. [of planet Mars

    NASA Technical Reports Server (NTRS)

    Banin, A.; Clark, B. C.; Waenke, H.

    1992-01-01

    The accumulated knowledge on the chemistry and mineralogy of Martian surface materials is reviewed. Pertinent information obtained by direct analyses of the soil on Mars by the Viking Landers, by remote sensing of Mars from flyby and orbiting spacecraft, by telescopic observations from earth, and through detailed analyses of the SNC meteorites presumed to be Martian rocks are summarized and analyzed. A compositional model for Mars soil, giving selected average elemental concentrations of major and trace elements, is suggested. It is proposed that the fine surface materials on Mars are a multicomponent mixture of weathered and nonweathered minerals. Smectite clays, silicate mineraloids similar to palagonite, and scapolite are suggested as possible major candidate components among the weathered minerals.

  8. Exothermic surface chemistry on aluminum particles promoting reactivity

    NASA Astrophysics Data System (ADS)

    Mulamba, Oliver; Pantoya, Michelle L.

    2014-10-01

    The exothermic surface chemistry associated with the alumina passivation shell surrounding aluminum (Al) particles and fluorine from fluoropolymer materials is investigated. In particular, polytetrafluoroethylene (PTFE) has been synthesized with varying chain lengths and combined with nanometric Al fuel particles. The Al-PTFE kinetics were analyzed using equilibrium diagnostics including differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) for calorific and phase change behavior coupled with additional flame speed measurements. The objective was to understand the effects of varying PTFE molecular structure on the kinetic and energy propagation behaviors of these composites. Results showed a pre-ignition reaction (PIR) with longer chained PTFE samples and not with the shorter chained PTFE samples. The PIR is attributed to fluorine dislodging hydroxyls from the alumina (Al2O3) passivation surface and forming Al-F structures. Composites exhibiting the PIR correspondingly result in significantly higher flame speeds. The PIR surface chemistry may contribute to promoting the melt dispersion mechanism (MDM) responsible for propagating energy in nano Al reactions. Composites with a PIR also have higher heats of combustion in both the PIR and main reaction exotherms. These results help elucidate the influence of molecular scale surface chemistry on macroscopic energy propagation.

  9. Evaluation of Surface Chemistries for Antibody Microarrays

    SciTech Connect

    Seurynck-Servoss, Shannon L.; White, Amanda M.; Baird, Cheryl L.; Rodland, Karin D.; Zangar, Richard C.

    2007-12-01

    Antibody microarrays are an emerging technology that promises to be a powerful tool for the detection of disease biomarkers. The current technology for protein microarrays has been primarily derived from DNA microarrays and is not fully characterized for use with proteins. For example, there are a myriad of surface chemistries that are commercially available for antibody microarrays, but no rigorous studies that compare these different surfaces. Therefore, we have used an enzyme-linked immunosorbent assay (ELISA) microarray platform to analyze 16 different commercially available slide types. Full standard curves were generated for 24 different assays. We found that this approach provides a rigorous and quantitative system for comparing the different slide types based on spot size and morphology, slide noise, spot background, lower limit of detection, and reproducibility. These studies demonstrate that the properties of the slide surface affect the activity of immobilized antibodies and the quality of data produced. Although many slide types can produce useful data, glass slides coated with poly-L-lysine or aminosilane, with or without activation with a crosslinker, consistently produce superior results in the ELISA microarray analyses we performed.

  10. Ferroelectric based catalysis: Switchable surface chemistry

    NASA Astrophysics Data System (ADS)

    Kakekhani, Arvin; Ismail-Beigi, Sohrab

    2015-03-01

    We describe a new class of catalysts that uses an epitaxial monolayer of a transition metal oxide on a ferroelectric substrate. The ferroelectric polarization switches the surface chemistry between strongly adsorptive and strongly desorptive regimes, circumventing difficulties encountered on non-switchable catalytic surfaces where the Sabatier principle dictates a moderate surface-molecule interaction strength. This method is general and can, in principle, be applied to many reactions, and for each case the choice of the transition oxide monolayer can be optimized. Here, as a specific example, we show how simultaneous NOx direct decomposition (into N2 and O2) and CO oxidation can be achieved efficiently on CrO2 terminated PbTiO3, while circumventing oxygen (and sulfur) poisoning issues. One should note that NOx direct decomposition has been an open challenge in automotive emission control industry. Our method can expand the range of catalytically active elements to those which are not conventionally considered for catalysis and which are more economical, e.g., Cr (for NOx direct decomposition and CO oxidation) instead of canonical precious metal catalysts. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

  11. The surface chemistry of cerium oxide

    DOE PAGESBeta

    Mullins, David R.

    2015-01-29

    Our review covers the structure of, and chemical reactions on, well-defined cerium oxide surfaces. Ceria, or mixed oxides containing ceria, are critical components in automotive three-way catalysts due to their well-known oxygen storage capacity. Ceria is also emerging as an important material in a number of other catalytic processes, particularly those involving organic oxygenates and the water–gas shift reaction. Ceria's acid–base properties, and thus its catalytic behavior, are closely related to its surface structure where different oxygen anion and cerium cation environments are present on the low-index structural faces. The actual structure of these various faces has been the focusmore » of a number of theoretical and experimental investigations. Ceria is also easily reducible from CeO2 to CeO2-X. The presence of oxygen vacancies on the surface often dramatically alters the adsorption and subsequent reactions of various adsorbates, either on a clean surface or on metal particles supported on the surface. We conducted surface science studies on the surfaces of thin-films rather than on the surfaces of bulk single crystal oxides. The growth, characterization and properties of these thin-films are also examined.« less

  12. The surface chemistry of cerium oxide

    SciTech Connect

    Mullins, David R.

    2015-01-29

    Our review covers the structure of, and chemical reactions on, well-defined cerium oxide surfaces. Ceria, or mixed oxides containing ceria, are critical components in automotive three-way catalysts due to their well-known oxygen storage capacity. Ceria is also emerging as an important material in a number of other catalytic processes, particularly those involving organic oxygenates and the water–gas shift reaction. Ceria's acid–base properties, and thus its catalytic behavior, are closely related to its surface structure where different oxygen anion and cerium cation environments are present on the low-index structural faces. The actual structure of these various faces has been the focus of a number of theoretical and experimental investigations. Ceria is also easily reducible from CeO2 to CeO2-X. The presence of oxygen vacancies on the surface often dramatically alters the adsorption and subsequent reactions of various adsorbates, either on a clean surface or on metal particles supported on the surface. We conducted surface science studies on the surfaces of thin-films rather than on the surfaces of bulk single crystal oxides. The growth, characterization and properties of these thin-films are also examined.

  13. Nanomaterial surface chemistry design for advancements in capillary electrophoresis modes.

    PubMed

    Ivanov, Michael R; Haes, Amanda J

    2011-01-01

    Tailored surface chemistry impacts nanomaterial function and stability in applications including in various capillary electrophoresis (CE) modes. Although colloidal nanoparticles were first integrated as colouring agents in artwork and pottery over 2000 years ago, recent developments in nanoparticle synthesis and surface modification increased their usefulness and incorporation in separation science. For instance, precise control of surface chemistry is critically important in modulating nanoparticle functionality and stability in dynamic environments. Herein, recent developments in nanomaterial pseudostationary and stationary phases will be summarized. First, nanomaterial core and surface chemistry compositions will be classified. Next, characterization methods will be described and related to nanomaterial function in various CE modes. Third, methods and implications of nanomaterial incorporation into CE will be discussed. Finally, nanoparticle-specific mechanisms likely involved in CE will be related to nanomaterial surface chemistry. Better understanding of surface chemistry will improve nanoparticle design for the integration into separation techniques. PMID:20967383

  14. Engineered microtopographies and surface chemistries direct cell attachment and function

    NASA Astrophysics Data System (ADS)

    Magin, Chelsea Marie

    Harrison, in 1914, first recognized that cells respond to physicochemical cues such as substratum topography when he observed that fibroblasts elongated while cultured on spider silk. Recently, techniques developed in the micro-electronics industry have been used to create molds for producing microscaled topographies with various shapes and spatial arrangements. Although these patterning techniques are well-established, very little is known about the mechanisms underlying cell sensing and response to microtopographies. In this work cellular micro-environments with varying surface topographies and chemistries were evaluated with marine organisms and mammalian cells to investigate cellular sensing and response. Biofouling---the accumulation of micro-organisms, plants, and animals on submerged surfaces---is an environmental and economic concern. Engineered topographies, replicated in polydimethylsiloxane elastomer (PDMSe) and functionalized poly(ethylene glycol)-dimethacrylate (PEGDMA) hydrogels, were evaluated for inhibition of marine fouling organism attachment. Microtopographies replicated in PDMSe inhibited attachment of the marine bacterium, Cobetia marina up to 99% versus smooth. The average normalized attachment densities of cells of C. marina and zoospores of the green algae Ulva on PDMSe topographies scaled inversely with the Engineered Roughness Index (ERIII), a representation of surface energy. Attachment densities of Ulva from four assays and C. marina from two growth phases to PDMSe surfaces scaled inversely with one equation: ERI II multiplied by the Reynolds number of the organism (Re) (R 2 = 0.77). The same microtopographies created in PDMSe reduced the initial attachment density and attachment strength of cells of the diatoms Navicula incerta and Seminavis robusta compared to smooth PDMSe. The average normalized attachment density of Navicula after exposure to shear stress (48 Pa) was correlated with the contact area between the diatom and a

  15. Wet oxidation of ordered mesoporous carbon FDU-15 by using (NH4)2S2O8 for fast adsorption of Sr(II): An investigation on surface chemistry and adsorption mechanism

    NASA Astrophysics Data System (ADS)

    Song, Yang; Ye, Gang; Chen, Jing; Lv, Dachao; Wang, Jianchen

    2015-12-01

    Surface modification of ordered mesoporous carbon (OMC) by wet oxidation provides an oxygen-enriched platform for complexation of metal ions. Here, we present a comprehensive study on the surface chemistry and textual property of OMC FDU-15 modified by wet oxidation using (NH4)2S2O8 as a benign oxidant. And, for the first time, the adsorption behavior and mechanism of wet-oxidized OMC FDU-15 toward Sr(II) in aqueous solutions were investigated. The mesostructural regularity of the OMC FDU-15 was well-reserved under wet oxidation. Compared to OMC CMK-type counterparts prepared via nanocasting, the OMC FDU-15 by soft template method showed much-enhanced structural stability. Due to the introduction of abundant oxygen-containing species, the oxidized OMC FDU-15 exhibited excellent hydrophilicity and dispersibility in aqueous solutions. The adsorption behavior toward Sr(II) was fully investigated, showing a super-fast adsorption kinetics (< 5 min to reach equilibrium) and a Langmuir adsorption isotherm. Moreover, an in-depth X-ray photoelectron spectroscopy analysis through deconvolution of high resolution C1s and O1s spectra was implemented to identify the chemical species of the surface functional groups, while probing the adsorption mechanism. The results suggested that oxygen donor atoms in Csbnd O single bonds mainly contribute to the adsorption of Sr(II) via formation of metal-ligand complexation.

  16. Investigating expanded chemistry in CMAQ clouds

    EPA Science Inventory

    Clouds and fogs significantly impact the amount, composition, and spatial distribution of gas and particulate atmospheric species, not least of which through the chemistry that occurs in cloud droplets.ᅠ Atmospheric sulfate is an important component of fine aerosol mass an...

  17. Impact Driven Chemistry on Europa's Surface

    NASA Astrophysics Data System (ADS)

    Khare, B. N.; NNa Mvondo, D.; Borucki, J. G.; Cruikshank, D. P.; Belisle, W. A.; Wilhite, P.; McKay, C. P.

    2005-08-01

    A new energy source for organic synthesis on simulated Europan surfaces, electrical discharge, light emission, and magnetic phenomena from impacts into the ice, has been studied [Borucki et al. J. Geophys. Res. 107 (E11) 5114 (2002)]. Part of the impactor's kinetic energy is converted into electrical potential. The mechanical disruption causes the release of energy as light, heat, and electrical and magnetic fields as secondary emissions that synthesizes complex organic material named tholin [Sagan and Khare, Nature 277, 102 (1979)] in the area of impact craters. The morphology of the impact craters indicates that tholin is the result of outflow from the fracture zone. Large pool of liquid water may exist for thousands of years as suggested for Titan [Thompson and Sagan, Eur. Space Agency Spec. Publ., ESA-SP, 338, 167 (1992)] and may also apply to Europa potentially driving prebiotic chemistry due to energy pumped in from the secondary emissions. We have detected 8.8 ppm of H2O2 from impact of a 1/4" iron bullet at 5.3 km/s over water ice at ca. -100 C. H2O2 has been detected on the surface of Europa [Carlson et al., Science 283, 2062 (1999)]. Further confirmation by Raman Scattering at 874.5 cm-1 and IR absorbance at 2854 cm-1 is continuing. Since the impactor is limited in the number of experiments we can run, other experiments used a laser induced plasma (LIP) to shock ice mixed with ammonium sulphate and methanol. We detected CH4, CO, N2O, C2H6, CH3CN, CH3COCH3, HCOOCH3 (methyl formate), and traces of HCN. LIP on a mixture of water and methanol ice produced CH4, CO, HCHO, ethanol, formic acid methylester, propanol, acetone, dimethoxyme, and possibly ethanone-1phenyl or other phenyl group. NH3 and methanol could be delivered on impact of comets while sulfur expelled from Io.

  18. Laboratory investigations on the role of sediment surface and ground water chemistry in transport of bacteria through a contaminated Sandy Aquifer

    USGS Publications Warehouse

    Scholl, M.A.; Harvey, R.W.

    1992-01-01

    The effects of pH and sediment surface characteristics on sorption of indigenous groundwater bacteria were determined using contaminated and uncontaminated aquifer material from Cape Cod, MA. Over the pH range of the aquifer (5-7), the extent of bacterial sorption onto sediment in uncontaminated groundwater was strongly pH-dependent, but relatively pH-insensitive in contaminated groundwater from the site. Bacterial sorption was also affected by the presence of oxyhydroxide coatings (iron, aluminum, and manganese). Surface coating effects were most pronounced in uncontaminated groundwater (pH 6.4 at 10??C). Desorption of attached bacteria (up to 14% of the total number of labeled cells added) occurred in both field and laboratory experiments upon adjustment of groundwater to pH 8. The dependence of bacterial sorption upon environmental conditions suggests that bacterial immobilization could change substantially over relatively short distances in contaminated, sandy aquifers and that effects caused by changes in groundwater geochemistry can be significant.

  19. Surface chemistry: Key to control and advance myriad technologies

    PubMed Central

    Yates, John T.; Campbell, Charles T.

    2011-01-01

    This special issue on surface chemistry is introduced with a brief history of the field, a summary of the importance of surface chemistry in technological applications, a brief overview of some of the most important recent developments in this field, and a look forward to some of its most exciting future directions. This collection of invited articles is intended to provide a snapshot of current developments in the field, exemplify the state of the art in fundamental research in surface chemistry, and highlight some possibilities in the future. Here, we show how those articles fit together in the bigger picture of this field. PMID:21245359

  20. INVESTIGATING ENVIRONMENTAL SINKS OF MACROLIDE ANTIBIOTICS WITH ANALYTICAL CHEMISTRY

    EPA Science Inventory

    Possible environmental sinks (wastewater effluents, biosolids, sediments) of macrolide antibiotics (i.e., azithromycin, roxithromycin and clarithromycin)are investigated using state-of-the-art analytical chemistry techniques.

  1. Elementary photocatalytic chemistry on TiO2 surfaces.

    PubMed

    Guo, Qing; Zhou, Chuanyao; Ma, Zhibo; Ren, Zefeng; Fan, Hongjun; Yang, Xueming

    2016-07-01

    Photocatalytic hydrogen production and pollutant degradation provided both great opportunities and challenges in the field of sustainable energy and environmental science. Over the past few decades, we have witnessed fast growing interest and efforts in developing new photocatalysts, improving catalytic efficiency and exploring the reaction mechanism at the atomic and molecular levels. Owing to its relatively high efficiency, nontoxicity, low cost and high stability, TiO2 becomes one of the most extensively investigated metal oxides in semiconductor photocatalysis. Fundamental studies on well characterized single crystals using ultrahigh vacuum based surface science techniques could provide key microscopic insight into the underlying mechanism of photocatalysis. In this review, we have summarized recent progress in the photocatalytic chemistry of hydrogen, water, oxygen, carbon monoxide, alcohols, aldehydes, ketones and carboxylic acids on TiO2 surfaces. We focused this review mainly on the rutile TiO2(110) surface, but some results on the rutile TiO2(011), anatase TiO2(101) and (001) surfaces are also discussed. These studies provided fundamental insights into surface photocatalysis as well as stimulated new investigations in this exciting field. At the end of this review, we have discussed how these studies can help us to develop new photocatalysis models. PMID:26335268

  2. Adsorption of perfluoroalkyl acids by carbonaceous adsorbents: Effect of carbon surface chemistry.

    PubMed

    Zhi, Yue; Liu, Jinxia

    2015-07-01

    Adsorption by carbonaceous sorbents is among the most feasible processes to remove perfluorooctane sulfonic (PFOS) and carboxylic acids (PFOA) from drinking and ground waters. However, carbon surface chemistry, which has long been recognized essential for dictating performance of such sorbents, has never been considered for PFOS and PFOA adsorption. Thus, the role of surface chemistry was systematically investigated using sorbents with a wide range in precursor material, pore structure, and surface chemistry. Sorbent surface chemistry overwhelmed physical properties in controlling the extent of uptake. The adsorption affinity was positively correlated carbon surface basicity, suggesting that high acid neutralizing or anion exchange capacity was critical for substantial uptake of PFOS and PFOA. Carbon polarity or hydrophobicity had insignificant impact on the extent of adsorption. Synthetic polymer-based Ambersorb and activated carbon fibers were more effective than activated carbon made of natural materials in removing PFOS and PFOA from aqueous solutions. PMID:25827692

  3. Surface Chemistry in Heterogeneous Catalysis: An Emerging Discipline.

    ERIC Educational Resources Information Center

    White, J. M.; Campbell, Charles T.

    1980-01-01

    Provides background data on surface chemistry as an emerging discipline. Highlights the important role which surfaces play in catalysis by focusing on the catalyzed oxidation of carbon monoxide. Provides a demonstration of how surfaces exert their influences in heterogeneous phenomena and illustrates how experimental problems in this field are…

  4. Field investigation of FGD system chemistry. Final report

    SciTech Connect

    Litherland, S.T.; Colley, J.D.; Glover, R.L.; Maller, G.; Behrens, G.P.

    1984-12-01

    Three full-scale wet limestone FGD systems were investigated to gain a better understanding of FGD system operation and chemistry. The three plants which participated in the program were South Mississippi Electric Power Association's R. D. Morrow Station, Colorado-Ute Electric Association's Craig Station, and Central Illinois Light Company's Duck Creek Station. Each FGD system was characterized with respect to SO/sub 2/ removal, liquid and solid phase chemistry, and calcium sulfite and calcium sulfate relative saturation. Mist eliminator chemistry and performance were documented at Morrow and Duck Creek. Solutions to severe mist eliminator scaling and pluggage were demonstrated at Duck Creek. A technical and econ

  5. Investigations in Marine Chemistry: Tide Pool Ecology.

    ERIC Educational Resources Information Center

    Schlenker, Richard M.

    Students investigated the salinity of tide pools at different levels in the intertidal zone. Data are analyzed collectively. Students graphed and discussed data. Included are suggestions for evaluation and further study. (Author)

  6. Modulation of human osteoblasts by metal surface chemistry.

    PubMed

    Hofstetter, Wilhelm; Sehr, Harald; de Wild, Michael; Portenier, Jeannette; Gobrecht, Jens; Hunziker, Ernst B

    2013-08-01

    The use of metal implants in dental and orthopedic surgery is continuously expanding and highly successful. While today longevity and load-bearing capacity of the implants fulfill the expectations of the patients, acceleration of osseointegration would be of particular benefit to shorten the period of convalescence. To further clarify the options to accelerate the kinetics of osseointegration, within this study, the osteogenic properties of structurally identical surfaces with different metal coatings were investigated. To assess the development and function of primary human osteoblasts on metal surfaces, cell viability, differentiation, and gene expression were determined. Titanium surfaces were used as positive, and surfaces coated with gold were used as negative controls. Little differences in the cellular parameters tested for were found when the cells were grown on titanium discs sputter coated with titanium, zirconium, niobium, tantalum, gold, and chromium. Cell number, activity of cell layer-associated alkaline phosphatase (ALP), and levels of transcripts encoding COL1A1 and BGLAP did not vary significantly in dependence of the surface chemistry. Treatment of the cell cultures with 1,25(OH)2 D3 /Dex, however, significantly increased ALP activity and BGLAP messenger RNA levels. The data demonstrate that the metal layer coated onto the titanium discs exerted little modulatory effects on cell behavior. It is suggested that the microenvironment regulated by the peri-implant tissues is more effective in regulating the tissue response than is the material of the implant itself. PMID:23359530

  7. Water at surfaces with tunable surface chemistries and the chiral imprint of water around DNA

    NASA Astrophysics Data System (ADS)

    Petersen, Poul

    Aqueous interfaces are ubiquitous in atmospheric chemistry and biological systems but are notoriously hard to probe experimentally. Surface-specific vibrational spectroscopy offers an avenue to directly probe the vibrational modes of the water OH stretching band but this method is challenging to implement to buried surfaces. Here we present results from sum-frequency generation (SFG) spectroscopy probing the buried interface between a functionalized surface and aqueous solutions. Studying such buried surfaces offers the advantage of being able to systematically tune the surface chemistry using self-assembled monolayers, i.e. the hydrophobic and hydrophilic character, and examine the effect on the interfacial water. In addition to water at these controlled surfaces, we have initiated studying water at biological surfaces. This includes the solvation structure around DNA. X-ray experiments at cryogenic temperatures have found crystallographic water in the minor grove of DNA giving rise to the notion of a spine of hydration surrounding DNA. Such structured water should exhibit a chiral structure adapted from DNA. We investigate if such a chiral water structure exist around DNA at room temperature using chiral SFG. This work was supported by the National Science Foundation under a NSF CAREER Grant (CHE-1151079).

  8. Investigations in Marine Chemistry: Salinity II.

    ERIC Educational Resources Information Center

    Schlenker, Richard M.

    Presented is a science activity in which the student investigates methods of calibration of a simple conductivity meter via a hands-on inquiry technique. Conductivity is mathematically compared to salinity using a point slope formula and graphical techniques. Sample solutions of unknown salinity are provided so that the students can sharpen their…

  9. Gas Plasma Surface Chemistry for Biological Assays.

    PubMed

    Sahagian, Khoren; Larner, Mikki

    2015-01-01

    Biological systems respond to and interact with surfaces. Gas plasma provides a scalable surface treatment method for designing interactive surfaces. There are many commercial examples of plasma-modified products. These include well plates, filtration membranes, dispensing tools, and medical devices. This chapter presents an overview of gas plasma technology and provides a guide to using gas plasma for modifying surfaces for research or product development. PMID:26160577

  10. Grain surface chemistry in star-forming regions

    NASA Astrophysics Data System (ADS)

    Taquet, Vianney

    2012-12-01

    The first stages of star formation are accompanied by an evolution of the chemistry, starting from simple molecules in cold dark clouds to the detection of complex organic molecules around Class 0 protostars. Although mostly composed of gas, these clouds also contain small amounts of microscopic dust. The contribution of this dust is nevertheless important because it acts as a catalyst for the formation of key molecules seen in cold interstellar ices, such as water or methanol. These ices are believed to be the first step towards the rich chemistry seen in the warm envelope of protostars. During my thesis, I focused on this first step and I did so by taking a twofold approach. i) Modelling. I have developed an astrochemical model coupling the chemistry in the gas phase and on the grain surfaces. This model follows the multilayer formation of interstellar ices and allows us to investigate the influence of key physical, chemical, and surface parameters, such as the grain porosity, on the chemical composition of ices via a multiparameter approach. The model has been applied to predict the chemical differentiation and the deuteration of interstellar ices. To this end, I have built up a chemical network taking into account the most recent experimental and theoretical works. I applied then the model to various cases. For example, I showed that ices are heterogeneous and their composition are sensitive to the physical conditions as well as several grain surface parameters. The high deuteration of formaldehyde, and methanol observed around low-mass protostars has been predicted by a dense (nH ∼ 5 × 10^6 cm-3) and fast (∼ 5000 years) phase while the lower deuteration of water is predicted for typical molecular cloud conditions. The deuterium fractionation is very sensitive and can be used as a tracer of the physical conditions. ii) Observations. I have been involved in observational projects whose goals are related to the grain surface chemical problems. I obtained the

  11. The chemistry and physics of zinc oxide surfaces

    NASA Astrophysics Data System (ADS)

    Wöll, Christof

    Metal oxides are virtually everywhere - only gold has the property not to form an oxide on its surface when exposed to the ambient. As a result, understanding the physics and chemistry of oxide surfaces is a topic of pronounced general interest and, of course, also a necessary prerequisite for many technical applications. The most important of these is certainly heterogeneous catalysis, but one has to realize that - under ambient conditions - virtually all phenomena occurring at liquid/metal and gas/metal interfaces are determined by the corresponding oxide. This applies in particular to friction phenomena, adhesion and corrosion. A necessary - but not necessarily sufficient - condition for unravelling the fundamentals governing this complex field is to analyze in some detail elementary chemical and physical processes at oxide surfaces. Although the Surface Science of metal surfaces has seen a major progress in the past decades, for oxides detailed experimental investigations for well-defined single crystal surfaces still represent a formidable challenge - mostly because of technical difficulties (charging), but to some extent also due to fundamental problems related to the stabilization of polar surfaces. As a result, the amount of information available for this class of materials is - compared to that at hand for metals - clearly not satisfactory. A particular disturbing lack of information is that about the presence of hydrogen at oxide surfaces - either as hydroxy-species or in form of metal hydrides. In the present review we will summarize recent experimental and theoretical information which has become available from single crystal studies on ZnO surfaces. While the number of papers dealing with another oxide, rutile TiO 2, is significantly larger (although titania does not exhibit a polar surface), also for zinc oxide a basis of experimental and theoretical knowledge as been accumulated, which - at least for the non-polar surfaces - allows to understand

  12. Scattering and Chemical Investigations of Semiconductor Surfaces.

    NASA Astrophysics Data System (ADS)

    Wallace, Robert Milo

    1988-12-01

    This two-part thesis describes: (i) the design of an ion scattering system to examine the surface and near-surface region of semiconductors, and (ii) the chemical reaction channels of unsaturated hydrocarbons on the silicon (100) surface. Details on the design and construction of an ultrahigh vacuum, high-energy ion scattering system are presented. The use of MeV ion scattering to investigate surface and near -surface regions of materials is described and the combination of ion scattering with complimentary surface science techniques is stressed. The thermal activation of chemical bonds of the adsorbed unsaturated hydrocarbon molecules ethylene, propylene, and acetylene is investigated on the Si(100)-(2 times 11) surface with a goal of understanding the surface chemistry of Si-C formation. The use of precision dosing techniques, Low Energy Electron Diffraction, Auger Electron Spectroscopy, and Temperature Programmed Desorption in the investigation of the remaining carbonaceous species is described. Comparisons of the adsorption and desorption behavior of these molecules is made in terms of the carbon -carbon double and triple bonds (ethylene to acetylene) and the methyl functional group (ethylene to propylene). We find that the monolayer saturation coverage of these hydrocarbons is in very good agreement with the number of dimer sites on the surface estimated from scanning-tunneling microscopy, which suggests that the bonding of these hydrocarbons to the Si(100) surface is similar. It is also found that ethylene, in particular, does not provide an efficient Si-C reaction channel upon thermal activation, with nearly 100% of the ethylene molecules desorbing. In contrast, acetylene is found to be very efficient in SiC formation: >=q90% of the adsorbed acetylene thermally dissociates and eventually leads to SiC formation. Propylene has an efficiency of roughly 70% upon heating. Evidence for the diffusion of carbon into the bulk is seen at >=q850 K for propylene and

  13. Chemistry of bimetallic and alloy surfaces

    SciTech Connect

    Koel, B.E.

    1992-01-01

    Recent research accomplishments included: a method for estimating surface reaction energetics, and application to ethylene decomposition on Pt(111); carbon Auger line shapes for adsorption/decomposition of ethylene on Ni(100) and C-C bonding in ''carbidic'' layers on metals; surface structure of Sn deposited on Pt(111) and Pt(100); chemisorption of CO, H[sub 2], O[sub 2] on ordered Sn/Pt(111) surface alloys; effects of K adatoms on H[sub 2] adsorption on Pt(111); effects of adsorbed K, O, and H on CO adsorption on Pt(111); hydrocarbon trapping, condensation on Pt(111); effects of C on cyclohexane dehydrogenation on Pt(111) surfaces; and SnPt(111) catalysis of benzene production from acetylene under uhv conditions.

  14. Supported organometallic complexes: Surface chemistry, spectroscopy, and catalysis

    SciTech Connect

    Marks, T.J.

    1991-01-01

    Adsorbing organometallic molecules onto the surfaces of inorganic supports such as Al{sub 2}O{sub 3}, MgCl{sub 2}, SiO{sub 2}, etc. can result in dramatic enhancements in catalytic activity. The reasons for this and the structures of the resulting surface organometallic centers are not well understood. We have addressed this problem using actinide and early transition metal complexes as model adsorbates. Characterization tools include catalytic and stoichiometric reaction chemistry, reaction kinetics and isotopic labeling, quantitative poisoning studies, model solution chemistry, and a wide array of surface-sensitive spectroscopies such as CPMAS NMR, EPR, and UV-VIS as well as titration calorimetry. These chemical and physical experiments are closely coupled to model solution chemistry to provide maximum information yield. 4 refs., 2 figs.

  15. The surface coat of chylomicrons: lipid chemistry.

    PubMed

    Zilversmit, D B

    1968-03-01

    Chylomicrons from the thoracic duct lymph of dogs fed corn oil were isolated by centrifugation and disrupted by either freezing and thawing or rotary evaporation and rehydration. A pellet, representing the surface coat, was isolated by centrifugation. Pellets isolated by freezing and thawing contained a higher percentage of saturated triglycerides than pellets isolated by rotary evaporation; the presence of saturated triglyceride in the pellet was probably an artifact of the preparation of the surface coat material at low temperature. Exchange of free cholesterol between surface and core lipid of chylomicrons was complete within 1 hr. The percentage of cholesterol in pellets of surface material isolated by freezing and thawing was about twice that found for pellets after rotary evaporation at 25-40 degrees C. Cholesteryl ester was not present in the surface lipid and that present in the core lipid did not exchange with serum lipoprotein cholesteryl ester. For phosphatidyl choline, the percentage of linoleic acid in lymph chylomicrons was markedly higher than that in clear lymph or plasma, while the percentage of arachidonic acid was lower. Sphingomyelin of lymph chylomicrons was characterized by very high levels of 16:0 and relatively small percentages of very long-chain fatty acids as compared with clear lymph or plasma. The data are consistent with the view that in lymph chylomicrons: (a) cholesteryl esters are dissolved in a core of triglycerides which contain fatty acids derived primarily from dietary fatty acids, (b) free cholesterol is partitioned between core and surface and is freely exchangeable between the two, (c) the phospholipid fractions are present on the surface and are intracellular in origin. PMID:5640497

  16. A model of Martian surface chemistry

    NASA Technical Reports Server (NTRS)

    Oyama, V. I.; Berdahl, B. J.

    1979-01-01

    Alkaline earth and alkali metal superoxides and peroxides, gamma-Fe2O3 and carbon suboxide polymer, are proposed to be constituents of the Martian surface material. These reactive substances explain the water modified reactions and thermal behaviors of the Martian samples demonstrated by all of the Viking Biology Experiments. It is also proposed that the syntheses of these substances result mainly from electrical discharges between wind-mobilized particles at Martian pressures; plasmas are initiated and maintained by these discharges. Active species in the plasma either combine to form or react with inorganic surfaces to create the reactive constituents.

  17. Supported organometallic complexes: Surface chemistry, spectroscopy, and catalysis

    SciTech Connect

    Marks, T.J.

    1992-02-01

    The long-range goal of this project is to elucidate and understand the surface chemistry and catalytic properties of well-defined, highly-reactive organometallic molecules (principally based upon abundant actinide, lanthanide, and early transition elements) adsorbed on metal oxides and halides. The nature of the adsorbed species is probed by a battery of chemical and physicochemical techniques, to understand the nature of the molecular-surface coordination chemistry and how this can give rise to extremely high catalytic activity. A complementary objective is to delineate the scope and mechanisms of the heterogeneous catalytic reactions, as well as to relate them both conceptually and functionally to model systems generated in solution.

  18. Organic chemistry on Titan: Surface interactions

    NASA Technical Reports Server (NTRS)

    Thompson, W. Reid; Sagan, Carl

    1992-01-01

    The interaction of Titan's organic sediments with the surface (solubility in nonpolar fluids) is discussed. How Titan's sediments can be exposed to an aqueous medium for short, but perhaps significant, periods of time is also discussed. Interactions with hydrocarbons and with volcanic magmas are considered. The alteration of Titan's organic sediments over geologic time by the impacts of meteorites and comets is discussed.

  19. Investigating the Effectiveness of Computer Simulations for Chemistry Learning

    ERIC Educational Resources Information Center

    Plass, Jan L.; Milne, Catherine; Homer, Bruce D.; Schwartz, Ruth N.; Hayward, Elizabeth O.; Jordan, Trace; Verkuilen, Jay; Ng, Florrie; Wang, Yan; Barrientos, Juan

    2012-01-01

    Are well-designed computer simulations an effective tool to support student understanding of complex concepts in chemistry when integrated into high school science classrooms? We investigated scaling up the use of a sequence of simulations of kinetic molecular theory and associated topics of diffusion, gas laws, and phase change, which we designed…

  20. Molecular Surface Chemistry by Metal Single Crystals and Nanoparticles from Vacuum to High Pressure.

    SciTech Connect

    Somorjai, Gabor A.; Park, Jeong Y.

    2008-04-05

    Model systems for studying molecular surface chemistry have evolved from single crystal surfaces at low pressure to colloidal nanoparticles at high pressure. Low pressure surface structure studies of platinum single crystals using molecular beam surface scattering and low energy electron diffraction techniques probe the unique activity of defects, steps and kinks at the surface for dissociation reactions (H-H, C-H, C-C, O{double_bond}O bonds). High-pressure investigations of platinum single crystals using sum frequency generation vibrational spectroscopy have revealed the presence and the nature of reaction intermediates. High pressure scanning tunneling microscopy of platinum single crystal surfaces showed adsorbate mobility during a catalytic reaction. Nanoparticle systems are used to determine the role of metal-oxide interfaces, site blocking and the role of surface structures in reactive surface chemistry. The size, shape and composition of nanoparticles play important roles in determining reaction activity and selectivity.

  1. Quantification of air plasma chemistry for surface disinfection

    NASA Astrophysics Data System (ADS)

    Pavlovich, Matthew J.; Clark, Douglas S.; Graves, David B.

    2014-12-01

    Atmospheric-pressure air plasmas, created by a variety of discharges, are promising sources of reactive species for the emerging field of plasma biotechnology because of their convenience and ability to operate at ambient conditions. One biological application of ambient-air plasma is microbial disinfection, and the ability of air plasmas to decontaminate both solid surfaces and liquid volumes has been thoroughly established in the literature. However, the mechanism of disinfection and which reactive species most strongly correlate with antimicrobial effects are still not well understood. We describe quantitative gas-phase measurements of plasma chemistry via infrared spectroscopy in confined volumes, focusing on air plasma generated via surface micro-discharge (SMD). Previously, it has been shown that gaseous chemistry is highly sensitive to operating conditions, and the measurements we describe here extend those findings. We quantify the gaseous concentrations of ozone (O3) and nitrogen oxides (NO and NO2, or NOx) throughout the established ‘regimes’ for SMD air plasma chemistry: the low-power, ozone-dominated mode; the high-power, nitrogen oxides-dominated mode; and the intermediate, unstable transition region. The results presented here are in good agreement with previously published experimental studies of aqueous chemistry and parameterized models of gaseous chemistry. The principal finding of the present study is the correlation of bacterial inactivation on dry surfaces with gaseous chemistry across these time and power regimes. Bacterial decontamination is most effective in ‘NOx mode’ and less effective in ‘ozone mode’, with the weakest antibacterial effects in the transition region. Our results underscore the dynamic nature of air plasma chemistry and the importance of careful chemical characterization of plasma devices intended for biological applications.

  2. Lunar surface chemistry: A new imaging technique

    USGS Publications Warehouse

    Andre, C.G.; Bielefeld, M.J.; Eliason, E.; Soderblom, L.A.; Adler, I.; Philpotts, J.A.

    1977-01-01

    Detailed chemical maps of the lunar surface have been constructed by applying a new weighted-filter imaging technique to Apollo 15 and Apollo 16 x-ray fluorescence data. The data quality improvement is amply demonstrated by (i) modes in the frequency distribution, representing highland and mare soil suites, which are not evident before data filtering and (ii) numerous examples of chemical variations which are correlated with small-scale (about 15 kilometer) lunar topographic features.

  3. Surface chemistry at the nanometer scale

    NASA Astrophysics Data System (ADS)

    Cao, Peigen

    This thesis describes research towards understanding surface chemical and physical processes, as well as their effects on the underlying substrate properties, at the nanometer and atomic scales. We demonstrate a method to tune the density of etch pits on Si(111) during the chlorination process so as to change the surface reactivity. Subsequent grafting of an azide group to replace chlorine demonstrates an example of non-oxidative passivation of silicon surfaces with new functionalities. Depending upon the solvent used in the azidation process, it is shown to yield different azidation kinetic rates, different final azide coverages, and different surface-area distributions. Scanning tunneling spectroscopy studies show that both chlorination and azidation processes significantly modify the surface electronic structures, with the former leading to a non-zero density of states at the Fermi level. Our studies on a new class of corrugation, i.e., wrinkles, in exfoliated graphene on SiO2 show that a "three-for-six" triangular pattern of atoms is exclusively and consistently observed on wrinkles, suggesting the local curvature of the wrinkle is a perturbation that breaks the six-fold symmetry of the graphene lattice. Lower electrical conductance is also found on the top of wrinkles compared to other regions of graphene. The wrinkles are characterized by the presence of midgap states, which is in agreement with recent theoretical predictions. A general method is also reported for reliably fabricating ultrahigh-density graphene nanoribbon (GNR) arrays. We have clearly observed how the properties of GNRs evolve as a function of number of graphene layers. The band gap (and so the on-off ratio) decreases as the number of layers increases. These results suggest that, in addition to single layer graphene, properties of GNRs of different thicknesses can also be harnessed for engineering GNRs as different building blocks towards FET applications. A novel imaging technique, graphene

  4. Role of Surface Chemistry in Nanoscale Electrokinetic Transport

    NASA Astrophysics Data System (ADS)

    Atalay, Selcuk

    This dissertation work presents the efforts to study the electrofluidics phenomena, with a focus on surface charge properties in nanoscale systems with the potential applications in imaging, energy conversion, ultrafiltration, DNA analysis/sequencing, DNA and protein transport, drug delivery, biological/chemical agent detection and micro/nano chip sensors. Since the ion or molecular or particle transport and also liquid confinement in nano-structures are strongly dominated by the surface charge properties, in regards of the fundamental understanding of electrofluidics at nanoscale, we have used surface charge chemistry properties based on 2-pK charging mechanism. Using this mechanism, we theoretically and analytically showed the surface charge properties of silica nanoparticles as a function of their size, pH level and salt ionic strength of aqueous solution. For a fixed particle size, the magnitude of the surface charge typically increases with an increase in pH or background salt concentration. Furthermore, we investigated the surface charge properties of a charged dielectric nanoparticle and flat wall in electrostatic interactions. According to the theoretical results strong interactions cause a non-uniform surface charge density on the nanoparticle and the plate as a result of the enhancement of proton concentration in the gap between the particle and the plate. This effect increases with decreased separation distance (Kh). We moreover investigated the ion confinement inside the nanospaces and using a continuum model, we showed the proton enhancement in extended nanochannels. The proton enrichment at the center of the nanochannel is significant when the bulk pH is medium high and the salt concentration is relatively low. The results gathered are informative for the development of biomimetic nanofluidic apparatuses and the interpretation of relevant experimental data. Later, we have developed an analytical model for electroosmotic ion transport inside p

  5. Effect of accelerated weathering on surface chemistry of modified wood

    NASA Astrophysics Data System (ADS)

    Temiz, Ali; Terziev, Nasko; Eikenes, Morten; Hafren, Jonas

    2007-04-01

    In this study, the effects of UV-light irradiation and water spray on colour and surface chemistry of scots pine sapwood samples were investigated. The specimens were treated with chromated copper arsenate (CCA), a metal-free propiconazol-based formulation, chitosan, furfuryl alcohol and linseed and tall oils. The weathering experiment was performed by cycles of 2 h UV-light irradiation followed by water spray for 18 min. The changes at the surface of the weathered samples were characterised by Fourier transform infrared spectroscopy (FT-IR); colour characterizations were performed by measuring CIELab parameters. The results show that all treatment methods except chitosan treatment provided lower colour changes than the control groups after 800 h exposure in weathering test cycle, but differences between chitosan and control were also small. The lowest colour changes were found on linseed oil (full cell process) and CCA treated wood. FT-IR results show that oil treatment (linseed and tall oil) decreased the intensities of a lignin specific peak (1500-1515 cm -1). Absorption band changes at 1630-1660 cm -1 were reduced by all treatments.

  6. The surface chemistry of dissolving labradorite feldspar

    NASA Astrophysics Data System (ADS)

    Casey, William H.; Westrich, Henry R.; Arnold, George W.; banfield, Jillian F.

    1989-04-01

    Elastic recoil detection (ERD) analysis was used in conjunction with Rutherford backscattering (RBS) analysis to determine depth profiles of hydrogen, silicon, aluminum and calcium in labradorite crystals reacted under various pH conditions. The inventory of hydrogen in the mineral is strongly affected by solution pH. Hydrogen extensively infiltrates the mineral during reaction for 264 hours with solutions in the pH range 1-3. Infiltration is accompanied by extensive removal of sodium, calcium and aluminum from the mineral. This incongruent reaction proceeds to several hundreds of angstroms of depth and produces a silicon-rich surface which is amorphous to electron diffraction. The amount of hydrogen in the reacted layer is much less than is predicted from knowledge of the quantity of cations leached from the feldspar. These low inventories of hydrogen suggest that hydrogen-bearing groups in the reacted layer repolymermize subsequent to ion exchange and depolymerization reactions. This repolymerization eliminates hydrogen from the layer. At higher pH conditions (pH > 5), hydrogen inventories in the crystals decrease with time relative to an unreacted reference crystal. Hydrogen does not infiltrate beyond the first few unit cells of feldspar. Thus, dissolution in slightly acid, near-neutral, and basic solutions proceeds at the immediate surface of the feldspar. Within the limit of the RBS technique, there is no evidence for incongruent dissolution at these conditions.

  7. Density Functional Theory in Surface Chemistry and Catalysis

    SciTech Connect

    Norskov, Jens

    2011-05-19

    Recent advances in the understanding of reactivity trends for chemistry at transition metal surfaces have enabled in silico design of heterogeneous catalysts in a few cases. Current status of the field is discussed with an emphasis on the role of coupling between theory and experiment and future challenges.

  8. Density functional theory in surface chemistry and catalysis

    PubMed Central

    Nørskov, Jens K.; Abild-Pedersen, Frank; Studt, Felix; Bligaard, Thomas

    2011-01-01

    Recent advances in the understanding of reactivity trends for chemistry at transition-metal surfaces have enabled in silico design of heterogeneous catalysts in a few cases. The current status of the field is discussed with an emphasis on the role of coupling theory and experiment and future challenges. PMID:21220337

  9. Long-term trends in precipitation and surface water chemistry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This chapter shows long-term data and trends in precipitation and surface water chemistry for each site. It contains a brief introduction to the topic, and methods of measurements, selection of variables, and their data source. It consists primarily of a large number of figures showing long-term da...

  10. Investigating the students' understanding of surface phenomena

    NASA Astrophysics Data System (ADS)

    Hamed, Kastro Mohamad

    1999-11-01

    This study investigated students' understanding of surface phenomena. The main purpose for conducting this research endeavor was to understand how students think about a complex topic about which they have little direct or formal instruction. The motivation for focusing on surface phenomena stemmed from an interest in integrating research and education. Despite the importance of surfaces and interfaces in research laboratories, in technological applications, and in everyday experiences, no previous systematic effort was done on pedagogy related to surface phenomena. The design of this research project was qualitative, exploratory, based on a Piagetian semi-structured clinical piloted interview, focused on obtaining a longitudinal view of the intended sample. The sampling was purposeful and the sample consisted of forty-four undergraduate students at Kansas State University. The student participants were enrolled in physics classes that spanned a wide academic spectrum. The data were analyzed qualitatively. The main themes that emerged from the analysis were: (a) students used analogies when confronted with novel situations, (b) students mixed descriptions and explanations, (c) students used the same explanation for several phenomena, (d) students manifested difficulties transferring the meaning of vocabulary across discipline boundaries, (e) in addition to the introductory chemistry classes, students used everyday experiences and job-related experiences as sources of knowledge, and (f) students' inquisitiveness and eagerness to investigate and discuss novel phenomena seemed to peak about the time students were enrolled in second year physics classes.

  11. Quantum Chemistry for Surface Segregation in Metal Alloys

    SciTech Connect

    Sholl, David

    2006-08-31

    Metal alloys are vital materials for the fabrication of high-flux, high-selectivity hydrogen separation membranes. A phenomenon that occurs in alloys that does not arise in pure metals is surface segregation, where the composition of the surface differs from the bulk composition. Little is known about the strength of surface segregation in the alloys usually considered for hydrogen membranes. Despite this lack of knowledge, surface segregation may play a decisive role in the ability of appropriately chosen alloys to be resistant to chemical poisoning, since membrane poisoning is controlled by surface chemistry. The aim of this Phase I project is to develop quantum chemistry approaches to assess surface segregation in a prototypical hydrogen membrane alloy, fcc Pd{sub 75}Cu{sub 25}. This alloy is known experimentally to have favorable surface properties as a poison resistant H{sub 2} purification membrane (Kamakoti et al., Science 307 (2005) 569-573), but previous efforts at modeling surfaces of this alloy have ignored the possible role of surface segregation (Alfonso et al., Surf. Sci. 546 (2003) 12-26).

  12. Surface Chemistry and Properties of Oxides as Catalyst Supports

    SciTech Connect

    DeBusk, Melanie Moses; Narula, Chaitanya Kumar; Contescu, Cristian I

    2015-01-01

    Heterogeneous catalysis relies on metal-oxides as supports for the catalysts. Catalyst supports are an indispensable component of most heterogeneous catalysts, but the role of the support is often minimized in light of the one played by the catalytically active species it supports. The active species of supported catalysts are located on the surface of the support where their contact with liquid or gas phase reactants will be greatest. Considering that support plays a major role in distribution and stability of active species, the absorption and retention of reactive species, and in some cases in catalytic reaction, the properties and chemistry that can occur at the surface of an oxide support are important for understanding their impact on the activity of a supported catalyst. This chapter examines this rich surface chemistry and properties of oxides used as catalyst supports, and explores the influence of their interaction with the active species.

  13. On the use of SPM to probe the interplay between polymer surface chemistry and polymer surface mechanics

    NASA Astrophysics Data System (ADS)

    Brogly, Maurice; Noel, Olivier; Awada, Houssein; Castelein, Gilles

    2007-03-01

    Adhesive properties of a polymer surface results from the complex contribution of surface chemistry and activation of sliding and dissipating mechanisms within the polymer surface layer. The purpose of this study is to dissociate the different contributions (chemical and mechanical) included in an AFM force-distance curve in order to establish relationships between the surface viscoelastic properties of the polymer, the surface chemistry of functionalized polymer surfaces and the adhesive forces, as determined by C-AFM experiments. Indeed we are interested in the measurements of local attractive or adhesive forces in AFM contact mode, of controlled chemical and mechanical model substrates. In order to investigate the interplay between mechanical or viscoelastic mechanisms and surface chemistry during the tip - polymer contact, we achieved force measurements on model PDMS polymer networks, whose surfaces are chemically controlled with the same functional groups as before (silicon substrates). On the basis of AFM nano-indentation experiments, surface Young moduli have been determined. The results show that the viscoelastic contribution is dominating in the adhesion force measurement. We propose an original model, which express the local adhesion force to the energy dissipated within the contact and the surface properties of the material (thermodynamic work of adhesion). Moreover we show that the dissipation function is related to Mc, the mass between crosslinks of the network.

  14. Microstructure and surface chemistry of amorphous alloys important to their friction and wear behavior

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Buckley, D. H.

    1983-01-01

    An investigation was conducted to examine the microstructure and surface chemistry of amorphous alloys, and their effects on tribological behavior. The results indicate that the surface oxide layers present on amorphous alloys are effective in providing low friction and a protective film against wear in air. Clustering and crystallization in amorphous alloys can be enhanced as a result of plastic flow during the sliding process at a low sliding velocity, at room temperature. Clusters or crystallines with sizes to 150 nm and a diffused honeycomb-shaped structure are produced on the wear surface. Temperature effects lead to drastic changes in surface chemistry and friction behavior of the alloys at temperatures to 750 C. Contaminants can come from the bulk of the alloys to the surface upon heating and impart to the surface oxides at 350 C and boron nitride above 500 C. The oxides increase friction while the boron nitride reduces friction drastically in vacuum.

  15. Cell preparation methods influence Escherichia coli D21g surface chemistry and transport in saturated sand

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The effect of cell preparation methods on the surface chemistry and deposition of Escherichia coli D21g was investigated over a range of ionic strength conditions. The cell preparation methods, which were considered, included filtration and centrifugation (at various speeds and for different duratio...

  16. Influence of surface structure and chemistry on water droplet splashing.

    PubMed

    Koch, Kerstin; Grichnik, Roland

    2016-08-01

    Water droplet splashing and aerosolization play a role in human hygiene and health systems as well as in crop culturing. Prevention or reduction of splashing can prevent transmission of diseases between animals and plants and keep technical systems such as pipe or bottling systems free of contamination. This study demonstrates to what extent the surface chemistry and structures influence the water droplet splashing behaviour. Smooth surfaces and structured replicas of Calathea zebrina (Sims) Lindl. leaves were produced. Modification of their wettability was done by coating with hydrophobizing and hydrophilizing agents. Their wetting was characterized by contact angle measurement and splashing behaviour was observed with a high-speed video camera. Hydrophobic and superhydrophilic surfaces generally showed fewer tendencies to splash than hydrophobic ones. Structuring amplified the underlying behaviour of the surface chemistries, increasing hydrophobic surfaces' tendency to splash and decreasing splash on hydrophilic surfaces by quickly transporting water off the impact point by capillary forces. The non-porous surface structures found in C. zebrina could easily be applied to technical products such as plastic foils or mats and coated with hydrophilizing agents to suppress splash in areas of increased hygiene requirements or wherever pooling of liquids is not desirable.This article is part of the themed issue 'Bioinspired hierarchically structured surfaces for green science'. PMID:27354737

  17. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors

    PubMed Central

    Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T.; Evoy, Stephane

    2016-01-01

    Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors. PMID:26985910

  18. Ferroelectrics: A pathway to switchable surface chemistry and catalysis

    NASA Astrophysics Data System (ADS)

    Kakekhani, Arvin; Ismail-Beigi, Sohrab; Altman, Eric I.

    2016-08-01

    It has been known for more than six decades that ferroelectricity can affect a material's surface physics and chemistry thereby potentially enhancing its catalytic properties. Ferroelectrics are a class of materials with a switchable electrical polarization that can affect surface stoichiometry and electronic structure and thus adsorption energies and modes; e.g., molecular versus dissociative. Therefore, ferroelectrics may be utilized to achieve switchable surface chemistry whereby surface properties are not fixed but can be dynamically controlled by, for example, applying an external electric field or modulating the temperature. Several important examples of applications of ferroelectric and polar materials in photocatalysis and heterogeneous catalysis are discussed. In photocatalysis, the polarization direction can control band bending at water/ferroelectric and ferroelectric/semiconductor interfaces, thereby facilitating charge separation and transfer to the electrolyte and enhancing photocatalytic activity. For gas-surface interactions, available results suggest that using ferroelectrics to support catalytically active transition metals and oxides is another way to enhance catalytic activity. Finally, the possibility of incorporating ferroelectric switching into the catalytic cycle itself is described. In this scenario, a dynamic collaboration of two polarization states can be used to drive reactions that have been historically challenging to achieve on surfaces with fixed chemical properties (e.g., direct NOx decomposition and the selective partial oxidation of methane). These predictions show that dynamic modulation of the polarization can help overcome some of the fundamental limitations on catalytic activity imposed by the Sabatier principle.

  19. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors.

    PubMed

    Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T; Evoy, Stephane

    2016-03-01

    Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors. PMID:26985910

  20. The Role of Surface Chemistry in Filter Feeding by Zooplankton

    NASA Astrophysics Data System (ADS)

    Gerritsen, Jeroen; Porter, Karen G.

    1982-06-01

    Surface chemistry of both particles and animals is important in filter feeding at low Reynolds number. Daphnia magna, fed mixtures of three sizes of polystyrene particles, retained particles that were smaller than the mesh size of the animals (1.0 micrometer) at greater efficiencies than predicted by a sieving model. Retention efficiency of the smallest particles (0.5 micrometer) was increased when negative surface charge on the particles was neutralized, and retention was decreased when a nonionic surfactant was added to reduce wettability.

  1. QM/MM investigations of organic chemistry oriented questions.

    PubMed

    Schmidt, Thomas C; Paasche, Alexander; Grebner, Christoph; Ansorg, Kay; Becker, Johannes; Lee, Wook; Engels, Bernd

    2014-01-01

    About 35 years after its first suggestion, QM/MM became the standard theoretical approach to investigate enzymatic structures and processes. The success is due to the ability of QM/MM to provide an accurate atomistic picture of enzymes and related processes. This picture can even be turned into a movie if nuclei-dynamics is taken into account to describe enzymatic processes. In the field of organic chemistry, QM/MM methods are used to a much lesser extent although almost all relevant processes happen in condensed matter or are influenced by complicated interactions between substrate and catalyst. There is less importance for theoretical organic chemistry since the influence of nonpolar solvents is rather weak and the effect of polar solvents can often be accurately described by continuum approaches. Catalytic processes (homogeneous and heterogeneous) can often be reduced to truncated model systems, which are so small that pure quantum-mechanical approaches can be employed. However, since QM/MM becomes more and more efficient due to the success in software and hardware developments, it is more and more used in theoretical organic chemistry to study effects which result from the molecular nature of the environment. It is shown by many examples discussed in this review that the influence can be tremendous, even for nonpolar reactions. The importance of environmental effects in theoretical spectroscopy was already known. Due to its benefits, QM/MM can be expected to experience ongoing growth for the next decade.In the present chapter we give an overview of QM/MM developments and their importance in theoretical organic chemistry, and review applications which give impressions of the possibilities and the importance of the relevant effects. Since there is already a bunch of excellent reviews dealing with QM/MM, we will discuss fundamental ingredients and developments of QM/MM very briefly with a focus on very recent progress. For the applications we follow a similar

  2. Effects of surface chemistry on hot corrosion life: Overview

    NASA Technical Reports Server (NTRS)

    Merutka, J.

    1982-01-01

    This program concentrates on analyzing a limited number of hot corroded components from the field and the carrying out of a series of controlled laboratory experiments to establish the effects of oxide scale and coating chemistry on hot corrosion life. This is to be determined principally from the length of the incubation period, the investigation of the mechanisms of hot corrosion attack, and the fitting of the data generated from the test exposure experiments to an empirical life prediction model.

  3. Grain Surface Chemistry and the Composition of Interstellar Ices

    NASA Technical Reports Server (NTRS)

    Tielens, A. G. G. M.

    2006-01-01

    Submicron sized dust grains are an important component of the interstellar medium. In particular they provide surface where active chemistry can take place. At the low temperatures (-10 K) of the interstellar medium, colliding gas phase species will stick, diffuse, react, and form an icy mantle on these dust grains. This talk will review the principles of grain surface chemistry and delineate important grain surface routes, focusing on reactions involving H, D, and O among each other and with molecules such as CO. Interstellar ice mantles can be studied through the fundamental vibrations of molecular species in the mid-infrared spectra of sources embedded in or located behind dense molecular clouds. Analysis of this type of data has provided a complex view of the composition of these ices and the processes involved. Specifically, besides grain surface chemistry, the composition of interstellar ices is also affected by thermal processing due to nearby newly formed stars. This leads to segregation between different ice components as well as outgassing. The latter results in the formation of a so-called Hot Core region with a gas phase composition dominated by evaporated mantle species. Studies of such regions provide thus a different view on the ice composition and the chemical processes involved. Interstellar ices can also be processed by FUV photons and high energy cosmic ray ions. Cosmic ray processing likely dominates the return of accreted species to the gas phase where further gas phase reactions can take place. These different chemical routes towards molecular complexity in molecular clouds and particularly regions of star formation will be discussed.

  4. A Chamber Investigation of Nitric Acid-Soot Aerosol Chemistry at 298 K

    SciTech Connect

    Disselkamp, Robert S.; Carpenter, Michael A.; Cowin, James P.

    2000-10-02

    Long-pathlength infrared absorption spectroscopy was used to investigate nitric acid-soot aerosol chemistry at 298 K and 0.5 % relative humidity. Experiments were performed by introducing nitric acid vapor (PHNO3~3 Pa, Ptotal~40 kPa) into a teflon-coated chamber and initiating acquisition of infrared spectra at 3 minute time intervals. After 36 minutes of data collection, soot powder was rapidly expanded into nitric acid contained in the chamber to generate a soot-HNO3 aerosol. Infrared spectra collected before, and after, soot introduction to the chamber were used to characterize chamber wall reaction processes and soot aerosol chemistry, respectively. Three soot types were investigated (Degussa FW2, Cabot Monarch 1000, and crystalline graphite), each yielding similar chemistry. Upon soot introduction to the chamber both HNO3 uptake and NO2 production occurred, with the molar ratio of HNO3 uptake to NO2 production varying from 1.2 to 2.9 for the three soot types studied. Unreacted HNO3 was present at the conclusion of each of the aerosol experiments, indicating incomplete conversion of HNO3 into NO2. This observation suggested that "active" sites at the soot surface responsible for the reduction of HNO3 are not regenerated (i.e., formed) in the reaction process. In essence, a titration occurred between these active sites and HNO3. The NO2 concentrations produced, the soot mass concentrations used, and the BET measured specific surface area of the powders allowed computation of the surface density of active sites of ~4.0x10-18 m2/active site (describing all three powders studied). This is the first reported measurement of surface density of active sites for nitric acid chemistry on soot. Since atmospheric heterogeneous reactions that exhibit surface deactivation may, in principle, affect trace gas concentration, we perform an assessment in this regard.

  5. Surface Chemistry and Water Dispersability of Carbon Black Materials

    SciTech Connect

    Contescu, Cristian I; Baker, Frederick S; Burchell, Timothy D

    2006-01-01

    Formulation of water-stable carbon black dispersions is a double-sided task, which requires selection of a proper dispersing agents and matching it with the properties of a specific carbon black. Among other properties that affect water dispersability of carbon blacks (particle size, surface area, and aggregate structure), surface chemistry plays a prime-order role. We have characterized physical and chemical properties of several carbon black materials, and correlated them with the stability of dispersions formed with ionic and non-ionic surfactants. In particular, chemical characterization of surface functional groups on carbon blacks based on potentiometric titration measurements (pKa spectra) provided a comprehensive picture of pH effects on dispersion stability. The results obtained were complemented by information from physical characterization methods, such as XPS and FTIR. The selection of a suitable dispersing agent able to withstand large pH variations will be discussed.

  6. Role of surface chemistry in the ignition of pyrotechnic materials

    SciTech Connect

    Moddeman, W.E.; Collins, L.W.; Wang, P.S.; Wittberg, T.N.

    1980-01-01

    The surface chemistry of fuels has been shown to play a key role in the ignition of pyrotechnic materials. Since these fuels are usually easily oxidized, the surface must provide protection from undesirable oxidation processes such as pyrophoricity while permitting the desirable pyrotechnic reactions. For both titanium and aluminum, these criteria are met by metal oxide coatings which control the accessibility of the fuel to the oxidizer. However, we have shown that the mechanisms through which this control is exerted are substantially different. The ignition of titanium based pyrotechnics seems to be kinetically controlled by the dissolution of the titanium oxide coating to generate a reactive surface for the pyrotechnic reaction. Reactions of aluminum seem to depend on diffusion of aluminum (or oxygen at higher temperatures) through its oxide coating. It was also shown that the accessibility of aluminum can be improved by alloying.

  7. Isothermal microcalorimetry to investigate non specific interactions in biophysical chemistry.

    PubMed

    Ball, Vincent; Maechling, Clarisse

    2009-10-01

    Isothermal titration microcalorimetry (ITC) is mostly used to investigate the thermodynamics of "specific" host-guest interactions in biology as well as in supramolecular chemistry. The aim of this review is to demonstrate that ITC can also provide useful information about non-specific interactions, like electrostatic or hydrophobic interactions. More attention will be given in the use of ITC to investigate polyelectrolyte-polyelectrolyte (in particular DNA-polycation), polyelectrolyte-protein as well as protein-lipid interactions. We will emphasize that in most cases these "non specific" interactions, as their definition will indicate, are favoured or even driven by an increase in the entropy of the system. The origin of this entropy increase will be discussed for some particular systems. We will also show that in many cases entropy-enthalpy compensation phenomena occur. PMID:20111693

  8. Isothermal Microcalorimetry to Investigate Non Specific Interactions in Biophysical Chemistry

    PubMed Central

    Ball, Vincent; Maechling, Clarisse

    2009-01-01

    Isothermal titration microcalorimetry (ITC) is mostly used to investigate the thermodynamics of “specific” host-guest interactions in biology as well as in supramolecular chemistry. The aim of this review is to demonstrate that ITC can also provide useful information about non-specific interactions, like electrostatic or hydrophobic interactions. More attention will be given in the use of ITC to investigate polyelectrolyte-polyelectrolyte (in particular DNA-polycation), polyelectrolyte-protein as well as protein-lipid interactions. We will emphasize that in most cases these “non specific” interactions, as their definition will indicate, are favoured or even driven by an increase in the entropy of the system. The origin of this entropy increase will be discussed for some particular systems. We will also show that in many cases entropy-enthalpy compensation phenomena occur. PMID:20111693

  9. Saltwater icephobicity: Influence of surface chemistry on saltwater icing

    PubMed Central

    Carpenter, Katherine; Bahadur, Vaibhav

    2015-01-01

    Most studies on icephobicity focus on ice formation with pure water. This manuscript presents studies to understand the influence of surfaces on saltwater ice nucleation and propagation. Experiments are conducted to quantify the influence of surface chemistry on saltwater ice nucleation and to understand the utility of superhydrophobic surfaces for saltwater icephobicity. These experiments are conducted with pure water and two sodium chloride solutions, which represent the salinity of seawater and briny produced water. It is seen that the presence of salt slows down the ice front propagation velocity significantly. Saltwater droplet impact dynamics on superhydrophobic surfaces are also different from pure water. Saltwater droplets retract more and a greater fraction of impacting liquid is repelled from the superhydrophobic surface. It is seen that the greater bounciness of saltwater droplets is a result of slower ice nucleation propagation kinetics. These experiments indicate that superhydrophobic surfaces will have better resistance to impact icing with saltwater than pure water and can remain useful at temperatures as low as −40 °C. Overall, this work is a starting point for further studies on heterogeneous nucleation in saltwater and serves as a bridge between the widely studied freshwater icephobic surfaces and saltwater-related applications. PMID:26626958

  10. Saltwater icephobicity: Influence of surface chemistry on saltwater icing

    NASA Astrophysics Data System (ADS)

    Carpenter, Katherine; Bahadur, Vaibhav

    2015-12-01

    Most studies on icephobicity focus on ice formation with pure water. This manuscript presents studies to understand the influence of surfaces on saltwater ice nucleation and propagation. Experiments are conducted to quantify the influence of surface chemistry on saltwater ice nucleation and to understand the utility of superhydrophobic surfaces for saltwater icephobicity. These experiments are conducted with pure water and two sodium chloride solutions, which represent the salinity of seawater and briny produced water. It is seen that the presence of salt slows down the ice front propagation velocity significantly. Saltwater droplet impact dynamics on superhydrophobic surfaces are also different from pure water. Saltwater droplets retract more and a greater fraction of impacting liquid is repelled from the superhydrophobic surface. It is seen that the greater bounciness of saltwater droplets is a result of slower ice nucleation propagation kinetics. These experiments indicate that superhydrophobic surfaces will have better resistance to impact icing with saltwater than pure water and can remain useful at temperatures as low as -40 °C. Overall, this work is a starting point for further studies on heterogeneous nucleation in saltwater and serves as a bridge between the widely studied freshwater icephobic surfaces and saltwater-related applications.

  11. Bacterial response to different surface chemistries fabricated by plasma polymerization on electrospun nanofibers.

    PubMed

    Abrigo, Martina; Kingshott, Peter; McArthur, Sally L

    2015-01-01

    Control over bacterial attachment and proliferation onto nanofibrous materials constitutes a major challenge for a variety of applications, including filtration membranes, protective clothing, wound dressings, and tissue engineering scaffolds. To develop effective devices, the interactions that occur between bacteria and nanofibers with different morphological and physicochemical properties need to be investigated. This paper explores the influence of fiber surface chemistry on bacterial behavior. Different chemical functionalities were generated on the surface of electrospun polystyrene nanofibers through plasma polymerization of four monomers (acrylic acid, allylamine, 1,7-octadiene, and 1,8-cineole). The interactions of Escherichia coli with the surface modified fibers were investigated through a combination of scanning electron microscopy and confocal laser scanning microscopy. Fiber wettability, surface charge, and chemistry were found to affect the ability of bacterial cells to attach and proliferate throughout the nanofiber meshes. The highest proportion of viable cells attachment occurred on the hydrophilic amine rich coating, followed by the hydrophobic octadiene. The acrylic acid coating rich in carboxyl groups showed a significantly lower attraction of bacterial cells. The 1,8-cineole retained the antibacterial activity of the monomer, resulting with a high proportion of dead isolated cells attached onto the fibers. Results showed that the surface chemistry properties of nanofibrous membranes can be strategically tuned to control bacterial behavior. PMID:26251319

  12. Investigating Multireference Character and Correlation in Quantum Chemistry.

    PubMed

    Coe, J P; Paterson, M J

    2015-09-01

    We review a range of multireference diagnostics for quantum chemistry and discuss them in terms of choices of the molecular orbitals. We show how an approach1 of P.-O. Löwdin can also be viewed as quantifying the electron correlation via the spatial entanglement relative to a single determinant. We consider three example systems from quantum chemistry that exhibit three different combinations of multireference character and correlation: not strongly multireference and not strongly correlated, strongly multireference but not strongly correlated, and strongly multireference together with strong correlation. We find that a multireference measure (MR) does not change substantially with the cutoff used for a Monte Carlo configuration interaction calculation and investigate the effect of using natural orbitals. We see that a coupled-cluster singles and doubles diagnostic and a density-functional theory diagnostic give a correct general prediction of the multireference character for these systems. We also look at the issue of multireference character for a collection of noninteracting hydrogen molecules and the effect of basis size on the multireference character of a stretched hydrogen molecule. PMID:26575914

  13. The surface chemistry of GaAs atomic layer epitaxy

    SciTech Connect

    Creighton, J.R.; Banse, B.A.

    1991-01-01

    In this paper we review three proposed mechanisms for GaAs ALE and review or present data support or contradiction of these mechanisms. Surface chemistry results clearly demonstrated that TMGa irreversibly chemisorbs on the Ga-rich GaAs(100) surface. The reactive sticking coefficient (RSC) of TMGa on the adsorbate-free Ga-rich GaAs(100) surface was measured to be {approximately}0.5, conclusively demonstrating that the selective adsorption'' mechanism of ALE is not valid. We describe kinetic evidence for methyl radical desorption in support of the adsorbate inhibition'' mechanism. The methyl radical desorption rates determined by temperature programmed desorption (TPD) demonstrate that desorption is at least a factor of {approximately}10 faster from the As-rich c(2 {times} 8)/(2 {times} 4) surface than from the Ga-rich surface. It is disparity in CH{sub 3} desorption rates between the As-rich and Ga-rich surfaces that is largely responsible for GaAs ALE behavior. A gallium alkyl radical (e.g. MMGa) is also observed during TPD and molecular beam experiments, in partial support of the flux balance'' mechanism. Stoichiometry issues of ALE are also discussed. We have discovered that arsine exposures typical of atmospheric pressure and reduced pressure ALE lead to As coverages {ge} 1 ML, which provides the likely solution to the stoichiometry question regarding the arsine cycle. 32 refs., 6 figs.

  14. Gridded global surface ozone metrics for atmospheric chemistry model evaluation

    NASA Astrophysics Data System (ADS)

    Sofen, E. D.; Bowdalo, D.; Evans, M. J.; Apadula, F.; Bonasoni, P.; Cupeiro, M.; Ellul, R.; Galbally, I. E.; Girgzdiene, R.; Luppo, S.; Mimouni, M.; Nahas, A. C.; Saliba, M.; Tørseth, K.

    2016-02-01

    The concentration of ozone at the Earth's surface is measured at many locations across the globe for the purposes of air quality monitoring and atmospheric chemistry research. We have brought together all publicly available surface ozone observations from online databases from the modern era to build a consistent data set for the evaluation of chemical transport and chemistry-climate (Earth System) models for projects such as the Chemistry-Climate Model Initiative and Aer-Chem-MIP. From a total data set of approximately 6600 sites and 500 million hourly observations from 1971-2015, approximately 2200 sites and 200 million hourly observations pass screening as high-quality sites in regionally representative locations that are appropriate for use in global model evaluation. There is generally good data volume since the start of air quality monitoring networks in 1990 through 2013. Ozone observations are biased heavily toward North America and Europe with sparse coverage over the rest of the globe. This data set is made available for the purposes of model evaluation as a set of gridded metrics intended to describe the distribution of ozone concentrations on monthly and annual timescales. Metrics include the moments of the distribution, percentiles, maximum daily 8-hour average (MDA8), sum of means over 35 ppb (daily maximum 8-h; SOMO35), accumulated ozone exposure above a threshold of 40 ppbv (AOT40), and metrics related to air quality regulatory thresholds. Gridded data sets are stored as netCDF-4 files and are available to download from the British Atmospheric Data Centre (doi: 10.5285/08fbe63d-fa6d-4a7a-b952-5932e3ab0452). We provide recommendations to the ozone measurement community regarding improving metadata reporting to simplify ongoing and future efforts in working with ozone data from disparate networks in a consistent manner.

  15. Gridded global surface ozone metrics for atmospheric chemistry model evaluation

    NASA Astrophysics Data System (ADS)

    Sofen, E. D.; Bowdalo, D.; Evans, M. J.; Apadula, F.; Bonasoni, P.; Cupeiro, M.; Ellul, R.; Galbally, I. E.; Girgzdiene, R.; Luppo, S.; Mimouni, M.; Nahas, A. C.; Saliba, M.; Tørseth, K.; Wmo Gaw, Epa Aqs, Epa Castnet, Capmon, Naps, Airbase, Emep, Eanet Ozone Datasets, All Other Contributors To

    2015-07-01

    The concentration of ozone at the Earth's surface is measured at many locations across the globe for the purposes of air quality monitoring and atmospheric chemistry research. We have brought together all publicly available surface ozone observations from online databases from the modern era to build a consistent dataset for the evaluation of chemical transport and chemistry-climate (Earth System) models for projects such as the Chemistry-Climate Model Initiative and Aer-Chem-MIP. From a total dataset of approximately 6600 sites and 500 million hourly observations from 1971-2015, approximately 2200 sites and 200 million hourly observations pass screening as high-quality sites in regional background locations that are appropriate for use in global model evaluation. There is generally good data volume since the start of air quality monitoring networks in 1990 through 2013. Ozone observations are biased heavily toward North America and Europe with sparse coverage over the rest of the globe. This dataset is made available for the purposes of model evaluation as a set of gridded metrics intended to describe the distribution of ozone concentrations on monthly and annual timescales. Metrics include the moments of the distribution, percentiles, maximum daily eight-hour average (MDA8), SOMO35, AOT40, and metrics related to air quality regulatory thresholds. Gridded datasets are stored as netCDF-4 files and are available to download from the British Atmospheric Data Centre (doi:10.5285/08fbe63d-fa6d-4a7a-b952-5932e3ab0452). We provide recommendations to the ozone measurement community regarding improving metadata reporting to simplify ongoing and future efforts in working with ozone data from disparate networks in a consistent manner.

  16. Quantifying the surface chemistry of 3D matrices in situ

    NASA Astrophysics Data System (ADS)

    Tzeranis, Dimitrios S.; So, Peter T. C.; Yannas, Ioannis V.

    2014-03-01

    Despite the major role of the matrix (the insoluble environment around cells) in physiology and pathology, there are very few and limited methods that can quantify the surface chemistry of a 3D matrix such as a biomaterial or tissue ECM. This study describes a novel optical-based methodology that can quantify the surface chemistry (density of adhesion ligands for particular cell adhesion receptors) of a matrix in situ. The methodology utilizes fluorescent analogs (markers) of the receptor of interest and a series of binding assays, where the amount of bound markers on the matrix is quantified via spectral multi-photon imaging. The study provides preliminary results for the quantification of the ligands for the two major collagen-binding integrins (α1β1, α2β1) in porous collagen scaffolds that have been shown to be able to induce maximum regeneration in transected peripheral nerves. The developed methodology opens the way for quantitative descriptions of the insoluble microenvironment of cells in physiology and pathology, and for integrating the matrix in quantitative models of cell signaling. α

  17. The hydrochemistry of glacial Ebba River (Petunia Bay, Central Spitsbergen): Groundwater influence on surface water chemistry

    NASA Astrophysics Data System (ADS)

    Dragon, Krzysztof; Marciniak, Marek; Szpikowski, Józef; Szpikowska, Grażyna; Wawrzyniak, Tomasz

    2015-10-01

    The article presents the investigation of surface water chemistry changes of the glacial Ebba River (Central Spitsbergen) during three melting seasons of 2008, 2009 and 2010. The twice daily water chemistry analyses allow recognition of the surface water chemistry differentiation. The surface water chemistry changes are related to the river discharge and changes in the influence of different water balance components during each melting season. One of the most important process that influence river water component concentration increase is groundwater inflow from active layer occurring on the valley area. The significance of this process is the most important at the end of the melting season when temperatures below 0 °C occur on glaciers (resulting in a slowdown of melting of ice and snow and a smaller recharge of the river by the water from the glaciers) while the flow of groundwater is still active, causing a relatively higher contribution of groundwater to the total river discharge. The findings presented in this paper show that groundwater contribution to the total polar river water balance is more important than previously thought and its recognition allow a better understanding of the hydrological processes occurring in a polar environment.

  18. Surface chemistry, morphological analysis and properties of cellulose nanocrystals with gradiented sulfation degrees.

    PubMed

    Lin, Ning; Dufresne, Alain

    2014-05-21

    The process of sulfuric acid-hydrolysis of cellulose fibers for the preparation of cellulose nanocrystals (CNs) includes an esterification reaction between acid and cellulose molecules, which induces the covalent coupling of sulfate groups on the surface of prepared CNs. Negatively charged sulfate groups play an important role in both surface chemistry and physical properties of CNs. This study explored the strategy of introducing a gradient of sulfate groups on the surface of CNs, and further investigated the effect of the sulfation degree on surface chemistry, morphology, dimensions, and physical properties of different CN samples. Based on the discussion of their surface chemistry, the selection of different cross-section models was reported to significantly affect the calculation of the degree of substitution of sulfate groups on CNs. A new ellipsoid cross-section model was proposed on the basis of AFM observations. The effect of sulfate groups on crystal properties and thermal stability was discussed and validated, and the birefringence behavior of nanocrystal suspensions was observed. PMID:24706023

  19. Early osseointegration driven by the surface chemistry and wettability of dental implants

    PubMed Central

    SARTORETTO, Suelen Cristina; ALVES, Adriana Terezinha Neves Novellino; RESENDE, Rodrigo Figueiredo Britto; CALASANS-MAIA, José; GRANJEIRO, José Mauro; CALASANS-MAIA, Mônica Diuana

    2015-01-01

    Objective The objective of this study was to investigate the impact of two different commercially available dental implants on osseointegration. The surfaces were sandblasting and acid etching (Group 1) and sandblasting and acid etching, then maintained in an isotonic solution of 0.9% sodium chloride (Group 2). Material and Methods X-ray photoelectron spectroscopy (XPS) was employed for surface chemistry analysis. Surface morphology and topography was investigated by scanning electron microscopy (SEM) and confocal microscopy (CM), respectively. Contact angle analysis (CAA) was employed for wetting evaluation. Bone-implant-contact (BIC) and bone area fraction occupied (BAFO) analysis were performed on thin sections (30 μm) 14 and 28 days after the installation of 10 implants from each group (n=20) in rabbits’ tibias. Statistical analysis was performed by ANOVA at the 95% level of significance considering implantation time and implant surface as independent variables. Results Group 2 showed 3-fold less carbon on the surface and a markedly enhanced hydrophilicity compared to Group 1 but a similar surface roughness (p>0.05). BIC and BAFO levels in Group 2 at 14 days were similar to those in Group 1 at 28 days. After 28 days of installation, BIC and BAFO measurements of Group 2 were approximately 1.5-fold greater than in Group 1 (p<0.05). Conclusion The surface chemistry and wettability implants of Group 2 accelerate osseointegration and increase the area of the bone-to-implant interface when compared to those of Group 1. PMID:26221922

  20. Surface chemistry of CO2 - Adsorption of carbon dioxide on clean surfaces at ultrahigh vacuum

    NASA Astrophysics Data System (ADS)

    Burghaus, Uwe

    2014-05-01

    Carbon dioxide chemistry has attracted significant interest in recent years. Although the field is diverse, a current and more comprehensive review of the surface science literature may be of interest for a variety of communities since environmental chemistry, energy technology, materials science, catalysis, and nanocatalysis are certainly affected by gas-surface properties. The review describes surface phenomena and characterization strategies highlighting similarities and differences, instead of providing only a list of system-specific information. The various systems are roughly distinguished as those that clearly form carbonates and those that merely physisorb CO2 at ultra-high vacuum conditions. Nevertheless, extended sections about specific systems including rarely studied surfaces and unusual materials are included, making this review also useful as a reference.

  1. Surface Enzyme Chemistries for Ultrasensitive Microarray Biosensing with SPR Imaging.

    PubMed

    Fasoli, Jennifer B; Corn, Robert M

    2015-09-01

    The sensitivity and selectivity of surface plasmon resonance imaging (SPRI) biosensing with nucleic acid microarrays can be greatly enhanced by exploiting various nucleic acid ligases, nucleases, and polymerases that manipulate the surface-bound DNA and RNA. We describe here various examples from each of these different classes of surface enzyme chemistries that have been incorporated into novel detection strategies that either drastically enhance the sensitivity of or create uniquely selective methods for the SPRI biosensing of proteins and nucleic acids. A dual-element generator-detector microarray approach that couples a bioaffinity adsorption event on one microarray element to nanoparticle-enhanced SPRI measurements of nucleic acid hybridization adsorption on a different microarray element is used to quantitatively detect DNA, RNA, and proteins at femtomolar concentrations. Additionally, this dual-element format can be combined with the transcription and translation of RNA from surface-bound double-stranded DNA (dsDNA) templates for the on-chip multiplexed biosynthesis of aptamer and protein microarrays in a microfluidic format; these microarrays can be immediately used for real-time SPRI bioaffinity sensing measurements. PMID:25641598

  2. Surface Enzyme Chemistries for Ultrasensitive Microarray Biosensing with SPR Imaging

    PubMed Central

    2015-01-01

    The sensitivity and selectivity of surface plasmon resonance imaging (SPRI) biosensing with nucleic acid microarrays can be greatly enhanced by exploiting various nucleic acid ligases, nucleases, and polymerases that manipulate the surface-bound DNA and RNA. We describe here various examples from each of these different classes of surface enzyme chemistries that have been incorporated into novel detection strategies that either drastically enhance the sensitivity of or create uniquely selective methods for the SPRI biosensing of proteins and nucleic acids. A dual-element generator–detector microarray approach that couples a bioaffinity adsorption event on one microarray element to nanoparticle-enhanced SPRI measurements of nucleic acid hybridization adsorption on a different microarray element is used to quantitatively detect DNA, RNA, and proteins at femtomolar concentrations. Additionally, this dual-element format can be combined with the transcription and translation of RNA from surface-bound double-stranded DNA (dsDNA) templates for the on-chip multiplexed biosynthesis of aptamer and protein microarrays in a microfluidic format; these microarrays can be immediately used for real-time SPRI bioaffinity sensing measurements. PMID:25641598

  3. Effects of wood fiber surface chemistry on strength of wood-plastic composites

    NASA Astrophysics Data System (ADS)

    Migneault, Sébastien; Koubaa, Ahmed; Perré, Patrick; Riedl, Bernard

    2015-07-01

    Because wood-plastic composites (WPC) strength relies on fiber-matrix interaction at fiber surface, it is likely that fiber surface chemistry plays an important role in WPC strength development. The objective of the present study is to investigate the relationships between fiber surface chemical characteristics and WPC mechanical properties. Different fibers were selected and characterized for surface chemical characteristics using X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (FTIR). WPC samples were manufactured at 40% fiber content and with six different fibers. High density polyethylene was used as matrix and maleated polyethylene (MAPE) was used as compatibility agent. WPC samples were tested for mechanical properties and fiber-matrix interface was observed with scanning electron microscope. It was found WPC strength decreases as the amount of unoxidized carbon (assigned to lignin and extractives) measured with XPS on fiber surface increases. In the opposite case, WPC strength increases with increasing level of oxidized carbon (assigned to carbohydrates) on fiber surface. The same conclusions were found with FTIR where WPC strength decreases as lignin peaks intensity increases. Esterification reaction of fibers with MAPE occurs on polar sites of carbohydrates, such as hydroxyls (Osbnd H). Thus, fibers with carbohydrates-rich surface, such as cellulose pulp, produced stronger WPC samples. Other factors such as mechanical interlocking and fiber morphology interfered with the effects of fiber surface chemistry.

  4. Genotoxicity of Copper Oxide Nanoparticles with Different Surface Chemistry on Rat Bone Marrow Mesenchymal Stem Cells.

    PubMed

    Zhang, Wenjing; Jiang, Pengfei; Chen, Wei; Zheng, Botuo; Mao, Zhengwei; Antipov, Alexei; Correia, Manuel; Larsen, Erik H; Gao, Changyou

    2016-06-01

    The surface chemistry of nanoparticles (NPs) is one of the critical factors determining their cellular responses. In this study, the cytotoxicity and genotoxicity of copper oxide (CuO) NPs with a similar size but different surface chemistry to rat bone marrow mesenchymal stem cells (MSCs) were investigated. The morphology, size and surface charge of four types of CuO NPs, i.e., CuO-core, CuO-COOH, CuO-NH2 and CuO-PEG NPs, were characterized by TEM, dynamic light scattering (DLS) and zeta-potential measurement, respectively. All of the four CuO NPs had a negative surface charge around -10 mV and showed a similar tendency to form agglomerates with a size of -200 nm in cell culture environment. The cytotoxicity of CuO NPs to MSCs at various concentrations and incubation periods were firstly evaluated. The CuO NPs showed dose-dependent and time-dependent toxicity to MSCs, and their surface chemistry had influence on the toxicity to some extent too. The intracellular reactive oxygen species (ROS) level of MSCs was then quantified. Finally, the genotoxicity of the CuO NPs was studied by comet assay. The results suggest that the genotoxicity of CuO NPs was mainly dependent on NPs concentration, and was only slightly influenced by their surface chemistry. The osteogenic and adipogenic differentiation abilities of the MSCs exposed to different CuO NPs were studied by Alizarin Res S and Oil Red O staining. The preliminary results showed that the exposure to 10 μg/mL CuO NPs will, not lead to significant impact on the differentiation potential of the MSCs. PMID:27427588

  5. What's on the Surface? Physics and Chemistry of Delta-Doped Surfaces

    NASA Technical Reports Server (NTRS)

    Hoenk, Michael

    2011-01-01

    Outline of presentation: 1. Detector surfaces and the problem of stability 2. Delta-doped detectors 3. Physics of Delta-doped Silicon 4. Chemistry of the Si-SiO2 Interface 5. Physics and Chemistry of Delta-doped Surfaces a. Compensation b. Inversion c. Quantum exclusion. Conclusions: 1. Quantum confinement of electrons and holes dominates the behavior of delta-doped surfaces. 2. Stability of delta-doped detectors: Delta-layer creates an approx 1 eV tunnel barrier between bulk and surface. 3. At high surface charge densities, Tamm-Shockley states form at the surface. 4. Surface passivation by quantum exclusion: Near-surface delta-layer suppresses T-S trapping of minority carriers. 5. The Si-SiO2 interface compensates the surface 6. For delta-layers at intermediate depth, surface inversion layer forms 7. Density of Si-SiO2 interface charge can be extremely high (>10(exp 14)/sq cm)

  6. Correlation between surface chemistry and ion energy dependence of the etch yield in multicomponent oxides etching

    SciTech Connect

    Berube, P.-M.; Poirier, J.-S.; Margot, J.; Stafford, L.; Ndione, P. F.; Chaker, M.; Morandotti, R.

    2009-09-15

    The influence of surface chemistry in plasma etching of multicomponent oxides was investigated through measurements of the ion energy dependence of the etch yield. Using pulsed-laser-deposited Ca{sub x}Ba{sub (1-x)}Nb{sub 2}O{sub 6} (CBN) and SrTiO{sub 3} thin films as examples, it was found that the etching energy threshold shifts toward values larger or smaller than the sputtering threshold depending on whether or not ion-assisted chemical etching is the dominant etching pathway and whether surface chemistry is enhancing or inhibiting desorption of the film atoms. In the case of CBN films etched in an inductively coupled Cl{sub 2} plasma, it is found that the chlorine uptake is inhibiting the etching reaction, with the desorption of nonvolatile NbCl{sub 2} and BaCl{sub 2} compounds being the rate-limiting step.

  7. Students' Written Arguments in General Chemistry Laboratory Investigations

    ERIC Educational Resources Information Center

    Choi, Aeran; Hand, Brian; Greenbowe, Thomas

    2013-01-01

    This study aimed to examine the written arguments developed by college freshman students using the Science Writing Heuristic approach in inquiry-based general chemistry laboratory classrooms and its relationships with students' achievement in chemistry courses. Fourteen freshman students participated in the first year of the study while 19…

  8. Ionic Liquids Can Permanently Modify Porous Silicon Surface Chemistry.

    PubMed

    Trivedi, Shruti; Coombs, Sidney G; Wagle, Durgesh V; Bhawawet, Nakara; Baker, Gary A; Bright, Frank V

    2016-08-01

    To develop ionic liquid/porous silicon (IL/pSi) microarrays we have contact pin-printed 20 hydrophobic and hydrophilic ionic liquids onto as-prepared, hydrogen-passivated porous silicon (ap-pSi) and then determined the individual IL spot size, shape and associated pSi surface chemistry. The results reveal that the hydrophobic ionic liquids oxidize the ap-pSi slightly. In contrast, the hydrophilic ionic liquids lead to heavily oxidized pSi (i.e., ox-pSi). The strong oxidation arises from residual water within the hydrophilic ILs that is delivered from these ILs into the ap-pSi matrix causing oxidation. This phenomenon is less of an issue in the hydrophobic ILs because their water solubility is substantially lower. PMID:27405109

  9. The impact of surface chemistry on the performance of localized solar-driven evaporation system

    PubMed Central

    Yu, Shengtao; Zhang, Yao; Duan, Haoze; Liu, Yanming; Quan, Xiaojun; Tao, Peng; Shang, Wen; Wu, Jianbo; Song, Chengyi; Deng, Tao

    2015-01-01

    This report investigates the influence of surface chemistry (or wettability) on the evaporation performance of free-standing double-layered thin film on the surface of water. Such newly developed evaporation system is composed of top plasmonic light-to-heat conversion layer and bottom porous supporting layer. Under solar light illumination, the induced plasmonic heat will be localized within the film. By modulating the wettability of such evaporation system through the control of surface chemistry, the evaporation rates are differentiated between hydrophilized and hydrophobized anodic aluminum oxide membrane-based double layered thin films. Additionally, this work demonstrated that the evaporation rate mainly depends on the wettability of bottom supporting layer rather than that of top light-to-heat conversion layer. The findings in this study not only elucidate the role of surface chemistry of each layer of such double-layered evaporation system, but also provide additional design guidelines for such localized evaporation system in applications including desalination, distillation and power generation. PMID:26337561

  10. The impact of surface chemistry on the performance of localized solar-driven evaporation system.

    PubMed

    Yu, Shengtao; Zhang, Yao; Duan, Haoze; Liu, Yanming; Quan, Xiaojun; Tao, Peng; Shang, Wen; Wu, Jianbo; Song, Chengyi; Deng, Tao

    2015-01-01

    This report investigates the influence of surface chemistry (or wettability) on the evaporation performance of free-standing double-layered thin film on the surface of water. Such newly developed evaporation system is composed of top plasmonic light-to-heat conversion layer and bottom porous supporting layer. Under solar light illumination, the induced plasmonic heat will be localized within the film. By modulating the wettability of such evaporation system through the control of surface chemistry, the evaporation rates are differentiated between hydrophilized and hydrophobized anodic aluminum oxide membrane-based double layered thin films. Additionally, this work demonstrated that the evaporation rate mainly depends on the wettability of bottom supporting layer rather than that of top light-to-heat conversion layer. The findings in this study not only elucidate the role of surface chemistry of each layer of such double-layered evaporation system, but also provide additional design guidelines for such localized evaporation system in applications including desalination, distillation and power generation. PMID:26337561

  11. The impact of surface chemistry on the performance of localized solar-driven evaporation system

    NASA Astrophysics Data System (ADS)

    Yu, Shengtao; Zhang, Yao; Duan, Haoze; Liu, Yanming; Quan, Xiaojun; Tao, Peng; Shang, Wen; Wu, Jianbo; Song, Chengyi; Deng, Tao

    2015-09-01

    This report investigates the influence of surface chemistry (or wettability) on the evaporation performance of free-standing double-layered thin film on the surface of water. Such newly developed evaporation system is composed of top plasmonic light-to-heat conversion layer and bottom porous supporting layer. Under solar light illumination, the induced plasmonic heat will be localized within the film. By modulating the wettability of such evaporation system through the control of surface chemistry, the evaporation rates are differentiated between hydrophilized and hydrophobized anodic aluminum oxide membrane-based double layered thin films. Additionally, this work demonstrated that the evaporation rate mainly depends on the wettability of bottom supporting layer rather than that of top light-to-heat conversion layer. The findings in this study not only elucidate the role of surface chemistry of each layer of such double-layered evaporation system, but also provide additional design guidelines for such localized evaporation system in applications including desalination, distillation and power generation.

  12. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Zachwieja, J.; Lagno, M.

    1992-06-24

    To better understand the surface chemical properties of coal and mineral pyrite, studies on the effect of flotation surfactants (frother and kerosene) on the degree of hydrophobicity have been conducted. The presence of either frother or kerosene enhanced the flotability of coal and mineral pyrite with a corresponding decrease in induction time over the pH range examined. Scanning electron microscopy (SEM) results indicate a correlation exists between the sample surface morphology and crystal structure and the observed hydrophobicity. As a result of the data obtained from the surface characterization studies, controlled surface oxidation was investigated as a possible pyrite rejection scheme in microbubble column flotation.

  13. Investigation of Venus Surface Properties

    NASA Technical Reports Server (NTRS)

    Ford, Peter G.

    2002-01-01

    Strong localized radar echoes have been observed at decimeter wavelengths from the highlands of Venus since the earliest radar maps were obtained over 30 years ago. These echoes are some five to ten times stronger than those from the presumably basaltic rocks seen at lower altitudes elsewhere on Venus. Observations of thermal emission from the visible disk of Venus at wavelengths corresponding to those used in the radar mapping confirm that the regions of high reflectivity also exhibit low emissivity, as expected from considerations of detailed thermodynamic balance. Two possibilities have been put forward to explain this unexpected aspect of the Venus highlands: 1) surface materials of high effective dielectric constant, probably associated with finite electrical conductivity, and 2) volume scattering associated with multiple scattering from a layer of very-low-loss material containing voids and extending down a few hundred wavelengths beneath the surface. Analogs to these two mechanisms are found elsewhere in the solar system, and each is capable of explaining the basic observations. as of the early 1990's. In 1993, however, it became possible to carry out a bistatic observation of the anomalous highland regions using the Magellan spacecraft, then in orbit about Venus. In this experiment the on-board telemetry transmitter was aimed at the planet's surface with its linear S-band polarization vector oriented at 45 deg to the spacecraft-Venus-Earth scattering plane. The pointing of the transmitting antenna was adjusted so that the spacecraft-to-illuminated-surface incidence angle equalled the Earth-to-Venus-surface incidence angle. In this way, the experiment emphasized the specular scattering component. A full Stokes-Vector analysis of the reflected signal as received on Earth was carried out as the illuminated region scanned across the highland regions of Venus. From the observed position angle of the echo, it was possible to calculate the Fresnel reflectivity of

  14. In Situ Quantification of Surface Chemistry in Porous Collagen Biomaterials.

    PubMed

    Tzeranis, Dimitrios S; Soller, Eric C; Buydash, Melissa C; So, Peter T C; Yannas, Ioannis V

    2016-03-01

    Cells inside a 3D matrix (such as tissue extracellular matrix or biomaterials) sense their insoluble environment through specific binding interactions between their adhesion receptors and ligands present on the matrix surface. Despite the critical role of the insoluble matrix in cell regulation, there exist no widely-applicable methods for quantifying the chemical stimuli provided by a matrix to cells. Here, we describe a general-purpose technique for quantifying in situ the density of ligands for specific cell adhesion receptors of interest on the surface of a 3D matrix. This paper improves significantly the accuracy of the procedure introduced in a previous publication by detailed marker characterization, optimized staining, and improved data interpretation. The optimized methodology is utilized to quantify the ligands of integrins α 1 β 1, α 2 β 1 on two kinds of matched porous collagen scaffolds, which are shown to possess significantly different ligand density, and significantly different ability to induce peripheral nerve regeneration in vivo. Data support the hypothesis that cell adhesion regulates contractile cell phenotypes, recently shown to be inversely related to organ regeneration. The technique provides a standardized way to quantify the surface chemistry of 3D matrices, and a means for introducing matrix effects in quantitative biological models. PMID:26369635

  15. Cassini atmospheric chemistry mapper. Volume 1. Investigation and technical plan

    NASA Technical Reports Server (NTRS)

    Smith, William Hayden; Baines, Kevin Hays; Drossart, Pierre; Fegley, Bruce; Orton, Glenn; Noll, Keith; Reitsema, Harold; Bjoraker, Gordon L.

    1990-01-01

    The Cassini Atmospheric Chemistry Mapper (ACM) enables a broad range of atmospheric science investigations for Saturn and Titan by providing high spectral and spatial resolution mapping and occultation capabilities at 3 and 5 microns. ACM can directly address the major atmospheric science objectives for Saturn and for Titan, as defined by the Announcement of Opportunity, with pivotal diagnostic measurements not accessible to any other proposed Cassini instrument. ACM determines mixing ratios for atmospheric molecules from spectral line profiles for an important and extensive volume of the atmosphere of Saturn (and Jupiter). Spatial and vertical profiles of disequilibrium species abundances define Saturn's deep atmosphere, its chemistry, and its vertical transport phenomena. ACM spectral maps provide a unique means to interpret atmospheric conditions in the deep (approximately 1000 bar) atmosphere of Saturn. Deep chemistry and vertical transport is inferred from the vertical and horizontal distribution of a series of disequilibrium species. Solar occultations provide a method to bridge the altitude range in Saturn's (and Titan's) atmosphere that is not accessible to radio science, thermal infrared, and UV spectroscopy with temperature measurements to plus or minus 2K from the analysis of molecular line ratios and to attain an high sensitivity for low-abundance chemical species in the very large column densities that may be achieved during occultations for Saturn. For Titan, ACM solar occultations yield very well resolved (1/6 scale height) vertical mixing ratios column abundances for atmospheric molecular constituents. Occultations also provide for detecting abundant species very high in the upper atmosphere, while at greater depths, detecting the isotopes of C and O, constraining the production mechanisms, and/or sources for the above species. ACM measures the vertical and horizontal distribution of aerosols via their opacity at 3 microns and, particularly, at 5

  16. Plant surface reactions: an ozone defence mechanism impacting atmospheric chemistry

    NASA Astrophysics Data System (ADS)

    Jud, W.; Fischer, L.; Canaval, E.; Wohlfahrt, G.; Tissier, A.; Hansel, A.

    2015-07-01

    Elevated tropospheric ozone concentrations are considered a toxic threat to plants, responsible for global crop losses with associated economic costs of several billion dollars per year. Plant injuries have been linked to the uptake of ozone through stomatal pores and oxidative damage of the internal leaf tissue. But a striking question remains: how much ozone effectively enters the plant through open stomata and how much is lost by chemical reactions at the plant surface? In this laboratory study we could show that semi-volatile organic compounds exuded by the glandular trichomes of different Nicotiana tabacum varieties are an efficient ozone sink at the plant surface. In our experiments, different diterpenoid compounds were responsible for a strongly variety dependent ozone uptake of plants under dark conditions, when stomatal pores are almost closed. Surface reactions of ozone were accompanied by prompt release of oxygenated volatile organic compounds, which could be linked to the corresponding precursor compounds: ozonolysis of cis-abienol (C20H34O) - a diterpenoid with two exocyclic double bonds - caused emissions of formaldehyde (HCHO) and methyl vinyl ketone (C4H6O). The ring-structured cembratrien-diols (C20H34O2) with three endocyclic double bonds need at least two ozonolysis steps to form volatile carbonyls such as 4-oxopentanal (C5H8O2), which we could observe in the gas phase, too. Fluid dynamic calculations were used to model ozone distribution in the diffusion limited leaf boundary layer under daylight conditions. In the case of an ozone-reactive leaf surface, ozone gradients in the vicinity of stomatal pores are changed in such a way, that ozone flux through the open stomata is strongly reduced. Our results show that unsaturated semi-volatile compounds at the plant surface should be considered as a source of oxygenated volatile organic compounds, impacting gas phase chemistry, as well as efficient ozone sink improving the ozone tolerance of plants.

  17. Effect of Surface Chemistry on Gene Transfer Efficiency Mediated by Surface-induced DNA-doped Nanocomposites

    PubMed Central

    Sun, Bingbing; Yi, Minchang; Yacoob, Christina C.; Nguyen, Hai T.; Shen, Hong

    2011-01-01

    Surface-induced biomineralization represents an effective way to immobilize DNA molecules onto biomaterial surfaces for introducing DNA into cells in contact with or in an approximate distance to biomaterial surfaces. Our previous studies have investigated how the composition of mineralizing solutions affects the composition and pH responsiveness of nanocomposites and thus gene transfer efficiency in different cell types. In this study, we investigated how the functional groups of a biomaterial surface would affect the induction and crystallographic properties of nanocomposites and thus the gene transfer efficiency. Self-assembled monolayers (SAMs) with different terminus were used to control the functional groups of a surface. We demonstrated that the induction of DNA-doped nanocomposites depended on the surface functional groups, which is consistent with previous studies. The crystallographic properties did not vary significantly with the functional groups. DNA-doped nanocomposites induced by different surface functional groups resulted in different cellular uptake of DNA and thus gene transfer efficiency. The differential cellular uptake may be attributed to the interactions between nanocomposites and functional groups. The weaker inducer resulted in higher cellular uptake thus higher gene transfer efficiency. Together with others and our previous studies, our current results suggest that surface-mediated gene transfer by DNA-doped nanocomposites can be modulated through both mineralizing solutions and surface chemistries. PMID:22198137

  18. Adsorption of pentacene on (100) vicinal surfaces: role of coordination, surface chemistry and vdWs effects

    NASA Astrophysics Data System (ADS)

    Matos, Jeronimo; Kara, Abdelkader

    2015-03-01

    In contrast to low miller index surfaces, vicinal surfaces are characterized by steps and step edges that not only present an interesting atomic landscape for the adsorption organic molecules, but also a unique electronic structure resulting in part from the low coordinated atoms at the step edges. The adsorption of pentacene on the stepped (511), (711), (911) surfaces (respectively 3, 4 and 5-atom wide terraces) of Cu and Ag (coinage transition metals); Pt (reactive transition metal); and Ni (reactive, magnetic transition metal) are studied using density functional theory, in order to investigate the support effects arising from differing surface chemistry. We compare the adsorption energy, adsorption geometry and electronic structure predicted by the PBE functional with those obtained from one of the optimized vdW-DF methods: optB88-vdW. Work supported by the U.S. Department of Energy Basic Energy Science under Contract No. DE-FG02-11ER16243.

  19. Surface-Enhanced Raman Spectroscopy as a Probe of the Surface Chemistry of Nanostructured Materials.

    PubMed

    Dick, Susan; Konrad, Magdalena P; Lee, Wendy W Y; McCabe, Hannah; McCracken, John N; Rahman, Taifur M D; Stewart, Alan; Xu, Yikai; Bell, Steven E J

    2016-07-01

    Surface-enhanced Raman spectroscopy (SERS) is now widely used as a rapid and inexpensive tool for chemical/biochemical analysis. The method can give enormous increases in the intensities of the Raman signals of low-concentration molecular targets if they are adsorbed on suitable enhancing substrates, which are typically composed of nanostructured Ag or Au. However, the features of SERS that allow it to be used as a chemical sensor also mean that it can be used as a powerful probe of the surface chemistry of any nanostructured material that can provide SERS enhancement. This is important because it is the surface chemistry that controls how these materials interact with their local environment and, in real applications, this interaction can be more important than more commonly measured properties such as morphology or plasmonic absorption. Here, the opportunity that this approach to SERS provides is illustrated with examples where the surface chemistry is both characterized and controlled in order to create functional nanomaterials. PMID:26822589

  20. Functional surface chemistry of carbon-based nanostructures

    NASA Astrophysics Data System (ADS)

    Abdula, Daner

    The recently discovered abilities to synthesize single-walled carbon nanotubes and prepare single layer graphene have spurred interest in these sp2-bonded carbon nanostructures. In particular, studies of their potential use in electronic devices are many as silicon integrated circuits are encountering processing limitations, quantum effects, and thermal management issues due to rapid device scaling. Nanotube and graphene implementation in devices does come with significant hurdles itself. Among these issues are the ability to dope these materials and understanding what influences defects have on expected properties. Because these nanostructures are entirely all-surface, with every atom exposed to ambient, introduction of defects and doping by chemical means is expected to be an effective route for addressing these issues. Raman spectroscopy has been a proven characterization method for understanding vibrational and even electronic structure of graphene, nanotubes, and graphite, especially when combined with electrical measurements, due to a wealth of information contained in each spectrum. In Chapter 1, a discussion of the electronic structure of graphene is presented. This outlines the foundation for all sp2-bonded carbon electronic properties and is easily extended to carbon nanotubes. Motivation for why these materials are of interest is readily gained. Chapter 2 presents various synthesis/preparation methods for both nanotubes and graphene, discusses fabrication techniques for making devices, and describes characterization methods such as electrical measurements as well as static and time-resolved Raman spectroscopy. Chapter 3 outlines changes in the Raman spectra of individual metallic single-walled carbon nantoubes (SWNTs) upon sidewall covalent bond formation. It is observed that the initial degree of disorder has a strong influence on covalent sidewall functionalization which has implications on developing electronically selective covalent chemistries and

  1. Molecular potential energy surfaces for interstellar chemistry and fusion applications

    NASA Astrophysics Data System (ADS)

    Braams, Bastiaan J.; Huang, Xinchuan; Jin, Zhong; Xie, Zhen; Zhang, Xiubin; Bowman, Joel M.; Sharma, Amit Raj; Scheider, Ralf

    2006-04-01

    In the Born-Oppenheimer approximation the electronic Schr"odinger equation is solved given the nuclear positions as parameters, and this defines the potential energy surface. We have used computational invariant theory and the MAGMA computer algebra system as an aid to develop representations for the potential energy and dipole moment surfaces that are fully invariant under permutations of like nuclei, extending an approach that for 3-body and 4-body systems has a long history, e.g. [J. N. Murrell et al. Molecular Potential Energy Functions, Wiley, 1984]. A many-body (cluster) expansion is used to describe reaction complexes. The methods have been applied in an almost routine way for systems of up to 7 nuclei, including several molecules that are of interest for interstellar chemistry and for the issue of hydrocarbon breakdown in fusion edge plasma: H5^+, CH5, CH5^+, C2H3^+, and their fragments, with C2H5^+ on the way. The mathematical and computional methods and the hydrocarbon applications will be presented.

  2. Surface Chemistry at Size-Selected Nano-Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Roberts, Jeffrey

    2005-03-01

    A method has been developed to conduct surface chemistry and extract surface kinetic rates from size-selected aerosol nanoparticles. The measurements encompass broad ranges of particle size, phase, and composition. Results will be presented on the uptake of water by aerosolized soot nanoparticles of radius between 10 and 40 nm. Water uptake was monitored by tandem differential mobility analysis (T-DMA), which is capable of measuring changes in particle diameter as little as 0.2 nm. Soot particles were produced in an ethene diffusion flame and extracted into an atmospheric pressure aerosol flow tube reactor. The particles were subjected to various thermal and oxidative treatments, and the effects of these treatments on the ability of soot to adsorb monolayer quantities of water was determined. The results are important because soot nucleates atmospheric cloud particles. More generally, the results represent one of the first kinetic and mechanistic studies of gas-phase nanoparticle reactivity. Co-author: Henry Ajo, University of Minnesota

  3. Surface chemistry of gold nanorods: origin of cell membrane damage and cytotoxicity

    NASA Astrophysics Data System (ADS)

    Wang, Liming; Jiang, Xiumei; Ji, Yinglu; Bai, Ru; Zhao, Yuliang; Wu, Xiaochun; Chen, Chunying

    2013-08-01

    We investigated how surface chemistry influences the interaction between gold nanorods (AuNRs) and cell membranes and the subsequent cytotoxicity arising from them in a serum-free cell culture system. Our results showed that the AuNRs coated with cetyl trimethylammonium bromide (CTAB) molecules can generate defects in the cell membrane and induce cell death, mainly due to the unique bilayer structure of CTAB molecules on the surface of the rods rather than their charge. Compared to CTAB-capped nanorods, positively charged polyelectrolyte-coated, i.e. poly(diallyldimethyl ammonium chloride) (PDDAC), AuNRs show improved biocompatibility towards cells. Thus, the present results indicate that the nature of surface molecules, especially their packing structures on the surface of AuNRs rather than surface charge, play a more crucial role in determining cytotoxicity. These findings about interfacial interactions could also explain the effects of internalized AuNRs on the structures or functions of organelles. This study will help understanding of the toxic nature of AuNRs and guide rational design of the surface chemistry of AuNRs for good biocompatibility in pharmaceutical therapy.

  4. Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces

    NASA Astrophysics Data System (ADS)

    McBriarty, Martin E.

    Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

  5. Surface chemistry dependent immunostimulative potential of porous silicon nanoplatforms.

    PubMed

    Shahbazi, Mohammad-Ali; Fernández, Tahia D; Mäkilä, Ermei M; Le Guével, Xavier; Mayorga, Cristobalina; Kaasalainen, Martti H; Salonen, Jarno J; Hirvonen, Jouni T; Santos, Hélder A

    2014-11-01

    Nanoparticles (NPs) have been suggested for immunotherapy applications in order to optimize the delivery of immuno-stimulative or -suppressive molecules. However, low attention towards the impact of the NPs' physicochemical properties has presented a major hurdle for developing efficient immunotherapeutic agents. Here, the effects of porous silicon (PSi) NPs with different surface chemistries were evaluated on human monocyte-derived dendritic cells (MDDCs) and lymphocytes in order to highlight the importance of the NPs selection in immuno-stimulative or -suppressive treatment. Although all the PSi NPs showed high biocompatibility, only thermally oxidized PSi (TOPSi) and thermally hydrocarbonized PSi (THCPSi) NPs were able to induce very high rate of immunoactivation by enhancing the expression of surface co-stimulatory markers of the MDDCs (CD80, CD83, CD86, and HLA-DR), inducing T-cell proliferation, and also the secretion of interleukins (IL-1β, IL-4, IL-6, IL-10, IL-12, IFN-γ, and TNF-α). These results indicated a balanced increase in the secretion of Th1, Th2, and Treg cytokines. Moreover, undecylenic acid functionalized THCPSi, as well as poly(methyl vinyl ether-alt-maleic acid) conjugated to (3-aminopropyl)triethoxysilane functionalized thermally carbonized PSi and polyethyleneimine conjugated undecylenic acid functionalized THCPSi NPs showed moderate immunoactivation due to the mild increase in the above-mentioned markers. By contrast, thermally carbonized PSi (TCPSi) and (3-aminopropyl)triethoxysilane functionalized TCPSi NPs did not induce any immunological responses, suggesting that their application could be in the delivery of immunosuppressive molecules. Overall, our findings suggest all the NPs containing more nitrogen or oxygen on the outermost backbone layer have lower immunostimulatory effect than NPs with higher C-H structures on the surface. PMID:25123922

  6. Analysis of temporal evolution of quantum dot surface chemistry by surface-enhanced Raman scattering

    PubMed Central

    Doğan, İlker; Gresback, Ryan; Nozaki, Tomohiro; van de Sanden, Mauritius C. M.

    2016-01-01

    Temporal evolution of surface chemistry during oxidation of silicon quantum dot (Si-QD) surfaces were probed using surface-enhanced Raman scattering (SERS). A monolayer of hydrogen and chlorine terminated plasma-synthesized Si-QDs were spin-coated on silver oxide thin films. A clearly enhanced signal of surface modes, including Si-Clx and Si-Hx modes were observed from as-synthesized Si-QDs as a result of the plasmonic enhancement of the Raman signal at Si-QD/silver oxide interface. Upon oxidation, a gradual decrease of Si-Clx and Si-Hx modes, and an emergence of Si-Ox and Si-O-Hx modes have been observed. In addition, first, second and third transverse optical modes of Si-QDs were also observed in the SERS spectra, revealing information on the crystalline morphology of Si-QDs. An absence of any of the abovementioned spectral features, but only the first transverse optical mode of Si-QDs from thick Si-QD films validated that the spectral features observed from Si-QDs on silver oxide thin films are originated from the SERS effect. These results indicate that real-time SERS is a powerful diagnostic tool and a novel approach to probe the dynamic surface/interface chemistry of quantum dots, especially when they involve in oxidative, catalytic, and electrochemical surface/interface reactions. PMID:27389331

  7. Analysis of temporal evolution of quantum dot surface chemistry by surface-enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Doğan, Ilker; Gresback, Ryan; Nozaki, Tomohiro; van de Sanden, Mauritius C. M.

    2016-07-01

    Temporal evolution of surface chemistry during oxidation of silicon quantum dot (Si-QD) surfaces were probed using surface-enhanced Raman scattering (SERS). A monolayer of hydrogen and chlorine terminated plasma-synthesized Si-QDs were spin-coated on silver oxide thin films. A clearly enhanced signal of surface modes, including Si-Clx and Si-Hx modes were observed from as-synthesized Si-QDs as a result of the plasmonic enhancement of the Raman signal at Si-QD/silver oxide interface. Upon oxidation, a gradual decrease of Si-Clx and Si-Hx modes, and an emergence of Si-Ox and Si-O-Hx modes have been observed. In addition, first, second and third transverse optical modes of Si-QDs were also observed in the SERS spectra, revealing information on the crystalline morphology of Si-QDs. An absence of any of the abovementioned spectral features, but only the first transverse optical mode of Si-QDs from thick Si-QD films validated that the spectral features observed from Si-QDs on silver oxide thin films are originated from the SERS effect. These results indicate that real-time SERS is a powerful diagnostic tool and a novel approach to probe the dynamic surface/interface chemistry of quantum dots, especially when they involve in oxidative, catalytic, and electrochemical surface/interface reactions.

  8. Chemoselective modification of viral surfaces via bioorthogonal click chemistry.

    PubMed

    Rubino, Frederick A; Oum, Yoon Hyeun; Rajaram, Lakshmi; Chu, Yanjie; Carrico, Isaac S

    2012-01-01

    The modification of virus particles has received a significant amount of attention for its tremendous potential for impacting gene therapy, oncolytic applications and vaccine development. Current approaches to modifying viral surfaces, which are mostly genetics-based, often suffer from attenuation of virus production, infectivity and cellular transduction. Using chemoselective click chemistry, we have developed a straightforward alternative approach which sidesteps these issues while remaining both highly flexible and accessible. The goal of this protocol is to demonstrate the effectiveness of using bioorthogonal click chemistry to modify the surface of adenovirus type 5 particles. This two-step process can be used both therapeutically or analytically, as it allows for chemoselective ligation of targeting molecules, dyes or other molecules of interest onto proteins pre-labeled with azide tags. The three major advantages of this method are that (1) metabolic labeling demonstrates little to no impact on viral fitness, (2) a wide array of effector ligands can be utilized, and (3) it is remarkably fast, reliable and easy to access. In the first step of this procedure, adenovirus particles are produced bearing either azidohomoalanine (Aha, a methionine surrogate) or the unnatural sugar O-linked N-azidoacetylglucosamine (O-GlcNAz), both of which contain the azide (-N3) functional group. After purification of the azide-modified virus particles, an alkyne probe containing the fluorescent TAMRA moiety is ligated in a chemoselective manner to the pre-labeled proteins or glycoproteins. Finally, an SDS-PAGE analysis is performed to demonstrate the successful ligation of the probe onto the viral capsid proteins. Aha incorporation is shown to label all viral capsid proteins (Hexon, Penton and Fiber), while O-GlcNAz incorporation results in labeling of Fiber only. In this evolving field, multiple methods for azide-alkyne ligation have been successfully developed; however only the

  9. Investigation of Varied Strontium-Transuranic Precipitation Chemistries for Crossflow

    SciTech Connect

    Nash, C.A.

    2000-07-27

    Precipitation chemistries for strontium and transuranic (TRU) removal have been tested for crossflow filterability and lanthanide removal with simulants of Hanford tank 241-AN-107 supernate. This is the initial work indicating the usefulness of a strontium and permanganate precipitation process as applied to the Hanford River Protection Project. Precipitations with both ferric and ferrous iron were shown to be at least two orders of magnitude less filterable than a 0.1 gpm/ft target average flux that was desired at the time. A precipitate from a strontium nitrate strike alone was found to filter easily and to make the desired average flux. Other chemistries tested included precipitant of lanthanum(III), nickel (II), calcium (II), and a redox chemistry using sodium permanganate. Of these chemistries a strontium and permanganate strike including calcium provided the highest filter flux compared to the other chemistries. It showed the most promise in lanthanide removal as well. This work provides a promising direction for further work to achieve both acceptable filterability and decontamination for Envelope C wastes to be treated by the Hanford River Protection Project. The work reported here was originally intended to satisfy needs for crossflow filter testing of a strontium and ferric precipitation method for treating Envelope C using a 241-AN-107 simulant.

  10. Capturing Conformation-Dependent Molecule-Surface Interactions When Surface Chemistry Is Heterogeneous.

    PubMed

    Mabry, Joshua N; Kastantin, Mark; Schwartz, Daniel K

    2015-07-28

    Molecular building blocks, such as carbon nanotubes and DNA origami, can be fully integrated into electronic and optical devices if they can be assembled on solid surfaces using biomolecular interactions. However, the conformation and functionality of biomolecules depend strongly on the local chemical environment, which is highly heterogeneous near a surface. To help realize the potential of biomolecular self-assembly, we introduce here a technique to spatially map molecular conformations and adsorption, based on single-molecule fluorescence microscopy. On a deliberately patterned surface, with regions of varying hydrophobicity, we characterized the conformations of adsorbed helicogenic alanine-lysine copeptides using Förster resonance energy transfer. The peptides adopted helical conformations on hydrophilic regions of the surface more often than on hydrophobic regions, consistent with previous ensemble-averaged observations of α-helix surface stability. Interestingly, this dependence on surface chemistry was not due to surface-induced unfolding, as the apparent folding and unfolding dynamics were usually much slower than desorption. The most significant effect of surface chemistry was on the adsorption rate of molecules as a function of their initial conformational state. In particular, regions with higher adsorption rates attracted more molecules in compact, disordered coil states, and this difference in adsorption rates dominated the average conformation of the ensemble. The correlation between adsorption rate and average conformation was also observed on nominally uniform surfaces. Spatial variations in the functional state of adsorbed molecules would strongly affect the success rates of surface-based molecular assembly and can be fully understood using the approach developed in this work. PMID:26079177

  11. Chromate removal by surface-modified nanoscale zero-valent iron: Effect of different surface coatings and water chemistry.

    PubMed

    Dong, Haoran; He, Qi; Zeng, Guangming; Tang, Lin; Zhang, Chang; Xie, Yankai; Zeng, Yalan; Zhao, Feng; Wu, Yanan

    2016-06-01

    This study investigated the correlation between the colloidal stability and reactivity of surface-modified nano zero-valent iron (SM-nZVI) as affected by the surface coating (i.e., polyacrylic acid [PAA] and starch) under various geochemical conditions. Generally, the colloidal stability of nZVI was enhanced with increasing loading of surface coating, while there is an optimum loading for the most efficient Cr(VI) removal by SM-nZVI. At lower loadings than the optimum loading, the surface coating could enhance the particle stabilization, facilitating the Cr(VI) reduction by providing more available surface sites. However, the over-loaded surface coating on the surface of nZVI particles decreased the Cr(VI) reduction due to the occupation of the reactive sites and the inhibition of the mass transfer of Cr(VI) ions from water to the particle surface by providing the electrostatic or steric repulsion. The effects of Ca(2+) ions or humic acid (HA) on the colloidal stability and reactivity of PAA-modified nZVI (P-nZVI) and starch-modified nZVI (S-nZVI) were examined. Differing stability behavior and reactivity were observed for different SM-nZVI. It was found that the presence of Ca(2+) or HA altered surface chemistry of SM-nZVI, the particle-particle interaction and the particle-contaminant interaction, and hence influencing the stability behavior and reactivity of the particles. PMID:26970032

  12. Don Quixote Pond Sediments: Surface and Subsurface Chemistry and Mineralogy

    NASA Astrophysics Data System (ADS)

    Englert, P. A. J.; Bishop, J. L.; Patel, S.; Gibson, E. K.; Koeberl, C.

    2014-12-01

    Don Quixote Pond, like Don Juan Pond in the South Fork of Wright Valley, Antarctica, is a model for calcium and chlorine weathering and distribution on Mars. It is located in the western part of the North Fork about 100 m above Mean Seawater Level; its brine is seasonally frozen [1]. Field observations show zones of discoloration which grow lighter with distance from the pond edges. Four sediment cores, a set of radial surface samples, special surface samples, and samples of local rocks were obtained [2]. We report on chemical and mineral analyses of traverse samples and on two cores. Core DQ20 is a northeastern shoreline core. Its soluble salt concentration exceeds 200 micromoles/g in the top 5 cm, and then falls to less than 70 micromoles/g at the permafrost depth of 15 cm. These concentrations are low when compared to similarly positioned locations at Don Juan Pond and to cores from Prospect Mesa close to Lake Vanda, Wright Valley. Halite, soda niter, tachyhydrite and/bischovite are suggested from the ionic molar relationships Measured halite concentrations of surface samples, collected along a traverse of 35 m from the pond outwards, range from over 5% to trace amounts, decreasing with distance. Gypsum is also present in almost all of these samples ranging from 0.2% to 2.6%, but does not exhibit a trend. However, in core DQ35, located at a distance of 15 m along the traverse, gypsum decreases from 2.5% to 0.6% from the surface to the permafrost depth of 12 cm. While DQ35 and radial samples show high quartz and albite abundance, samples that contained visible encrustations and evaporites are low in these minerals and rich in highly diverse alteration products. Don Juan Basin ponds may have formed by a complex surface water mobilization of weathering products [3] and local groundwater action [4,5]. In contrast, Don Quixote pond mineralogy and chemistry may be consistent with a less complex shallow and deep groundwater system origin [1]. [1] Harris H

  13. An Investigation into the Effectiveness of Problem-Based Learning in a Physical Chemistry Laboratory Course

    ERIC Educational Resources Information Center

    Gurses, Ahmet; Acikyildiz, Metin; Dogar, Cetin; Sozbilir, Mustafa

    2007-01-01

    The aim of this study was to investigate the effectiveness of a problem-based learning (PBL) approach in a physical chemistry laboratory course. The parameters investigated were students' attitudes towards a chemistry laboratory course, scientific process skills of students and their academic achievement. The design of the study was one group…

  14. Surface chemistry and physics of deuterium retention in lithiated graphite

    SciTech Connect

    Taylor, C. N.; Krstic, Predrag S; Allain, J. P.; Heim, B.; Skinner, C. H.; Kugel, H.

    2011-01-01

    Lithium wall conditioning in TFTR, CDX-U, T-11M, TJ-II and NSTX is found to yield enhanced plasma performance manifest, in part, through improved deuterium particle control. X-ray photoelectron spectroscopy (XPS) experiments examine the affect of D irradiation on lithiated graphite and show that the surface chemistry of lithiated graphite after D ion bombardment (500 eV/amu) is fundamentally different from that of non-Li conditioned graphite. Instead of simple LiD bonding seen in pure liquid Li, graphite introduces additional complexities. XPS spectra show that Li-O-D (533.0 {+-} 0.6 eV) and Li-C-D (291.4 {+-} 0.6 eV) bonds, for a nominal Li dose of 2 {micro}m, become 'saturated' with D at fluences between 3.8 and 5.2 x 10{sup 17} cm{sup -2}. Atomistic modeling indicate that Li-O-D-C interactions may be a result of multibody effects as opposed to molecular bonding.

  15. Influence of anode surface chemistry on microbial fuel cell operation.

    PubMed

    Santoro, Carlo; Babanova, Sofia; Artyushkova, Kateryna; Cornejo, Jose A; Ista, Linnea; Bretschger, Orianna; Marsili, Enrico; Atanassov, Plamen; Schuler, Andrew J

    2015-12-01

    Self-assembled monolayers (SAMs) modified gold anodes are used in single chamber microbial fuel cells for organic removal and electricity generation. Hydrophilic (N(CH3)3(+), OH, COOH) and hydrophobic (CH3) SAMs are examined for their effect on bacterial attachment, current and power output. The different substratum chemistry affects the community composition of the electrochemically active biofilm formed and thus the current and power output. Of the four SAM-modified anodes tested, N(CH3)3(+) results in the shortest start up time (15 days), highest current achieved (225 μA cm(-2)) and highest MFC power density (40 μW cm(-2)), followed by COOH (150 μA cm(-2) and 37 μW cm(-2)) and OH (83 μA cm(-2) and 27 μW cm(-2)) SAMs. Hydrophobic SAM decreases electrochemically active bacteria attachment and anode performance in comparison to hydrophilic SAMs (CH3 modified anodes 7 μA cm(-2) anodic current and 1.2 μW cm(-2) MFC's power density). A consortium of Clostridia and δ-Proteobacteria is found on all the anode surfaces, suggesting a synergistic cooperation under anodic conditions. PMID:26025340

  16. Surface-chemistry-sensitive spectral features of In-Ga-Zn-O thin film: Cleaned, air-passivated, and sputter-phase-separated surfaces

    NASA Astrophysics Data System (ADS)

    Kang, Se Jun; Baik, Jae Yoon; Thakur, Anup; Kim, Hyeong-Do; Shin, Hyun-Joon; Chung, JaeGwan; Lee, Jaecheol; Lee, JaeHak

    2011-07-01

    The photoelectron spectral features and corresponding energy band diagrams of amorphous indium gallium zinc oxide ( a-IGZO) thin films were investigated for different surface chemistries. Cleaned-IGZO surface had a deep subgap state (DSS), the binding energy (BE) of which expanded to ˜1.5 eV. When stored in air, IGZO surface became contaminant passivated and DSS became negligible. Sputtering resulted in phase separation of surface into metallic In and lesser In and Zn containing IGZO. Compared with IGZO, the air-passivated surface and phase-separated surface, respectively, had a more weakly conducting environment and a higher BE spectral shift.

  17. Students' Written Arguments in General Chemistry Laboratory Investigations

    NASA Astrophysics Data System (ADS)

    Choi, Aeran; Hand, Brian; Greenbowe, Thomas

    2012-11-01

    This study aimed to examine the written arguments developed by college freshman students using the Science Writing Heuristic approach in inquiry-based general chemistry laboratory classrooms and its relationships with students' achievement in chemistry courses. Fourteen freshman students participated in the first year of the study while 19 freshman students participated in the second year of the study. Two frameworks, an analytical and a holistic argument framework, were developed to evaluate the written argument generated by students. The analytical framework scored each argument component separately and allocated a Total Argument score while the holistic framework evaluated the arguments holistically. Three hundred and sixty-eight samples from 33 students were evaluated. Stepwise regression analyses revealed that the evidence and the claims-evidence relationship components were identified as the most important predictors of the Total Argument and the Holistic Argument scores. Students' argument scores were positively correlated with their achievement, as measured by the final grade received for the general chemistry laboratory and the general chemistry lecture course.

  18. Effects of Tailored Surface Chemistry on Desorption Electrospray Ionization Mass Spectrometry: a Surface-Analytical Study by XPS and AFM

    NASA Astrophysics Data System (ADS)

    Penna, Andrea; Careri, Maria; Spencer, Nicholas D.; Rossi, Antonella

    2015-08-01

    Since it was proposed for the first time, desorption electrospray ionization-mass spectrometry (DESI-MS) has been evaluated for applicability in numerous areas. Elucidations of the ionization mechanisms and the subsequent formation of isolated gas-phase ions have been proposed so far. In this context, the role of both surface and pneumatic effects on ion-formation yield has recently been investigated. Nevertheless, the effect of the surface chemistry has not yet been completely understood. Functionalized glass surfaces have been prepared, in order to tailor surface performance for ion formation. Three substrates were functionalized by depositing three different silanes [3-mercaptopropyltriethoxysilane (MTES), octyltriethoxysilane (OTES), and 1H,1H,2H,2H-perfluorooctyltriethoxy-silane (FOTES)] from toluene solution onto standard glass slides. Surface characterization was carried out by contact-angle measurements, tapping-mode atomic force microscopy, and X-ray photoelectron spectroscopy. Morphologically homogeneous and thickness-controlled films in the nm range were obtained, with surface free energies lying between 15 and 70 mJ/m2. These results are discussed, together with those of DESI-MS on low-molecular-weight compounds such as melamine, tetracycline, and lincomycin, also taking into account the effects of the sprayer potential and its correlation with surface wettability. The results demonstrate that ion-formation efficiency is affected by surface wettability, and this was demonstrated operating above and below the onset of the electrospray.

  19. LABORATORY AND COMPUTATIONAL CHEMISTRY INVESTIGATIONS OF THE GAS PHASE ATMOSPHERIC CHEMISTRY OF AIR TOXIC COMPOUNDS

    EPA Science Inventory

    A full assessment of the impact of the release of air toxic compounds into the atmospheric requires a detailed understanding of their atmospheres lifetimes and fates. To address this issue a detailed review of the atmospheric chemistry of each of these classes was carried out t...

  20. Preliminary findings of the Viking gas exchange experiment and a model for Martian surface chemistry

    NASA Technical Reports Server (NTRS)

    Oyama, V. I.; Berdahl, B. J.; Carle, G. C.

    1977-01-01

    Earlier results reported from the Viking Lander-1 experiment are reexamined and interpreted in terms of a model of the Martian soil surface morphology and chemistry. Major events in the gas exchange experiment (GEX) first cycle are tabulated and data are presented on the sample processing and transport environments experienced by the soil samples. Oxygen and CO2 evolved from humidified Martian soil in GEX and slight changes in N2 present are investigated. A soil model involving iron oxide coating on silicate material is entertained to yield a mechanistic explanation of the experimental findings, and invocation of biotic processes is eschewed.

  1. Surface chemistry and surface electronic properties of ZnO single crystals and nanorods

    SciTech Connect

    Uhlrich, J. J.; Olson, D. C.; Hsu, J. W. P.; Kuech, T. F.

    2009-03-15

    The surface chemistry of ZnO single crystals of (0001) and (1010) orientations and ZnO nanorods was studied using x-ray and ultraviolet photoelectron spectroscopies. Air drying and UV-ozone preparations were studied in particular as chemical treatments that could be applied to poly(3-hexylthiophene) (P3HT)-ZnO solar cells to enhance performance. The UV-ozone treatment showed negligible effect by photoelectron spectroscopy on the ZnO single crystal surfaces, but brought about electronic shifts consistent with increased upward band bending by {approx}0.25 eV on the ZnO nanorod surface. Modest interface dipoles of {approx}0.15 and {approx}0.25 eV were measured between P3HT and the (1010) and (0001) single crystal orientations, respectively, with the dipole moment pointing from ZnO to the P3HT layer. The sol-gel films showed evidence of forming a small interface dipole in the opposite direction, which illustrates the difference in surface chemistry between the solution-grown ZnO and the ZnO single crystals.

  2. The influence of carbon surface chemistry on supported palladium nanoparticles in heterogeneous reactions.

    PubMed

    Ding, Yuxiao; Zhang, Liyun; Wu, Kuang-Hsu; Feng, Zhenbao; Shi, Wen; Gao, Qiang; Zhang, Bingsen; Su, Dang Sheng

    2016-10-15

    The surface chemistry of nanocarbon support can tailor chemical properties of precious metal nanoparticle/nanocarbon hybrid catalyst in heterogeneous reactions. We report on modified reduced graphene oxide (rGO) support with ionic liquid-derived carbonaceous surface for palladium nanoparticle (Pd NPs) decoration and their actions in different heterogeneous reactions. The surface chemistry of support materials was characterized in detail, and the influence of which on the formation and distribution of metal particles was further investigated. Three different types of reactions including Suzuki-Miyaura coupling reaction, CO oxidation and phenol reduction were examined in terms of reactivity and selectivity. The roles of substituted nitrogen in graphitic lattice and grafted groups on the carbon surface were exploited. Nitrogen-doping can give rise to changes in electronic properties of supported metals, and the Lewis basicity of the doped nitrogen atoms can favor the adsorption of acidic reactants in phenol reduction. The grafted groups derived a negative impact to the Suzuki-Miyaura coupling reaction, due to the involvement of larger reactant molecules, despite that they could prevent significant sintering of Pd NPs in the CO oxidation. PMID:27442144

  3. Surface chemistry relevant to material processing for semiconductor devices

    NASA Astrophysics Data System (ADS)

    Okada, Lynne Aiko

    Metal-oxide-semiconductor (MOS) structures are the core of many modern integrated circuit (IC) devices. Each material utilized in the different regions of the device has its own unique chemistry. Silicon is the base semiconductor material used in the majority of these devices. With IC device complexity increasing and device dimensions decreasing, understanding material interactions and processing becomes increasingly critical. Hsb2 desorption is the rate-limiting step in silicon growth using silane under low temperature conditions. Activation energies for Hsb2 desorption measured during Si chemical vapor deposition (CVD) versus single-crystal studies are found to be significantly lower. It has been proposed that defect sites on the silicon surface could explain the observed differences. Isothermal Hsb2 desorption studies using laser induced thermal desorption (LITD) techniques have addressed this issue. The growth of low temperature oxides is another relevant issue for fabrication of IC devices. Recent studies using 1,4-disilabutane (DSB) (SiHsb3CHsb2CHsb2SiHsb3) at 100sp°C in ambient Osb2 displayed the successful low temperature growth of silicon dioxide (SiOsb2). However, these studies provided no information about the deposition mechanism. We performed LITD and Fourier transform infrared (FTIR) studies on single-crystal and porous silicon surfaces to examine the adsorption, decomposition, and desorption processes to determine the deposition mechanism. Titanium nitride (TiN) diffusion barriers are necessary in modern metallization structures. Controlled deposition using titanium tetrachloride (TiClsb4) and ammonia (NHsb3) has been demonstrated using atomic layered processing (ALP) techniques. We intended to study the sequential deposition method by monitoring the surface intermediates using LITD techniques. However, formation of a Cl impurity source, ammonium chloride (NHsb4sp+Clsp-), was observed, thereby, limiting our ability for effective studies. Tetrakis

  4. ATR-FTIR Spectroscopy in the Undergraduate Chemistry Laboratory: Part II--A Physical Chemistry Laboratory Experiment on Surface Adsorption

    ERIC Educational Resources Information Center

    Schuttlefield, Jennifer D.; Larsen, Sarah C.; Grassian, Vicki H.

    2008-01-01

    Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy is a useful technique for measuring the infrared spectra of solids and liquids as well as probing adsorption on particle surfaces. The use of FTIR-ATR spectroscopy in organic and inorganic chemistry laboratory courses as well as in undergraduate research was presented…

  5. Biophysical evaluation of cells on nanotubular surfaces: the effects of atomic ordering and chemistry

    PubMed Central

    Shokuhfar, Tolou; Hamlekhan, Azhang; Chang, Jen-Yung; Choi, Chang Kyoung; Sukotjo, Cortino; Friedrich, Craig

    2014-01-01

    After the implantation of a biomaterial in the body, the first interaction occurs between the cells in contact with the biomaterial surface. Therefore, evaluating the cell–substrate interface is crucial for designing a successful implant. In this study, the interaction of MC3T3 osteoblasts was studied on commercially pure and alloy (Ti6Al4V) Ti surfaces treated with amorphous and crystalline titanium dioxide nanotubes. The results indicated that the presence of nanotubes increased the density of osteoblast cells in comparison to bare surfaces (no nanotubes). More importantly, our finding shows that the chemistry of the substrate affects the cell density rather than the morphology of the cells. A novel approach based on the focused ion beam technique was used to investigate the biophysical cell–substrate interaction. The analysis revealed that portions of the cells migrated inside the crystalline nanotubes. This observation was correlated with the super hydrophilic properties of the crystalline nanotubes. PMID:25143725

  6. Chemistry and catalysis at the surface of nanomaterials

    NASA Astrophysics Data System (ADS)

    White, Brian Edward

    This thesis will delve into three main areas of nanomaterials research: (I) Designing, building, and utilizing a chemical vapor deposition (CVD) system for the growth of CNTs; (II) Aqueous suspensions of carbon nanotubes (CNT) solubilized by various surfactants, and the oxidative chemistry that can occur at CNT surfaces; (III) Catalytic CO oxidation over supported Cu2O nanoparticle systems. An introduction to nanomaterials in general, with a particular emphasis on carbon nanotubes and nanoparticles will be given in Chapter one. Chapter two provides a summary of common techniques used to grow carbon nanotubes, and introduces a new method we have developed. This method is based on previous chemical vapor deposition techniques, but uses liquids, specifically ethanol, as the carbon source. Using ethanol has several advantages, including ease of use and safety, as well as chemical benefits. Our new process affords long, aligned, single-walled nanotubes, with a relatively narrow diameter distribution. This method can also be used to grow CNTs across slits, which can then be studied spectroscopically. In Chapter three CNT-surfactant aqueous suspensions will be discussed in depth, including a new robust polymer surfactant. Poly(maleic acid/octyl vinyl ether) (PMAOVE) is stable over a large range of temperatures and pH values, and is well suited for the study of the oxidative chemistry that can occur on SWNT surfaces. Our aqueous suspensions were found to be quite stable by zeta potential studies and their emissive properties exhibited a pH dependence, quenching at higher concentrations of H+. We attribute this dependence to chemisorbed oxygen and its protonation at lower pH values. By heating the suspensions of SWNTs, O2 can be driven off, thus eliminating the dependence on pH. We also reproducibly add oxygen back into the system in the form of 1DeltaO2 , obtained from an endoperoxide. This method allows us to calculate the number of oxygen molecules needed for

  7. Research program to investigate the fundamental chemistry of technetium

    SciTech Connect

    Shuh, David K.; Lukens, Wayne W.; Burns, Carol J.

    2003-12-19

    The objective of this research is to increase the knowledge of the fundamental technetium chemistry that is necessary to address challenges to the safe, long-term remediation of high-level waste posed by this element. These challenges may be divided into two categories: unexpected behavior of technetium in high-level waste tanks at the Hanford and Savannah River Sites and the behavior of technetium in waste forms.

  8. Pattern recognition used to investigate multivariate data in analytical chemistry

    SciTech Connect

    Jurs, P.C.

    1986-06-06

    Pattern recognition and allied multivariate methods provide an approach to the interpretation of the multivariate data often encountered in analytical chemistry. Widely used methods include mapping and display, discriminant development, clustering, and modeling. Each has been applied to a variety of chemical problems, and examples are given. The results of two recent studies are shown, a classification of subjects as normal or cystic fibrosis heterozygotes and simulation of chemical shifts of carbon-13 nuclear magnetic resonance spectra by linear model equations.

  9. Properties Data for Adhesion and Surface Chemistry of Aluminum: Sapphire-Aluminum, Single-Crystal Couple

    NASA Technical Reports Server (NTRS)

    Miyoshi, Kazuhisa; Pohlchuck, Bobby; Whitle, Neville C.; Hector, Louis G., Jr.; Adams, Jim

    1998-01-01

    An investigation was conducted to examine the adhesion and surface chemistry of single-crystal aluminum in contact with single-crystal sapphire (alumina). Pull-off force (adhesion) measurements were conducted under loads of 0. I to I mN in a vacuum of 10(exp -1) to 10(exp -9) Pa (approx. 10(exp -10) to 10(exp -11) torr) at room temperature. An Auger electron spectroscopy analyzer incorporated directly into an adhesion-measuring vacuum system was primarily used to define the chemical nature of the surfaces before and after adhesion measurements. The surfaces were cleaned by argon ion sputtering. With a clean aluminum-clean -sapphire couple the mean value and standard deviation of pull-off forces required to separate the surfaces were 3015 and 298 micro-N, respectively. With a contaminated aluminum-clean sapphire couple these values were 231 and 241 micro-N. The presence of a contaminant film on the aluminum surface reduced adhesion by a factor of 13. Therefore, surfaces cleanliness, particularly aluminum cleanliness, played an important role in the adhesion of the aluminum-sapphire couples. Pressures on the order of 10(exp -8) to 10(exp -9) Pa (approx. 10(exp -10) to 10(exp -11) torr) maintained a clean aluminum surface for only a short time (less then 1 hr) but maintained a clean sapphire surface, once it was achieved, for a much longer time.

  10. Combined effects of surface conditions, boundary layer dynamics and chemistry on diurnal SOA evolution

    NASA Astrophysics Data System (ADS)

    Janssen, R. H. H.; Vilà-Guerau de Arellano, J.; Ganzeveld, L. N.; Kabat, P.; Jimenez, J. L.; Farmer, D. K.; van Heerwaarden, C. C.; Mammarella, I.

    2012-08-01

    We study the combined effects of land surface conditions, atmospheric boundary layer dynamics and chemistry on the diurnal evolution of biogenic secondary organic aerosol in the atmospheric boundary layer, using a model that contains the essentials of all these components. First, we evaluate the model for a case study in Hyytiälä, Finland, and find that it is able to satisfactorily reproduce the observed dynamics and gas-phase chemistry. We show that the exchange of organic aerosol between the free troposphere and the boundary layer (entrainment) must be taken into account in order to explain the observed diurnal cycle in organic aerosol (OA) concentration. An examination of the budgets of organic aerosol and terpene concentrations show that the former is dominated by entrainment, while the latter is mainly driven by emission and chemical transformation. We systematically investigate the role of the land surface, which governs both the surface energy balance partitioning and terpene emissions, and the large-scale atmospheric process of vertical subsidence. Entrainment is especially important for the dilution of organic aerosol concentrations under conditions of dry soils and low terpene emissions. Subsidence suppresses boundary layer growth while enhancing entrainment. Therefore, it influences the relationship between organic aerosol and terpene concentrations. Our findings indicate that the diurnal evolution of secondary organic aerosols (SOA) in the boundary layer is the result of coupled effects of the land surface, dynamics of the atmospheric boundary layer, chemistry, and free troposphere conditions. This has potentially some consequences for the design of both field campaigns and large-scale modeling studies.

  11. Investigating Titan's Atmospheric Chemistry at Low Temperature with the Titan Haze Simulation Experiment

    NASA Astrophysics Data System (ADS)

    Sciamma-O'Brien, E. M.; Salama, F.

    2012-12-01

    Titan, Saturn's largest satellite, possesses a dense atmosphere (1.5 bar at the surface) composed mainly of N2 and CH4. The solar radiation and electron bombardment from Saturn's magnetosphere induces a complex organic chemistry between these two constituents leading to the production of more complex molecules and subsequently to solid aerosols. These aerosols in suspension in the atmosphere form the haze layers giving Titan its characteristic orange color. Since 2004, the instruments onboard the Cassini orbiter have produced large amounts of observational data, unraveling a chemistry much more complex than what was first expected, particularly in Titan's upper atmosphere. Neutral, positively and negatively charged heavy molecules have been detected in the ionosphere of Titan, including benzene (C6H6) and toluene (C6H5CH3). The presence of these critical precursors of polycyclic aromatic hydrocarbon (PAH) compounds suggests that PAHs might play a role in the production of Titan's aerosols. The aim of the Titan Haze Simulation (THS) experiment, developed at the NASA Ames COSmIC facility, is to study the chemical pathways that link the simple molecules resulting from the first steps of the N2-CH4 chemistry to benzene, and to PAHs and nitrogen-containing PAHs (PANHs) as precursors to the production of solid aerosols. In the THS experiment, Titan's atmospheric chemistry is simulated by plasma in the stream of a supersonic expansion. With this unique design, the gas mixture is cooled to Titan-like temperature (~150K) before inducing the chemistry by plasma discharge. Due to the short residence time of the gas in the plasma discharge, the THS experiment can be used to probe the first and intermediate steps of Titan's chemistry by injecting different gas mixtures in the plasma. The products of the chemistry are detected and studied using two complementary techniques: Cavity Ring Down Spectroscopy and Time-Of-Flight Mass Spectrometry. Thin tholin deposits are also produced

  12. Mimicking enzymatic active sites on surfaces for energy conversion chemistry.

    PubMed

    Gutzler, Rico; Stepanow, Sebastian; Grumelli, Doris; Lingenfelder, Magalí; Kern, Klaus

    2015-07-21

    Metal-organic supramolecular chemistry on surfaces has matured to a point where its underlying growth mechanisms are well understood and structures of defined coordination environments of metal atoms can be synthesized in a controlled and reproducible procedure. With surface-confined molecular self-assembly, scientists have a tool box at hand which can be used to prepare structures with desired properties, as for example a defined oxidation number and spin state of the transition metal atoms within the organic matrix. From a structural point of view, these coordination sites in the supramolecular structure resemble the catalytically active sites of metallo-enzymes, both characterized by metal centers coordinated to organic ligands. Several chemical reactions take place at these embedded metal ions in enzymes and the question arises whether these reactions also take place using metal-organic networks as catalysts. Mimicking the active site of metal atoms and organic ligands of enzymes in artificial systems is the key to understanding the selectivity and efficiency of enzymatic reactions. Their catalytic activity depends on various parameters including the charge and spin configuration in the metal ion, but also on the organic environment, which can stabilize intermediate reaction products, inhibits catalytic deactivation, and serves mostly as a transport channel for the reactants and products and therefore ensures the selectivity of the enzyme. Charge and spin on the transition metal in enzymes depend on the one hand on the specific metal element, and on the other hand on its organic coordination environment. These two parameters can carefully be adjusted in surface confined metal-organic networks, which can be synthesized by virtue of combinatorial mixing of building synthons. Different organic ligands with varying functional groups can be combined with several transition metals and spontaneously assemble into ordered networks. The catalytically active metal

  13. Molecular metal catalysts on supports: organometallic chemistry meets surface science.

    PubMed

    Serna, Pedro; Gates, Bruce C

    2014-08-19

    -support bonding and structure, which identify the supports as ligands with electron-donor properties that influence reactivity and catalysis. Each of the catalyst design variables has been varied independently, illustrated by mononuclear and tetranuclear iridium on zeolite HY and on MgO and by isostructural rhodium and iridium (diethylene or dicarbonyl) complexes on these supports. The data provide examples resolving the roles of the catalyst design variables and place the catalysis science on a firm foundation of organometallic chemistry linked with surface science. Supported molecular catalysts offer the advantages of characterization in the absence of solvents and with surface-science methods that do not require ultrahigh vacuum. Families of supported metal complexes have been made by replacement of ligands with others from the gas phase. Spectroscopically identified catalytic reaction intermediates help to elucidate catalyst performance and guide design. The methods are illustrated for supported complexes and clusters of rhodium, iridium, osmium, and gold used to catalyze reactions of small molecules that facilitate identification of the ligands present during catalysis: alkene dimerization and hydrogenation, H-D exchange in the reaction of H2 with D2, and CO oxidation. The approach is illustrated with the discovery of a highly active and selective MgO-supported rhodium carbonyl dimer catalyst for hydrogenation of 1,3-butadiene to give butenes. PMID:25036259

  14. Spatial And Temporal Variation In The Dissolved Trace Element Chemistry Of Chesapeake Bay Surface Waters

    NASA Astrophysics Data System (ADS)

    Dorval, E.; Hannigan, R.; Jones, C.

    2001-12-01

    Surface waters were collected from sea grass beds around the Chesapeake Bay of Virginia as well as from the mouths of the York, James, Potomac and Rappahannock rivers and Tangier and Smith islands. These sea grass beds represent the nursery habitats for a variety of sport fish including Spotted Sea Trout and Weakfish. Trace element ratios of fish otoliths record the unique chemistries of bodies of water in which the fish live. The data presented here represent the initial results of a "ground-truthing" investigation of the relationships between the water and otolith chemistry. Waters were collected bi-monthly (July through September) from 30 sites around the western and eastern shore of Chesapeake Bay including major tributaries and Tangier and Smith islands. Water was collected using trace metal clean procedures including filtration through a 0.45 uM filter and acidification in the field to pH < 2 with ultra-pure nitric acid. Dissolved trace element composition was measured by sector field ICP-MS. The trace element chemistry of samples show both spatial and temporal variation. Using discriminant analysis it is not possible to statistically classify samples to the respective zones (western shore, eastern shore or islands) but it is possible to separate samples from the Tangier and Smith island sites from the eastern and western shore sites. Elements that allow this classification include Ce and Th, which are found in higher concentration in the samples from the island sites than in the eastern and western shore samples. These relationships follow the trends observed in pH and dissolved oxygen likely related to a restricted flow regime between the islands and the eastern shore. Mg/Ca and Sr/Ca ratios are unique for the sea grass beds along the western shore and allow the distinction of beds located between the York and Rappahannock rivers from those between the Rappahannock and Potomac rivers. Sr and Ba concentrations are variable between sites along the eastern

  15. Tuning of nanoparticle biological functionality through controlled surface chemistry and characterisation at the bioconjugated nanoparticle surface

    NASA Astrophysics Data System (ADS)

    Hristov, Delyan R.; Rocks, Louise; Kelly, Philip M.; Thomas, Steffi S.; Pitek, Andrzej S.; Verderio, Paolo; Mahon, Eugene; Dawson, Kenneth A.

    2015-12-01

    We have used a silica - PEG based bionanoconjugate synthetic scheme to study the subtle connection between cell receptor specific recognition and architecture of surface functionalization chemistry. Extensive physicochemical characterization of the grafted architecture is capable of capturing significant levels of detail of both the linker and grafted organization, allowing for improved reproducibility and ultimately insight into biological functionality. Our data suggest that scaffold details, propagating PEG layer architecture effects, determine not only the rate of uptake of conjugated nanoparticles into cells but also, more significantly, the specificity of pathways via which uptake occurs.

  16. Roles of surface chemistry on safety and electrochemistry in lithium ion batteries.

    PubMed

    Lee, Kyu Tae; Jeong, Sookyung; Cho, Jaephil

    2013-05-21

    Motivated by new applications including electric vehicles and the smart grid, interest in advanced lithium ion batteries has increased significantly over the past decade. Therefore, research in this field has intensified to produce safer devices with better electrochemical performance. Most research has focused on the development of new electrode materials through the optimization of bulk properties such as crystal structure, ionic diffusivity, and electric conductivity. More recently, researchers have also considered the surface properties of electrodes as critical factors for optimizing performance. In particular, the electrolyte decomposition at the electrode surface relates to both a lithium ion battery's electrochemical performance and safety. In this Account, we give an overview of the major developments in the area of surface chemistry for lithium ion batteries. These ideas will provide the basis for the design of advanced electrode materials. Initially, we present a brief background to lithium ion batteries such as major chemical components and reactions that occur in lithium ion batteries. Then, we highlight the role of surface chemistry in the safety of lithium ion batteries. We examine the thermal stability of cathode materials: For example, we discuss the oxygen generation from cathode materials and describe how cells can swell and heat up in response to specific conditions. We also demonstrate how coating the surfaces of electrodes can improve safety. The surface chemistry can also affect the electrochemistry of lithium ion batteries. The surface coating strategy improved the energy density and cycle performance for layered LiCoO2, xLi2MnO3·(1 - x)LiMO2 (M = Mn, Ni, Co, and their combinations), and LiMn2O4 spinel materials, and we describe a working mechanism for these enhancements. Although coating the surfaces of cathodes with inorganic materials such as metal oxides and phosphates improves the electrochemical performance and safety properties of

  17. The Consequences of Surface Confinement on Free Radical Chemistry

    SciTech Connect

    Birtt, P.F.; Buchanan, A.C., III

    1999-08-22

    Mass transport limitations impact the thermochemical processing of fossil and renewable energy resources, which involves the breakdown of cross-linked, macromolecular networks. To Investigate the molecular level details of the consequences of molecular confinement on high temperature (275-500°C) free-radical reaction pathways, we have been examining the pyrolysis of model compounds attached to the surface of non-porous silica nanoparticles through a thermally robust Si-O-Caryl, tetha. Pyrolysis of silica-immobilized diphenylalkanes and related ethers have been studied in detail and compared with the corresponding behavior in fluid phases. The diffusional constraints can lead to reduced rates of radical termination on the surface, and enhancement of neophyl-like rearrangements, cyclization-dehydrogenation pathways, and ipso- aromatic substitutions. Furthermore, studies of two-component surfaces have revealed the importance of a radical relay mechanism involving rapid serial hydrogen transfer steps resulting from the molecular pre-organization on the low fractal dimension silica surface. Key findings are reviewed in this paper, and the implications of these results for fuel processing are described.

  18. Aluminum in acidic surface waters: chemistry, transport, and effects.

    PubMed Central

    Driscoll, C T

    1985-01-01

    Ecologically significant concentrations of Al have been reported in surface waters draining "acid-sensitive" watersheds that are receiving elevated inputs of acidic deposition. It has been hypothesized that mineral acids from atmospheric deposition have remobilized Al previously precipitated within the soil during soil development. This Al is then thought to be transported to adjacent surface waters. Dissolved mononuclear Al occurs as aquo Al, as well as OH-, F-, SO4(2-), and organic complexes. Although past investigations have often ignored non-hydroxide complexes of Al, it appears that organic and F complexes are the predominant forms of Al in dilute (low ionic strength) acidic surface waters. The concentration of inorganic forms of Al increases exponentially with decreases in solution pH. This response is similar to the theoretical pH dependent solubility of Al mineral phases. The concentration of organic forms of Al, however, is strongly correlated with variations in organic carbon concentration of surface waters rather than pH. Elevated concentrations of Al in dilute acidic waters are of interest because: Al is an important pH buffer; Al may influence the cycling of important elements like P, organic carbon, and trace metals; and Al is potentially toxic to aquatic organisms. An understanding of the aqueous speciation of Al is essential for an evaluation of these processes. PMID:3935428

  19. Degradation of Environmental Contaminants with Water-Soluble Cobalt Catalysts: An Integrative Inorganic Chemistry Investigation

    ERIC Educational Resources Information Center

    Evans, Alexandra L.; Messersmith, Reid E.; Green, David B.; Fritsch, Joseph M.

    2011-01-01

    We present an integrative laboratory investigation incorporating skills from inorganic chemistry, analytical instrumentation, and physical chemistry applied to a laboratory-scale model of the environmental problem of chlorinated ethylenes in groundwater. Perchloroethylene (C[subscript 2]Cl[subscript 4], PCE) a common dry cleaning solvent,…

  20. Using Think-Aloud Protocols to Investigate Secondary School Chemistry Teachers' Misconceptions about Chemical Equilibrium

    ERIC Educational Resources Information Center

    Cheung, Derek

    2009-01-01

    Secondary school chemistry teachers' understanding of chemical equilibrium was investigated through interviews using the think-aloud technique. The interviews were conducted with twelve volunteer chemistry teachers in Hong Kong. Their teaching experience ranged from 3 to 18 years. They were asked to predict what would happen to the equilibrium…

  1. An Investigation of College Chemistry Students' Understanding of Structure-Property Relationships

    ERIC Educational Resources Information Center

    Cooper, Melanie M.; Corley, Leah M.; Underwood, Sonia M.

    2013-01-01

    The connection between the molecular-level structure of a substance and its macroscopic properties is a fundamental concept in chemistry. Students in college-level general and organic chemistry courses were interviewed to investigate how they used structure-property relationships to predict properties such as melting and boiling points. Although…

  2. Electronically non-adiabatic influences in surface chemistry and dynamics.

    PubMed

    Wodtke, Alec M

    2016-07-01

    Electronically nonadiabatic interactions between molecules and metal surfaces are now well known. Evidence is particularly clear from studies of diatomic molecules that molecular vibration can be strongly coupled to electrons of the metal leading to efficient energy transfer between these two kinds of motion. Since molecular vibration is the same motion needed for bond breaking, it is logical to postulate that electronically nonadiabatic influences on surface chemical reaction probabilities would be strong. Still there are few if any examples where such influences have been clearly investigated. This review recounts the evidence for and against the aforementioned postulate emphasizing reacting systems that have yet to receive full attention and where electronically nonadiabatic influence of reaction probabilities might be clearly demonstrated. PMID:27152489

  3. Ice surface chemistry relevant to stratospheric ozone depletion

    NASA Astrophysics Data System (ADS)

    Geiger, Franz Martin

    The surface specific nonlinear laser spectroscopy method second harmonic generation (SHG) is used to investigate the heterogeneously catalyzed hydrolysis of chlorine nitrate (ClONO2) on ice, a key reaction in stratospheric ozone depletion occurring in the presence of polar stratospheric cloud (PSC) ice particles formed during the polar winter. The reaction, yielding hypochlorous acid (HOCl) and nitric acid (HNO3), is studied directly and in real time on a single crystal basal ice (Ih) surface maintained under typical conditions of the polar stratosphere. The ice crystal is kept in equilibrium with its vapor pressure. Polarization studies are consistent with the clean basal ice surface at 158K being 3m symmetric, in contrast to proposals by others that the surface is disordered. The symmetry is retained upon HNO3 adsorption; this observation disagrees with proposals by others that this could cause surface melting. A SHG spectrum from 290 to 310 nm is obtained from HOCl on ice; this spectrum resembles the electronic spectrum of HOCl and serves as an identification tool for adsorbed HOCl. HOCl adsorption onto ice is instantaneous and occurs in registry with the underlying ice lattice. Measured isothermal rate constants for HOCl desorption from ice result in an activation energy for desorption of 36 +/- 2 kJ/mol. When submonolayer amounts of ClONO2 are hydrolyzed on the ice surface, the SHG vs. time traces show no changes for hundreds of seconds, then a sigmoidal increase, and eventually a constant value. The SHG increase is related to the appearance of HOCl. Predosing experiments show that the delay times are due to autocatalysis, with the HOCl product being a possible autocatalyst. The HNO3 co-product, on the other hand, acts as a surface poison and inhibits HOCl desorption. A molecular reaction mechanism, based on one proposed by Bianco and Hynes, is presented and discussed in light of the obtained experimental data, supporting ab initio calculations, and numerical

  4. Elementary surface chemistry during CuO/Al nanolaminate-thermite synthesis: copper and oxygen deposition on aluminum (111) surfaces.

    PubMed

    Lanthony, Cloé; Guiltat, Mathilde; Ducéré, Jean Marie; Verdier, Agnes; Hémeryck, Anne; Djafari-Rouhani, Mehdi; Rossi, Carole; Chabal, Yves J; Estève, Alain

    2014-09-10

    The surface chemistry associated with the synthesis of energetic nanolaminates controls the formation of the critical interfacial layers that dominate the performances of nanothermites. For instance, the interaction of Al with CuO films or CuO with Al films needs to be understood to optimize Al/CuO nanolaminates. To that end, the chemical mechanisms occurring during early stages of molecular CuO adsorption onto crystalline Al(111) surfaces are investigated using density functional theory (DFT) calculations, leading to the systematic determination of their reaction enthalpies and associated activation energies. We show that CuO undergoes dissociative chemisorption on Al(111) surfaces, whereby the Cu and O atoms tend to separate from each other. Both Cu and O atoms form islands with different properties. Copper islanding fosters Cu insertion (via surface site exchange mechanism) into the subsurface, while oxygen islands remain stable at the surface. Above a critical local oxygen coverage, aluminum atoms are extracted from the Al surface, leading to oxygen-aluminum intermixing and the formation of aluminum oxide (γ-alumina). For Cu and O co-deposition, copper promotes oxygen-aluminum interaction by oxygen segregation and separates the resulting oxide from the Al substrate by insertion into Al and stabilization below the oxide front, preventing full mixing of Al, Cu, and O species. PMID:25089744

  5. Monsoon Season Surface Water Chemistry Response Following Wildfire: 2003 Aspen Fire in Sabino Canyon, Arizona

    NASA Astrophysics Data System (ADS)

    Einloth, S. L.; Chief, K. D.; Ekwurzel, B.; Nijssen, B.; Ferré, P. A.

    2003-12-01

    The Aspen Fire in the Coronado National Forest north of Tucson burned in excess of 80,000 acres and destroyed more than 300 structures. Exposed, burned soils are highly vulnerable to intense monsoon rains, leading to increases in surface runoff, peak flows, and erosion rates. As part of an integrated investigation of the hydrologic impacts of this fire, we rapidly mobilized a field sampling campaign during the 2003 monsoon season that began immediately following the resolution of the fire. Stream water chemistry serves as an integrated signal of many watershed processes: precipitation, runoff, infiltration, soil hydrophobic layers, ash deposition in the stream, debris flows, and subsequent water/ash chemical equilibrium reactions. The portion of the watershed that has been burned by the Aspen fire covers a wide range of elevation and vegetation zones of the Santa Catalina Mountains. Many biogeochemical and hydrological processes within this area were altered by a sudden lack of vegetation and changes in soil properties following a fire: evapotranspiration, litter volume, organic decomposition, leaching, cation exchange, anion sorption, nutrient uptake, and soil hydrophobic layers. Surface water and precipitation samples were collected following an event-based sampling strategy, while soil samples were collected in each vegetation and burn severity regime. Precipitation samples were collected to characterize temperature and elevation effects on precipitation chemistry, in particular stable isotopes. The surface water chemistry changes measured throughout each hydrograph event can be linked to air permeameter results, a rapid measurement for soil hydraulic conductivity, for the different burn severity and vegetation zone regimes. Both nutrient and suspended sediment loads greatly increased following the fire. A debris flow mobilized large diameter boulders. Stream gauge flow event peaks were larger than expected given concurrent extensive precipitation gauge network

  6. Surface chemistry of hierarchical nanosprings for sensing and catalysis

    NASA Astrophysics Data System (ADS)

    Fouetio Kengne, Blaise-Alexis

    Silica nanosprings (NS) were grown and their surface chemistry was modified depending upon the application. For explosive detection, NS were subsequently coated with ZnO, decorated with metal nanoparticles, and functionalized with thiols; while NS supported cobalt catalysts (Co/NS) were prepared for Fischer-Tropsch synthesis (FTS). Scanning and transmission electron microscopies (SEM and TEM), X-ray diffraction (XRD), N2 physisorption, H2-temperatature programmed reduction (H2-TPR, and X-ray and ultraviolet photoelectron spectroscopies (XPS and UPS) have been used to characterize the hierarchical NS. Based on XPS analysis of the thiolated NS, a single S 2p core level is observed for 4-mercaptobenzoic acid and11-(1-pyrenyl)-1-undecathiol, which is assigned to the S-Au bond. The S 2p core level of L-cysteine, 6-mercaptohexanol and DL-thioctic acid consists of two doublets, where one is S-Au bond and the other is the S-Zn bond. UPS analysis shows that the hybridization of the S 3p states and the Au d-bands produces antibonding and bonding states, above and below the Au d-bands, which is characteristic of molecular chemisorption on Au nanoparticles. Gas sensors functionalized with functionalized with 4-mercaptobenzoic acid and 6-mercaptohexanol showed the strongest responses to ammonium nitrate by factors of 4 to 5, respectively, relative to the less responsive thiols. For FTS, even though Co/NS had 75 times less gravimetric Co content than the reference catalyst, without being fully reduced, it still showed higher activity. This is attributed to higher Co dispersion on NS and greater gases acessibility. In situ XPS has been used to monitor the reduction of Co/NS. The analysis shows that cobalt is present in the starting catalyst as a Co 3O4 spinel phase. At 385 ºC and 10-6 Torr of H2 a two-step reduction from Co3O4 to CoO and then to Co0 is observed, which is consistent with H2-TPR results. The two reduction steps are concurrent. The reduction saturates at the value

  7. Surface Chemistry of Nanocellulose Fibers Directs Monocyte/Macrophage Response.

    PubMed

    Hua, Kai; Ålander, Eva; Lindström, Tom; Mihranyan, Albert; Strømme, Maria; Ferraz, Natalia

    2015-09-14

    The effect of surface functionalization of nanofibrillated cellulose (NFC) on monocyte/macrophage (MM) behavior is investigated to understand how the physicochemical properties of nanocelluloses influence the interactions of such materials with biological systems. Films of anionic (a-), cationic (c-), and unmodified (u-) NFC were synthesized and characterized in terms of surface charge. THP-1 monocytes were cultured on the surface of the films for 24 h in the presence and absence of lipopolysaccharide, and the cell response was evaluated in terms of cell adhesion, morphology, and secretion of TNF-α, IL-10, and IL-1ra. The results show that MMs cultured on carboxymethylated-NFC films (a-NFC) are activated toward a proinflammatory phenotype, whereas u-NFC promotes a mild activation of the studied cells. The presence of hydroxypropyltrimethylammonium groups on c-NFC, however, does not promote the activation of MMs, indicating that c-NFC closely behaves as an inert material in terms of MM activation. None of the materials is able to directly activate the MMs toward an anti-inflammatory response. These results may provide a foundation for the design of future NFC-based materials with the ability to control MM activation and may expand the use of NFC in biomedical applications. PMID:26247827

  8. Investigating the impact of adding an environmental focus to a developmental chemistry class

    NASA Astrophysics Data System (ADS)

    Robelia, Beth A.

    Making chemistry more relevant to students has been a goal of many curriculum projects. None of these projects have investigated how specific applications of chemistry impact student learning or environmental mindset. The goal of this study was to examine how focusing attention on environmental issues as applications of chemistry concepts would affect students' understanding of general chemistry or environmental chemistry as well environmental attitudes, behaviors and knowledge. Special attention was paid to how women responded to the addition of an environmental focus because prior research indicated women hold more pro-environmental attitudes but are less knowledgeable about environmental topics. The quasi-experimental design used two treatment groups and a comparison group. Both treatment groups received instruction with a Science-Technology-Society orientation, one group focused on environmental applications of chemistry while the other drew applications of chemistry from a number of different fields students might be familiar with such as health care, food science and forensics. The comparison groups used mainly traditional examples from chemistry laboratories. In order to avoid testing the effect of the instructor, two people co-taught both treatment sections. Students in all three groups took a general chemistry assessment at the beginning and end of the course. The treatment groups took a pre and post environmental chemistry assessment and a survey of their environmental attitudes, behaviors and knowledge. Results indicate that students in the environmentally focused section may have made slight gains in general chemistry knowledge. Gains in environmental chemistry knowledge were not significantly different. Students also made modest gains in environmental attitude. Results for women mirrored results for the classes as a whole.

  9. Research Program to Investigate the Fundamental Chemistry of Technetium

    SciTech Connect

    Edelstein, Norman M.; Burns, Carol J.; Shuh, David D.; Lukens, Wayne

    2000-06-01

    Technetium (99Tc, half-life = 2.13x105 years, b-emitter) is one of the radionuclides of major concern for nuclear waste disposal. This concern is due to the long half-life of 99Tc, the ease with which pertechnetate, TcO4 -, migrates in the geosphere, and the corresponding regulatory considerations. The problem of mobility of pertechnetate in the environment is compounded by the fact that pertechnetate is the thermodynamically stable form of technetium in aerobic environments. These two factors present challenges for the safe, long term immobilization of technetium in waste forms. Because of the stability of pertechnetate, technetium has been assumed to exist as pertechnetate in the aqueous phase of nuclear waste tanks. However, recent studies indicate that a significant fraction of the technetium is in a different chemical form. This program addresses the fundamental solution chemistry of technetium in the waste tank environment, and in a second part, the stability of technetium in various waste forms. The chemistry of this element will be studied in aqueous solutions at high pH, with various added salts such as nitrate, nitrite, and organic complexants, and as a function of radiation dose, to determine whether radiolysis effects can reduce TcO4 -. A separate facet of this research is the search for chemical forms of technetium that may be thermodynamically and/or kinetically stable and may be incorporated in various waste forms for long term storage. This phase of the program will address the problem of the possible oxidation of lower valent technetium species in various waste form matrices and the subsequent leaching of the highly soluble TcO4 -.

  10. Regional relationships between geomorphic/hydrologic parameters and surface water chemistry relative to acidic deposition

    SciTech Connect

    Rochelle, B.P.; Liff, C.I.; Campbell, W.G.; Cassell, D.L.; Church, M.R.

    1989-01-01

    The authors determined geomorphic and hydrologic parameters for 144 forested, lake watersheds in the Northeast (NE) of the United States based primarily on measurements from topographic maps. These parameters were used to test for relationships with selected surface water chemistry relevant to acidic deposition. Analyses were conducted on regional and subregional scales delineated based on soils, land use, physiography, total sulfur deposition and statistical clustering of selected geomorphic/hydrologic parameters. Significant relationships were found among the geomorphic/hydrologic parameters and the surface water chemistry for the NE. Elevation had the most significant relationship with surface water chemistry, particularly in the mountainous areas of the NE. Other factors occurring consistently as significant predictors of surface water chemistry were maximum relief, relief ratio, runoff, and estimates of basin elongation. Results suggest that elevational parameters might be surrogates for other watershed characteristics, such as soils or spatial deposition patterns.

  11. FROZEN GROUND CONTROL ON SNOWMELT FLOWPATHS AND SURFACE WATER CHEMISTRY IN TWO ALPINE BASINS

    EPA Science Inventory

    This study will increase our understanding of how snowmelt flowpaths are influenced by frozen ground in mid-latitude alpine basins. It also will elucidate how these flowpaths dictate surface water chemistry in relation to snowmelt.

  12. Bactericidal effects of plasma-modified surface chemistry of silicon nanograss

    NASA Astrophysics Data System (ADS)

    Ostrikov, Kola; Macgregor-Ramiasa, Melanie; Cavallaro, Alex; (Ken Ostrikov, Kostya; Vasilev, Krasimir

    2016-08-01

    The surface chemistry and topography of biomaterials regulate the adhesion and growth of microorganisms in ways that are still poorly understood. Silicon nanograss structures prepared via inductively coupled plasma etching were coated with plasma deposited nanometer-thin polymeric films to produce substrates with controlled topography and defined surface chemistry. The influence of surface properties on Staphylococcus aureus proliferation is demonstrated and explained in terms of nanograss substrate wetting behaviour. With the combination of the nanograss topography; hydrophilic plasma polymer coatings enhanced antimicrobial activity while hydrophobic coatings reduced it. This study advances the understanding of the effects of surface wettability on the bactericidal properties of reactive nano-engineered surfaces.

  13. Combining hierarchical surface roughness with fluorinated surface chemistry to preserve superhydrophobicity after organic contamination

    NASA Astrophysics Data System (ADS)

    Wang, Chih-Feng; Hung, Shih-Wei; Kuo, Shiao-Wei; Chang, Chi-Jung

    2014-11-01

    Surfaces exhibiting superhydrophobicity are attracting commercial and academic attention because of their potential applications in, for example, self-cleaning utensils, microfluidic systems, and microelectronic devices. In this study, we prepared a fluorinated superhydrophobic surface displaying nanoscale roughness, a superhydrophobic surface possessing a micro- and nanoscale binary structure, and a fluorinated superhydrophobic surface possessing such a binary structure. We investigated the effects of the (i) hierarchy of the surface topography and (ii) the surface chemical composition of the superhydrophobic carbon nanotube/polybenzoxazine coatings on their ability to retain superhydrophobicity upon contamination with particles and organic matter, an important characteristic for maintaining non-wetting properties under outdoor conditions. We have found that the topographical microstructure and the surface chemical composition are both important factors for preservation of the non-wetting properties of such superhydrophobic surfaces upon contamination with organic matter.

  14. Rosetta/VIRTIS investigation of the chemistry and activity of comet 67P/Churyumov-Gerasimenko

    NASA Astrophysics Data System (ADS)

    Bockelee-Morvan, Dominique; Drossart, Pierre; Piccioni, Giuseppe; Migliorini, Alessandra; Erard, Stéphane; Capaccioni, Fabrizio; Filacchione, Gianrico; Fougere, Nicolas; Leyrat, Cedric; Crovisier, Jacques; Capaccioni, Fabrizio

    2016-07-01

    The composition of cometary ices inside cometary nuclei provides clues to the chemistry of the protoplanetary disk where they formed, 4.6 Gyr ago. These ices sublimate when the body approches the Sun, so that the coma molecular species give insights on the nucleus surface and sub-surface composition. So far, most investigations of the coma chemical composition were performed from telescopic observations from the ground or space plateforms. Since August 2014, the ESA/Rosetta spacecraft has been investigating the nucleus and inner coma of 67P/Churyumov-Gerasimenko. This talk will present an overview of the results obtained by the Visual and Infrared Thermal Imaging Spectrometer (VIRTIS) instrument onboard Rosetta, focussing on observations of molecular species. VIRTIS is composed of two channels. The VIRTIS-M channel is a spectro-imager covering the 0.27-5.1 microns range, which allowed us to map the spatial distribution of H2O and CO2 (Migliorini et al. 2016, A&A in press). VIRTIS-H is a high-spectral resolution spectrometer covering the 2-5 microns range. Spectra obtained with VIRTIS-H show signatures of H2O, CO2 (both fundamental and hot bands), 13CO2, CH4 and other C-H bearing species (Bockelee-Morvan et al. A&A, 583, A6,2015). VIRTIS is a key instrument to investigate regional, diurnal and seasonal variations of the comet outgassing.

  15. Influence of the carbon fiber surface microstructure on the surface chemistry generated by a thermo-chemical surface treatment

    NASA Astrophysics Data System (ADS)

    Vautard, F.; Ozcan, S.; Paulauskas, F.; Spruiell, J. E.; Meyer, H.; Lance, M. J.

    2012-11-01

    Carbon fibers made of textile and aerospace grade polyacrylonitrile precursor fibers were surface treated by a continuous gas phase thermochemical treatment. The surface chemistry generated by the surface treatment was characterized by X-ray photoelectron spectroscopy. The surface and the average entire microstructure of the fibers were characterized by Raman spectroscopy and X-ray diffraction, respectively. Depending on the grade of the precursor, the final surface concentration of oxygen was comprised between 14% and 24%, whereas the typical commercial electrochemical surface treatments led to concentrations of around 8% with the same fibers. The final concentration of oxygen was directly correlated to the size of the crystallites which was a function of the grade of the polyacrylonitrile precursor and to the corresponding surface microstructure. The thermochemical surface treatment enabled a better control of the nature of the oxygen-containing functionalities as well. Whatever the grade of the precursor, desired hydroxyl groups and carboxylic acid functionalities were preferably generated, which is observed to be difficult with electrochemical surface treatments.

  16. Influence of the carbon fiber surface microstructure on the surface chemistry generated by a thermo-chemical surface treatment

    SciTech Connect

    Vautard, Frederic; Ozcan, Soydan; Paulauskas, Felix L; Spruiell, J. E.; Meyer III, Harry M; Lance, Michael J

    2012-01-01

    Carbon fibers made of textile and aerospace grade polyacrylonitrile precursor fibers were surface treated by a continuous gas phase thermo-chemical treatment. The surface chemistry generated by the surface treatment was characterized by X-ray photoelectron spectroscopy. The surface and the average entire micro-structure of the fibers were characterized by Raman spectroscopy and X-ray diffraction, respectively. Depending on the grade of the precursor, the final surface concentration of oxygen was comprised between 14% and 24%, whereas the typical commercial electro-chemical surface treatments led to concentrations of around 8% with the same fibers. The final concentration of oxygen was directly correlated to the size of the crystallites which was a function of the grade of the polyacrylonitrile precursor and to the corresponding surface micro-structure. The thermo-chemical surface treatment enabled a better control of the nature of the oxygen-containing functionalities as well. Whatever the grade of the precursor, desired hydroxyl groups and carboxylic acid functionalities were preferably generated, which was not observed with electro-chemical surface treatments.

  17. Random Phase Approximation in Surface Chemistry: Water Splitting on Iron.

    PubMed

    Karlický, František; Lazar, Petr; Dubecký, Matúš; Otyepka, Michal

    2013-08-13

    The reaction of water with zero-valent iron (anaerobic corrosion) is a complex chemical process involving physisorption and chemisorption events. We employ random phase approximation (RPA) along with gradient-corrected and hybrid density functional theory (DFT) functionals to study the reaction of water with the Fe atom and Fe(100) surface. We show that the involvement of the exact electron exchange and nonlocal correlation effects in RPA improves the description of all steps of the reaction on the Fe surface with respect to standard [meaning local density approximation (LDA) or generalized gradient approximation (GGA)] DFT methods. The reaction profile calculated by range-separated hybrid functional HSE06 agrees reasonably well with the RPA profile, which makes HSE06 a computationally less demanding alternative to RPA. We also investigate the reaction of the Fe atom with water using DFT, RPA, and coupled-cluster through the perturbative triples complete basis set [CCSD(T)-3s3p-DKH/CBS] method. Local DFT methods significantly underestimate reaction barriers, while the reaction kinetics and thermodynamics from RPA agree with the reference CCSD(T) data. Both systems, i.e., the Fe atom and Fe(100), provide the same reaction mechanism, indicating that anaerobic corrosion is a stepwise process involving one-electron steps, with the first reaction step (formation of the HFeOH intermediate) representing the rate-limiting step. PMID:26584120

  18. Effect of Surface Chemistry on Water Interaction with Cu(111).

    PubMed

    Antony, Andrew C; Liang, Tao; Akhade, Sneha A; Janik, Michael J; Phillpot, Simon R; Sinnott, Susan B

    2016-08-16

    The interfacial dynamics of water in contact with bare, oxidized, and hydroxylated copper surfaces are examined using classical molecular dynamics (MD) simulations. A third-generation charge-optimized many-body (COMB3) potential is used in the MD simulations to investigate the adsorption of water molecules on Cu(111), and the results are compared to the findings of density functional theory (DFT) calculations. The adsorption energies and structures predicted by COMB3 are generally consistent with those determined with DFT. The COMB3 potential is then used to investigate the wetting behavior of water nanodroplets on Cu(111) at 20, 130, and 300 K. At room temperature, the simulations predict that the spreading rate of the base radius, R0, of a water droplet with a diameter of about 1.5 nm exhibits a spreading rate of R0 ≈ t(0.16) and a final base radius of 3.5 nm. At 20 and 130 K, water droplets are predicted to retain their structure after adsorption on Cu(111) and to undergo minimal spreading in agreement with scanning tunneling microscopy data. When the same water droplet encounters a reconstructed, oxidized Cu(111) surface, the classical MD simulations predict wetting with a spreading rate of R ≈ t(0.14) and a final base radius of 3.0 nm. Similarly, our MD simulations predict a spreading rate of R ≈ t(0.14) and a final base radius of 2.5 nm when water encounters OH-covered Cu(111). These results indicate that oxidation and hydroxylation cause a reduction in the degree of spreading and final base radius that is directly associated with a decreased spreading rate for water nanodroplets on copper. PMID:27442055

  19. Comparison of surface modification chemistries in mouse, porcine, and human islets.

    PubMed

    SoRelle, Jeffrey A; Kanak, Mazhar A; Itoh, Takeshi; Horton, Joshua M; Naziruddin, Bashoo; Kane, Robert R

    2015-03-01

    Beta cell replacement therapy, the transplantation of isolated pancreatic islets by intraportal infusion, offers patients with brittle type 1 diabetes blood glucose regulation with a minimally invasive technique. Chemical modification of islets prior to transplantation, providing a nanothin barrier that potentially includes active protective compounds, has been proposed as a strategy to minimize the inflammatory and immune reactions that often significantly limit graft function and duration. Chemical modification also has the potential to allow the use of alternative sources of islets, such as porcine islets, for transplantation. This investigation compared three orthogonal covalent islet modification techniques across three species (human, porcine, and murine), using multiple measures to determine biocompatibility and effectiveness. All three conjugation chemistries were well tolerated, and the overall efficiency, gross uniformity, and stability of the surface modifications were dependent upon the conjugation chemistry as well as the islet source (human, porcine, or murine). Notably, the reductive modification of surface disulfides was shown to afford intense and long-lasting modification of human islets. This study demonstrates that murine, human, and porcine islets tolerate a variety of covalent modifications, that these modifications are relatively stable, and that the murine islet model may not be predictive for some chemical contexts. PMID:24829144

  20. Seventh BES (Basic Energy Sciences) catalysis and surface chemistry research conference

    SciTech Connect

    Not Available

    1990-03-01

    Research programs on catalysis and surface chemistry are presented. A total of fifty-seven topics are included. Areas of research include heterogeneous catalysis; catalysis in hydrogenation, desulfurization, gasification, and redox reactions; studies of surface properties and surface active sites; catalyst supports; chemical activation, deactivation; selectivity, chemical preparation; molecular structure studies; sorption and dissociation. Individual projects are processed separately for the data bases. (CBS)

  1. Surface and coordination chemistry related to GaAs

    NASA Astrophysics Data System (ADS)

    Keys, Andrea

    The vapor phase structures of Al(tBU)3 and Ga(tBU)3 have been investigated by gas phase electron diffraction and consist of planar three-coordinate monomers. Salient structural parameters (ra) include: Al-C = 2.005(3) A, Ga-C = 2.034(2) A. The geometries are controlled by inter-ligand interactions. The electron diffraction structures are compared to those determined by ab initio calculations for M(tBU)3 (M = Al, Ga, In). To understand the most suitable linkages for the surface of GaAs, model compounds were synthesized by reacting Ga(tBU)3 and [tBu2Ga(mu-Cl]2 with one molar equivalent of varying ligands. The synthesized compounds include chlorides, benzenethiolate, dithiocarbamates, carboxylates, amides, benzohydroxamate, and phenylphosphonate. The Ga ⋯ Ga and Ga-ligand interatomic distances for these compounds, as well as Group 15 and 16 donor bridging ligands, are compared to the values for the surface of GaAs and cubic-GaS in order to determine their suitability as linkage groups for self-assembled monolayers. The most suitable linkages were determined to be benzenethiol and phenylphophonic acid, and these were used to grow self-assembled monolayers on {100} GaAs. Carboxylic acid was also used, to determine the success of the organometallic model compounds in predicting the suitability of ligands for surface reaction. Self-assembled monolayers were also grown on Al2O3, using carboxylic acids and phenylphosphonic acids as the surface linkages. Metallo-organic chemical vapor deposition was performed using single-source precursors ( tBU)2Ga(S2CNR2). The tert -butyl gallium bis-dialkyl-dithiocarbamate compounds, (tBu)Ga(S2CNR2)2, are formed as minor products via ligand disproportionation reactions. Gallium sulfide (GaS) thin films have been grown at 375-425°C by atmospheric pressure metal-organic chemical vapor deposition using compounds (tBu) 2Ga(S2CNMe2) and (tBu)2Ga(S 2CNEt2) as single source precursors. Polycrystalline samples of the chalcogenides InSe, In2Se3

  2. Spectroscopic and computational investigation of actinium coordination chemistry.

    PubMed

    Ferrier, Maryline G; Batista, Enrique R; Berg, John M; Birnbaum, Eva R; Cross, Justin N; Engle, Jonathan W; La Pierre, Henry S; Kozimor, Stosh A; Lezama Pacheco, Juan S; Stein, Benjamin W; Stieber, S Chantal E; Wilson, Justin J

    2016-01-01

    Actinium-225 is a promising isotope for targeted-α therapy. Unfortunately, progress in developing chelators for medicinal applications has been hindered by a limited understanding of actinium chemistry. This knowledge gap is primarily associated with handling actinium, as it is highly radioactive and in short supply. Hence, Ac(III) reactivity is often inferred from the lanthanides and minor actinides (that is, Am, Cm), with limited success. Here we overcome these challenges and characterize actinium in HCl solutions using X-ray absorption spectroscopy and molecular dynamics density functional theory. The Ac-Cl and Ac-OH2O distances are measured to be 2.95(3) and 2.59(3) Å, respectively. The X-ray absorption spectroscopy comparisons between Ac(III) and Am(III) in HCl solutions indicate Ac(III) coordinates more inner-sphere Cl(1-) ligands (3.2±1.1) than Am(III) (0.8±0.3). These results imply diverse reactivity for the +3 actinides and highlight the unexpected and unique Ac(III) chemical behaviour. PMID:27531582

  3. Spectroscopic and computational investigation of actinium coordination chemistry

    PubMed Central

    Ferrier, Maryline G.; Batista, Enrique R.; Berg, John M.; Birnbaum, Eva R.; Cross, Justin N.; Engle, Jonathan W.; La Pierre, Henry S.; Kozimor, Stosh A.; Lezama Pacheco, Juan S.; Stein, Benjamin W.; Stieber, S. Chantal E.; Wilson, Justin J.

    2016-01-01

    Actinium-225 is a promising isotope for targeted-α therapy. Unfortunately, progress in developing chelators for medicinal applications has been hindered by a limited understanding of actinium chemistry. This knowledge gap is primarily associated with handling actinium, as it is highly radioactive and in short supply. Hence, AcIII reactivity is often inferred from the lanthanides and minor actinides (that is, Am, Cm), with limited success. Here we overcome these challenges and characterize actinium in HCl solutions using X-ray absorption spectroscopy and molecular dynamics density functional theory. The Ac–Cl and Ac–OH2O distances are measured to be 2.95(3) and 2.59(3) Å, respectively. The X-ray absorption spectroscopy comparisons between AcIII and AmIII in HCl solutions indicate AcIII coordinates more inner-sphere Cl1– ligands (3.2±1.1) than AmIII (0.8±0.3). These results imply diverse reactivity for the +3 actinides and highlight the unexpected and unique AcIII chemical behaviour. PMID:27531582

  4. Research program to investigate the fundamental chemistry of technetium

    SciTech Connect

    McKeown, David A.; Buechele, Andrew C.; Lukens, Wayne W.; Muller, Isabelle S.; Shuh, David K.; Pegg, Ian L.

    2007-10-12

    The objective of this research is to increase the knowledge of the fundamental technetium chemistry necessary to address challenges to the safe, long-term disposal of high-level nuclear waste posed by this element. The primary issues examined during the course of this project were the behavior of technetium and its surrogate rhenium during waste vitrification and glass corrosion. Since the redox behavior of technetium can play a large role in determining its volatility, one goal of this research was to better understand the behavior of technetium in glass as a function of the redox potential of the glass melt. In addition, the behavior of rhenium was examined, since rhenium is commonly used as a surrogate for technetium in waste vitrification studies. A number of glasses similar to Hanford Low Activity Waste (LAW) glasses were prepared under controlled atmospheres. The redox state of the glass was determined from the Fe(II)/Fe(III) ratio in the cooled glass, and the speciation of technetium and rhenium was determined by x-ray absorption fine structure (XAFS) spectroscopy. The behavior of rhenium and technetium during glass alteration was also examined using the vapor hydration test (VHT).

  5. PES Surface Modification Using Green Chemistry: New Generation of Antifouling Membranes.

    PubMed

    Nady, Norhan

    2016-01-01

    A major limitation in using membrane-based separation processes is the loss of performance due to membrane fouling. This drawback can be addressed thanks to surface modification treatments. A new and promising surface modification using green chemistry has been recently investigated. This modification is carried out at room temperature and in aqueous medium using green catalyst (enzyme) and nontoxic modifier, which can be safely labelled "green surface modification". This modification can be considered as a nucleus of new generation of antifouling membranes and surfaces. In the current research, ferulic acid modifier and laccase bio-catalyst were used to make poly(ethersulfone) (PES) membrane less vulnerable to protein adsorption. The blank and modified PES membranes are evaluated based on e.g., their flux and protein repellence. Both the blank and the modified PES membranes (or laminated PES on silicon dioxide surface) are characterized using many techniques e.g., SEM, EDX, XPS and SPM, etc. The pure water flux of the most modified membranes was reduced by 10% on average relative to the blank membrane, and around a 94% reduction in protein adsorption was determined. In the conclusions section, a comparison between three modifiers-ferulic acid, and two other previously used modifiers (4-hydroxybenzoic acid and gallic acid)-is presented. PMID:27096873

  6. PES Surface Modification Using Green Chemistry: New Generation of Antifouling Membranes

    PubMed Central

    Nady, Norhan

    2016-01-01

    A major limitation in using membrane-based separation processes is the loss of performance due to membrane fouling. This drawback can be addressed thanks to surface modification treatments. A new and promising surface modification using green chemistry has been recently investigated. This modification is carried out at room temperature and in aqueous medium using green catalyst (enzyme) and nontoxic modifier, which can be safely labelled “green surface modification”. This modification can be considered as a nucleus of new generation of antifouling membranes and surfaces. In the current research, ferulic acid modifier and laccase bio-catalyst were used to make poly(ethersulfone) (PES) membrane less vulnerable to protein adsorption. The blank and modified PES membranes are evaluated based on e.g., their flux and protein repellence. Both the blank and the modified PES membranes (or laminated PES on silicon dioxide surface) are characterized using many techniques e.g., SEM, EDX, XPS and SPM, etc. The pure water flux of the most modified membranes was reduced by 10% on average relative to the blank membrane, and around a 94% reduction in protein adsorption was determined. In the conclusions section, a comparison between three modifiers—ferulic acid, and two other previously used modifiers (4-hydroxybenzoic acid and gallic acid)—is presented. PMID:27096873

  7. Nanostructured surfaces investigated by quantitative morphological studies.

    PubMed

    Perani, Martina; Carapezzi, Stefania; Mutta, Geeta Rani; Cavalcoli, Daniela

    2016-05-01

    The morphology of different surfaces has been investigated by atomic force microscopy and quantitatively analyzed in this paper. Two different tools have been employed to this scope: the analysis of the height-height correlation function and the determination of the mean grain size, which have been combined to obtain a complete characterization of the surfaces. Different materials have been analyzed: SiO x N y , InGaN/GaN quantum wells and Si nanowires, grown with different techniques. Notwithstanding the presence of grain-like structures on all the samples analyzed, they present very diverse surface design, underlying that this procedure can be of general use. Our results show that the quantitative analysis of nanostructured surfaces allows us to obtain interesting information, such as grain clustering, from the comparison of the lateral correlation length and the grain size. PMID:27004458

  8. Nanostructured surfaces investigated by quantitative morphological studies

    NASA Astrophysics Data System (ADS)

    Perani, Martina; Carapezzi, Stefania; Rani Mutta, Geeta; Cavalcoli, Daniela

    2016-05-01

    The morphology of different surfaces has been investigated by atomic force microscopy and quantitatively analyzed in this paper. Two different tools have been employed to this scope: the analysis of the height-height correlation function and the determination of the mean grain size, which have been combined to obtain a complete characterization of the surfaces. Different materials have been analyzed: SiO x N y , InGaN/GaN quantum wells and Si nanowires, grown with different techniques. Notwithstanding the presence of grain-like structures on all the samples analyzed, they present very diverse surface design, underlying that this procedure can be of general use. Our results show that the quantitative analysis of nanostructured surfaces allows us to obtain interesting information, such as grain clustering, from the comparison of the lateral correlation length and the grain size.

  9. Adsorption of hydrogen sulfide onto activated carbon fibers: effect of pore structure and surface chemistry.

    PubMed

    Feng, Wenguo; Kwon, Seokjoon; Borguet, Eric; Vidic, Radisav

    2005-12-15

    To understand the nature of H2S adsorption onto carbon surfaces under dry and anoxic conditions, the effects of carbon pore structure and surface chemistry were studied using activated carbon fibers (ACFs) with different pore structures and surface areas. Surface pretreatments, including oxidation and heattreatment, were conducted before adsorption/desorption tests in a fixed-bed reactor. Raw ACFs with higher surface area showed greater adsorption and retention of sulfur, and heat treatment further enhanced adsorption and retention of sulfur. The retained amount of hydrogen sulfide correlated well with the amount of basic functional groups on the carbon surface, while the desorbed amount reflected the effect of pore structure. Temperature-programmed desorption (TPD) and thermal gravimetric analysis (TGA) showed that the retained sulfurous compounds were strongly bonded to the carbon surface. In addition, surface chemistry of the sorbent might determine the predominant form of adsorbate on the surface. PMID:16475362

  10. Physics and chemistry on well-defined semiconductor and oxide surfaces

    SciTech Connect

    Chen, Peijun

    1992-12-31

    High resolution electron energy loss spectroscopy (HREELS) and other surface spectroscopic techniques have been employed to investigate the following two classes of surface/interface phenomena on well-defined semiconductor and oxide surfaces: (i) the fundamental physical and chemical processes involved in gas-solid interaction on silicon single crystal surfaces, and (ii) the physical and chemical properties of metal-oxide interfaces. The particular systems reported in this dissertation are: NH{sub 3}, PH{sub 3} and B{sub 10}H{sub 14} on Si(111)-(7 x 7); NH{sub 3} on Si(100)-(2 x 1); atomic H on Si(111)-(7 x 7) and boron-modified Si(111); Al on Al{sub 2}O{sub 3} and Sn on SiO{sub 2}. On silicon surfaces, the surface dangling bonds function as the primary adsorption sites where surface chemical processes take place. The unambiguous identification of surface species by vibrational spectroscopy allow the elementary steps involved in these surface chemical processes to be followed on a molecular level. For adsorbate such as NH{sub 3} and PH{sub 3}, the nature of the initial low temperature (100-300 K) adsorption is found to be dissociative, while that for B{sub 10}H{sub 14} is non-dissociative. This has been deduced based upon the presence (or absence) of specific characteristic vibrational mode(s) on surface. By following the evolution of surface species as a function of temperature, the elementary steps leading to silicon nitride thin film growth and doping of silicon are elucidated. In the case of NH{sub 3} on Si(111)-(7 x7) and Si(100)-(2 x 1), a detailed understanding on the role of substrate surface structure is controlling the surface reactivity has been gained on the basis of a Si adatom backbond-strain relief mechanism on the Si(111)-(7 x 7). The electronic modification to Si(111) surface by subsurface boron doping has been shown to quench its surface chemistry, even for the most aggressive atomic H.

  11. Role(s) of adsorbed water in the surface chemistry of environmental interfaces.

    PubMed

    Rubasinghege, Gayan; Grassian, Vicki H

    2013-04-18

    The chemistry of environmental interfaces such as oxide and carbonate surfaces under ambient conditions of temperature and relative humidity is of great interest from many perspectives including heterogeneous atmospheric chemistry, heterogeneous catalysis, photocatalysis, sensor technology, corrosion science, and cultural heritage science. As discussed here, adsorbed water plays important roles in the reaction chemistry of oxide and carbonate surfaces with indoor and outdoor pollutant molecules including nitrogen oxides, sulfur dioxide, carbon dioxide, ozone and organic acids. Mechanisms of these reactions are just beginning to be unraveled and found to depend on the details of the reaction mechanism as well as the coverage of water on the surface. As discussed here, adsorbed water can: (i) alter reaction pathways and surface speciation relative to the dry surface; (ii) hydrolyze reactants, intermediates and products; (iii) enhance surface reactivity by providing a medium for ionic dissociation; (iv) inhibit surface reactivity by blocking sites; (v) solvate ions; (vi) enhance ion mobility on surfaces and (vii) alter the stability of surface adsorbed species. In this feature article, drawing on research that has been going on for over a decade on the reaction chemistry of oxide and carbonate surfaces under ambient conditions of temperature and relative humidity, a number of specific examples showing the multi-faceted roles of adsorbed water are presented. PMID:23417201

  12. The Role of Surface Chemistry in Adhesion and Wetting of Gecko Toe Pads

    NASA Astrophysics Data System (ADS)

    Badge, Ila; Stark, Alyssa Y.; Paoloni, Eva L.; Niewiarowski, Peter H.; Dhinojwala, Ali

    2014-10-01

    An array of micron-sized setal hairs offers geckos a unique ability to walk on vertical surfaces using van der Waals interactions. Although many studies have focused on the role of surface morphology of the hairs, very little is known about the role of surface chemistry on wetting and adhesion. We expect that both surface chemistry and morphology are important, not only to achieve optimum dry adhesion but also for increased efficiency in self-cleaning of water and adhesion under wet conditions. Here, we used a plasma-based vapor deposition process to coat the hairy patterns on gecko toe pad sheds with polar and non-polar coatings without significantly perturbing the setal morphology. By a comparison of wetting across treatments, we show that the intrinsic surface of gecko setae has a water contact angle between 70-90°. As expected, under wet conditions, adhesion on a hydrophilic surface (glass) was lower than that on a hydrophobic surface (alkyl-silane monolayer on glass). Surprisingly under wet and dry conditions the adhesion was comparable on the hydrophobic surface, independent of the surface chemistry of the setal hairs. This work highlights the need to utilize morphology and surface chemistry in developing successful synthetic adhesives with desirable adhesion and self-cleaning properties.

  13. The Role of Surface Chemistry in Adhesion and Wetting of Gecko Toe Pads

    PubMed Central

    Badge, Ila; Stark, Alyssa Y.; Paoloni, Eva L.; Niewiarowski, Peter H.; Dhinojwala, Ali

    2014-01-01

    An array of micron-sized setal hairs offers geckos a unique ability to walk on vertical surfaces using van der Waals interactions. Although many studies have focused on the role of surface morphology of the hairs, very little is known about the role of surface chemistry on wetting and adhesion. We expect that both surface chemistry and morphology are important, not only to achieve optimum dry adhesion but also for increased efficiency in self-cleaning of water and adhesion under wet conditions. Here, we used a plasma-based vapor deposition process to coat the hairy patterns on gecko toe pad sheds with polar and non-polar coatings without significantly perturbing the setal morphology. By a comparison of wetting across treatments, we show that the intrinsic surface of gecko setae has a water contact angle between 70–90°. As expected, under wet conditions, adhesion on a hydrophilic surface (glass) was lower than that on a hydrophobic surface (alkyl-silane monolayer on glass). Surprisingly under wet and dry conditions the adhesion was comparable on the hydrophobic surface, independent of the surface chemistry of the setal hairs. This work highlights the need to utilize morphology and surface chemistry in developing successful synthetic adhesives with desirable adhesion and self-cleaning properties. PMID:25323067

  14. The role of surface chemistry in adhesion and wetting of gecko toe pads.

    PubMed

    Badge, Ila; Stark, Alyssa Y; Paoloni, Eva L; Niewiarowski, Peter H; Dhinojwala, Ali

    2014-01-01

    An array of micron-sized setal hairs offers geckos a unique ability to walk on vertical surfaces using van der Waals interactions. Although many studies have focused on the role of surface morphology of the hairs, very little is known about the role of surface chemistry on wetting and adhesion. We expect that both surface chemistry and morphology are important, not only to achieve optimum dry adhesion but also for increased efficiency in self-cleaning of water and adhesion under wet conditions. Here, we used a plasma-based vapor deposition process to coat the hairy patterns on gecko toe pad sheds with polar and non-polar coatings without significantly perturbing the setal morphology. By a comparison of wetting across treatments, we show that the intrinsic surface of gecko setae has a water contact angle between 70-90°. As expected, under wet conditions, adhesion on a hydrophilic surface (glass) was lower than that on a hydrophobic surface (alkyl-silane monolayer on glass). Surprisingly under wet and dry conditions the adhesion was comparable on the hydrophobic surface, independent of the surface chemistry of the setal hairs. This work highlights the need to utilize morphology and surface chemistry in developing successful synthetic adhesives with desirable adhesion and self-cleaning properties. PMID:25323067

  15. Analytical Chemistry of Surfaces: Part III. Ion Spectroscopy.

    ERIC Educational Resources Information Center

    Hercules, David M.; Hercules, Shirley H.

    1984-01-01

    The fundamentals of two surface techniques--secondary-ion mass spectrometry (SIMS) and ion-scattering spectrometry (ISS)--are discussed. Examples of how these techniques have been applied to surface problems are provided. (JN)

  16. Analytical Chemistry of Surfaces: Part I. General Aspects.

    ERIC Educational Resources Information Center

    Hercules, David M.; Hercules, Shirley H.

    1984-01-01

    Reviews various spectroscopic techniques currently used to analyze real physical surfaces that bound two actual phases. Problems inherent in analyzing these surfaces and possible approaches that may be taken are considered. (JN)

  17. Supported organometallic complexes: Surface chemistry, spectroscopy, and catalysis

    SciTech Connect

    Marks, T.J.

    1990-02-01

    The goal of our program is to define those modes of interaction that take place between organometallic molecules and inorganic surfaces and, ultimately, to correlate various molecule-surface structures with catalytic properties.

  18. Transient Catalytic Combustor Model With Detailed Gas and Surface Chemistry

    NASA Technical Reports Server (NTRS)

    Struk, Peter M.; Dietrich, Daniel L.; Mellish, Benjamin P.; Miller, Fletcher J.; Tien, James S.

    2005-01-01

    In this work, we numerically investigate the transient combustion of a premixed gas mixture in a narrow, perfectly-insulated, catalytic channel which can represent an interior channel of a catalytic monolith. The model assumes a quasi-steady gas-phase and a transient, thermally thin solid phase. The gas phase is one-dimensional, but it does account for heat and mass transfer in a direction perpendicular to the flow via appropriate heat and mass transfer coefficients. The model neglects axial conduction in both the gas and in the solid. The model includes both detailed gas-phase reactions and catalytic surface reactions. The reactants modeled so far include lean mixtures of dry CO and CO/H2 mixtures, with pure oxygen as the oxidizer. The results include transient computations of light-off and system response to inlet condition variations. In some cases, the model predicts two different steady-state solutions depending on whether the channel is initially hot or cold. Additionally, the model suggests that the catalytic ignition of CO/O2 mixtures is extremely sensitive to small variations of inlet equivalence ratios and parts per million levels of H2.

  19. Complex surface concentration gradients by stenciled "electro click chemistry".

    PubMed

    Hansen, Thomas S; Lind, Johan U; Daugaard, Anders E; Hvilsted, Søren; Andresen, Thomas L; Larsen, Niels B

    2010-10-19

    Complex one- or two-dimensional concentration gradients of alkynated molecules are produced on azidized conducting polymer substrates by stenciled "electro click chemistry". The latter describes the local electrochemical generation of catalytically active Cu(I) required to complete a "click reaction" between alkynes and azides at room temperature. A stencil on the counter electrode defines the shape and multiplicity of the gradient(s) on the conducting polymer substrate, while the specific reaction conditions control gradient steepness and the maximum concentration deposited. Biologically active ligands including cell binding peptides are patterned in gradients by this method without losing their biological function or the conductivity of the polymer. PMID:20860406

  20. Chemistry of Stream Sediments and Surface Waters in New England

    USGS Publications Warehouse

    Robinson, Gilpin R., Jr.; Kapo, Katherine E.; Grossman, Jeffrey N.

    2004-01-01

    Summary -- This online publication portrays regional data for pH, alkalinity, and specific conductance for stream waters and a multi-element geochemical dataset for stream sediments collected in the New England states of Connecticut, Maine, Massachusetts, New Hampshire, Rhode Island, and Vermont. A series of interpolation grid maps portray the chemistry of the stream waters and sediments in relation to bedrock geology, lithology, drainage basins, and urban areas. A series of box plots portray the statistical variation of the chemical data grouped by lithology and other features.

  1. THE INTEGRATED USE OF COMPUTATIONAL CHEMISTRY, SCANNING PROBE MICROSCOPY, AND VIRTUAL REALITY TO PREDICT THE CHEMICAL REACTIVITY OF ENVIRONMENTAL SURFACES

    EPA Science Inventory

    In the last decade three new techniques scanning probe microscopy (SPM), virtual reality (YR) and computational chemistry ave emerged with the combined capability of a priori predicting the chemically reactivity of environmental surfaces. Computational chemistry provides the cap...

  2. Effect of surface chemistry on the integrin induced pathway in regulating vascular endothelial cells migration.

    PubMed

    Shen, Yang; Gao, Min; Ma, Yunlong; Yu, Hongchi; Cui, Fu-zhai; Gregersen, Hans; Yu, Qingsong; Wang, Guixue; Liu, Xiaoheng

    2015-02-01

    The migration of vascular endothelial cells (ECs) is essential for reendothelialization after implantation of cardiovascular biomaterials. Reendothelialization is largely determined by surface properties of implants. In this study, surfaces modified with various chemical functional groups (CH3, NH2, COOH, OH) prepared by self-assembled monolayers (SAMs) were used as model system. Expressions and distributions of critical proteins in the integrin-induced signaling pathway were examined to explore the mechanisms of surface chemistry regulating EC migration. The results showed that SAMs modulated cell migration were in the order CH3>NH2>OH>COOH, determined by differences in the expressions of focal adhesion components and Rho GTPases. Multiple integrin subunits showed difference in a surface chemistry-dependent manner, which induced a stepwise activation of signaling cascades associated with EC migration. This work provides a broad overview of surface chemistry regulated endothelial cell migration and establishes association among the surface chemistry, cell migration behavior and associated integrin signaling events. Understanding the relationship between these factors will help us to understand the surface/interface behavior between biomaterials and cells, reveal molecular mechanism of cells sensing surface characterization, and guide surface modification of cardiovascular implanted materials. PMID:25575348

  3. Research Program to Investigate the Fundamental Chemistry of Technetium

    SciTech Connect

    Pegg, Ian

    2005-06-01

    Research Progress and Implications Portions of two Tc glasses, LBNL-118 (Hanford AP-101 tank formulation) and LBNL-121 (higher organic content Hanford AN-107 tank formulation), were placed in vapor hydration test (VHT) stainless steel pressure vessels and exposed to a hydrous atmosphere at 238 C for 24.9 days. After being removed from the vessels, complete sample alteration is clearly visible for both samples. X-ray absorption spectra were then collected on these samples to characterize the Tc speciation within the alteration layers. The X-ray fluorescence signal was significantly improved for both VHT samples compared with that collected for the corresponding unaltered glasses, so much so that X ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data could be collected for each VHT sample. This signal improvement for the VHT samples indicates that a significant amount of the Tc in the original glasses has migrated closer to the VHT sample surface; this surface enrichment results in a stronger Tc X ray signal than is the case for the more homogeneously distributed Tc in the original glasses.

  4. Surface modification of nanoporous 1,2-polybutadiene by atom transfer radical polymerization or click chemistry.

    PubMed

    Guo, Fengxiao; Jankova, Katja; Schulte, Lars; Vigild, Martin E; Ndoni, Sokol

    2010-02-01

    Surface-initiated atom transfer radical polymerization (ATRP) and click chemistry were used to obtain functional nanoporous polymers based on nanoporous 1,2-polybutadiene (PB) with gyroid morphology. The ATRP monolith initiator was prepared by immobilizing bromoester initiators onto the pore walls through two different methodologies: (1) three-step chemical conversion of double bonds of PB into bromoisobutyrate, and (2) photochemical functionalization of PB with bromoisobutyrate groups. Azide functional groups were attached onto the pore walls before click reaction with alkynated MPEG. Following ATRP-grafting of hydrophilic polyacrylates and click of MPEG, the originally hydrophobic samples transformed into hydrophilic nanoporous materials. The successful modification was confirmed by infrared spectroscopy, contact angle measurements and measurements of spontaneous water uptake, while the morphology was investigated by small-angle X-ray scattering and transmission electron microscopy. PMID:20099923

  5. (90377) SEDNA: INVESTIGATION OF SURFACE COMPOSITIONAL VARIATION

    SciTech Connect

    Barucci, M. A.; De Bergh, C.; Merlin, F.; Morea Dalle Ore, C.; Cruikshank, D.; Alvarez-Candal, A.; Dumas, C.

    2010-12-15

    The dwarf planet (90377) Sedna is one of the most remote solar system objects accessible to investigations. To better constrain its surface composition and to investigate the possible heterogeneity of the surface of Sedna, several observations have been carried out at ESO-VLT with the powerful spectrometer SINFONI observing simultaneously the H and K bands. The analyzed spectra (obtained in 2005, 2007, and 2008) show a non-uniform spectral signature, particularly in the K band. Spectral modeling using the Shkuratov radiative transfer code for surface scattering has been performed using the various sets of data, including previous observations at visible wavelengths and photometry at 3.6 and 4.5 {mu}m by the Spitzer Space Telescope. The visible and near-infrared spectra can be modeled with organic materials (triton and titan tholin), serpentine, and H{sub 2}O ice in fairly significant amounts, and CH{sub 4}, N{sub 2}, and C{sub 2}H{sub 6} in varying trace amounts. One of the spectra obtained in 2005 October shows a different signature in the K band and is best modeled with CH{sub 3}OH in place of CH{sub 4}, with reduced amounts of serpentine and with the addition of olivine. The compositional surface heterogeneity can give input on the past history as well clues to the origin of this peculiar, distant object.

  6. Hierarchical Hydrodynamic Flow Confinement: Efficient Use and Retrieval of Chemicals for Microscale Chemistry on Surfaces

    PubMed Central

    2014-01-01

    We devised, implemented, and tested a new concept for efficient local surface chemistry that we call hierarchical hydrodynamic flow confinement (hierarchical HFC). This concept leverages the hydrodynamic shaping of multiple layers of liquid to address challenges inherent to microscale surface chemistry, such as minimal dilution, economical consumption of reagent, and fast liquid switching. We illustrate two modes of hierarchical HFC, nested and pinched, by locally denaturing and recovering a 26 bp DNA with as little as 2% dilution and by efficiently patterning an antibody on a surface, with a 5 μm resolution and a 100-fold decrease of reagent consumption compared to microcontact printing. In addition, valveless switching between nanoliter volumes of liquids was achieved within 20 ms. We believe hierarchical HFC will have broad utility for chemistry on surfaces at the microscale. PMID:24625080

  7. NOx Binding and Dissociation: Enhanced Ferroelectric Surface Chemistry by Catalytic Monolayers

    NASA Astrophysics Data System (ADS)

    Kakekhani, Arvin; Ismail-Beigi, Sohrab

    2013-03-01

    NOx molecules are regulated air pollutants produced during automotive combustion. As part of an effort to design viable catalysts for NOx decomposition operating at higher temperatures that would allow for improved fuel efficiency, we examine NOx chemistry on ferroelectric perovskite surfaces. Changing the direction of ferroelectric polarization can modify surface electronic properties and may lead to switchable surface chemistry. Here, we describe our recent work on potentially enhanced surface chemistry using catalytic RuO2 monolayers on perovskite ferroelectric substrates. In addition to thermodynamic stabilization of the RuO2 layer, we present results on the polarization-dependent binding of NO, O2, N2, and atomic O and N. We present results showing that one key problem with current catalysts, involving the difficulty of releasing dissociation products (especially oxygen), can be ameliorated by this method. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

  8. Geothermal chemistry/exploration investigations at Dixie Valley, Nevada

    SciTech Connect

    Goff, F.; Bergfeld, D.; Counce, D.; Janik, C.J.; Bruton, C.J.; Nimz, G.

    1998-12-01

    Dixie Valley geothermal field has continuously produced electric power since 1988. At the request of Oxbow Geothermal Corp. and the US Department of Energy, the authors have organized an inter-agency team of investigators to examine several topics of concern regarding management and behavior of the resource. These topics include scaling of the injection system, recharge of the reservoir, geochemical monitoring of the reservoir, and development of increased fumarolic activity north of the power plant.

  9. The Effects of Surface Chemistry on the Properties of Proteins Confined in Nano-porous Materials

    SciTech Connect

    Garrett, Latasha M; O'Neill, Hugh Michael

    2007-01-01

    The entrapment of proteins using the sol-gel route provides a means to retain its native properties and artificially reproduce the molecular crowding and confinement experienced by proteins in the cell allowing investigation of the physico-chemical and structural properties of biomolecules at the biotic/abiotic interface. The biomolecules are spatially separated and 'caged' in the gel structure but solutes can freely permeate the matrix. Thus, properties such as the folding of ensembles of individual molecules can be examined in the absence of aggregation effects that can occur in solution studies. Green fluorescent protein from Aequorea coerulescens was used as a model protein to examine the unfolding/re-folding properties of protein in silica gels. The recombinant protein was isolated and purified from Escherichia coli extracts by cell lysis, three-phase partitioning, dialysis, and anion exchange chromatography. The purity of the protein was greater than 90% as judged by SDS PAGE gel analysis. Sol-gels were synthesized using tetramethylorthosilicate (TMOS) in combination with, methyltrimethoxyorthosilane (MTMOS), ethyltrimethoxyorthosilane (ETMOS), 3-aminopropyltriethoxysilane (APTES), and 3-glycidoxypropyltrimethoxysilane (GPTMS). The acid induced denaturation and renaturation of GFP was analyzed by UV-visible, fluorescence, and circular dichroism (CD) spectroscopies. No renaturation was observed in gels that were made with TMOS only, and in the presence of APTES, MTMOS, and ETMOS. However, in gels that were made with GPTMS, the CD and UV-visible spectra indicated that the protein had refolded. The fluorescence emission spectrum indicated that approximately 20% of fluorescence had returned. This study highlights the importance of the surface chemistry of the silica gels for the refolding properties of the entrapped GFP. Future studies will investigate the effect of surface chemistry on the thermal and solvent stability of the entrapped protein.

  10. THE EFFECTS OF SURFACE CHEMISTRY ON THE PROPERTIES OF PROTEINS CONFINED IN NANO-POROUS MATERIALS

    SciTech Connect

    Garrett, L. M.; O'Neill, H.

    2007-01-01

    The entrapment of proteins using the sol-gel route provides a means to retain its native properties and artifi cially reproduce the molecular crowding and confi nement experienced by proteins in the cell allowing investigation of the physico-chemical and structural properties of biomolecules at the biotic/abiotic interface. The biomolecules are spatially separated and ‘caged’ in the gel structure but solutes can freely permeate the matrix. Thus, properties such as the folding of ensembles of individual molecules can be examined in the absence of aggregation effects that can occur in solution studies. Green fl uorescent protein from Aequorea coerulescens was used as a model protein to examine the unfolding/re-folding properties of protein in silica gels. The recombinant protein was isolated and purifi ed from Escherichia coli extracts by cell lysis, three-phase partitioning, dialysis, and anion exchange chromatography. The purity of the protein was greater than 90% as judged by SDS PAGE gel analysis. Sol-gels were synthesized using tetramethylorthosilicate (TMOS) in combination with, methyltrimethoxyorthosilane (MTMOS), ethyltrimethoxyorthosilane (ETMOS), 3-aminopropyltriethoxysilane (APTES), and 3-glycidoxypropyltrimethoxysilane (GPTMS). The acid induced denaturation and renaturation of GFP was analyzed by UV-visible, fl uorescence, and circular dichroism (CD) spectroscopies. No renaturation was observed in gels that were made with TMOS only, and in the presence of APTES, MTMOS, and ETMOS. However, in gels that were made with GPTMS, the CD and UV-visible spectra indicated that the protein had refolded. The fl uorescence emission spectrum indicated that approximately 20% of fl uorescence had returned. This study highlights the importance of the surface chemistry of the silica gels for the refolding properties of the entrapped GFP. Future studies will investigate the effect of surface chemistry on the thermal and solvent stability of the entrapped protein.

  11. Control of pyrite surface chemistry in physical coal cleaning. Final report

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Richardson, P.E.

    1993-05-19

    In Part I, Surface Chemistry of Coal Pyrite the mechanisms responsible for the inefficient rejection of coal pyrite were investigated using a number of experimental techniques. The test results demonstrate that the hydrophobicity of coal pyrite is related to the surface products formed during oxidation in aqueous solutions. During oxidation, a sulfur-rich surface layer is produced in near neutral pH solutions. This surface layer is composed mainly of sulfur species in the form of an iron-polysulfide along with a smaller amount of iron oxide/hydroxides. The floatability coal pyrite increases dramatically in the presence of frothers and hydrocarbon collectors. These reagents are believed to absorb on the weakly hydrophobic pyrite surfaces as a result of hydrophobic interaction forces. In Part III, Developing the Best Possible Rejection Schemes, a number of pyrite depressants were evaluated in column and conventional flotation tests. These included manganese (Mn) metal, chelating agents quinone and diethylenetriamine (DETA), and several commercially-available organic depressants. Of these, the additives which serve as reducing agents were found to be most effective. Reducing agents were used to prevent pyrite oxidation and/or remove oxidation products present on previously oxidized surfaces. These data show that Mn is a significantly stronger depressant for pyrite than quinone or DETA. Important factors in determining the pyrite depression effect of Mn include the slurry solid content during conditioning, the addition of acid (HCl), and the amount of Mn. The acid helps remove the oxide layer from the surface of Mn and promotes the depression of pyrite by Mn.

  12. Surface chemistry and catalysis on well-defined epitaxial iron-oxide layers

    NASA Astrophysics Data System (ADS)

    Weiss, Werner; Ranke, Wolfgang

    2002-03-01

    Metal-oxide-based catalysts are used for many important synthesis reactions in the chemical industry. A better understanding of the catalyst operation can be achieved by studying elementary reaction steps on well-defined model catalyst systems. For the dehydrogenation of ethylbenzene to styrene in the presence of steam both unpromoted and potassium promoted iron-oxide catalysts are active. Here we review the work done over unpromoted single-crystalline FeO(1 1 1), Fe3O4(1 1 1) and α- Fe2O3(0 0 0 1) films grown epitaxially on Pt(1 1 1) substrates. Their geometric and electronic surface structures were characterized by STM, LEED, electron microscopy and electron spectroscopic techniques. In an integrative approach, the interaction of water, ethylbenzene and styrene with these films was investigated mainly by thermal desorption and photoelectron emission spectroscopy. The adsorption-desorption energetics and kinetics depend on the oxide surface terminations and are correlated to the electronic structures and acid-base properties of the corresponding oxide phases, which reveal insight into the nature of the active sites and into the catalytic function of semiconducting oxides in general. Catalytic studies, using a batch-reactor arrangement at high gas pressures and post-reaction surface analysis, showed that only α- Fe2O3(0 0 0 1) containing surface defects is catalytically active, whereas Fe3O4(1 1 1) is always inactive. This can be related to the elementary adsorption and desorption properties observed in ultrahigh vacuum, which indicates that the surface chemical properties of the iron-oxide films do not change significantly across the “pressure-gap”. A model is proposed according to which the active site involves a regular acidic surface site and a defect site next to it. The results on metal-oxide surface chemistry also have implications for other fields such as environmental science, biophysics and chemical sensors.

  13. Chemistry of atmosphere-surface interactions on Venus and Mars

    NASA Technical Reports Server (NTRS)

    Fegley, Bruce, Jr.; Treiman, Allan H.

    1992-01-01

    Earth-based, earth-orbital, and spacecraft observational data are used in the present evaluation of Venus atmosphere-surface interactions to quantitatively characterize the reactions between C, H, S, Cl, F, and N gases and plausible surface minerals. Calculation results are used to predict stable minerals and mineral assemblages on the Venus surface, in order to ascertain which (if any) of the atmospheric gases are buffeted by mineral assemblages. Chemical equilibrium calculations using extant thermodynamic data on scapolite minerals predict that carbonate-bearing scapolite and sulfate meionite are unstable on the surface of Venus, while chloride-bearing scapolite is stable.

  14. NATIONAL SURFACE WATER SURVEY: WESTERN LAKE SURVEY (PHASE 1 - SYNOPTIC CHEMISTRY) QUALITY ASSURANCE PLAN

    EPA Science Inventory

    The purpose of the National Surface Water Survey of the National Acid Precipitation Assessment Program is to evaluate the present water chemistry of lakes and streams, to determine the status of certain biotic resources, and to select regionally representative surface waters for ...

  15. 3D Printed Potential and Free Energy Surfaces for Teaching Fundamental Concepts in Physical Chemistry

    ERIC Educational Resources Information Center

    Kaliakin, Danil S.; Zaari, Ryan R.; Varganov, Sergey A.

    2015-01-01

    Teaching fundamental physical chemistry concepts such as the potential energy surface, transition state, and reaction path is a challenging task. The traditionally used oversimplified 2D representation of potential and free energy surfaces makes this task even more difficult and often confuses students. We show how this 2D representation can be…

  16. Geochemistry and Organic Chemistry on the Surface of Titan

    NASA Technical Reports Server (NTRS)

    Lunine, J. I.; Beauchamp, P.; Beauchamp, J.; Dougherty, D.; Welch, C.; Raulin, F.; Shapiro, R.; Smith, M.

    2001-01-01

    Titan's atmosphere produces a wealth of organic products from methane and nitrogen. These products, deposited on the surface in liquid and solid form, may interact with surface ices and energy sources to produce compounds of exobiological interest. Additional information is contained in the original extended abstract.

  17. Analytical Chemistry of Surfaces: Part II. Electron Spectroscopy.

    ERIC Educational Resources Information Center

    Hercules, David M.; Hercules, Shirley H.

    1984-01-01

    Discusses two surface techniques: X-ray photoelectron spectroscopy (ESCA) and Auger electron spectroscopy (AES). Focuses on fundamental aspects of each technique, important features of instrumentation, and some examples of how ESCA and AES have been applied to analytical surface problems. (JN)

  18. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Zachwieja, J.B.; Lagno, M.L.

    1992-06-24

    Correlation of the hydrophobicity measurements of coal and mineral pyrite with changes in the surface composition of the samples as determined by x-ray photoelectron spectroscopy (XPS) reveals that similar surface oxidation products are found on both mineral and coal pyrite samples. The surface oxidation layer of these samples is comprised of different amounts of hydrophilic species (iron hydroxy-oxides and/or iron oxides) and hydrophobic species (polysulfide or elemental sulfur). The resulting hydrophobicity of these samples may be attributed to the ratio of hydrophilic (surface oxides) to hydrophobic (sulfur-containing) species in the surface oxidation layer. Also, coal pyrite samples were found to exhibit a greater degree of superficial oxidation and a less hydrophobic character as compared to the mineral pyrite samples.

  19. Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Park, Joong Sun; An, Jihwan; Lee, Min Hwan; Prinz, Fritz B.; Lee, Wonyoung

    2015-11-01

    We report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created with yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte-electrode interfaces of solid oxide fuel cells for higher electrochemical performance.

  20. Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

    SciTech Connect

    Park, Joong Sun; An, Jihwan; Lee, Min Hwan; Prinz, Friedrich B.; Lee, Wonyoung

    2015-07-10

    In this study, we report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created with yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte electrode interfaces of solid oxide fuel cells for higher electrochemical performance.

  1. Hexametaphosphate effects on tooth surface conditioning film chemistry--in vitro and in vivo studies.

    PubMed

    Busscher, Henk J; White, Donald J; van der Mei, Henny C; Baig, Arif A; Kozak, Kathy M

    2002-01-01

    These studies compared the effects of Crest Dual Action Whitening dentifrice with sodium hexametaphosphate and control commercial dentifrices on the surface chemistry of conditioning film-coated dental enamel in vitro and in vivo. Conditioning film chemistry was studied by measurements of film thickness, ability to wet the surface/surface energy, conditioning film chemical composition and zeta potential. Laboratory and in vivo studies demonstrated that brushing and chemical-only treatment of pellicle-coated enamel surfaces produced marked changes in surface chemistry. Brushing of surfaces with all commercial dentifrices significantly reduced pellicle film quantity. Effects on non-brushed areas, of significance in the clinical situation, were different for different dentifrices. For dentifrice chemical treatments, calcium phosphate surface active builders, such as pyrophosphate and hexametaphosphate, produced stronger effects than standard (non-tartar control) dentifrices, peroxide baking soda dentifrices and dentifrices formulated with carboxylate polymers, viz. Colgate Total with copolymer. Crest Dual Action Whitening hexametaphosphate dentifrice removed more pellicle conditioning film, produced a lower zeta potential, produced the largest changes in film composition and had the greatest impact on surface free energies of the tested dentifrices. Crest Dual Action Whitening dentifrice also produced lasting changes in the reacquisition of pellicle conditioning film, as established by in vitro cycling immersion studies. Crest Dual Action Whitening dentifrice produced stronger and more lasting effects on surface film chemistry than low molecular weight pyrophosphate (Crest Tartar Control) or other polymeric-based dentifrice systems (Colgate Total). These surface chemistries may contribute to the unique clinical actions of hexametaphosphate established in recently reported, randomized clinical studies of tartar control, stain prevention and stain removal effects. PMID

  2. Surface chemistry controls crystallinity of ZnSnanoparticles

    SciTech Connect

    Gilbert, Benjamin; Huang, Feng; Lin, Zhang; Goodell, Carmen; Zhang, Hengzhong; Banfield Jillian F.

    2005-12-20

    Combined small-angle and high energy wide-angle x-ray scattering measurements of nanoparticle size and structure permit interior strain and disorder to be directly observed in the real-space pair distribution function (PDF). PDF analysis showed that samples of ZnS nanoparticle with similar mean diameters (3.2-3.6 nm) but synthesized and treated differently possess a dramatic range of interior disorder. We used Fourier transform infra-red spectroscopy to detect the surface species and the nature of surface chemical interactions. Our results suggest that there is a direct correlation between the strength of surface-ligand interactions and interior crystallinity.

  3. The surface chemistry of metal-organic frameworks.

    PubMed

    McGuire, Christina V; Forgan, Ross S

    2015-03-28

    Metal-organic frameworks (MOFs) have received particular attention over the last 20 years as a result of their attractive properties offering potential applications in a number of areas. Typically, these characteristics are tuned by functionalisation of the bulk of the MOF material itself. This Feature Article focuses instead on modification of MOF particles at their surfaces only, which can also offer control over the bulk properties of the material. The differing surface modification techniques available to the synthetic chemist will be discussed, with a focus on the effect of surface modification of MOFs on their fundamental properties and application in adsorption, catalysis, drug delivery and other areas. PMID:25116412

  4. Effects of Surface Chemistry on the Porous Structure of Coal

    SciTech Connect

    Radovic, Ljubisa R; Hatcher, Patrick G

    1997-05-01

    In this report, 129 Xe nuclear magnetic resonance spectroscopy of xenon gas adsorbed in coal is used to describe some poorly understood features of coal microporous structure, particularly in establishing that a connected network exists, the type of connectivity, and its changes with the rank of coal. Micropore size scale and distribution are also considered. Two methods are developed which are new and versatile tools for the investigation of porous structure. Both utilize xenon gas that is in motion, while undergoing diffusion or exchange in coal, to describe the connectivity of the micropore structure of coal. Time tracking of the adsorption process by NMR, selective saturation, and saturation transfer techniques were used to obtain new information on the coal rank dependence of porous structure. In addition, an existing 129 Xe chemical shift-pore diameter model was used to calculate micropore diameters for coals, as well as for a microporous carbon, before and after pore-size alteration. In the initial study performed, straightforward 129 Xe NMR spectra at equilibrium xenon adsorption at a series of pressures were acquired for a rank-varied set of six coals. Acquisition of the NMR signal as an echo was tested and found to improve spectral quality. The spectra were used to calculate micropore diameters for the six coals. These range from 5.6 to 7.5 and exhibit a minimum value for the intermediate coal rank. The smallest pores occur in coals of about 82-85% carbon; at both lower and higher coal ranks, the average micropore size tends to be larger. The changes in the spectra with coal rank and surface area were explored. Signal linewidths were found to decrease with increasing coal rank and were interpreted in terms of increasing chemical or physical homogeneity of the coal as rank increases. The packing density of powdered coal was found to alter the spectral appearance in a high volatile bituminous coal, which is preliminary evidence that exchange affects the

  5. Research Program to Investigate the Fundamental Chemistry of Technetium

    SciTech Connect

    Shuh, David K.; Burns, Carol J.; Lukens, Wayne W. Jr.

    2001-06-15

    Technetium (99Tc, half-life = 2.13x105 years, b-emitter) is one of the radionuclides of major concern for nuclear waste disposal. This concern is due to the long half-life of 99Tc, the ease with which pertechnetate, TcO4 -, migrates in the geosphere, difficulties in incorporating technetium into glass waste forms, and the corresponding regulatory considerations. The problem of mobility of pertechnetate in the environment is compounded by the fact that pertechnetate is the thermodynamically stable form of technetium in oxidizing environments. Because of this stability, pertechnetate was presumed to be the predominant chemical form of technetium in the aqueous phase of nuclear waste tanks. However, studies have indicated that a significant fraction of the technetium is in a different chemical form. These factors present challenges the separation and immobilization of technetium. The objective of this project is to investigate the chemical behavior of technetium so that the se problems may be understood and the challenges addressed.

  6. Reaction chemistry and ligand exchange at cadmium selenide nanocrystal surfaces

    SciTech Connect

    Owen, Jonathan; Park, Jungwon; Trudeau, Paul-Emile; Alivisatos, A. Paul

    2008-12-02

    Chemical modification of nanocrystal surfaces is fundamentally important to their assembly, their implementation in biology and medicine, and greatly impacts their electrical and optical properties. However, it remains a major challenge owing to a lack of analytical tools to directly determine nanoparticle surface structure. Early nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) studies of CdSe nanocrystals prepared in tri-n-octylphosphine oxide (1) and tri-n-octylphosphine (2), suggested these coordinating solvents are datively bound to the particle surface. However, assigning the broad NMR resonances of surface-bound ligands is complicated by significant concentrations of phosphorus-containing impurities in commercial sources of 1, and XPS provides only limited information about the nature of the phosphorus containing molecules in the sample. More recent reports have shown the surface ligands of CdSe nanocrystals prepared in technical grade 1, and in the presence of alkylphosphonic acids, include phosphonic and phosphinic acids. These studies do not, however, distinguish whether these ligands are bound datively, as neutral, L-type ligands, or by X-type interaction of an anionic phosphonate/phosphinate moiety with a surface Cd{sup 2+} ion. Answering this question would help clarify why ligand exchange with such particles does not proceed generally as expected based on a L-type ligand model. By using reagents with reactive silicon-chalcogen and silicon-chlorine bonds to cleave the ligands from the nanocrystal surface, we show that our CdSe and CdSe/ZnS core-shell nanocrystal surfaces are likely terminated by X-type binding of alkylphosphonate ligands to a layer of Cd{sup 2+}/Zn{sup 2+} ions, rather than by dative interactions. Further, we provide spectroscopic evidence that 1 and 2 are not coordinated to our purified nanocrystals.

  7. Affinity Induced Surface Functionalization of Liposomes Using Cu-Free Click Chemistry.

    PubMed

    Bak, Martin; Jølck, Rasmus I; Eliasen, Rasmus; Andresen, Thomas L

    2016-07-20

    Functionalization of nanoparticles is a key element for improving specificity of drug delivery systems toward diseased tissue or cells. In the current study we report a highly efficient and chemoselective method for post-functionalization of liposomes with biomacromolecules, which equally well can be used for functionalization of other nanoparticles or solid surfaces. The method exploits a synergistic effect of having both affinity and covalent anchoring tags on the surface of the liposome. This was achieved by synthesizing a peptide linker system that uses Cu-free strain-promoted click chemistry in combination with histidine affinity tags. The investigation of post-functionalization of PEGylated liposomes was performed with a cyclic RGDfE peptide. By exploring both affinity and covalent tags a 98 ± 2.0% coupling efficiency was achieved, even a diluted system showed a coupling efficiency of 87 ± 0.2%. The reaction kinetics and overall yield were quantified by HPLC. The results presented here open new possibilities for constructing complex nanostructures and functionalized surfaces. PMID:27269516

  8. Surface chemistry and spectroscopy of the β-galactosidase Langmuir monolayer.

    PubMed

    Crawford, Nicholas F; Micic, Miodrag; Orbulescu, Jhony; Weissbart, Daniel; Leblanc, Roger M

    2015-09-01

    The changes of interfacial properties of β-galactosidase introduced into different pH environments are investigated through surface chemistry and in situ spectroscopy. Conditions for an optimal Langmuir monolayer formation were firstly obtained by varying the subphase salt concentration and the surface-pressure area isotherm was used to extrapolate the limiting molecular area of the enzyme monolayer to be around 42,000 Å(2) molecule(-1). Surface pressure stability measurements held at 20 mN/m for 90 min along with compression-decompression cycles revealed no aggregate formation at the air-water interface. Consistent with the data obtained from the isotherm, in situ UV-Vis and fluorescence spectroscopy shows a steep rise in absorbance and photoluminescence intensity correlating to with a switch from a liquid-expanded to a liquid-condensed phase. A decrease in subphase pH increased the electrostatic repulsion as the enzyme was protonated, leading to an expanded monolayer. Infrared absorption-reflection spectroscopy demonstrates that the enzyme adopts mainly β-sheet conformation at the air-water interface before and during the compression. PMID:25985424

  9. Macroform and microform-induced change in redox-sensitive chemistries of river channel surface sediments

    NASA Astrophysics Data System (ADS)

    Byrne, P.; Zhang, H.; Heathwaite, A. L.; Binley, A.; Ullah, S.; Kaeser, D.; Heppell, C. M.; Lansdown, K.; Trimmer, M.

    2012-04-01

    In-stream geomorphological features such as riffle-pool sequences (macroforms) can produce steep hydraulic gradients which induce flow in and out of the riverbed - hyporheic exchange flow (HEF). The acceleration of flow over channel obstacles such as large cobbles and boulders (microforms) can create variation in surface-subsurface pressure gradients and generation of HEF. HEF in shallow surface sediments affect the transformation of redox-sensitive chemical forms and, therefore, the attenuation or release of nutrients in river systems. Here, we examine the relationship between stream geomorphological environment (microform and macroform) and concentration profiles of redox-sensitive species (nitrate, sulphate, iron, manganese) in shallow (15cm) subsurface sediments. In-situ passive samplers (diffusive equilibrium in thin films - DET) are used to obtain biogeochemical data from armoured environments at fine scale (cm) depth resolution where there is strong upwelling. The probes were deployed in a 50m reach of the River Eden, Cumbria, UK, during baseflow conditions. The experimental setup allowed for the assessment of differences in redox-sensitive chemistries between a riffle and pool environment and between smooth and rough bed surfaces in the pool. The passive sensing basis of the DET methodology provided a means for investigating how HEF systems generated at two different geomorphological scales influence the concentration and spatial patterns of redox-sensitive species. DET's capability of measuring at high spatial resolution allowed the extent of hyporheic mixing to be targeted, even though it is often limited to the top few centimetres of sediment.

  10. Comparing intracellular stability and targeting of sulfobetaine quantum dots with other surface chemistries in live cells.

    PubMed

    Muro, Eleonora; Fragola, Alexandra; Pons, Thomas; Lequeux, Nicolas; Ioannou, Andriani; Skourides, Paris; Dubertret, Benoit

    2012-04-10

    The in vivo labeling of intracellular components with quantum dots (QDs) is very limited because of QD aggregation in the cell cytoplasm and/or QD confinement into lysosomal compartments. In order to improve intracellular targeting with QDs, various surface chemistries and delivery methods have been explored, but they have not yet been compared systematically with respect to the QD intracellular stability. In this work, the intracellular aggregation kinetics of QDs for three different surface chemistries based on ligand exchange or encapsulation with amphiphilic polymers are compared. For each surface chemistry, three delivery methods for bringing the nanoparticles into the cells are compared: electroporation, microinjection, and pinocytosis. It is concluded that the QD intracellular aggregation behavior is strongly dependent on the surface chemistry. QDs coated with dihydrolipoic acid-sulfobetaine (DHLA-SB) ligands diffuse freely in cells for longer periods of time than for QDs in the other chemistries tested, and they can access all cytoplasmic compartments. Even when conjugated to streptavidin, these DHLA-SB QDs remain freely diffusing inside the cytoplasm and unaggregated, and they are able to reach a biotinylated target inside HeLa cells. Such labeling was more efficient when compared to commercial streptavidin-conjugated QDs, which may be due to the smaller size of DHLA-SB QDs and/or to their superior intracellular stability. PMID:22378567

  11. Recovering ferromagnetic metal surfaces to fully exploit chemistry in molecular spintronics

    NASA Astrophysics Data System (ADS)

    Galbiati, Marta; Delprat, Sophie; Mattera, Michele; Mañas-Valero, Samuel; Forment-Aliaga, Alicia; Tatay, Sergio; Deranlot, Cyrile; Seneor, Pierre; Mattana, Richard; Petroff, Frédéric

    2015-05-01

    Organic spintronics is a new emerging field that promises to offer the full potential of chemistry to spintronics, as for example high versatility through chemical engineering and simple low cost processing. However, one key challenge that remains to be unlocked for further applications is the high incompatibility between spintronics key materials such as high Curie temperature Co, Ni, Fe (and their alloys) and wet chemistry. Indeed, the transition metal proneness to oxidation has so far hampered the integration of wet chemistry processes into the development of room temperature organic spintronics devices. As a result, they had mainly to rely on high vacuum physical processes, restraining the choice of available organic materials to a small set of sublimable molecules. In this letter, focusing on cobalt as an example, we show a wet chemistry method to easily and selectively recover a metallic surface from an air exposed oxidized surface for further integration into spintronics devices. The oxide etching process, using a glycolic acid based solution, proceeds without increasing the surface roughness and allows the retrieval of an oxygen-free chemically active cobalt layer. This unlocks the full potential of wet chemistry processes towards room temperature molecular spintronics with transition metals electrodes. We demonstrate this by the grafting of alkylthiols self-assembled monolayers on recovered oxidized cobalt surfaces.

  12. Vesper - Venus Chemistry and Dynamics Orbiter - A NASA Discovery Mission Proposal: Submillimeter Investigation of Atmospheric Chemistry and Dynamics

    NASA Technical Reports Server (NTRS)

    Chin, Gordon

    2011-01-01

    Vesper conducts a focused investigation of the chemistry and dynamics of the middle atmosphere of our sister planet- from the base of the global cloud cover to the lower thermosphere. The middle atmosphere controls the stability of the Venus climate system. Vesper determines what processes maintain the atmospheric chemical stability, cause observed variability of chemical composition, control the escape of water, and drive the extreme super-rotation. The Vesper science investigation provides a unique perspective on the Earth environment due to the similarities in the middle atmosphere processes of both Venus and the Earth. Understanding key distinctions and similarities between Venus and Earth will increase our knowledge of how terrestrial planets evolve along different paths from nearly identical initial conditions.

  13. Biotite surface chemistry as a function of aqueous fluid composition

    NASA Astrophysics Data System (ADS)

    Bray, Andrew W.; Benning, Liane G.; Bonneville, Steeve; Oelkers, Eric H.

    2014-03-01

    The chemical composition and charge of the biotite near-surface, in contact with NaCl bearing aqueous solutions at 25 °C from pH 1 to 12, have been derived via zeta potential measurements and potentiometric titrations performed for 20 and 60 min in batch reactors. Zeta potential measurements yielded an isoelectric point of pH 3.0 (±0.2) and batch potentiometric titrations yielded a pH of immersion of 9.66 (S.D. 0.24). From batch potentiometric titrations we determined both the proton consumption and the metal release from the biotite surface as a function of pH. Potassium removal from the near-surface of biotite is only slightly dependent on pH with a minimum of ˜6 atoms nm-2 removed at the immersion pH, corresponding to an average depletion depth of ˜1.5 nm. In contrast, the release of Mg, Al and Fe is strongly pH-dependent as those metals are preferentially removed from the biotite surface at pH less than 9 (Mg) and 4 (Al, Fe). The average depletion depth of Mg, Al, and Fe increases with decreasing pH, reaching on average ˜2 nm at pH ˜1. The removal of K, Mg, Al, and Fe is not charge conservative, resulting in a relative negative charge in the biotite near-surface. Taken together, our results indicate that the composition of the biotite surface varies dramatically as a function of pH. At basic conditions, the biotite near-surface is K depleted and likely hydrogen enriched. At near-neutral conditions, the biotite near-surface is comprised of only the Si and Al tetrahedral, and the Fe(II) octahedral framework, following the removal of both alkali metals and Mg. Finally, at acidic conditions, the biotite near-surface is comprised exclusively of a remnant Si, O and H framework. The results of these experiments give an indication of the composition and charge of the biotite surface in the natural environment, following contact with water, for example in the vadose zone, and can help us understand weathering reactions in these systems.

  14. Investigations of Titan's topography and surface roughness

    NASA Astrophysics Data System (ADS)

    Sharma, Priyanka

    Saturn's moon, Titan is a geomorphologically active planetary object, and its surface is influenced by multiple processes like impact cratering, fluvial and aeolian erosion, lacustrine processes, tectonics, cryovolcanism and mantling. Disentangling the processes that compete to shape Titan's landscape is difficult in the absence of global topography data. In this thesis, I utilize techniques in topographic statistics, fractal theory, study of terrestrial analogs and landscape evolution modeling to characterize Titan's topography and surface roughness and investigate the relative roles of surface processes in sculpting its landscape. I mapped the shorelines of 290 North Polar Titanian lakes using the Cassini Synthetic Aperture Radar dataset. The fractal dimensions of the shorelines were calculated via the divider/ruler method and box-counting method, at length scales of (1--10) km and found to average 1.27 and 1.32, respectively. The inferred power-spectral exponent of Titan's topography was found to be ≤ 2, which is lower than the values obtained from the global topography of the Earth or Venus. In order to interpret fractal dimensions of Titan's shorelines in terms of the surficial processes at work, I repeated a similar statistical analysis with 114 terrestrial analogous lakes formed by different processes, using C-band radar backscatter data from the Shuttle Radar Topography Mission (SRTM). I found different lake generation mechanisms on Earth produce 'statistically different' shorelines; however, no specific set of processes could be identified for forming Titanian lake basins. Using the Cassini RADAR altimetry data, I investigated Titan's global surface roughness and calculated median absolute slopes, average relief and Hurst exponent (H) for the surface of Titan. I detected a clear trend with latitude in these roughness parameters. Equatorial regions had the smallest slopes, lowest values of H and smallest intra-footprint relief, compared to the mid

  15. Effect of substratum surface chemistry and surface energy on attachment of marine bacteria and algal spores.

    PubMed

    Ista, Linnea K; Callow, Maureen E; Finlay, John A; Coleman, Sarah E; Nolasco, Aleece C; Simons, Robin H; Callow, James A; Lopez, Gabriel P

    2004-07-01

    Two series of self-assembled monolayers (SAMs) of omega-substituted alkanethiolates on gold were used to systematically examine the effects of varying substratum surface chemistry and energy on the attachment of two model organisms of interest to the study of marine biofouling, the bacterium Cobetia marina (formerly Halomonas marina) and zoospores of the alga Ulva linza (formerly Enteromorpha linza). SAMs were formed on gold-coated glass slides from solutions containing mixtures of methyl- and carboxylic acid-terminated alkanethiols and mixtures of methyl- and hydroxyl-terminated alkanethiols. C. marina attached in increasing numbers to SAMs with decreasing advancing water contact angles (theta(AW)), in accordance with equation-of-state models of colloidal attachment. Previous studies of Ulva zoospore attachment to a series of mixed methyl- and hydroxyl-terminated SAMs showed a similar correlation between substratum theta(AW) and zoospore attachment. When the hydrophilic component of the SAMs was changed to carboxylate, however, the profile of attachment of Ulva was significantly different, suggesting that a more complex model of interfacial energetics is required. PMID:15240295

  16. Effect of Substratum Surface Chemistry and Surface Energy on Attachment of Marine Bacteria and Algal Spores

    PubMed Central

    Ista, Linnea K.; Callow, Maureen E.; Finlay, John A.; Coleman, Sarah E.; Nolasco, Aleece C.; Simons, Robin H.; Callow, James A.; Lopez, Gabriel P.

    2004-01-01

    Two series of self-assembled monolayers (SAMs) of ω-substituted alkanethiolates on gold were used to systematically examine the effects of varying substratum surface chemistry and energy on the attachment of two model organisms of interest to the study of marine biofouling, the bacterium Cobetia marina (formerly Halomonas marina) and zoospores of the alga Ulva linza (formerly Enteromorpha linza). SAMs were formed on gold-coated glass slides from solutions containing mixtures of methyl- and carboxylic acid-terminated alkanethiols and mixtures of methyl- and hydroxyl-terminated alkanethiols. C. marina attached in increasing numbers to SAMs with decreasing advancing water contact angles (θAW), in accordance with equation-of-state models of colloidal attachment. Previous studies of Ulva zoospore attachment to a series of mixed methyl- and hydroxyl-terminated SAMs showed a similar correlation between substratum θAW and zoospore attachment. When the hydrophilic component of the SAMs was changed to carboxylate, however, the profile of attachment of Ulva was significantly different, suggesting that a more complex model of interfacial energetics is required. PMID:15240295

  17. Mussel-inspired surface chemistry for multifunctional coatings.

    PubMed

    Lee, Haeshin; Dellatore, Shara M; Miller, William M; Messersmith, Phillip B

    2007-10-19

    We report a method to form multifunctional polymer coatings through simple dip-coating of objects in an aqueous solution of dopamine. Inspired by the composition of adhesive proteins in mussels, we used dopamine self-polymerization to form thin, surface-adherent polydopamine films onto a wide range of inorganic and organic materials, including noble metals, oxides, polymers, semiconductors, and ceramics. Secondary reactions can be used to create a variety of ad-layers, including self-assembled monolayers through deposition of long-chain molecular building blocks, metal films by electroless metallization, and bioinert and bioactive surfaces via grafting of macromolecules. PMID:17947576

  18. Supported organometallic complexes: Surface chemistry, spectroscopy, and catalysis. Progress report, February 1, 1991--January 31, 1992

    SciTech Connect

    Marks, T.J.

    1992-02-01

    The long-range goal of this project is to elucidate and understand the surface chemistry and catalytic properties of well-defined, highly-reactive organometallic molecules (principally based upon abundant actinide, lanthanide, and early transition elements) adsorbed on metal oxides and halides. The nature of the adsorbed species is probed by a battery of chemical and physicochemical techniques, to understand the nature of the molecular-surface coordination chemistry and how this can give rise to extremely high catalytic activity. A complementary objective is to delineate the scope and mechanisms of the heterogeneous catalytic reactions, as well as to relate them both conceptually and functionally to model systems generated in solution.

  19. Effect of Space Radiation Processing on Lunar Soil Surface Chemistry: X-Ray Photoelectron Spectroscopy Studies

    NASA Technical Reports Server (NTRS)

    Dukes, C.; Loeffler, M.J.; Baragiola, R.; Christoffersen, R.; Keller, J.

    2009-01-01

    Current understanding of the chemistry and microstructure of the surfaces of lunar soil grains is dominated by a reference frame derived mainly from electron microscopy observations [e.g. 1,2]. These studies have shown that the outermost 10-100 nm of grain surfaces in mature lunar soil finest fractions have been modified by the combined effects of solar wind exposure, surface deposition of vapors and accretion of impact melt products [1,2]. These processes produce surface-correlated nanophase Feo, host grain amorphization, formation of surface patinas and other complex changes [1,2]. What is less well understood is how these changes are reflected directly at the surface, defined as the outermost 1-5 atomic monolayers, a region not easily chemically characterized by TEM. We are currently employing X-ray Photoelectron Spectroscopy (XPS) to study the surface chemistry of lunar soil samples that have been previously studied by TEM. This work includes modification of the grain surfaces by in situ irradiation with ions at solar wind energies to better understand how irradiated surfaces in lunar grains change their chemistry once exposed to ambient conditions on earth.

  20. Delivery of minimally dispersed liquid interfaces for sequential surface chemistry.

    PubMed

    Ostromohov, N; Bercovici, M; Kaigala, G V

    2016-08-01

    We present a method for sequential delivery of reagents to a reaction site with minimal dispersion of their interfaces. Using segmented flow to encapsulate the reagents as droplets, the dispersion between reagent plugs remains confined in a limited volume, while being transmitted to the reaction surface. In close proximity to the target surface, we use a passive array of microstructures for removal of the oil phase such that the original reagent sequence is reconstructed, and only the aqueous phase reaches the reaction surface. We provide a detailed analysis of the conditions under which the method can be applied and demonstrate maintaining a transition time of 560 ms between reagents transported to a reaction site over a distance of 60 cm. We implemented the method using a vertical microfluidic probe on an open surface, allowing contact-free interaction with biological samples, and demonstrated two examples of assays implemented using the method: measurements of receptor-ligand reaction kinetics and of the fluorescence response of immobilized GFP to local variations in pH. We believe that the method can be useful for studying the dynamic response of cells and proteins to various stimuli, as well as for highly automated multi-step assays. PMID:27354032

  1. The Australian methane budget: Interpreting surface and train-borne measurements using a chemistry transport model

    NASA Astrophysics Data System (ADS)

    Fraser, Annemarie; Chan Miller, Christopher; Palmer, Paul I.; Deutscher, Nicholas M.; Jones, Nicholas B.; Griffith, David W. T.

    2011-10-01

    We investigate the Australian methane budget from 2005-2008 using the GEOS-Chem 3D chemistry transport model, focusing on the relative contribution of emissions from different sectors and the influence of long-range transport. To evaluate the model, we use in situ surface measurements of methane, methane dry air column average (XCH4) from ground-based Fourier transform spectrometers (FTSs), and train-borne surface concentration measurements from an in situ FTS along the north-south continental transect. We use gravity anomaly data from Gravity Recovery and Climate Experiment to describe the spatial and temporal distribution of wetland emissions and scale it to a prior emission estimate, which better describes observed atmospheric methane variability at tropical latitudes. The clean air sites of Cape Ferguson and Cape Grim are the least affected by local emissions, while Wollongong, located in the populated southeast with regional coal mining, samples the most locally polluted air masses (2.5% of the total air mass versus <1% at other sites). Averaged annually, the largest single source above background of methane at Darwin is long-range transport, mainly from Southeast Asia, accounting for ˜25% of the change in surface concentration above background. At Cape Ferguson and Cape Grim, emissions from ruminant animals are the largest source of methane above background, at approximately 20% and 30%, respectively, of the surface concentration. At Wollongong, emissions from coal mining are the largest source above background representing 60% of the surface concentration. The train data provide an effective way of observing transitions between urban, desert, and tropical landscapes.

  2. Hydrogeologic controls of surface-water chemistry in the Adirondack region of New York State

    USGS Publications Warehouse

    Peters, N.E.; Driscoll, C.T.

    1987-01-01

    Relationships between surface-water discharge, water chemistry, and watershed geology were investigated to evaluate factors affecting the sensitivity of drainage waters in the Adirondack region of New York to acidification by atmospheric deposition. Instantaneous discharge per unit area was derived from relationships between flow and staff-gage readings at 10 drainage basins throughout the region. The average chemical composition of the waters was assessed from monthly samples collected from July 1982 through July 1984. The ratio of flow at the 50-percent exceedence level to the flow at the 95-percent exceedence level of flow duration was negatively correlated with mean values of alkalinity or acid-neutralizing capacity (ANC), sum of basic cations (SBC), and dissolved silica, for basins containing predominantly aluminosilicate minerals and little or no carbonate-bearing minerals. Low ratios are indicative of systems in which flow is predominately derived from surface- and ground-water storage, whereas high ratios are characteristic of watersheds with variable flow that is largely derived from surface runoff. In an evaluation of two representative surface-water sites, concentrations of ANC, SBC, and dissolved silica, derived primarily from soil mineral weathering reactions. decreased with increasing flow. Furthermore, the ANC was highest at low flow when the percentage of streamflow derived from ground water was maximum. As flow increased, the ANC decreased because the contribution of dilute surface runoff and lateral flow through the shallow acidic soil horizons to total flow increased. Basins having relatively high ground-water contributions to total flow, in general, have large deposits of thick till or stratified drift. A major factor controlling the sensitivity of these streams and lakes to acidification is the relative contribution of ground water to total discharge. ?? 1987 Martinus Nijhoff/Dr W. Junk Publishers.

  3. Surface chemistry for stable and smart molecular and biomolecular interfaces via photochemical grafting of alkenes.

    PubMed

    Wang, Xiaoyu; Landis, Elizabeth C; Franking, Ryan; Hamers, Robert J

    2010-09-21

    Many emerging fields such as biotechnology and renewable energy require functionalized surfaces that are "smart" and highly stable. Surface modification schemes developed previously have often been limited to simple molecules or have been based on weakly bound layers that have limited stability. In this Account, we report on recent developments enabling the preparation of molecular and biomolecular interfaces that exhibit high selectivity and unprecedented stability on a range of covalent materials including diamond, vertically aligned carbon nanofibers, silicon, and metal oxides. One particularly successful pathway to ultrastable interfaces involves the photochemical grafting of organic alkenes to the surfaces. Bifunctional alkenes with a suitable functional group at the distal end can directly impart functionality and can serve as attachment points for linking complex structures such as DNA and proteins. The successful application of photochemical grafting to a surprisingly wide range of materials has motivated researchers to better understand the underlying photochemical reaction mechanisms. The resulting studies using experimental and computational methods have provided fundamental insights into the electronic structure of the molecules and the surface control photochemical reactivity. Such investigations have revealed the important role of a previously unrecognized process, photoelectron emission, in initiating photochemical grafting of alkenes to surfaces. Molecular and biomolecular interfaces formed on diamond and other covalent materials are leading to novel types of molecular electronic interfaces. For example, electrical, optical, or electromechanical structures that convert biological information directly into analytical signals allow for direct label-free detection of DNA and proteins. Because of the preferential adherence of molecules to graphitic edge-plane sites, the grafting of redox-active species to vertically aligned carbon nanofibers leads to

  4. Impact of Surface Chemistry on Copper Deposition in Mesoporous Silicon.

    PubMed

    Darwich, Walid; Garron, Anthony; Bockowski, Piotr; Santini, Catherine; Gaillard, Frédéric; Haumesser, Paul-Henri

    2016-08-01

    An easy, efficient, and safe process is developed to metallize mesoporous silicon (PSi) with Cu from the decomposition of a solution of mesitylcopper (CuMes) in an imidazolium-based ionic liquid (IL), [C1C4Im][NTf2]. The impregnation of a solution of CuMes in IL affords the deposition of metallic islands not only on the surface but also deep within the pores of a mesoporous Si layer with small pores below 10 nm. Therefore, this process is well suited to efficiently and completely metallize PSi layers. An in-depth mechanistic study shows that metal deposition is due to the reduction of CuMes by surface silane groups rather than by Si oxidation as observed in aqueous or water-containing media. This could open a new route to the chemical metallization of PSi by less-noble metals difficult to attain by a conventional displacement reaction. PMID:27368422

  5. Mechanical work makes important contributions to surface chemistry at steps

    PubMed Central

    Francis, M. F.; Curtin, W. A.

    2015-01-01

    The effect of mechanical strain on the binding energy of adsorbates to late transition metals is believed to be entirely controlled by electronic factors, with tensile stress inducing stronger binding. Here we show, via computation, that mechanical strain of late transition metals can modify binding at stepped surfaces opposite to well-established trends on flat surfaces. The mechanism driving the trend is mechanical, arising from the relaxation of stored mechanical energy. The mechanical energy change can be larger than, and of opposite sign than, the energy changes due to electronic effects and leads to a violation of trends predicted by the widely accepted electronic ‘d-band’ model. This trend has a direct impact on catalytic activity, which is demonstrated here for methanation, where biaxial tension is predicted to shift the activity of nickel significantly, reaching the peak of the volcano plot and comparable to cobalt and ruthenium. PMID:25677075

  6. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Ou, Z.S.

    1992-06-24

    The successful separation of pyrite from coal by flotation is dependent to a large extent upon the selectivity of the process, and the use of a pyrite depressant is one of the most important and cost-effective techniques for achieving this. This report evaluates the effects of three factors on the floatability of pyrite. These are (1) the superficial oxidation of pyrite, (2) the contamination of pyrite surfaces by carbonaceous matter, and (3) pulp redox potentials. XPS (x-ray photoelectron spectroscopy) and IR spectrometry have been used to identify surface reaction products. Microflotation, laboratory-scale conventional flotation and microbubble column flotation were used to quantify the effects of these factors. It was found that low (reducing) pulp potentials are effective depressants of pyrite (more so for fresh, unoxidized samples than for oxidized samples), whilst at the same time do not materially affect coal flotation.

  7. Surface snow chemistry across Antarctic wind glaze and antidune fields

    NASA Astrophysics Data System (ADS)

    Dixon, D. A.; Mayewski, P. A.; Korotkikh, E.; Sneed, S. B.; Handley, M.; Introne, D.; Scambos, T. A.

    2011-12-01

    This is the first study to measure more than 25 chemical constituents in the surface snow and firn across extensive regions of Antarctica. We present major ion, trace element, heavy metal, rare earth element and oxygen isotope data from a series of surface snow samples and shallow firn sections collected along four US ITASE traverses across East and West Antarctica. In each sample we measure dissolved concentrations of Na+, K+, Mg2+, Ca2+, Cl-, NO3-, SO42-, and MS- using ion chromatography and total concentrations of Sr, Cd, Cs, Ba, La, Ce, Pr, Pb, Bi, U, As, Al, S, Ca, Ti, V, Cr, Mn, Fe, Co, Na, Mg, Li, and K using inductively coupled plasma sector field mass spectrometry. We also measure δ18O by isotope ratio mass spectrometry. The 2002/2003 traverse began at Byrd Surface Camp, West Antarctica, and ended close to South Pole, East Antarctica. The 2003/2004 traverse began at South Pole, passed through AGO4 in central East Antarctica before turning north and finishing at Taylor Dome. The combined 2006/2007 and 2007/2008 traverses started out at Taylor Dome and headed south, passing through the Byrd Glacier drainage basin and ending at South Pole. In this study, we utilize satellite remote sensing measurements of microwave backscatter and grain size to assist in the identification of glaze/dune areas across Antarctica and show how chemical concentrations are higher in these areas, precluding them from containing useful high-resolution chemical climate records. The majority of the non-glaze/dune samples in this study exhibit similar, or lower, concentrations to those from previous studies. Consequently, the results presented here comprise a conservative baseline for Antarctic surface snow chemical concentrations.

  8. Engineering novel cell surface chemistry for selective tumor cell targeting

    SciTech Connect

    Bertozzi, C.R. |

    1997-12-31

    A common feature of many different cancers is the high expression level of the two monosaccharides sialic acid and fucose within the context of cell-surface associated glycoconjugates. A correlation has been made between hypersialylation and/or hyperfucosylation and the highly metastatic phenotype. Thus, a targeting strategy based on sialic acid or fucose expression would be a powerful tool for the development of new cancer cell-selective therapies and diagnostic agents. We have discovered that ketone groups can be incorporated metabolically into cell-surface associated sialic acids. The ketone is can be covalently ligated with hydrazide functionalized proteins or small molecules under physiological conditions. Thus, we have discovered a mechanism to selectively target hydrazide conjugates to highly sialylated cells such as cancer cells. Applications of this technology to the generation of novel cancer cell-selective toxins and MRI contrast reagents will be discussed, in addition to progress towards the use of cell surface fucose residues as vehicles for ketone expression.

  9. Investigating Massive Dust Events Using a Coupled Weather-Chemistry Model

    NASA Astrophysics Data System (ADS)

    Raman, A.; Arellano, A. F.

    2012-12-01

    Prediction of local to regional scale dust events is challenging due to the complex nature of key processes driving emission, transport, and deposition of mineral dust. In particular, it is difficult to map precisely the sources of mineral dust across heterogeneous land surface properties and land-use changes. This is especially true for Arizona haboobs. These dust storm events are typically driven by thunderstorms and down-bursts over arid regions generating high atmospheric loading of dust in the order of hundreds to thousands of microgram per cubic meter. Modeling and prediction of these events are further complicated by the limitations in satellite-derived and in-situ measurements of dust and related geophysical variables. Here, we investigate the capability of a coupled weather-chemistry model in predicting Arizona haboobs. In particular, this research focuses on the simulation of July 5, 2011 Phoenix haboob using Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) and Goddard Chemistry Aerosol Radiation and Transport Model (GOCART) dust scheme. We evaluate the ability of WRF-Chem in simulating the haboob using satellite retrievals of aerosol extinction properties and mass concentrations from Moderate Resolution Imaging Spectroradiometer (MODIS), Cloud-Aerosol Lidar and Infrared Pathfinder Satellite (CALIPSO) and high resolution SEVIRI false color dust product, in conjunction with in-situ PM10 and PM2.5 measurements. The study uses a nested modeling domain covering Utah, California and Arizona at a horizontal resolution of 5.4 km (outer) and 1.8 km (inner). Boundary conditions for the model are obtained from NOAA Global Forecasting System six-hourly forecast. We present results illustrating the key features of the haboobs, such as the cold pools and surface wind speeds driving the horizontal and vertical structure of the dust, as well as the patterns of dust transport and deposition. Although the spatio-temporal patterns of the haboob

  10. Investigation into the hydrodynamic performance of fouling-release surfaces

    NASA Astrophysics Data System (ADS)

    Quinn, Ronan Declan

    Silicone fouling release coatings provide the only proven biocide free antifouling method, available to ship and boat operators. These surfaces rely on hydrodynamic forces for the removal of fouling and there is interest in understanding the relationship between biofouling and the hydrodynamic forces required for removal. This research investigated the feasibility of predicting the release of cylinders adhered to silicone with epoxy under hydrodynamic loading using a simple point load adhesion measurement. Adhesion and material science, fracture mechanics and hydrodynamics are complex subjects and a detailed review is presented. Experiments were designed and divided into two main categories. Laboratory measurements, which were undertaken to investigate the factors that affect the adhesion of epoxy to fouling release surfaces, and hydrodynamic experiments that were designed to understand the forces and moments imparted on known shapes. The laboratory experiments determined that the stress at failure of epoxy to a silicone fouling release type surface is determined by coating thickness, rate of loading, how the load is applied, chemistry of the interface, and the mechanical properties of the coating. The hydrodynamic experiments were conducted from a test section built into the hull of a 9 meter power vessel. Glass panels were mounted into an instrument such that the coating surface became an integral part of the boat hull. The instrument included, a pitot static tube, to measure the boundary layer velocity, a six component force balance, to measure the forces and moments imparted on these shapes, and the test glass panel. The panels were coated with a clear silicone and cylinders were adhered using epoxy to the coating. This setup enabled the interface between the silicone and epoxy to be viewed using a high speed digital video camera. From these experiments it was determined that it is possible to relatively predict the failure of a cylinder of any length and

  11. Inquiry-Based Arson Investigation for General Chemistry Using GC-MS

    ERIC Educational Resources Information Center

    Maurer, Marta K.; Bukowski, Michael R.; Menachery, Mary D.; Zatorsky, Adam R.

    2010-01-01

    We have developed a two-week guided-inquiry laboratory in which first-semester general chemistry students investigate a suspected arson using gas chromatography--mass spectrometry and paper chromatography. In the process of evaluating evidence from the crime scene, students develop and test hypotheses and learn the fundamentals of chromatography,…

  12. Analysis of Verbal Interactions during an Extended, Open-Inquiry General Chemistry Laboratory Investigation

    ERIC Educational Resources Information Center

    Krystyniak, Rebecca A.; Heikkinen, Henry W.

    2007-01-01

    This study explores effects of participation by second-semester college general chemistry students in an extended, open-inquiry laboratory investigation. Verbal interactions among a student lab team and with their instructor over three open-inquiry laboratory sessions and two non-inquiry sessions were recorded, transcribed, and analyzed. Coding…

  13. Catalytic peptide hydrolysis by mineral surface: Implications for prebiotic chemistry

    NASA Astrophysics Data System (ADS)

    Marshall-Bowman, Karina; Ohara, Shohei; Sverjensky, Dimitri A.; Hazen, Robert M.; Cleaves, H. James

    2010-10-01

    The abiotic polymerization of amino acids may have been important for the origin of life, as peptides may have been components of the first self-replicating systems. Though amino acid concentrations in the primitive oceans may have been too dilute for significant oligomerization to occur, mineral surface adsorption may have provided a concentration mechanism. As unactivated amino acid polymerization is thermodynamically unfavorable and kinetically slow in aqueous solution, we studied mainly the reverse reaction of polymer degradation to measure the impact of mineral surface catalysis on peptide bonds. Aqueous glycine (G), diglycine (GG), diketopiperazine (DKP), and triglycine (GGG) were reacted with minerals (calcite, hematite, montmorillonite, pyrite, rutile, or amorphous silica) in the presence of 0.05 M, pH 8.1, KHCO 3 buffer and 0.1 M NaCl as background electrolyte in a thermostatted oven at 25, 50 or 70 °C. Below 70 °C, reaction kinetics were too sluggish to detect catalytic activity over amenable laboratory time-scales. Minerals were not found to have measurable effects on the degradation or elongation of G, GG or DKP at 70 °C in solution. At 70 °C pyrite was the most catalytic mineral with detectible effects on the degradation of GGG, although several others also displayed catalytic behavior. GGG degraded ˜1.5-4 times faster in the presence of pyrite than in control reactions, depending on the ratio of solution concentration to mineral surface area. The rate of pyrite catalysis of GGG hydrolysis was found to be saturable, suggesting the presence of discrete catalytic sites on the mineral surface. The mineral-catalyzed degradation of GGG appears to occur via a GGG → DKP + G mechanism, rather than via GGG → GG + G, as in solution-phase reactions. These results are compatible with many previous findings and suggest that minerals may have assisted in peptide synthesis in certain geological settings, specifically by speeding the approach to equilibrium

  14. Effects of steam activation on the pore structure and surface chemistry of activated carbon derived from bamboo waste

    NASA Astrophysics Data System (ADS)

    Zhang, Yan-Juan; Xing, Zhen-Jiao; Duan, Zheng-Kang; Li, Meng; Wang, Yin

    2014-10-01

    The effects of steam activation on the pore structure evolution and surface chemistry of activated carbon (AC) obtained from bamboo waste were investigated. Nitrogen adsorption-desorption isotherms revealed that higher steam activation temperatures and/or times promoted the creation of new micropores and widened the existing micropores, consequently decreasing the surface area and total pore volume. Optimum conditions included an activation temperature of 850 °C, activation time of 120 min, and steam flush generated from deionized water of 0.2 cm3 min-1. Under these conditions, AC with a BET surface area of 1210 m2 g-1 and total pore volume of 0.542 cm-3 g-1was obtained. Changes in surface chemistry were determined through Boehm titration, pH measurement, Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). Results revealed the presence of a large number of basic groups on the surface of the pyrolyzed char and AC. Steam activation did not affect the species of oxygen-containing groups but changed the contents of these species when compared with pyrolyzed char. Scanning electron microscopy was used to observe the surface morphology of the products. AC obtained under optimum conditions showed a monolayer adsorption capacity of 330 mg g-1 for methylene blue (MB), which demonstrates its excellent potential for MB adsorption applications.

  15. Recent Advances in chemistry and pharmacology of 2-methoxyestradiol: An anticancer investigational drug.

    PubMed

    Kumar, B Sathish; Raghuvanshi, Dushyant Singh; Hasanain, Mohammad; Alam, Sarfaraz; Sarkar, Jayanta; Mitra, Kalyan; Khan, Feroz; Negi, Arvind S

    2016-06-01

    2-Methoxyestradiol (2ME2), an estrogen hormone metabolite is a potential cancer chemotherapeutic agent. Presently, it is an investigational drug under various phases of clinical trials alone or in combination therapy. Its anticancer activity has been attributed to its antitubulin, antiangiogenic, pro-apoptotic and ROS induction properties. This anticancer drug candidate has been explored extensively in last twenty years for its detailed chemistry and pharmacology. Present review is an update of its chemistry and biological activity. It also extends an assessment of potential of 2ME2 and its analogues as possible anticancer drug in future. PMID:27020471

  16. Transition metal oxides deposited on rhodium and platinum: Surface chemistry and catalysis

    SciTech Connect

    Boffa, A B

    1994-07-01

    The surface chemistry and catalytic reactivity of transition metal oxides deposited on Rh and Pt substrates has been examined in order to establish the role of oxide-metal interactions in influencing catalytic activity. The oxides investigated included titanium oxide (TiOx), vanadium oxide (VOx), iron oxide (FeOx), zirconium oxide (ZrOx), niobium oxide (NbOx), tantalum oxide (TaOx), and tungsten oxide (WOx). The techniques used to characterize the sample included AES, XPS, LEED, TPD, ISS, and STM. After characterization of the surface in UHV, the sample was enclosed in an atmospheric reaction cell to measure the influence of the oxide deposits on the catalytic activity of the pure metal for CO and CO{sub 2} hydrogenation. The oxide deposits were found to strongly enhance the reactivity of the Rh foil. The rates of methane formation were promoted by up to 15 fold with the maximum in rate enhancement occurring at oxide coverages of approximately 0.5 ML. TiOx TaOx, and NbOx were the most effective promoters and were stable in the highest oxidation states during both reactions (compared to VOx, WOx, and FeOx). The trend in promoter effectiveness was attributed to the direct relationship between oxidation state and Lewis acidity. Bonding at the metal oxide/metal interface between the oxygen end of adsorbed CO and the Lewis acidic oxide was postulated to facilitate C-O bond dissociation and subsequent hydrogenation. 192 refs.

  17. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Zachwieja, J.; Lagno, M.

    1990-01-17

    To better understand the flotation behavior of coal pyrite, studies have been initiated to characterize the floatability of coal pyrite and mineral pyrite. The hydrophobicity of coal material pyrite was examined over a range of pH and oxidation times. The results indicate that surface oxidation plays an important role in coal and mineral pyrite hydrophobicity. The hydrophobicity of mineral pyrite decreases with increasing oxidation time (20 min. to 5 hr.) and increasing pH (pH 4.6 to 9.2), with maximum depression occurring at pH 9.2. However, coal pyrite exhibited low floatability, even at the lowest oxidation time, over the entire pH range. X-ray photoelectron spectroscopy (XPS) results suggest the growth of an oxidized iron layer as being responsible for the deterioration in floatability, while a sulfur-containing species present on the sample surfaces may promote floatability. Preliminary studies of the effect of frother indicate an enhancement in the floatability of both coal and mineral pyrite over the entire pH range.

  18. Defining an optimal surface chemistry for pluripotent stem cell culture in 2D and 3D

    NASA Astrophysics Data System (ADS)

    Zonca, Michael R., Jr.

    Surface chemistry is critical for growing pluripotent stem cells in an undifferentiated state. There is great potential to engineer the surface chemistry at the nanoscale level to regulate stem cell adhesion. However, the challenge is to identify the optimal surface chemistry of the substrata for ES cell attachment and maintenance. Using a high-throughput polymerization and screening platform, a chemically defined, synthetic polymer grafted coating that supports strong attachment and high expansion capacity of pluripotent stem cells has been discovered using mouse embryonic stem (ES) cells as a model system. This optimal substrate, N-[3-(Dimethylamino)propyl] methacrylamide (DMAPMA) that is grafted on 2D synthetic poly(ether sulfone) (PES) membrane, sustains the self-renewal of ES cells (up to 7 passages). DMAPMA supports cell attachment of ES cells through integrin beta1 in a RGD-independent manner and is similar to another recently reported polymer surface. Next, DMAPMA has been able to be transferred to 3D by grafting to synthetic, polymeric, PES fibrous matrices through both photo-induced and plasma-induced polymerization. These 3D modified fibers exhibited higher cell proliferation and greater expression of pluripotency markers of mouse ES cells than 2D PES membranes. Our results indicated that desirable surfaces in 2D can be scaled to 3D and that both surface chemistry and structural dimension strongly influence the growth and differentiation of pluripotent stem cells. Lastly, the feasibility of incorporating DMAPMA into a widely used natural polymer, alginate, has been tested. Novel adhesive alginate hydrogels have been successfully synthesized by either direct polymerization of DMAPMA and methacrylic acid blended with alginate, or photo-induced DMAPMA polymerization on alginate nanofibrous hydrogels. In particular, DMAPMA-coated alginate hydrogels support strong ES cell attachment, exhibiting a concentration dependency of DMAPMA. This research provides a

  19. Exploring Silica Chemistry at Biological Interfaces: Kinetic and Thermodynamic Drivers of Surface Nucleation

    NASA Astrophysics Data System (ADS)

    Wallace, A. F.; Dove, P. M.

    2006-12-01

    Biochemical investigations have begun to yield information about structural and chemical properties of organic macromolecules involved in biosilicification processes. However, the mechanisms by which these molecules mediate biosilica formation remain unclear. The formation of mineralized structures in organisms is rooted in processes taking place at the nanoscale, and therefore, molecular level investigative probes are required. Insights into how mineral formation occurs within living organisms can be gained by conducting experimental studies with simple model systems that emulate key features of biological systems. Our approach utilizes a novel AFM-based approach to measure the dependence of amorphous silica nucleation kinetics on the chemical and structural nature of the underlying substrate. Model biological surfaces terminated with carboxyl, hydroxyl, and amine moieties were generated through the spontaneous adsorption of {ω}-alkanethiol self-assembled monolayers onto ultra-flat (111) surfaces of gold. Silica nucleation experiments used supersaturated solutions of silicic acid that were produced by the acid catalyzed hydrolysis of tetramethyl orthosilicate. Measurements of surface nucleation rate were conducted under conditions that simulate current views of conditions within silica deposition vesicles of major diatom species, (e.g. ambient temperature, pH = 5.0, NaCl = 0.1 mol/kg). Aqueous silicate levels were varied to examine dependencies on saturation state. Analysis of the kinetic data within the framework of nucleation theory quantifies the height of the kinetic barrier to silica formation, and the net energy of silica-substrate solution interfaces. By conducting experiments for COOH, NH3+, and OH-functionalized substrates, we determine the kinetic and thermodynamic controls of functional chemistry on heterogeneous nucleation of amorphous silica. The findings are providing new insights into how biochemical interfaces mediate the onset of silica formation.

  20. Theoretical investigation of gas-surface interactions

    NASA Technical Reports Server (NTRS)

    Dyall, Kenneth G.

    1994-01-01

    The goal of this project was to develop computational tools for the calculation of the electronic structure of molecules containing heavy atoms, and to use these tools in the study of catalytic processes, with the overall objective of gaining an understanding of the catalytic process which could be used to design more efficient catalysts. The main catalytic system of interest was the combustion of hydrogen on platinum surfaces. Under this project, a flexible Dirac-Hartree-Fock (DHF) program has been developed, a code to calculate DHF correlation energies at the second-order Moeller-Plesset perturbation (PP2) level is almost complete, and code to include correlation at the MCSCF and MCSCF/MP2 level is planned. The tools so far developed have been validated and used to calibrate some more approximate methods, and applied to investigate the importance of relativistic effects in the bonding of hydrogen to platinum.

  1. Investigation of the ion beryllium surface interaction

    SciTech Connect

    Guseva, M.I.; Birukov, A.Yu.; Gureev, V.M.

    1995-09-01

    The self -sputtering yield of the Be was measured. The energy dependence of the Be self-sputtering yield agrees well with that calculated by W. Eckstein et. al. Below 770 K the self-sputtering yield is temperature independent; at T{sub irr}.> 870 K it increases sharply. Hot-pressed samples at 370 K were implanted with monoenergetic 5 keV hydrogen ions and with a stationary plasma (flux power {approximately} 5 MW/m{sup 2}). The investigation of hydrogen behavior in beryllium shows that at low doses hydrogen is solved, but at doses {ge} 5x10{sup 22} m{sup -2} the bubbles and channels are formed. It results in hydrogen profile shift to the surface and decrease of its concentration. The sputtering results in further concentration decrease at doses > 10{sup 25}m{sup -2}.

  2. Challenges in Teaching "Colloid and Surface Chemistry"--A Danish Experience

    ERIC Educational Resources Information Center

    Kontogeorgis, Georgios M.; Vigild, Martin E.

    2009-01-01

    Seven years ago we were asked, as one of our first teaching duties at the Technical University of Denmark (DTU), to teach a 5 ECTS point course on "Colloid and Surface Chemistry". The topic is itself at the same time exciting and demanding, largely due to its multidisciplinary nature. Several "local" requirements posed additional challenges. The…

  3. Eley-Rideal surface chemistry: Direct reactivity of gas phase atomic hydrogen with adsorbed species

    SciTech Connect

    Weinberg, W.H.

    1996-10-01

    Selected examples of Eley-Rideal surface chemistry are presented in order to review this field. Reactions on Ru(100) only are considered. The specific examples employed are: (i) hydrogenation of oxygen atoms, (ii) hydrogenation of CO, (iii) formation of dihydrogen, and (iv) hydrogenation of formate. 80 refs., 8 figs.

  4. Modeling aerosol surface chemistry and gas-particle interaction kinetics with K2-SURF: PAH oxidation

    NASA Astrophysics Data System (ADS)

    Shiraiwa, M.; Garland, R.; Pöschl, U.

    2009-04-01

    Atmospheric aerosols are ubiquitous in the atmosphere. They have the ability to impact cloud properties, radiative balance and provide surfaces for heterogeneous reactions. The uptake of gaseous species on aerosol surfaces impacts both the aerosol particles and the atmospheric budget of trace gases. These subsequent changes to the aerosol can in turn impact the aerosol chemical and physical properties. However, this uptake, as well as the impact on the aerosol, is not fully understood. This uncertainty is due not only to limited measurement data, but also a dearth of comprehensive and applicable modeling formalizations used for the analysis, interpretation and description of these heterogeneous processes. Without a common model framework, comparing and extrapolating experimental data is difficult. In this study, a novel kinetic surface model (K2-SURF) [Ammann & Pöschl, 2007; Pöschl et al., 2007] was used to describe the oxidation of a variety of polycyclic aromatic hydrocarbons (PAHs). Integrated into this consistent and universally applicable kinetic and thermodynamic process model are the concepts, terminologies and mathematical formalizations essential to the description of atmospherically relevant physicochemical processes involving organic and mixed organic-inorganic aerosols. Within this process model framework, a detailed master mechanism, simplified mechanism and parameterizations of atmospheric aerosol chemistry are being developed and integrated in analogy to existing mechanisms and parameterizations of atmospheric gas-phase chemistry. One of the key aspects to this model is the defining of a clear distinction between various layers of the particle and surrounding gas phase. The processes occurring at each layer can be fully described using known fluxes and kinetic parameters. Using this system there is a clear separation of gas phase, gas-surface and surface bulk transport and reactions. The partitioning of compounds can be calculated using the flux

  5. Global Transcriptomic Analysis of Model Human Cell Lines Exposed to Surface-Modified Gold Nanoparticles: The Effect of Surface Chemistry

    PubMed Central

    Grzincic, E. M.; Yang, J. A.; Drnevich, J.; Falagan-Lotsch, P.; Murphy, C. J.

    2015-01-01

    Gold nanoparticles (Au NPs) are attractive for biomedical applications not only for their remarkable physical properties, but also for the ease of which their surface chemistry can be manipulated. Many applications involve functionalization of the Au NP surface in order to improve biocompatibility, attach targeting ligands or carry drugs. However, changes in cells exposed to Au NPs of different surface chemistries have been observed, and little is known about how Au NPs and their surface coatings may impact cellular gene expression. The gene expression of two model human cell lines, human dermal fibroblasts (HDF) and prostate cancer cells (PC3) was interrogated by microarray analysis of over 14,000 human genes. The cell lines were exposed to four differently functionalized Au NPs: citrate, poly(allylamine hydrochloride) (PAH), and lipid coatings combined with alkanethiols or PAH. Gene functional annotation categories and weighted gene correlation network analysis were used in order to connect gene expression changes to common cellular functions and to elucidate expression patterns between Au NP samples. Coated Au NPs affect genes implicated in proliferation, angiogenesis, and metabolism in HDF cells, and inflammation, angiogenesis, proliferation apoptosis regulation, survival and invasion in PC3 cells. Subtle changes in surface chemistry, such as the initial net charge, lability of the ligand, and underlying layers greatly influence the degree of expression change and the type of cellular pathway affected. PMID:25491924

  6. Informatics guided discovery of surface structure-chemistry relationships in catalytic nanoparticles

    SciTech Connect

    Andriotis, Antonis N.; Mpourmpakis, Giannis; Broderick, Scott Rajan, Krishna; Datta, Somnath; Sunkara, Mahendra; Menon, Madhu

    2014-03-07

    A data driven discovery strategy based on statistical learning principles is used to discover new correlations between electronic structure and catalytic activity of metal surfaces. From the quantitative formulations derived from this informatics based model, a high throughput computational framework for predicting binding energy as a function of surface chemistry and adsorption configuration that bypasses the need for repeated electronic structure calculations has been developed.

  7. Control of pyrite surface chemistry in physical coal cleaning

    SciTech Connect

    Luttrell, G.H.; Yoon, R.H.; Zachwieja, J.B.; Lagno, M.L.

    1990-01-01

    Several pyrite depressants have been evaluated for their effectiveness in depressing coal pyrite. A novel reagent, NVT, has been synthesized and shown to be selective for the separation of coal from coal pyrite by froth flotation. This organic reagent contains no sulfur group in its structure and exhibits a stronger affinity toward pyrite than toward coal. The effects of a number of parameters such as pH, reagent concentration and flotation time on flotation response were investigated in a microflotation cell and a bench-scale Denver flotation cell. The reagent has demonstrated good performance at relatively low concentrations when compared to the commercially available sulfur-based pyrite depressants. 8 figs.

  8. Venting temperature determines surface chemistry of magnetron sputtered TiN films

    NASA Astrophysics Data System (ADS)

    Greczynski, G.; Mráz, S.; Hultman, L.; Schneider, J. M.

    2016-01-01

    Surface properties of refractory ceramic transition metal nitride thin films grown by magnetron sputtering are essential for resistance towards oxidation necessary in all modern applications. Here, typically neglected factors, including exposure to residual process gases following the growth and the venting temperature Tv, each affecting the surface chemistry, are addressed. It is demonstrated for the TiN model materials system that Tv has a substantial effect on the composition and thickness-evolution of the reacted surface layer and should therefore be reported. The phenomena are also shown to have impact on the reliable surface characterization by x-ray photoelectron spectroscopy.

  9. Studies of the surface reactivity of metal oxyhydroxides and sulfides with relevance to environmental chemistry

    NASA Astrophysics Data System (ADS)

    Pierre-Louis, Andro-Marc

    With the benefits of an ever increasing advance of industrialization around the globe come formidable environmental problems. Three environmental problems that have relevance to the research described in this thesis are the 1) buildup of atmospheric CO2 gas through the burning of fossil fuels, 2) eutrophication of aquatic systems, and 3) the acidification of environments from acid mine drainage (AMD) resulting from coal-mining activities. In particular research is presented in this thesis that investigated the surface chemistry of CO2 and phosphate (PO43-) on a suite of environmentally relevant iron oxyhydroxide materials and the chemistry of phospholipid molecules on environmentally relevant iron sulfide surfaces to suppress AMD. To develop a microscopic understanding of the surface chemistry of the different systems, an array of experimental and computational techniques were used in the research. Techniques included X-ray photoelectron spectroscopy, atomic adsorption, X-ray diffraction, scanning transmission microscopy with electron dispersive X-ray spectroscopy (STEM/EDS), ion chromatography (IC), and attenuated total reflectance Fourier transform Infrared (ATR-FTIR). Results from the latter technique were interpreted with the aid of density function theory (DFT) calculations. Iron oxyhydroxides, which consisted of ferrihydrite (FeOOH), goethite (α-FeOOH), ferrimagnetic ferrihydrite (FerriFh), and aluminum-doped iron oxyhydroxide (content from 0-100 mol%) were synthesized and studied before and after exposure to gaseous CO2, CO32-, and PO43- species. FeOOH and mixed Al/Fe oxyhydroxide surfaces showed high affinities for the formation of carbonate and bicarbonate species upon exposure to gaseous CO2. Within the Al/Fe oxyhydroxide circumstance, a low Al level of incorporation in the iron oxyhydroxide structure caused a slight increase in surface area and increase in the amount of oxyanion (e.g., CO32- or PO43-) adsorption up to an Al level of 30 mol%. Significant

  10. Studies of the surface reactivity of metal oxyhydroxides and sulfides with relevance to environmental chemistry

    NASA Astrophysics Data System (ADS)

    Pierre-Louis, Andro-Marc

    With the benefits of an ever increasing advance of industrialization around the globe come formidable environmental problems. Three environmental problems that have relevance to the research described in this thesis are the 1) buildup of atmospheric CO2 gas through the burning of fossil fuels, 2) eutrophication of aquatic systems, and 3) the acidification of environments from acid mine drainage (AMD) resulting from coal-mining activities. In particular research is presented in this thesis that investigated the surface chemistry of CO2 and phosphate (PO43-) on a suite of environmentally relevant iron oxyhydroxide materials and the chemistry of phospholipid molecules on environmentally relevant iron sulfide surfaces to suppress AMD. To develop a microscopic understanding of the surface chemistry of the different systems, an array of experimental and computational techniques were used in the research. Techniques included X-ray photoelectron spectroscopy, atomic adsorption, X-ray diffraction, scanning transmission microscopy with electron dispersive X-ray spectroscopy (STEM/EDS), ion chromatography (IC), and attenuated total reflectance Fourier transform Infrared (ATR-FTIR). Results from the latter technique were interpreted with the aid of density function theory (DFT) calculations. Iron oxyhydroxides, which consisted of ferrihydrite (FeOOH), goethite (α-FeOOH), ferrimagnetic ferrihydrite (FerriFh), and aluminum-doped iron oxyhydroxide (content from 0-100 mol%) were synthesized and studied before and after exposure to gaseous CO2, CO32-, and PO43- species. FeOOH and mixed Al/Fe oxyhydroxide surfaces showed high affinities for the formation of carbonate and bicarbonate species upon exposure to gaseous CO2. Within the Al/Fe oxyhydroxide circumstance, a low Al level of incorporation in the iron oxyhydroxide structure caused a slight increase in surface area and increase in the amount of oxyanion (e.g., CO32- or PO43-) adsorption up to an Al level of 30 mol%. Significant

  11. The surface chemistry of vinyl iodide on Pt(111)

    SciTech Connect

    Liu, Z.M.; Zhou, X.L.; Buchanan, D.A.

    1992-03-11

    Regardless of exposure, only submonolayer amounts of vinyl iodide (CH{sub 2}CHI) decompose, either during adsorption on Pt(111) at 100 K or during subsequent heating to 165 K. The remainder desorbs molecularly. The dissociation products are vinyl (CH{sub 2}CH) fragments, an important C{sub 2} intermediate in hydrocarbon catalysis, and atomic iodine. Using the tools of surface science the authors have explored the formation and subsequent reactions of vinyl species in the presence of unavoidable coadsorbed atomic iodine. While some vinyl exists up to 450 K, there are two important and competitive lower temperature reaction channels which lead to ethylidyne (CCH{sub 3}) and ethylene (CH{sub 2}CH{sub 2}). From these results, the authors conclude that the rate of ethylidyne formation from adsorbed ethylene is controlled by the rate at which the first C-H bond in ethylene breaks, and in agreement with Zaera, the authors find that vinyl is a facile intermediate in the process. 28 refs., 12 figs., 3 tabs.

  12. Effects of surface chemistry on hot corrosion life

    NASA Technical Reports Server (NTRS)

    Fryxell, R. E.

    1985-01-01

    Burner rig tests were conducted under the following conditions: 900 C, hourly thermal cycling, 0.5 ppm sodium as MaCl in the gas stream, velocity 0.3 Mach. The alloys are Udiment 700, Rene 80, uncoated and with RT21, Codep, or NiCoCrAlY coatings. These tests were completed for specimens in the as-processed condition and after aging at 1100 C in oxidizing or inert evnivronments for time up to 600 hours. Coil inductance changes used for periodic nondestructive inspection of specimens were useful in following the course of corrosion. Typical sulfidation was observed in all cases, structurally similar to that observed for service-run turbine components. Aging at cuased a severe decrease in hot corrosion life of RT21 and Codep coatings and a significant but less decrease in the life of the NiCoCrAlY coating. The extent of these decreases was much greater for all three coatings on U700 substrates than on Rene 80 substrates. Coating/substrate interdiffusion rather than by surface oxidation.

  13. Catalyst design for enhanced sustainability through fundamental surface chemistry.

    PubMed

    Personick, Michelle L; Montemore, Matthew M; Kaxiras, Efthimios; Madix, Robert J; Biener, Juergen; Friend, Cynthia M

    2016-02-28

    Decreasing energy consumption in the production of platform chemicals is necessary to improve the sustainability of the chemical industry, which is the largest consumer of delivered energy. The majority of industrial chemical transformations rely on catalysts, and therefore designing new materials that catalyse the production of important chemicals via more selective and energy-efficient processes is a promising pathway to reducing energy use by the chemical industry. Efficiently designing new catalysts benefits from an integrated approach involving fundamental experimental studies and theoretical modelling in addition to evaluation of materials under working catalytic conditions. In this review, we outline this approach in the context of a particular catalyst-nanoporous gold (npAu)-which is an unsupported, dilute AgAu alloy catalyst that is highly active for the selective oxidative transformation of alcohols. Fundamental surface science studies on Au single crystals and AgAu thin-film alloys in combination with theoretical modelling were used to identify the principles which define the reactivity of npAu and subsequently enabled prediction of new reactive pathways on this material. Specifically, weak van der Waals interactions are key to the selectivity of Au materials, including npAu. We also briefly describe other systems in which this integrated approach was applied. PMID:26755756

  14. Surface Chemistry of Trimethyl Phosphate on α-Fe2O3

    SciTech Connect

    Henderson, Michael A.

    2011-12-01

    The chemistry of trimethyl phosphate (TMP) was examined on the (012) crystallographic face of hematite (α-Fe2O3) using temperature programmed desorption (TPD), high resolution electron energy loss spectroscopy (HREELS), static secondary ion mass spectrometry (SSIMS) and Auger electron spectroscopy (AES). TMP binds to Fe3+ sites on the clean α-Fe2O3(012) surface through lone pairs on the P=O oxygen atom. A small portion of adsorbed TMP desorbs without decomposition, however, the majority of adsorbed TMP decomposes in a two step process on the clean surface. The first step, occurring at or below room temperature (RT), likely involves displacement or substitution of one –OCH3 group to form surface methoxy groups and adsorbed dimethyl phosphate (DMP). In the second step, DMP decomposes above 500 K to a 1:1 ratio of gaseous methanol and formaldehyde with phosphate left on the surface. Identification of these steps was confirmed using the chemistry of methanol on the clean surface. Coadsorption of TMP and water led to a small degree of hydrolysis between these two molecules in the multilayer, but no significant change in the chemistry on the surface. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  15. Ammonia removal using activated carbons: effect of the surface chemistry in dry and moist conditions.

    PubMed

    Gonçalves, Maraisa; Sánchez-García, Laura; Oliveira Jardim, Erika de; Silvestre-Albero, Joaquín; Rodríguez-Reinoso, Francisco

    2011-12-15

    The effect of surface chemistry (nature and amount of oxygen groups) in the removal of ammonia was studied using a modified resin-based activated carbon. NH(3) breakthrough column experiments show that the modification of the original activated carbon with nitric acid, that is, the incorporation of oxygen surface groups, highly improves the adsorption behavior at room temperature. Apparently, there is a linear relationship between the total adsorption capacity and the amount of the more acidic and less stable oxygen surface groups. Similar experiments using moist air clearly show that the effect of humidity highly depends on the surface chemistry of the carbon used. Moisture highly improves the adsorption behavior for samples with a low concentration of oxygen functionalities, probably due to the preferential adsorption of ammonia via dissolution into water. On the contrary, moisture exhibits a small effect on samples with a rich surface chemistry due to the preferential adsorption pathway via Brønsted and Lewis acid centers from the carbon surface. FTIR analyses of the exhausted oxidized samples confirm both the formation of NH(4)(+) species interacting with the Brønsted acid sites, together with the presence of NH(3) species coordinated, through the lone pair electron, to Lewis acid sites on the graphene layers. PMID:22049916

  16. Relating surface chemistry and oxygen surface exchange in LnBaCo2O(5+δ) air electrodes.

    PubMed

    Téllez, Helena; Druce, John; Kilner, John A; Ishihara, Tatsumi

    2015-01-01

    The surface and near-surface chemical composition of electroceramic materials often shows significant deviations from that of the bulk. In particular, layered materials, such as cation-ordered LnBaCo2O(5+δ) perovskites (Ln = lanthanide), undergo surface and sub-surface restructuring due to the segregation of the divalent alkaline-earth cation. These processes can take place during synthesis and processing steps (e.g. deposition, sintering or annealing), as well as at temperatures relevant for the operation of these materials as air electrodes in solid oxide fuel cells and electrolysers. Furthermore, the surface segregation in these double perovskites shows fast kinetics, starting at temperatures as low as 400 °C over short periods of time and leading to a decrease in the transition metal surface coverage exposed to the gas phase. In this work, we use a combination of stable isotope tracer labeling and surface-sensitive ion beam techniques to study the oxygen transport properties and their relationship with the surface chemistry in ordered LnBaCo2O(5+δ) perovskites. Time-of-Flight Secondary-Ion Mass Spectrometry (ToF-SIMS) combined with (18)O isotope exchange was used to determine the oxygen tracer diffusion (D*) and surface exchange (k*) coefficients. Furthermore, Low Energy Ion Scattering (LEIS) was used for the analysis of the surface and near surface chemistry as it provides information from the first mono-atomic layer of the materials. In this way, we could relate the compositional modifications (e.g. cation segregation) taking place at the electrochemically-active surface during the exchange at high temperatures and the oxygen transport properties in double perovskite electrode materials to further our understanding of the mechanism of the surface exchange process. PMID:26212446

  17. Surface chemistry : a non-negligible parameter in determining optical properties of small colloidal metal nanoparticles.

    SciTech Connect

    Sun, Y.; Gray, S. K.; Peng, S.

    2011-01-01

    Surface chemistry can become pronounced in determining the optical properties of colloidal metal nanoparticles as the nanoparticles become so small (diameters <20 nm) that the surface atoms, which can undergo chemical interactions with the environment, represent a significant fraction of the total number of atoms although this effect is often ignored. For instance, formation of chemical bonds between surface atoms of small metal nanoparticles and capping molecules that help stabilize the nanoparticles can reduce the density of conduction band electrons in the surface layer of metal atoms. This reduced electron density consequently influences the frequency-dependent dielectric constant of the metal atoms in the surface layer and, for sufficiently high surface to volume ratios, the overall surface plasmon resonance (SPR) absorption spectrum. The important role of surface chemistry is highlighted here by carefully analyzing the classical Mie theory and a multi-layer model is presented to produce more accurate predictions by considering the chemically reduced density of conduction band electrons in the outer shell of metal atoms in nanoparticles. Calculated absorption spectra of small Ag nanoparticles quantitatively agree with the experimental results for our monodispersed Ag nanoparticles synthesized via a well-defined chemical reduction process, revealing an exceptional size-dependence of absorption peak positions: the peaks first blue-shift followed by a turnover and a dramatic red-shift as the particle size decreases. A comprehensive understanding of the relationship between surface chemistry and optical properties is beneficial to exploit new applications of small colloidal metal nanoparticles, such as colorimetric sensing, electrochromic devices, and surface enhanced spectroscopies.

  18. The effect of injection molding conditions on the near-surface rubber morphology, surface chemistry, and adhesion performance of semi-crystalline and amorphous polymers

    NASA Astrophysics Data System (ADS)

    Weakley-Bollin, Shannon Christine

    This thesis investigated the effect of injection molding processing variables, resin formulation and mold material on the resulting morphology and properties of semi-crystalline and amorphous polymers in parts molded on large presses with fully developed flow. Five different polymer resins and two different coating types were investigated, and the near-surface morphology was found to be dependent on material formulation, processing parameters, and geometry. For painted TPO, changes in the near-surface rubber morphology and surface chemistry based on material and processing conditions had no significant effect on the adhesion performance. For metal plated ABS, the adhesion performance was found to be heavily dependent on the rubber surface morphology, which varied with material formulation and processing conditions. One of the most significant findings was that forged aluminum injection molding tooling had little effect on the surface morphology or adhesion performance of either polypropylene or the two TPO formulations examined, despite the five-fold increase in thermal conductivity over traditional tool steel. Surface chemistry, however, was found to be affected by cooling rate, depending on material formulation. A UV stabilizer additive was found concentrated at 2.5 atomic percent on the surface of the aluminum molded part, but not the steel molded part, demonstrating a possible opportunity for using additives and aluminum tooling to create "designer surfaces". Processing conditions were found to have a competing role in metal plated ABS, where conditions that lowered surface stress and improved adhesion by a factor of 15 also increased the amount of bulk molded-in stress by nearly 7%. Both factors were found to play an important role in adhesion performance due to the effect of surface stress on the quality of the resulting etch structure. The bulk stress must be minimized to due to the large mechanical and thermal mismatch between the polymer and metal layers

  19. Giant magnetoresistive biosensors for molecular diagnosis: surface chemistry and assay development

    NASA Astrophysics Data System (ADS)

    Yu, Heng; Osterfeld, Sebastian J.; Xu, Liang; White, Robert L.; Pourmand, Nader; Wang, Shan X.

    2008-08-01

    Giant magnetoresistive (GMR) biochips using magnetic nanoparticle as labels were developed for molecular diagnosis. The sensor arrays consist of GMR sensing strips of 1.5 μm or 0.75 μm in width. GMR sensors are exquisitely sensitive yet very delicate, requiring ultrathin corrosion-resistive passivation and efficient surface chemistry for oligonucleotide probe immobilization. A mild and stable surface chemistry was first developed that is especially suitable for modifying delicate electronic device surfaces, and a practical application of our GMR biosensors was then demonstrated for detecting four most common human papillomavirus (HPV) subtypes in plasmids. We also showed that the DNA hybridization time could potentially be reduced from overnight to about ten minutes using microfluidics.

  20. Pretreatment-dependent surface chemistry of wood nanocellulose for pH-sensitive hydrogels.

    PubMed

    Chinga-Carrasco, Gary; Syverud, Kristin

    2014-09-01

    Nanocellulose from wood is a promising material with potential in various technological areas. Within biomedical applications, nanocellulose has been proposed as a suitable nano-material for wound dressings. This is based on the capability of the material to self-assemble into 3D micro-porous structures, which among others have an excellent capacity of maintaining a moist environment. In addition, the surface chemistry of nanocellulose is suitable for various applications. First, OH-groups are abundant in nanocellulose materials, making the material strongly hydrophilic. Second, the surface chemistry can be modified, introducing aldehyde and carboxyl groups, which have major potential for surface functionalization. In this study, we demonstrate the production of nanocellulose with tailor-made surface chemistry, by pre-treating the raw cellulose fibres with carboxymethylation and periodate oxidation. The pre-treatments yielded a highly nanofibrillated material, with significant amounts of aldehyde and carboxyl groups. Importantly, the poly-anionic surface of the oxidized nanocellulose opens up for novel applications, i.e. micro-porous materials with pH-responsive characteristics. This is due to the swelling capacity of the 3D micro-porous structures, which have ionisable functional groups. In this study, we demonstrated that nanocellulose gels have a significantly higher swelling degree in neutral and alkaline conditions, compared to an acid environment (pH 3). Such a capability can potentially be applied in chronic wounds for controlled and intelligent release of antibacterial components into biofilms. PMID:24713295

  1. Pretreatment-dependent surface chemistry of wood nanocellulose for pH-sensitive hydrogels

    PubMed Central

    Syverud, Kristin

    2014-01-01

    Nanocellulose from wood is a promising material with potential in various technological areas. Within biomedical applications, nanocellulose has been proposed as a suitable nano-material for wound dressings. This is based on the capability of the material to self-assemble into 3D micro-porous structures, which among others have an excellent capacity of maintaining a moist environment. In addition, the surface chemistry of nanocellulose is suitable for various applications. First, OH-groups are abundant in nanocellulose materials, making the material strongly hydrophilic. Second, the surface chemistry can be modified, introducing aldehyde and carboxyl groups, which have major potential for surface functionalization. In this study, we demonstrate the production of nanocellulose with tailor-made surface chemistry, by pre-treating the raw cellulose fibres with carboxymethylation and periodate oxidation. The pre-treatments yielded a highly nanofibrillated material, with significant amounts of aldehyde and carboxyl groups. Importantly, the poly-anionic surface of the oxidized nanocellulose opens up for novel applications, i.e. micro-porous materials with pH-responsive characteristics. This is due to the swelling capacity of the 3D micro-porous structures, which have ionisable functional groups. In this study, we demonstrated that nanocellulose gels have a significantly higher swelling degree in neutral and alkaline conditions, compared to an acid environment (pH 3). Such a capability can potentially be applied in chronic wounds for controlled and intelligent release of antibacterial components into biofilms. PMID:24713295

  2. An Investigation of the Effects of Reader Characteristics on Reading Comprehension Of a General Chemistry Text

    NASA Astrophysics Data System (ADS)

    Neiles, Kelly Y.

    There is great concern in the scientific community that students in the United States, when compared with other countries, are falling behind in their scientific achievement. Increasing students' reading comprehension of scientific text may be one of the components involved in students' science achievement. To investigate students' reading comprehension this quantitative study examined the effects of different reader characteristics, namely, students' logical reasoning ability, factual chemistry knowledge, working memory capacity, and schema of the chemistry concepts, on reading comprehension of a chemistry text. Students' reading comprehension was measured through their ability to encode the text, access the meanings of words (lexical access), make bridging and elaborative inferences, and integrate the text with their existing schemas to make a lasting mental representation of the text (situational model). Students completed a series of tasks that measured the reader characteristic and reading comprehension variables. Some of the variables were measured using new technologies and software to investigate different cognitive processes. These technologies and software included eye tracking to investigate students' lexical accessing and a Pathfinder program to investigate students' schema of the chemistry concepts. The results from this study were analyzed using canonical correlation and regression analysis. The canonical correlation analysis allows for the ten variables described previously to be included in one multivariate analysis. Results indicate that the relationship between the reader characteristic variables and the reading comprehension variables is significant. The resulting canonical function accounts for a greater amount of variance in students' responses then any individual variable. Regression analysis was used to further investigate which reader characteristic variables accounted for the differences in students' responses for each reading comprehension

  3. An investigation of student understanding in the undergraduate organic chemistry laboratory

    NASA Astrophysics Data System (ADS)

    Grutsch, John Leo, Jr.

    Laboratory activities in organic chemistry involve a mixture of sophisticated logic and empirical observation that requires the integration of mechanistic thought, laboratory technique, and problem-solving skills. In an effort to understand how students develop the thought processes and problem-solving skills necessary for laboratory work in organic chemistry, student understanding of how the interaction between a reaction system (reactants or starting material(s), reagent(s), and/or solvent), experimental variables (pH, temperature, concentrations, etc), provides a result of interest (yield, selectivity, purity, etc.) for an experiment performed in the organic chemistry laboratory was investigated through the collection of responses to questions posed on pre-laboratory quizzes followed by in-depth interviews during which student volunteers discussed their responses along with their experiences in the laboratory. The conceptual change theory of learning which assumes new conceptions are understood, judged, acquired, or rejected in a conceptual context was used as a theoretical paradigm to examine students responses to questions posed on pre-laboratory quizzes and transcripts of the interviews with student volunteers. Students were found to not have developed a mechanistic understanding of how the interaction between a reaction system (reactants or starting material(s), reagent(s), and/or solvent), experimental variables (pH, temperature, concentrations, etc), provides a result of interest (yield, selectivity, purity, etc.) for an experiment performed in the organic chemistry laboratory. However, students' prior exposure to and understanding of chemical concepts was found to simultaneously assist and hinder in their development of a partial mechanistic understanding of how a reaction system (reactants or starting material(s), reagent(s), and/or solvent), experimental variables (pH, temperature, concentrations, etc), interact to provide a result of interest (yield

  4. Influence of surface microstructure and chemistry on osteoinduction and osteoclastogenesis by biphasic calcium phosphate discs.

    PubMed

    Davison, N L; Su, J; Yuan, H; van den Beucken, J J J P; de Bruijn, J D; Barrère-de Groot, F

    2015-01-01

    It has been reported that surface microstructural dimensions can influence the osteoinductivity of calcium phosphates (CaPs), and osteoclasts may play a role in this process. We hypothesised that surface structural dimensions of ≤ 1 μm trigger osteoinduction and osteoclast formation irrespective of macrostructure (e.g., concavities, interconnected macropores, interparticle space) or surface chemistry. To test this, planar discs made of biphasic calcium phosphate (BCP: 80% hydroxyapatite, 20% tricalcium phosphate) were prepared with different surface structural dimensions - either ~ 1 μm (BCP1150) or ~ 2-4 μm (BCP1300) - and no macropores or concavities. A third material was made by sputter coating BCP1150 with titanium (BCP1150Ti), thereby changing its surface chemistry but preserving its surface structure and chemical reactivity. After intramuscular implantation in 5 dogs for 12 weeks, BCP1150 formed ectopic bone in 4 out of 5 samples, BCP1150Ti formed ectopic bone in 3 out of 5 samples, and BCP1300 formed no ectopic bone in any of the 5 samples. In vivo, large multinucleated osteoclast-like cells densely colonised BCP1150, smaller osteoclast-like cells formed on BCP1150Ti, and osteoclast-like cells scarcely formed on BCP1300. In vitro, RAW264.7 cells cultured on the surface of BCP1150 and BCP1150Ti in the presence of osteoclast differentiation factor RANKL (receptor activator for NF-κB ligand) proliferated then differentiated into multinucleated osteoclast-like cells with positive tartrate resistant acid phosphatase (TRAP) activity. However, cell proliferation, fusion, and TRAP activity were all significantly inhibited on BCP1300. These results indicate that of the material parameters tested - namely, surface microstructure, macrostructure, and surface chemistry - microstructural dimensions are critical in promoting osteoclastogenesis and triggering ectopic bone formation. PMID:26091730

  5. Nanoporous Gold as a Neural Interface Coating: Effects of Topography, Surface Chemistry, and Feature Size

    DOE PAGESBeta

    Chapman, Christopher A. R.; Chen, Hao; Stamou, Marianna; Biener, Juergen; Biener, Monika M.; Lein, Pamela J.; Seker, Erkin

    2015-02-23

    We report that designing neural interfaces that maintain close physical coupling of neurons to an electrode surface remains a major challenge for both implantable and in vitro neural recording electrode arrays. Typically, low-impedance nanostructured electrode coatings rely on chemical cues from pharmaceuticals or surface-immobilized peptides to suppress glial scar tissue formation over the electrode surface (astrogliosis), which is an obstacle to reliable neuron–electrode coupling. Nanoporous gold (np-Au), produced by an alloy corrosion process, is a promising candidate to reduce astrogliosis solely through topography by taking advantage of its tunable length scale. In the present in vitro study on np-Au’s interactionmore » with cortical neuron–glia co-cultures, we demonstrate that the nanostructure of np-Au achieves close physical coupling of neurons by maintaining a high neuron-to-astrocyte surface coverage ratio. Atomic layer deposition-based surface modification was employed to decouple the effect of morphology from surface chemistry. Additionally, length scale effects were systematically studied by controlling the characteristic feature size of np-Au through variations in the dealloying conditions. In conclusion, our results show that np-Au nanotopography, not surface chemistry, reduces astrocyte surface coverage while maintaining high neuronal coverage and may enhance neuron–electrode coupling through nanostructure-mediated suppression of scar tissue formation.« less

  6. Nanoporous Gold as a Neural Interface Coating: Effects of Topography, Surface Chemistry, and Feature Size

    SciTech Connect

    Chapman, Christopher A. R.; Chen, Hao; Stamou, Marianna; Biener, Juergen; Biener, Monika M.; Lein, Pamela J.; Seker, Erkin

    2015-02-23

    We report that designing neural interfaces that maintain close physical coupling of neurons to an electrode surface remains a major challenge for both implantable and in vitro neural recording electrode arrays. Typically, low-impedance nanostructured electrode coatings rely on chemical cues from pharmaceuticals or surface-immobilized peptides to suppress glial scar tissue formation over the electrode surface (astrogliosis), which is an obstacle to reliable neuron–electrode coupling. Nanoporous gold (np-Au), produced by an alloy corrosion process, is a promising candidate to reduce astrogliosis solely through topography by taking advantage of its tunable length scale. In the present in vitro study on np-Au’s interaction with cortical neuron–glia co-cultures, we demonstrate that the nanostructure of np-Au achieves close physical coupling of neurons by maintaining a high neuron-to-astrocyte surface coverage ratio. Atomic layer deposition-based surface modification was employed to decouple the effect of morphology from surface chemistry. Additionally, length scale effects were systematically studied by controlling the characteristic feature size of np-Au through variations in the dealloying conditions. In conclusion, our results show that np-Au nanotopography, not surface chemistry, reduces astrocyte surface coverage while maintaining high neuronal coverage and may enhance neuron–electrode coupling through nanostructure-mediated suppression of scar tissue formation.

  7. Nanoporous gold as a neural interface coating: effects of topography, surface chemistry, and feature size.

    PubMed

    Chapman, Christopher A R; Chen, Hao; Stamou, Marianna; Biener, Juergen; Biener, Monika M; Lein, Pamela J; Seker, Erkin

    2015-04-01

    Designing neural interfaces that maintain close physical coupling of neurons to an electrode surface remains a major challenge for both implantable and in vitro neural recording electrode arrays. Typically, low-impedance nanostructured electrode coatings rely on chemical cues from pharmaceuticals or surface-immobilized peptides to suppress glial scar tissue formation over the electrode surface (astrogliosis), which is an obstacle to reliable neuron-electrode coupling. Nanoporous gold (np-Au), produced by an alloy corrosion process, is a promising candidate to reduce astrogliosis solely through topography by taking advantage of its tunable length scale. In the present in vitro study on np-Au's interaction with cortical neuron-glia co-cultures, we demonstrate that the nanostructure of np-Au achieves close physical coupling of neurons by maintaining a high neuron-to-astrocyte surface coverage ratio. Atomic layer deposition-based surface modification was employed to decouple the effect of morphology from surface chemistry. Additionally, length scale effects were systematically studied by controlling the characteristic feature size of np-Au through variations in the dealloying conditions. Our results show that np-Au nanotopography, not surface chemistry, reduces astrocyte surface coverage while maintaining high neuronal coverage and may enhance neuron-electrode coupling through nanostructure-mediated suppression of scar tissue formation. PMID:25706691

  8. Nanoporous Gold as a Neural Interface Coating: Effects of Topography, Surface Chemistry, and Feature Size

    PubMed Central

    Chapman, Christopher A. R.; Chen, Hao; Stamou, Marianna; Biener, Juergen; Biener, Monika M.; Lein, Pamela J.; Seker, Erkin

    2015-01-01

    Designing neural-electrode interfaces that maintain close physical coupling of neurons to the electrode surface remains a major challenge for both implantable and in vitro neural recording electrode arrays. Typically, low-impedance nanostructured electrode coatings rely on chemical cues from pharmaceuticals or surface-immobilized peptides to suppress glial scar tissue formation over the electrode surface (astrogliosis), which is an obstacle to reliable neuron-electrode coupling. Nanoporous gold (np-Au), produced by an alloy corrosion process, is a promising candidate to reduce astrogliosis solely through topography by taking advantage of its tunable length scale. In the present in vitro study on np-Au’s interaction with cortical neuron-glia co-cultures, we demonstrate that the nanostructure of np-Au is achieving close physical coupling of neurons through maintaining a high neuron-to-astrocyte surface coverage ratio. Atomic layer deposition-based surface modification was employed to decouple the effect of morphology from surface chemistry. Additionally, length scale effects were systematically studied by controlling the characteristic feature size of np-Au through variations of the dealloying conditions. Our results show that np-Au nanotopography, not surface chemistry, reduces astrocyte surface coverage while maintaining high neuronal coverage, and may enhance the neuron-electrode coupling through nanostructure-mediated suppression of scar tissue formation. PMID:25706691

  9. Investigation of Enhanced Surface Spray Cooling

    NASA Technical Reports Server (NTRS)

    Silk, Eric A.; Kim, Jungho; Kiger, Ken

    2004-01-01

    Experiments were conducted to study the effects of enhanced surfaces on heat transfer during spray cooling. The surface enhancements consisted of cubic pin fins, pyramids, and straight fins (uniform cross sectional straight fins) machined on the top surface of copper heater blocks. Each had a cross-sectional area of 2.0 square cm. Measurements were also obtained on a heater block with a flat surface for baseline comparison purposes. A 2x2 nozzle array was used with PF-5060 as the working fluid. Thermal performance data was obtained under nominally degassed (chamber pressure of 41.4 kPa ) and gassy conditions (chamber with N2 gas at 101 kPa). The results show that the straight fins had the largest enhancement in heat flow. Critical heat flux (CHF) for this surface showed an increase of 55% in comparison to the flat surface for the nominally degassed condition. The cubic pin finned and pyramid surfaces provided slightly more than half the heat flux enhancement (30% - 40% greater than the flat surface) of the straight fins. The gassy case showed that the straight fins again provided the largest enhancement (48%) in CHF relative to the flat surface. This was followed by the cubic pin fins, and pyramids which had increases of 31% and 18% respectively. No significant effect was observed in the surface temperature at which CHF occurs for either portion of the study.

  10. Heterogeneously catalyzed hydrolysis of chlorine nitrate: Fourier-transform ion cyclotron resonance investigations of stratospheric chemistry

    NASA Astrophysics Data System (ADS)

    Schindler, Thomas; Berg, Christian; Niedner-Schatteburg, Gereon; Bondybey, Vladimir E.

    1996-03-01

    High resolution Fourier-transform ion cyclotron resonance (FT-ICR) mass spectroscopy is used to investigate reactions of large ionic water clusters H+(H2O)n and X-(H2O)n (n=1-100, X=O or OH). Reactions of the clusters with chlorine nitrate, important ``reservoir compound'' involved in the stratospheric ozone chemistry, are investigated to evaluate the importance of heterogeneously catalyzed reactions for ozone depletion. It is found that reactions of both cationic and anionic clusters result in effective hydrolysis of chlorine nitrate and return of the more active hypochlorous acid, HOCl into the gas phase. The chemistry of clusters is discussed, and its validity and relevance as a model for ``real life'' processes in the so-called polar stratospheric clouds (PSC's) is assessed.

  11. Investigations of Global Chemistry-Climate Interactions and Organic Aerosol Using Atmospheric Modeling

    NASA Astrophysics Data System (ADS)

    Pye, Havala Olson Taylor

    Aerosol, or particulate matter (PM), is an important component of the atmosphere responsible for negative health impacts, environmental degradation, reductions in visibility, and climate change. In this work, the global chemical transport model, GEOS-Chem, is used as a tool to examine chemistry-climate interactions and organic aerosols. GEOS-Chem is used to simulate present-day (year 2000) and future (year 2050) sulfate, nitrate, and ammonium aerosols and investigate the potential effects of changes in climate and emissions on global budgets and U.S. air quality. Changes in a number of meteorological parameters, such as temperature and precipitation, are potentially important for aerosols and could lead to increases or decreases in PM concentrations. Although projected changes in sulfate and nitrate precursor emissions favor lower PM concentrations over the U.S., projected increases in ammonia emissions could result in higher nitrate concentrations. The organic aerosol simulation in GEOS-Chem is updated to include aerosol from primary semivolatile organic compounds (SVOCS), intermediate volatility compounds (IVOCs), NOx dependent terpene aerosol, and aerosol from isoprene + NO3 reaction. SVOCs are identified as the largest global source of organic aerosol even though their atmospheric transformation is highly uncertain and emissions are probably underestimated. As a result of significant nighttime terpene emissions, fast reaction of monoterpenes with the nitrate radical, and high aerosol yields from NO3 oxidation, biogenic hydrocarbons reacting with the nitrate radical are expected to be a major contributor to surface level aerosol concentrations in anthropogenically influenced areas such as the United States. Globally, 69 to 88 Tg/yr of aerosol is predicted to be produced annually, approximately 22 to 24 Tg/yr of which is from biogenic hydrocarbons.

  12. Role of the surface chemistry of activated carbons in dye removal from aqueous solution

    NASA Astrophysics Data System (ADS)

    Zhou, Hua-lei; Zhen, Wen-juan; Zhu, Qian; Wu, Xiao-bin; Chang, Zhi-dong; Li, Wen-jun

    2015-07-01

    Commercial activated carbons were modified by a series of chemical or physical treatments using H2O2, NH3, and heating under N2 flow without notably changing their pore structures. The resultant carbons were characterized by N2 adsorption and Bohem titration and then used to remove Ponceau 4R, methyl orange and brilliant blue from aqueous solutions. Surface chemistry was found to play a significantly different role in removing these three compounds. The removal of anionic Ponceau 4R increases with increasing carbon surface basicity due to the predominant dispersive interaction mechanism. In contrast, surface chemistry has little effect on the removal of anionic methyl orange, which can be explained by two parallel mechanisms involving electrostatic and dispersive interactions due to the basic amine group in a dye molecule. The influence of surface chemistry on the removal of amphoteric brilliant blue dye can also be ignored due to a weak interaction between the carbons and dye molecules, which is resulted from strong cohesive energy from electrostatic forces inside amphoteric dye molecules.

  13. Laboratory Study of Titan's Surface Chemistry Induced by Meteoritic Impact Processing: Laser-Simulated Hypervelocity Impact on Ices

    NASA Astrophysics Data System (ADS)

    Nna-Mvondo, D.; Khare, B. N.; McKay, C. P.

    2008-12-01

    Titan's dense atmosphere, mostly composed of nitrogen and some methane, allows easy formation of long chains of organic molecules and high-molecular-weight organic solids, known as tholins. Over geologic time, both tholins and condensates of the organic gases accumulate in substantial amounts on the surface as liquid and solid. Titan's surface is then a repository of interesting organic molecules generated in the almost complete absence of water but sitting on top of ice. Until recently, researchers have been very careful in their speculations about what might be happening after these molecules get to the surface of Titan. What kind of organic chemistry occurs on the surface? Titan's thick atmosphere protects the surface and organics from harmful cosmic rays and ultraviolet radiation. It has been suggested that these organics could have been subjected to impact processing on Titan's and participate in the formation of products relevant to life such as amino acids, carboxylic acids, purines and pyrimidines. Subsequent impacts would probably have recycled some of the organic material back into the atmosphere. Furthermore the presence of condensable agents (C2N2, HCN, etc.) along with a natural concentrating mechanism makes polymerization of amino acids or others species likely. Laboratory simulations of meteoritic impact shocks onto Titan's icy surface have not yet been carried out, but preliminary experiments have been performed for planetary icy satellites. In these previous experiments, the possible chemical production induced by micrometeorite impact shocks on ices has been studied using a high-energy pulsed Nd-YAG laser to reproduce the shock phenomena during hypervelocity micrometeorite impacts into the icy material. The results show the production of various organics and inorganics. Here we have decided to extend those experiments to a simulated Titan's environment in order to study the effect of meteoritic impacts on the organic chemistry occurring on Titan

  14. Dissolution rates and surface chemistry of feldspar glass and crystal. Final technical report, June 15, 1995 - August 14, 2001

    SciTech Connect

    Brantley, S.; Pantano, C.

    2002-06-11

    Final report summarizing the completed work of the project entitled 'Dissolution of Feldspar in the Field and Laboratory.' One of the highly debated questions today in low-temperature geochemical kinetics centers upon the rate and mechanism of dissolution of feldspar, the most common mineral in the crust. In this project, the mechanisms of feldspar dissolution were investigated by emphasizing experiments with feldspar glass and crystal while comparing surface and solution chemistry. Specifically, laboratory work focused on the structure of altered surface layers on feldspars, the rate of dissolution of feldspar crystal and glass, and the presence of porosity and surface coatings on feldspars. In a complementary field project, the use of Sr concentrations and isotopic ratios were used to calculate feldspar dissolution rates.

  15. Major Successes of Theory-and-Experiment-Combined Studies in Surface Chemistry and Heterogeneous Catalysis.

    SciTech Connect

    Somorjai, Gabor A.; Li, Yimin

    2009-11-21

    Experimental discoveries followed by theoretical interpretations that pave the way of further advances by experimentalists is a developing pattern in modern surface chemistry and catalysis. The revolution of modern surface science started with the development of surface-sensitive techniques such as LEED, XPS, AES, ISS and SIMS, in which the close collaboration between experimentalists and theorists led to the quantitative determination of surface structure and composition. The experimental discovery of the chemical activity of surface defects and the trends in the reactivity of transitional metals followed by the explanations from the theoretical studies led to the molecular level understanding of active sites in catalysis. The molecular level knowledge, in turn, provided a guide for experiments to search for new generation of catalysts. These and many other examples of successes in experiment-and-theory-combined studies demonstrate the importance of the collaboration between experimentalists and theorists in the development of modern surface science.

  16. Exploitation of desilylation chemistry in tailor-made functionalization on diverse surfaces

    PubMed Central

    Fu, Yongchun; Chen, Songjie; Kuzume, Akiyoshi; Rudnev, Alexander; Huang, Cancan; Kaliginedi, Veerabhadrarao; Baghernejad, Masoud; Hong, Wenjing; Wandlowski, Thomas; Decurtins, Silvio; Liu, Shi-Xia

    2015-01-01

    Interface engineering to attain a uniform and compact self-assembled monolayer at atomically flat surfaces plays a crucial role in the bottom-up fabrication of organic molecular devices. Here we report a promising and operationally simple approach for modification/functionalization not only at ultraflat single-crystal metal surfaces, M(111) (M=Au, Pt, Pd, Rh and Ir) but also at the highly oriented pyrolytic graphite surface, upon efficient in situ cleavage of trimethylsilyl end groups of the molecules. The obtained self-assembled monolayers are ultrastable within a wide potential window. The carbon–surface bonding on various substrates is confirmed by shell-isolated nanoparticle-enhanced Raman spectroscopy. Application of this strategy in tuning surface wettability is also demonstrated. The most valuable finding is that a combination of the desilylation with the click chemistry represents an efficient method for covalent and tailor-made functionalization of diverse surfaces. PMID:25758661

  17. Electrically Responsive Surfaces: Experimental and Theoretical Investigations

    PubMed Central

    2016-01-01

    Conspectus Stimuli-responsive surfaces have sparked considerable interest in recent years, especially in view of their biomimetic nature and widespread biomedical applications. Significant efforts are continuously being directed at developing functional surfaces exhibiting specific property changes triggered by variations in electrical potential, temperature, pH and concentration, irradiation with light, or exposure to a magnetic field. In this respect, electrical stimulus offers several attractive features, including a high level of spatial and temporal controllability, rapid and reverse inducement, and noninvasiveness. In this Account, we discuss how surfaces can be designed and methodologies developed to produce electrically switchable systems, based on research by our groups. We aim to provide fundamental mechanistic and structural features of these dynamic systems, while highlighting their capabilities and potential applications. We begin by briefly describing the current state-of-the-art in integrating electroactive species on surfaces to control the immobilization of diverse biological entities. This premise leads us to portray our electrically switchable surfaces, capable of controlling nonspecific and specific biological interactions by exploiting molecular motions of surface-bound electroswitchable molecules. We demonstrate that our self-assembled monolayer-based electrically switchable surfaces can modulate the interactions of surfaces with proteins, mammalian and bacterial cells. We emphasize how these systems are ubiquitous in both switching biomolecular interactions in highly complex biological conditions while still offering antifouling properties. We also introduce how novel characterization techniques, such as surface sensitive vibrational sum-frequency generation (SFG) spectroscopy, can be used for probing the electrically switchable molecular surfaces in situ. SFG spectroscopy is a technique that not only allowed determining the structural

  18. Electrically Responsive Surfaces: Experimental and Theoretical Investigations.

    PubMed

    Cantini, Eleonora; Wang, Xingyong; Koelsch, Patrick; Preece, Jon A; Ma, Jing; Mendes, Paula M

    2016-06-21

    Stimuli-responsive surfaces have sparked considerable interest in recent years, especially in view of their biomimetic nature and widespread biomedical applications. Significant efforts are continuously being directed at developing functional surfaces exhibiting specific property changes triggered by variations in electrical potential, temperature, pH and concentration, irradiation with light, or exposure to a magnetic field. In this respect, electrical stimulus offers several attractive features, including a high level of spatial and temporal controllability, rapid and reverse inducement, and noninvasiveness. In this Account, we discuss how surfaces can be designed and methodologies developed to produce electrically switchable systems, based on research by our groups. We aim to provide fundamental mechanistic and structural features of these dynamic systems, while highlighting their capabilities and potential applications. We begin by briefly describing the current state-of-the-art in integrating electroactive species on surfaces to control the immobilization of diverse biological entities. This premise leads us to portray our electrically switchable surfaces, capable of controlling nonspecific and specific biological interactions by exploiting molecular motions of surface-bound electroswitchable molecules. We demonstrate that our self-assembled monolayer-based electrically switchable surfaces can modulate the interactions of surfaces with proteins, mammalian and bacterial cells. We emphasize how these systems are ubiquitous in both switching biomolecular interactions in highly complex biological conditions while still offering antifouling properties. We also introduce how novel characterization techniques, such as surface sensitive vibrational sum-frequency generation (SFG) spectroscopy, can be used for probing the electrically switchable molecular surfaces in situ. SFG spectroscopy is a technique that not only allowed determining the structural orientation of

  19. Modelling interstellar physics and chemistry: implications for surface and solid-state processes.

    PubMed

    Williams, David; Viti, Serena

    2013-07-13

    We discuss several types of regions in the interstellar medium of the Milky Way and other galaxies in which the chemistry appears to be influenced or dominated by surface and solid-state processes occurring on or in interstellar dust grains. For some of these processes, for example, the formation of H₂ molecules, detailed experimental and theoretical approaches have provided excellent fundamental data for incorporation into astrochemical models. In other cases, there is an astrochemical requirement for much more laboratory and computational study, and we highlight these needs in our description. Nevertheless, in spite of the limitations of the data, it is possible to infer from astrochemical modelling that surface and solid-state processes play a crucial role in astronomical chemistry from early epochs of the Universe up to the present day. PMID:23734052

  20. Variation in Adirondack, New York, lakewater chemistry as function of surface area

    SciTech Connect

    Sullivan, T.J. ); Kugler, D.L.; Johnson, C.B.; Rosenbaum, B.J. ); Small, M.J. ); Landers, D.H. ); Overton, W.S. ); Kretser, W.A.; Gallagher, J. )

    1990-02-01

    Data from a recent survey conducted by the Adirondack Lake Survey Corporation were used to evaluate the influence of lake surface area on the acid-base status of lakes in Adirondack State Park, New York. Acid neutralizing capacity (ANC) in the small lakes (<4 ha) occurred more frequently at extreme values (>200, <0 {mu}eq L{sup {minus}1}), whereas larger lakes tended to be intermediate in ANC. Consequently, acidic (ANC {le} 0) and low-pH lakes were typically small. The small lakes also exhibited lower Ca{sup 2+} concentration and higher dissolved organic carbon than did larger lakes. Lakes {ge} 4 ha were only half as likely to be acidic as were lakes {ge} 1 ha in area. These data illustrate the dependence of lake chemistry on lake surface area and the importance of the lower lake area limit for a statistical survey of lakewater chemistry.

  1. A longitudinal investigation of student learning in general chemistry with the Guided Inquiry Approach

    NASA Astrophysics Data System (ADS)

    Daubenmire, Patrick L.

    The Guided Inquiry Approach to learning chemistry utilizes cooperative learning and guided activities that emphasize students' understanding and application of chemistry concepts. Published worksheets provide students with a set of data or a model, "Critical Thinking Questions" which help students discover underlying patterns and concepts, and "Skill Development Exercises," which ask students to apply their constructed concepts. The instructor acts as a guide checking responses and intervening when necessary or when requested by the group. Cooperative learning approaches are in keeping with theoretical explanations of how students learn. Research supports that cooperative learning approaches have significant and positive effects on students' achievement, persistence, and attitudes in science courses. Research is needed to analyze how cooperative learning works. This research investigates how learning takes place during Guided Inquiry classes. A mixed methods research design was used. Subjects were members of two sections of second semester general chemistry, instructed by two different professors, which utilized the Guided Inquiry Approach at a small college in the Northeast United States. Subjects were categorized on logical reasoning ability and levels of confidence to succeed in chemistry. Guided Inquiry groups were videotaped once every week for ten weeks. Qualitative aspects identified Phases and Bridges of learning during Guided Inquiry. They are described as: Phase I - Confirmation Phase, Phase II - Group Interactive Phase, Phase III - Confirmation/Rehearsal Phase, Phase IV - Missionary Phase, Tutor Bridge, and Mentor Bridge. These Phases were verified by student interviews and through interobserver reliability. Triangulation of data was completed by measuring the differential effect of Guided Inquiry on traditional and conceptual chemistry achievement (multivariate within and between groups) and students' change in confidence to succeed in chemistry

  2. Global transcriptomic analysis of model human cell lines exposed to surface-modified gold nanoparticles: the effect of surface chemistry

    NASA Astrophysics Data System (ADS)

    Grzincic, E. M.; Yang, J. A.; Drnevich, J.; Falagan-Lotsch, P.; Murphy, C. J.

    2015-01-01

    Gold nanoparticles (Au NPs) are attractive for biomedical applications not only for their remarkable physical properties, but also for the ease of which their surface chemistry can be manipulated. Many applications involve functionalization of the Au NP surface in order to improve biocompatibility, attach targeting ligands or carry drugs. However, changes in cells exposed to Au NPs of different surface chemistries have been observed, and little is known about how Au NPs and their surface coatings may impact cellular gene expression. The gene expression of two model human cell lines, human dermal fibroblasts (HDF) and prostate cancer cells (PC3) was interrogated by microarray analysis of over 14 000 human genes. The cell lines were exposed to four differently functionalized Au NPs: citrate, poly(allylamine hydrochloride) (PAH), and lipid coatings combined with alkanethiols or PAH. Gene functional annotation categories and weighted gene correlation network analysis were used in order to connect gene expression changes to common cellular functions and to elucidate expression patterns between Au NP samples. Coated Au NPs affect genes implicated in proliferation, angiogenesis, and metabolism in HDF cells, and inflammation, angiogenesis, proliferation apoptosis regulation, survival and invasion in PC3 cells. Subtle changes in surface chemistry, such as the initial net charge, lability of the ligand, and underlying layers greatly influence the degree of expression change and the type of cellular pathway affected.Gold nanoparticles (Au NPs) are attractive for biomedical applications not only for their remarkable physical properties, but also for the ease of which their surface chemistry can be manipulated. Many applications involve functionalization of the Au NP surface in order to improve biocompatibility, attach targeting ligands or carry drugs. However, changes in cells exposed to Au NPs of different surface chemistries have been observed, and little is known about how

  3. Modeling the surface chemistry of biomass model compounds on oxygen-covered Rh(100).

    PubMed

    Caglar, B; Niemantsverdriet, J W Hans; Weststrate, C J Kees-Jan

    2016-08-24

    Rhodium-based catalysts are potential candidates to process biomass and serve as a representation of the class of noble metal catalysts for biomass-related processes. Biomass can be processed in aqueous media (hydrolysis and aqueous phase reforming), and in this case the surface chemistry involves hydroxyl (OH) species. In our study this was modelled by the presence of pre-adsorbed oxygen. Ethylene glycol, with a hydroxyl group on every carbon atom, serves as a model compound to understand the conversion of biomass derived molecules into desirable chemicals on catalytically active metal surfaces. Ethanol (containing one OH group) serves as a reference molecule for ethylene glycol (containing two OH groups) to understand the interaction of C-OH functionalities with a Rh(100) surface. The surface chemistry of ethylene glycol and ethanol in the presence of pre-adsorbed oxygen on a Rh(100) surface has been studied via temperature programmed reaction spectroscopy (TPRS) and reflection absorption infrared spectroscopy (RAIRS) using various coverages of O(ad) and ethylene glycol and ethanol. Pre-adsorbed oxygen alters the decomposition chemistry of both compounds, thereby affecting the product distribution. Under an oxygen-lean condition, the selectivity to produce methane from ethanol is enhanced significantly (4.5-fold with respect to that obtained on the oxygen-free surface). For ethylene glycol, oxygen-lean conditions promote the formation of formaldehyde, with 10-15% selectivity. In addition, with Oad present the fraction of molecules that decompose on the surface increases 2-fold for ethanol and 1.5-fold for ethylene glycol, due to fast O-H bond activation by pre-adsorbed oxygen. Under oxygen-rich conditions, the decomposition products are mainly oxidized to carbon dioxide and water for both molecules. In this condition, the promotion effect provided by adsorbed oxygen for the dissociative adsorption of ethanol and ethylene glycol is reduced due to the site blocking

  4. Enhancing single-nanoparticle surface-chemistry by plasmonic overheating in an optical trap.

    PubMed

    Ni, Weihai; Ba, Haojin; Lutich, Andrey A; Jäckel, Frank; Feldmann, Jochen

    2012-09-12

    Surface-chemistry of individual, optically trapped plasmonic nanoparticles is modified and accelerated by plasmonic overheating. Depending on the optical trapping power, gold nanorods can exhibit red shifts of their plasmon resonance (i.e., increasing aspect ratio) under oxidative conditions. In contrast, in bulk exclusively blue shifts (decreasing aspect ratios) are observed. Supported by calculations, we explain this finding by local temperatures in the trap exceeding the boiling point of the solvent that cannot be achieved in bulk. PMID:22924589

  5. Precipitation chemistry - Atmospheric loadings to the surface waters of the Indian River lagoon basin by rainfall

    NASA Technical Reports Server (NTRS)

    Dreschel, Thomas W.; Madsen, Brooks C.; Maull, Lee A.; Hinkle, C. R.; Knott, William M., III

    1990-01-01

    Rain volume and chemistry monitoring as part of the Kennedy Space Center Long Term Environmental Monitoring Program included the years 1984-1987 as part of the National Atmospheric Deposition Program. Atmospheric deposition in rainfall consisted primarily of sea salt and hydrogen ion, sulfate, nitrate, and ammonium ions. The deposition of nitrogen (a principal plant nutrient) was on the order of 200-300 metric tons per year to the surface waters.

  6. Does filler surface chemistry impact filler dispersion, polymer dynamics and conductivity in nanofilled solid polymer electrolytes?

    NASA Astrophysics Data System (ADS)

    Ganapatibhotla, Lalitha; Maranas, Janna

    2012-02-01

    We study the impact of nanofiller surface chemistry on filler dispersion, polymer dynamics and ionic conductivity in acidic α-Al2O3 filled PEO+LiClO4 solid polymer electrolytes (SPEs).SPEs are the key to light-weight and high energy density rechargeable Li ion batteries but suffer from low room temperature ionic conductivity. Addition of ceramic nanofillers improves conductivity of SPEs and their surface chemistry influences extent of conductivity enhancement. The ionic conductivity of acidic α-Al2O3 filled SPE is enhanced for salt concentrations at and below eutectic, while neutral γ-Al2O3 filler enhances conductivity only at eutectic composition. Li ion motion is coupled to segmental mobility of polymer and we study how this is affected by addition of α-Al2O3 using quasi-elastic neutron scattering. Aggregation extent of nanoparticles in SPE matrix, a less explored factor in filled SPEs, can affect segmental mobility of polymer. This can vary with surface chemistry of particles and we quantify this using small angle neutron scattering. All measurements are performed as a function of Li concentration, nanoparticle loading and temperature.

  7. The contribution of inflammasome components on macrophage response to surface nanotopography and chemistry

    PubMed Central

    Christo, Susan; Bachhuka, Akash; Diener, Kerrilyn R.; Vasilev, Krasimir; Hayball, John D.

    2016-01-01

    Implantable devices have become an established part of medical practice. However, often a negative inflammatory host response can impede the integration and functionality of the device. In this paper, we interrogate the role of surface nanotopography and chemistry on the potential molecular role of the inflammasome in controlling macrophage responses. To achieve this goal we engineered model substrata having precisely controlled nanotopography of predetermined height and tailored outermost surface chemistry. Bone marrow derived macrophages (BMDM) were harvested from genetically engineered mice deficient in the inflammasome components ASC, NLRP3 and AIM2. These cells were then cultured on these nanoengineered substrata and assessed for their capacity to attach and express pro-inflammatory cytokines. Our data provide evidence that the inflammasome components ASC, NLRP3 and AIM2 play a role in regulating macrophage adhesion and activation in response to surface nanotopography and chemistry. The findings of this paper are important for understanding the inflammatory consequences caused by biomaterials and pave the way to the rational design of future implantable devices having controlled and predictable inflammatory outcomes. PMID:27188492

  8. The contribution of inflammasome components on macrophage response to surface nanotopography and chemistry.

    PubMed

    Christo, Susan; Bachhuka, Akash; Diener, Kerrilyn R; Vasilev, Krasimir; Hayball, John D

    2016-01-01

    Implantable devices have become an established part of medical practice. However, often a negative inflammatory host response can impede the integration and functionality of the device. In this paper, we interrogate the role of surface nanotopography and chemistry on the potential molecular role of the inflammasome in controlling macrophage responses. To achieve this goal we engineered model substrata having precisely controlled nanotopography of predetermined height and tailored outermost surface chemistry. Bone marrow derived macrophages (BMDM) were harvested from genetically engineered mice deficient in the inflammasome components ASC, NLRP3 and AIM2. These cells were then cultured on these nanoengineered substrata and assessed for their capacity to attach and express pro-inflammatory cytokines. Our data provide evidence that the inflammasome components ASC, NLRP3 and AIM2 play a role in regulating macrophage adhesion and activation in response to surface nanotopography and chemistry. The findings of this paper are important for understanding the inflammatory consequences caused by biomaterials and pave the way to the rational design of future implantable devices having controlled and predictable inflammatory outcomes. PMID:27188492

  9. Genotoxic capacity of Cd/Se semiconductor quantum dots with differing surface chemistries

    PubMed Central

    Manshian, Bella B.; Soenen, Stefaan J.; Brown, Andy; Hondow, Nicole; Wills, John; Jenkins, Gareth J. S.; Doak, Shareen H.

    2016-01-01

    Quantum dots (QD) have unique electronic and optical properties promoting biotechnological advances. However, our understanding of the toxicological structure–activity relationships remains limited. This study aimed to determine the biological impact of varying nanomaterial surface chemistry by assessing the interaction of QD with either a negative (carboxyl), neutral (hexadecylamine; HDA) or positive (amine) polymer coating with human lymphoblastoid TK6 cells. Following QD physico-chemical characterisation, cellular uptake was quantified by optical and electron microscopy. Cytotoxicity was evaluated and genotoxicity was characterised using the micronucleus assay (gross chromosomal damage) and the HPRT forward mutation assay (point mutagenicity). Cellular damage mechanisms were also explored, focusing on oxidative stress and mitochondrial damage. Cell uptake, cytotoxicity and genotoxicity were found to be dependent on QD surface chemistry. Carboxyl-QD demonstrated the smallest agglomerate size and greatest cellular uptake, which correlated with a dose dependent increase in cytotoxicity and genotoxicity. Amine-QD induced minimal cellular damage, while HDA-QD promoted substantial induction of cell death and genotoxicity. However, HDA-QD were not internalised by the cells and the damage they caused was most likely due to free cadmium release caused by QD dissolution. Oxidative stress and induced mitochondrial reactive oxygen species were only partially associated with cytotoxicity and genotoxicity induced by the QD, hence were not the only mechanisms of importance. Colloidal stability, nanoparticle (NP) surface chemistry, cellular uptake levels and the intrinsic characteristics of the NPs are therefore critical parameters impacting genotoxicity induced by QD. PMID:26275419

  10. Effects of surface chemistry on the optical properties and cellular interaction of lanthanide-based nanoparticles

    NASA Astrophysics Data System (ADS)

    Pedraza, Francisco J.; Avalos, Julio C.; Mimun, Lawrence C.; Yust, Brian G.; Tsin, Andrew; Sardar, Dhiraj K.

    2015-03-01

    Fluorescent nanoparticles (NPs) such as KYb2F7:Tm3+ potential in biomedical applications due to their ability to absorb and emit within the biological window, where near infrared light is less attenuated by soft tissue. This results in less tissue damage and deeper tissue penetration making it a viable candidate in biological imaging. Another big factor in determining their ability to perform in a biological setting is the surface chemistry. Biocompatible coatings, including polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), pluronic and folic acid are commonly used because they pose several advantages such as ease of functionalization, better dispersion, and higher cellular uptake. To study the effects of the NP surface chemistry, KYb2F7:Tm3+ a solvothermal method using PEG, PVP, pluronic acid, and folic acid as a capping agent, followed by thorough optical characterizations. Optical changes were thoroughly studied and compared using absorption, emission, and quantum yield data. Cell viability was obtained by treating Rhesus Monkey Retinal Endothelial cells (RhREC) with KYb2F7:Tm3+ and counting viable cells following a 24 hour uptake period. The work presented will compare the optical properties and toxicity dependency on the surface chemistry on KYb2F7:Tm3+. The results will also indicate that KYb2F7:Tm3+ nanoparticles are viable candidates for various biomedical applications.

  11. Regulating Biocompatibility of Carbon Spheres via Defined Nanoscale Chemistry and a Careful Selection of Surface Functionalities

    PubMed Central

    Misra, Santosh K.; Chang, Huei-Huei; Mukherjee, Prabuddha; Tiwari, Saumya; Ohoka, Ayako; Pan, Dipanjan

    2015-01-01

    A plethora of nanoarchitectures have been evaluated preclincially for applications in early detection and treatment of diseases at molecular and cellular levels resulted in limited success of their clinical translation. It is important to identify the factors that directly or indirectly affect their use in human. We bring a fundamental understanding of how to adjust the biocompatibility of carbon based spherical nanoparticles (CNPs) through defined chemistry and a vigilant choice of surface functionalities. CNPs of various size are designed by tweaking size (2–250 nm), surface chemistries (positive, or negatively charged), molecular chemistries (linear, dendritic, hyperbranched) and the molecular weight of the coating agents (MW 400–20 kDa). A combination of in vitro assays as tools were performed to determine the critical parameters that may trigger toxicity. Results indicated that hydrodynamic sizes are potentially not a risk factor for triggering cellular and systemic toxicity, whereas the presence of a highly positive surface charge and increasing molecular weight enhance the chance of inducing complement activation. Bare and carboxyl-terminated CNPs did present some toxicity at the cellular level which, however, is not comparable to those caused by positively charged CNPs. Similarly, negatively charged CNPs with hydroxyl and carboxylic functionalities did not cause any hemolysis. PMID:26462751

  12. Regulating Biocompatibility of Carbon Spheres via Defined Nanoscale Chemistry and a Careful Selection of Surface Functionalities.

    PubMed

    Misra, Santosh K; Chang, Huei-Huei; Mukherjee, Prabuddha; Tiwari, Saumya; Ohoka, Ayako; Pan, Dipanjan

    2015-01-01

    A plethora of nanoarchitectures have been evaluated preclincially for applications in early detection and treatment of diseases at molecular and cellular levels resulted in limited success of their clinical translation. It is important to identify the factors that directly or indirectly affect their use in human. We bring a fundamental understanding of how to adjust the biocompatibility of carbon based spherical nanoparticles (CNPs) through defined chemistry and a vigilant choice of surface functionalities. CNPs of various size are designed by tweaking size (2-250 nm), surface chemistries (positive, or negatively charged), molecular chemistries (linear, dendritic, hyperbranched) and the molecular weight of the coating agents (MW 400-20 kDa). A combination of in vitro assays as tools were performed to determine the critical parameters that may trigger toxicity. Results indicated that hydrodynamic sizes are potentially not a risk factor for triggering cellular and systemic toxicity, whereas the presence of a highly positive surface charge and increasing molecular weight enhance the chance of inducing complement activation. Bare and carboxyl-terminated CNPs did present some toxicity at the cellular level which, however, is not comparable to those caused by positively charged CNPs. Similarly, negatively charged CNPs with hydroxyl and carboxylic functionalities did not cause any hemolysis. PMID:26462751

  13. Regulating Biocompatibility of Carbon Spheres via Defined Nanoscale Chemistry and a Careful Selection of Surface Functionalities

    NASA Astrophysics Data System (ADS)

    Misra, Santosh K.; Chang, Huei-Huei; Mukherjee, Prabuddha; Tiwari, Saumya; Ohoka, Ayako; Pan, Dipanjan

    2015-10-01

    A plethora of nanoarchitectures have been evaluated preclincially for applications in early detection and treatment of diseases at molecular and cellular levels resulted in limited success of their clinical translation. It is important to identify the factors that directly or indirectly affect their use in human. We bring a fundamental understanding of how to adjust the biocompatibility of carbon based spherical nanoparticles (CNPs) through defined chemistry and a vigilant choice of surface functionalities. CNPs of various size are designed by tweaking size (2-250 nm), surface chemistries (positive, or negatively charged), molecular chemistries (linear, dendritic, hyperbranched) and the molecular weight of the coating agents (MW 400-20 kDa). A combination of in vitro assays as tools were performed to determine the critical parameters that may trigger toxicity. Results indicated that hydrodynamic sizes are potentially not a risk factor for triggering cellular and systemic toxicity, whereas the presence of a highly positive surface charge and increasing molecular weight enhance the chance of inducing complement activation. Bare and carboxyl-terminated CNPs did present some toxicity at the cellular level which, however, is not comparable to those caused by positively charged CNPs. Similarly, negatively charged CNPs with hydroxyl and carboxylic functionalities did not cause any hemolysis.

  14. The contribution of inflammasome components on macrophage response to surface nanotopography and chemistry

    NASA Astrophysics Data System (ADS)

    Christo, Susan; Bachhuka, Akash; Diener, Kerrilyn R.; Vasilev, Krasimir; Hayball, John D.

    2016-05-01

    Implantable devices have become an established part of medical practice. However, often a negative inflammatory host response can impede the integration and functionality of the device. In this paper, we interrogate the role of surface nanotopography and chemistry on the potential molecular role of the inflammasome in controlling macrophage responses. To achieve this goal we engineered model substrata having precisely controlled nanotopography of predetermined height and tailored outermost surface chemistry. Bone marrow derived macrophages (BMDM) were harvested from genetically engineered mice deficient in the inflammasome components ASC, NLRP3 and AIM2. These cells were then cultured on these nanoengineered substrata and assessed for their capacity to attach and express pro-inflammatory cytokines. Our data provide evidence that the inflammasome components ASC, NLRP3 and AIM2 play a role in regulating macrophage adhesion and activation in response to surface nanotopography and chemistry. The findings of this paper are important for understanding the inflammatory consequences caused by biomaterials and pave the way to the rational design of future implantable devices having controlled and predictable inflammatory outcomes.

  15. XPS analysis of combustion aerosols for chemical composition, surface chemistry, and carbon chemical state.

    PubMed

    Vander Wal, Randy L; Bryg, Vicky M; Hays, Michael D

    2011-03-15

    Carbonaceous aerosols can vary in elemental content, surface chemistry, and carbon nano-structure. Each of these properties is related to the details of soot formation. Fuel source, combustion process (affecting formation and growth conditions), and postcombustion exhaust where oxidation occurs all contribute to the physical structure and surface chemistry of soot. Traditionally such physical and chemical parameters have been measured separately by various techniques. Presented here is the unified measurement of these characteristics using X-ray photoelectron spectroscopy (XPS). In the present study, XPS is applied to combustion soot collected from a diesel engine (running biodiesel and pump-grade fuels); jet engine; and institutional, plant, and residential oil-fired boilers. Elemental composition is mapped by a survey scan over a broad energy range. Surface chemistry and carbon nanostructure are quantified by deconvolution of high-resolution scans over the C1s region. This combination of parameters forms a distinct matrix of identifiers for the soots from these sources. PMID:21322576

  16. Surface topography and chemistry shape cellular behavior on wide band-gap semiconductors.

    PubMed

    Bain, Lauren E; Collazo, Ramon; Hsu, Shu-Han; Latham, Nicole Pfiester; Manfra, Michael J; Ivanisevic, Albena

    2014-06-01

    The chemical stability and electrical properties of gallium nitride make it a promising material for the development of biocompatible electronics, a range of devices including biosensors as well as interfaces for probing and controlling cellular growth and signaling. To improve the interface formed between the probe material and the cell or biosystem, surface topography and chemistry can be applied to modify the ways in which the device interacts with its environment. PC12 cells are cultured on as-grown planar, unidirectionally polished, etched nanoporous and nanowire GaN surfaces with and without a physisorbed peptide sequence that promotes cell adhesion. While cells demonstrate preferential adhesion to roughened surfaces over as-grown flat surfaces, the topography of that roughness also influences the morphology of cellular adhesion and differentiation in neurotypic cells. Addition of the peptide sequence generally contributes further to cellular adhesion and promotes development of stereotypic long, thin neurite outgrowths over alternate morphologies. The dependence of cell behavior on both the topographic morphology and surface chemistry is thus demonstrated, providing further evidence for the importance of surface modification for modulating bio-inorganic interfaces. PMID:24590161

  17. Screening rat mesenchymal stem cell attachment and differentiation on surface chemistries using plasma polymer gradients.

    PubMed

    Wang, Peng-Yuan; Clements, Lauren R; Thissen, Helmut; Tsai, Wei-Bor; Voelcker, Nicolas H

    2015-01-01

    It is well known that the surface chemistry of biomaterials is important for both initial cell attachment and the downstream cell response. Surface chemistry gradients are a new format that allows the screening of the subtleties of cell-surface interactions in high throughput. In this study, two surface chemical gradients were fabricated using diffusion control during plasma polymerization via a tilted mask. Acrylic acid (AA) plasma polymer gradients were coated on a uniform 1,7-octadiene (OD) plasma polymer layer to generate OD-AA plasma polymer gradients, whilst diethylene glycol dimethyl ether (DG) plasma polymer gradients were coated on a uniform AA plasma polymer layer to generate AA-DG plasma polymer gradients. Gradient surfaces were characterized by X-ray photoelectron spectroscopy, infrared microscopy mapping, profilometry, water contact angle (WCA) goniometry and atomic force microscopy. Cell attachment density and differentiation into osteo- and adipo-lineages of rat-bone-marrow mesenchymal stem cells (rBMSCs) was studied on gradients. Cell adhesion after 24 h culture was sensitive to the chemical gradients, resulting in a cell density gradient along the substrate. The slope of the cell density gradient changed between 24 and 6 days due to cell migration and growth. Induction of rBMSCs into osteoblast- and adipocyte-like cells on the two plasma polymer gradients suggested that osteogenic differentiation was sensitive to local cell density, but adipogenic differentiation was not. Using mixed induction medium (50% osteogenic and 50% adipogenic medium), thick AA plasma polymer coating (>40 nm thickness with ∼11% COOH component and 35° WCA) robustly supported osteogenic differentiation as determined by colony formation and calcium deposition. This study establishes a simple but powerful approach to the formation of plasma polymer based gradients, and demonstrates that MSC behavior can be influenced by small changes in surface chemistry. PMID:25246312

  18. The influences of the transfer method and particle surface chemistry on the dispersion of nanoparticles in nanocomposites

    NASA Astrophysics Data System (ADS)

    Pravaz, Olivier; Droz, Benoît; Schurtenberger, Peter; Dietsch, Hervé

    2012-10-01

    The synthesis via in situ polymerization and characterization of nanocomposites (NCs) made from silica (SiO2) nanoparticles in a methyl methacrylate (MMA) monomer matrix is reported. We first investigate the transfer of well-defined spherical silica nanoparticles (NPs) (average radius R = 24.2 +/- 3.2 nm) into the monomer solvent. We study the influence of two transfer methods and different surface chemistries on the resulting colloidal stability. The first transfer method consists of drying the silica particles into powder before dispersing them via ultrasonication in the MMA matrix. The second is based on repetitive centrifugations to exchange NPs from their synthetic milieu to pure MMA, avoiding the dried powder state. These transfer methods are compared for two kinds of NP surface chemistry, natural silanol (Si-OH) groups of the silica NPs and an additional silane coupling agent, namely 3-(trimethoxysilyl)propyl methacrylate (TPM), which mimics the monomeric group of the MMA dispersing milieu. We then characterize the morphology of the resulting nanocomposites prepared via in situ polymerization at a fixed amount of dispersed NPs (2.2 wt%; 1 vol%) using a combination of transmission electron microscopy (TEM) from ultramicrotomed nanocomposite films, thermogravimetry (TGA) and small angle X-ray scattering (SAXS).The synthesis via in situ polymerization and characterization of nanocomposites (NCs) made from silica (SiO2) nanoparticles in a methyl methacrylate (MMA) monomer matrix is reported. We first investigate the transfer of well-defined spherical silica nanoparticles (NPs) (average radius R = 24.2 +/- 3.2 nm) into the monomer solvent. We study the influence of two transfer methods and different surface chemistries on the resulting colloidal stability. The first transfer method consists of drying the silica particles into powder before dispersing them via ultrasonication in the MMA matrix. The second is based on repetitive centrifugations to exchange NPs from

  19. Correlation Between Surface Chemistry and Electrocatalytic Properties of Monodisperse Pt(x)Ni(1-x) Nanoparticles

    SciTech Connect

    Wang, Chao; Chi, Miaofang; Wang, Guofeng; Van der Vliet, Dennis; Li, Dongguo; More, Karren Leslie; Wang, Hsien-Hua; Schlueter, John; Markovic, Nenad; Stamenkovic, Vojislav

    2011-01-01

    Monodisperse and homogeneous Pt{sub x}Ni{sub 1-x} alloy nanoparticles of various compositions are synthesized via an organic solution approach in order to reveal the correlation between surface chemistry and their electrocatalytic properties. Atomic-level microscopic analysis of the compositional profile and modeling of nanoparticle structure are combined to follow the dependence of Ni dissolution on the initial alloy composition and formation of the Pt-skeleton nanostructures. The developed approach and acquired knowledge about surface structure-property correlation can be further generalized and applied towards the design of advanced functional nanomaterials.

  20. Effect of fullerenol surface chemistry on nanoparticle binding-induced protein misfolding

    NASA Astrophysics Data System (ADS)

    Radic, Slaven; Nedumpully-Govindan, Praveen; Chen, Ran; Salonen, Emppu; Brown, Jared M.; Ke, Pu Chun; Ding, Feng

    2014-06-01

    Fullerene and its derivatives with different surface chemistry have great potential in biomedical applications. Accordingly, it is important to delineate the impact of these carbon-based nanoparticles on protein structure, dynamics, and subsequently function. Here, we focused on the effect of hydroxylation -- a common strategy for solubilizing and functionalizing fullerene -- on protein-nanoparticle interactions using a model protein, ubiquitin. We applied a set of complementary computational modeling methods, including docking and molecular dynamics simulations with both explicit and implicit solvent, to illustrate the impact of hydroxylated fullerenes on the structure and dynamics of ubiquitin. We found that all derivatives bound to the model protein. Specifically, the more hydrophilic nanoparticles with a higher number of hydroxyl groups bound to the surface of the protein via hydrogen bonds, which stabilized the protein without inducing large conformational changes in the protein structure. In contrast, fullerene derivatives with a smaller number of hydroxyl groups buried their hydrophobic surface inside the protein, thereby causing protein denaturation. Overall, our results revealed a distinct role of surface chemistry on nanoparticle-protein binding and binding-induced protein misfolding.Fullerene and its derivatives with different surface chemistry have great potential in biomedical applications. Accordingly, it is important to delineate the impact of these carbon-based nanoparticles on protein structure, dynamics, and subsequently function. Here, we focused on the effect of hydroxylation -- a common strategy for solubilizing and functionalizing fullerene -- on protein-nanoparticle interactions using a model protein, ubiquitin. We applied a set of complementary computational modeling methods, including docking and molecular dynamics simulations with both explicit and implicit solvent, to illustrate the impact of hydroxylated fullerenes on the structure and

  1. Surface defects and chemistry on the SnO2(110) surface

    NASA Technical Reports Server (NTRS)

    Cox, David F.

    1990-01-01

    A variety of ultrahigh vacuum (UHV) surface science techniques have been used to characterize the structural, electronic and chemical properties of SnO2(110), a model catalytic surface. Two types of surface oxygen vacancies have been identified, each associated with different band gap (defect) electronic states. Adsorption experiments show that the interaction of simple gases with this surface occurs primarily through these oxygen vacancies and can show site-specificity to only one of the two types of vacancies.

  2. Oxidation of activated carbon fibers: Effect on pore size, surface chemistry, and adsorption properties

    SciTech Connect

    Mangun, C.L.; Benak, K.R.; Daley, M.A.; Economy, J.

    1999-12-01

    Activated carbon fibers (ACFs) were oxidized using both aqueous and nonaqueous treatments. As much as 29 wt% oxygen can be incorporated onto the pore surface in the form of phenolic hydroxyl, quinine, and carboxylic acid groups. The effect of oxidation on the pore size, pore volume, and the pore surface chemistry was thoroughly examined. The average micropore size is typically affected very little by aqueous oxidation while the micropore volume and surface area decreases with such a treatment. In contrast, the micropore size and micropore volume both increase with oxidation in air. Oxidation of the fibers produces surface chemistries in the pore that provide for enhanced adsorption of basic (ammonia) and polar (acetone) molecules at ambient and nonambient temperatures. The adsorption capacity of the oxidized fibers for acetone is modestly better than the untreated ACFs while the adsorption capacity for ammonia can increase up to 30 times compared to untreated ACFs. The pore surface chemical makeup was analyzed using elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and X-ray photoelectron spectroscopy (XPS).

  3. Instructional practices in chemistry classrooms across North Carolina: An investigation of inquiry-oriented instruction

    NASA Astrophysics Data System (ADS)

    McDuffie, Sarah Faye

    teachers who represented various levels on the Inquiry-Oriented Instructional Scale. Results of this study showed that most of the chemistry teachers in North Carolina public high schools used some inquiry-oriented instructional strategies during the 1998--99 school year. There was no statistically significant relationship between the levels of inquiry-oriented instruction and any of the demographic factors investigated.

  4. Investigation of Semiconductor Surface Structure by Transmission Ion Channeling.

    NASA Astrophysics Data System (ADS)

    Lyman, Paul Francis

    The primary thrust of this dissertation is the investigation of the composition and structure of two important surface systems on Si, and the study of how this structure evolves under the influence of ion bombardment or film growth. I have studied the initial stages of oxidation of Si immediately following removal of a surface oxide by an HF etch. I have also studied the structure of Ge deposited on clean Si(100) at low temperatures. These systems are of considerable technological interest, but were chosen because they naturally pose fundamental questions regarding physical and chemical processes at surfaces. In the study of the oxidation of Si, I have focused on the influence of the bombarding ion beam in altering the structure and composition of the surface layer. Thus, the system then provides a natural vehicle to study ion-induced chemistry. In the study of low-temperature growth of Ge, I have focused on the structure of the Ge layer and the evolution of that structure upon further deposition or upon heating. This simple system is a model one for observing strained semiconductor heteroepitaxial growth. The primary probe for these studies was transmission channeling of MeV ions. The sensitivity of this technique to correlations between the substrate and an overlayer allowed us to make the following observations. The O, Si and H bound in the thin oxide formed after an HF etch and H_2O rinse occupy preferred positions with respect to the Si matrix. Upon ion bombardment, the O further reacts with the Si (the reaction proceeds linearly with the ion fluence) and the portion of the H that is uncorrelated to the substrate is preferentially desorbed. For the case of Ge growth on Si(100)-(2 x 1) at room temperature, a substantial fraction of the Ge films is strained to occupy sites having the lattice constant of the Si substrate (pseudomorphic growth). A model for film growth is proposed in which pseudomorphic domains constitute roughly half of the Ge films up to a

  5. IR investigations of surfaces and adsorbates

    SciTech Connect

    Gwyn Williams

    2001-12-10

    Synchrotron infrared reflection-absorption measurements on single crystal metal surfaces with adsorbates have led to the determination of many key parameters related to the bonding vibrational modes and the dynamics of adsorbates. In particular, energy couplings between electrons and adsorbate motion have been shown to be a dominant mechanism on metal surfaces. Excellent agreement has been obtained with calculations for many of the observations, and the synergy between theory and experiment has led to a deeper understanding of the roles of electrons and phonons in determining the properties of interfaces and their roles in phenomena as diverse as friction, lubrication, catalysis and adhesion. Nonetheless, as the experiments are pushed harder, to describe such effects as co-adsorbed systems, disagreements continue to challenge the theory and our comprehension also is still evolving.

  6. A means to an interface: investigating monoethanolamine behavior at an aqueous surface.

    PubMed

    McWilliams, Laura E; Valley, Nicholas A; Wren, Sumi N; Richmond, Geraldine L

    2015-09-01

    The use of amine scrubbers to trap carbon dioxide from flue gas streams is one of the most promising avenues for atmospheric carbon dioxide reduction. However, modifications are necessary to efficiently scale these scrubbers for use in fossil fuel plants. Current advances in tailoring amines for CO2 capture involve improvements of bulk kinetic and thermodynamic parameters, with little consideration to surface chemistry and behavior. Aqueous alkanolamine solutions, such as monoethanolamine (MEA), are currently highly favored sorbents in CO2 post-combustion capture. Although numerous studies have explored MEA-CO2 chemistry at the macroscopic scale, few have investigated the role of the interface in the gas adsorption process. Additionally, as these amines become more industrially ubiquitous, their presence on and the need to understand their behavior at atmospheric and environmental surfaces will increase. This study investigates the surface behavior of monoethanolamine at the vapor/water interface, with particular focus on MEA's surface orientation and footprint. Using vibrational sum frequency spectroscopy, surface tensiometry, and computational techniques, MEA is found to adopt a constrained gauche interfacial conformation with its methylene backbone oriented toward the vapor phase and its functional groups solvated in the bulk solution. Computational and experimental analysis agree well, giving a complete picture with vibrational mode assignments and surface orientation of MEA. These findings can assist in the tailoring of amine structures or to facilitate improvements in engineering design to exploit favorable surface chemistry, as well as to serve as a starting point toward understanding aqueous amine surface behavior relevant to environmental systems. PMID:26220791

  7. Surface chemistry study of RuO2/IrO2/TiO2 mixed-oxide electrodes.

    PubMed

    Barison, Simona; Daolio, Sergio; Fabrizio, Monica; De Battisti, Achille

    2004-01-01

    DSA metal oxide electrodes such as the RuO(2)/IrO(2)/TiO(2) mixed system are widely studied for their excellent electrocatalytic activity. In order to understand their catalytic properties, the comprehension of the surface chemistry involved during electrochemical treatments is crucial. With this aim, RuO(2)/IrO(2)/TiO(2) mixed-oxide electrodes having various noble metal contents were studied by means of secondary ion mass spectrometry (SIMS). In particular, cathodic and anodic polarization and O(2) evolution reactions were carried out to test the electrode behaviour and SIMS analyses were performed after all these treatments. In this way, surface changes induced by electrochemical treatments and depending on electrode composition were widely investigated by SIMS, revealing, for example, the presence of hydration or preferential dissolution phenomena induced by electrochemical processing. PMID:14755612

  8. Investigating Surface Features on Nix and Hydra

    NASA Astrophysics Data System (ADS)

    Weaver, Harold A.; Barnouin, O. S.; Cheng, A. F.; Ernst, C. M.; Lauer, T. R.; Stern, S. A.; Olkin, C. B.; Ennico, K.; Young, L. A.

    2015-11-01

    The LORRI (Cheng et al. 2008,Space Sci. Rev. 140, 189) and MVIC (Reuter et al. 2008,Space Sci. Rev. 140, 129) imagers on the New Horizons (NH) spacecraft obtained spatially resolved measurements of Nix and Hydra, two of Pluto's four small moons. Nix was observed by LORRI in panchromatic light (350-850 nm) at resolutions up to 0.30 km/pix, and by MVIC in color (400-550 nm, 540-700 nm, 780-975 nm, 860-910 nm; the latter is centered on a weak CH4 band) at resolutions up to 2.0 km/pix. Hydra was observed by LORRI in panchromatic light at 1.1 km/pix, and by MVIC in color at 4.6 km/pix. The lossless versions of the images, which we will employ in our analysis, are scheduled for downlink in September and October 2015. After image deconvolutions, which typically double the spatial resolution, the NH images provide hundreds to thousands of pixels across the surfaces of Nix and Hydra. We will present results on our searches for craters, lineaments, and other features on the surfaces of Nix and Hydra. We will also present results on any correlations between morphological features and color and albedo variations on the surface. This work was supported by NASA's New Horizons project.

  9. Chemistry of bimetallic and alloys surfaces. Progress report, June 1, 1990--November 30, 1991

    SciTech Connect

    Koel, B.E.

    1991-10-18

    We have continued our work on elucidating the underlying principles that govern chemical reactions occurring on bimetallic and alloy surfaces. Our goal is to aid in the atomic level explanation of the reactivity and selectivity of alloy and bimetallic cluster catalysts and to provide a fundamental basis for the design of new catalysts with improved performance. Our approach is to use a battery of surface science methods to obtain fundamental data on the thermochemistry and kinetics of the adsorption and reaction of molecules on extensively characterized, single-crystal bimetallic surfaces. We measure changes in chemisorption bond strength, adsorption site distributions, and hydrocarbon fragment stability and reactivity and correlate these results with the geometric and electronic structure of the metal atoms on the surface. Often, our aim is to carefully design experiments that isolate the several factors (e.g., ensemble and ligand effects) that control surface chemistry and catalysis on bimetallic and alloy surfaces in order to better understand the importance of each contribution. In the past 18 months, we have continued to study how alkali promoters strongly affect the reactions of hydrocarbons on Pt and Ni surfaces by altering the electronic structure and inducing significant site-blocking effects. We have shown that bismuth coadsorption provides benchmark data on ensemble sizes required for chemical reactions on Pt and Ni surfaces. Surface alloys of Sn/Pt are being used for detailed probing of ensemble sizes and also reactive site requirements. 22 refs.

  10. Surface-initiated Polymerization of Azidopropyl Methacrylate and its Film Elaboration via Click Chemistry

    PubMed Central

    Saha, Sampa; Bruening, Merlin L.; Baker, Gregory L.

    2013-01-01

    Azidopropyl methacrylate (AzPMA), a functional monomer with a pendent azido group, polymerizes from surfaces and provides polymer brushes amenable to subsequent elaboration via click chemistry. In DMF at 50 °C, click reactions between poly(AzPMA) brushes and an alkynylated dye proceed with >90% conversion in a few minutes. However, in aqueous solutions, reaction with an alkyne-containing poly(ethylene glycol) methyl ether (mPEG, Mn=5000) gives <10% conversion after a 12-h reaction at room temperature. Formation of copolymers with AzPMA and polyethylene glycol methyl ether methacrylate (mPEGMA) enables control over the hydrophilicity and functional group density in the copolymer to increase the yield of aqueous click reactions. The copolymers show reaction efficiencies as high as 60%. These studies suggest that for aqueous applications such as bioconjugation via click chemistry, control over brush hydrophilicity is vital. PMID:24293702

  11. INLAND DISSOLVED SALT CHEMISTRY: STATISTICAL EVALUATION OF BIVARIATE AND TERNARY DIAGRAM MODELS FOR SURFACE AND SUBSURFACE WATERS

    EPA Science Inventory

    We compared the use of ternary and bivariate diagrams to distinguish the effects of atmospheric precipitation, rock weathering, and evaporation on inland surface and subsurface water chemistry. The three processes could not be statistically differentiated using bivariate models e...

  12. Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

    DOE PAGESBeta

    Park, Joong Sun; An, Jihwan; Lee, Min Hwan; Prinz, Friedrich B.; Lee, Wonyoung

    2015-07-10

    In this study, we report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created withmore » yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte electrode interfaces of solid oxide fuel cells for higher electrochemical performance.« less

  13. Monte Carlo studies of surface chemistry and nonthermal desorption involving interstellar grains

    PubMed Central

    Herbst, Eric; Cuppen, Herma M.

    2006-01-01

    Although still poorly understood, the chemistry that occurs on the surfaces of interstellar dust particles profoundly affects the growth of molecules in the interstellar medium. The most important surface reaction is the conversion of atomic to molecular hydrogen, which is a precursor for all subsequent molecular development and which occurs both in diffuse and dense interstellar clouds. Another set of surface reactions produces icy mantles of many monolayers in cold and dense regions of the interstellar medium. The monolayers are dominated by water ice but also contain CO, CO2, and occasionally methanol. In this work, we first review both our stochastic approach to the surface chemistry that can occur on small dust particles and how it has been applied to the problem of the formation of molecular hydrogen. This latter problem is strongly affected by the pulsed heating of smaller grains by photons. Photons are not the only source of pulsed heating; cosmic rays also can heat interstellar grains in a pulsed manner. Here, we calculate the heating by cosmic rays for different grain sizes and cosmic ray components. It is then shown that this mechanism is an important one for desorption of ice mantles. PMID:16894170

  14. Effect of Surface Chemistry on the Mechanisms and Governing Laws of Friction and Wear.

    PubMed

    Dai, Ling; Sorkin, Viacheslav; Zhang, Yong-Wei

    2016-04-01

    Recent studies have shown that interface chemistry, that is, the formation and breaking of chemical bonds across contacting interfaces, is closely related to the wear and friction behavior at the nanoscale. In reality, the dangling bond density (DBD) at contacting surfaces can vary greatly. Currently, it remains unclear how friction and wear mechanisms depend on DBDs and whether the Archard's law for wear and Amonton's law for friction are still applicable for contacting surfaces with different DBDs. In this work, we address these issues by studying the wear and friction behavior between two sliding diamond-like carbon surfaces by controlling DBDs via hydrogenation using molecular dynamics simulations. It is found that the chemical bond breaking and remaking across the contacting interface play the key role in determining the friction and wear behavior. During the sliding, a higher DBD leads to more chemical bond formations across the interface, causing stronger wear via either atom or cluster detachments. With the same DBD, a mechanism transition from an atom-by-atom to cluster detachments is observed by increasing the normal load. Remarkably, a fully saturated surface can exhibit a wearless friction. We further show that after necessary modifications, the Archard's law for wear and the Amonton's law for friction may be applicable at the nanoscale. The present work reveals insights into the effect of interface chemistry on the friction and wear, and it provides guidelines for effective antiwear design. PMID:27004415

  15. Effect of fullerenol surface chemistry on nanoparticle binding-induced protein misfolding.

    PubMed

    Radic, Slaven; Nedumpully-Govindan, Praveen; Chen, Ran; Salonen, Emppu; Brown, Jared M; Ke, Pu Chun; Ding, Feng

    2014-07-21

    Fullerene and its derivatives with different surface chemistry have great potential in biomedical applications. Accordingly, it is important to delineate the impact of these carbon-based nanoparticles on protein structure, dynamics, and subsequently function. Here, we focused on the effect of hydroxylation - a common strategy for solubilizing and functionalizing fullerene - on protein-nanoparticle interactions using a model protein, ubiquitin. We applied a set of complementary computational modeling methods, including docking and molecular dynamics simulations with both explicit and implicit solvent, to illustrate the impact of hydroxylated fullerenes on the structure and dynamics of ubiquitin. We found that all derivatives bound to the model protein. Specifically, the more hydrophilic nanoparticles with a higher number of hydroxyl groups bound to the surface of the protein via hydrogen bonds, which stabilized the protein without inducing large conformational changes in the protein structure. In contrast, fullerene derivatives with a smaller number of hydroxyl groups buried their hydrophobic surface inside the protein, thereby causing protein denaturation. Overall, our results revealed a distinct role of surface chemistry on nanoparticle-protein binding and binding-induced protein misfolding. PMID:24934397

  16. A First Principles Investigation of Proton Chemistry in Perovskite-Type Oxides

    NASA Astrophysics Data System (ADS)

    Tauer, Tania Allison

    Certain acceptor-doped perovskite-type oxides show significant promise for deployment into a number of electrochemical device applications, including fuel cells, batteries, and electrolyzers, owing to their rapid proton conductivities at high temperatures. However, limitations in bulk material hydration and slow grain boundary conductivities have reduced the viability of these materials in intermediate temperatures applications. This thesis work uses density functional theory to gain a fundamental understanding of proton and defect chemistry within various perovskite environments in order to identify strategies to increase proton concentration and improve overall proton conductivity. First, material hydration was probed within yttrium-doped barium cerate (BCY) to examine how the thermodynamics of material hydration are influenced by dopant concentration. A model was derived from solely first principle techniques to describe hydration within BCY as a function of dopant concentration, temperature, and partial pressure of water. The resulting model can be used to screen for favorable perovskite-dopant combinations with enhanced hydration capabilities. Next, defect segregation was investigated in the more complex interfacial environment to probe the origin of low proton conductivity across perovskite grain boundaries (GB). The results of this study suggest that screening for perovskite-dopant combinations with strong dopant-oxygen bond strengths may reduce the segregation of dopant ions and oxygen vacancies to the GB interface, mitigating the development of a positive GB core and enhancing proton conduction across the GB. Finally, proton stability was assessed at various interfacial regions within the perovskite material. An examination of proton adsorption at the BaZrO3-vacuum interface reveals a destabilization of protons in the first subsurface layer of the perovskite, yielding a potential barrier for proton diffusion into and out of the perovskite membrane. An

  17. Statistical demonstration of the relative effect of surface chemistry and roughness on human osteoblast short-term adhesion.

    PubMed

    Anselme, K; Bigerelle, M

    2006-05-01

    The effects of material composition, surface chemistry or surface topography on cell attachment (short-term adhesion) have been largely studied on bone-derived cells. However, no statistical demonstration of these effects has been performed until now. With this objective, we quantified the attachment after 24 hours of human osteoblasts on pure titanium, titanium alloy and stainless steel substrates presenting 6 different surface morphologies and 2 different roughness amplitude obtained by sand-blasting, electro-erosion, acid etching, polishing and machine-tooling. The coating by a gold-palladium layer of these surfaces allowed determining the relative effect of the surface roughness and of the surface chemistry. By multiple analysis of variance, we demonstrated that neither material composition nor surface roughness amplitude influenced cell attachment except on sandblasted pure titanium substrates. On the contrary, a high significant influence of the process used to produce the surface was observed meaning that the main influent factor on cell attachment could be either the surface morphology or the surface chemistry induced by the process. As the coating of surfaces by a gold-palladium layer decreased significantly the attachment of cells on the majority of substrates, we concluded that attachment is rather influenced by surface chemistry than by surface topography. PMID:16688588

  18. Investigation of Fuel Chemistry and Bed Performance in a Fluidized Bed Black Liquor Steam Reformer

    SciTech Connect

    Kevin Whitty

    2007-06-30

    University of Utah's project entitled 'Investigation of Fuel Chemistry and Bed Performance in a Fluidized Bed Black Liquor Steam Reformer' (DOE Cooperative Agreement DE-FC26-02NT41490) was developed in response to a solicitation released by the U.S. Department of Energy in December 2001, requesting proposals for projects targeted towards black liquor/biomass gasification technology support research and development. Specifically, the solicitation was seeking projects that would provide technical support for Department of Energy supported black liquor and biomass gasification demonstration projects under development at the time.

  19. Ground- and Surface-Water Chemistry of Handcart Gulch, Park County, Colorado, 2003-2006

    USGS Publications Warehouse

    Verplanck, Philip L.; Manning, Andrew H.; Kimball, Briant A.; McCleskey, R. Blaine; Runkel, Robert L.; Caine, Jonathan Saul; Adams, Monique; Gemery-Hill, Pamela A.; Fey, David L.

    2008-01-01

    As part of a multidisciplinary project to determine the processes that control ground-water chemistry and flow in mineralized alpine environments, ground- and surface-water samples from Handcart Gulch, Colorado were collected for analysis of inorganic solutes and water and dissolved sulfate stable isotopes in selected samples. The primary aim of this study was to document variations in ground-water chemistry in Handcart Gulch and to identify changes in water chemistry along the receiving stream of Handcart Gulch. Water analyses are reported for ground-water samples collected from 12 wells in Handcart Gulch, Colorado. Samples were collected between August 2003 and October 2005. Water analyses for surface-water samples are reported for 50 samples collected from Handcart Gulch and its inflows during a low-flow tracer injection on August 6, 2003. In addition, water analyses are reported for three other Handcart Gulch stream samples collected in September 2005 and March 2006. Reported analyses include field parameters (pH, specific conductance, temperature, dissolved oxygen, and Eh), major and trace constituents, oxygen and hydrogen isotopic composition of water and oxygen and sulfur isotopic composition of dissolved sulfate. Ground-water samples from this study are Ca-SO4 type and range in pH from 2.5 to 6.8. Most of the samples (75 percent) have pH values between 3.3 and 4.3. Surface water samples are also Ca-SO4 type and have a narrower range in pH (2.7?4.0). Ground- and surface-water samples vary from relatively dilute (specific conductance of 68 ?S/cm) to concentrated (specific conductance of 2,000 ?S/cm).

  20. Saturn Magnetospheric Impact on Surface Molecular Chemistry and Astrobiological Potential of Enceladus

    NASA Technical Reports Server (NTRS)

    Cooper, Paul D.; Cooper, John F.; Sittler, Edward C.; Burger, Matthew H.; Sturner, Steven J.; Rymer, Abigail M.

    2008-01-01

    The active south polar surface of Enceladus is exposed to strong chemical processing by direct interaction with charged plasma and energetic particles in the local magnetospheric environment of this icy moon. Chemical oxidation activity is suggested by detection of H202 at the surface in this region and less directly by substantial presence of C02, CO, and N2 in the plume gases. Molecular composition of the uppermost surface, including ejecta from plume activity, is radiolytically transformed mostly by penetrating energetic electrons with lesser effects from more depleted populations of energetic protons. The main sources of molecular plasma ions and E-ring dust grains in the magnetospheric environment are the cryovolcanic plume emissions from Enceladus. These molecular ions and the dust grains are chemically processed by magnetospheric interactions that further impact surface chemistry on return to Enceladus. For example, H20 neutrals dominating the emitted plume gas return to the surface mostly as H30+ ions after magnetospheric processing. Surface oxidant loading is further increased by return of radiolytically processed ice grains from the E-ring. Plume frost deposition and micrometeoroid gardening protect some fraction of newly produced molecular species from destruction by further irradiation. The evident horizontal and vertical mobility of surface ices in the south polar region drive mixing of these processed materials into the moon interior with potential impacts on deep ice molecular chemistry and plume gas production. Similarly as suggested previously for Europa, the externally driven source of radiolytic oxidants could affect evolution of life in any subsurface liquid water environments of Enceladus.

  1. Influence of mineral oil and additives on microhardness and surface chemistry of magnesium oxide (001) surface

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Shigaki, H.; Buckley, D. H.

    1982-01-01

    X-ray photoelectron spectroscopy analyses and hardness experiments were conducted with cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved into specimens along the /001/ surface, and indentations were made on the cleaved surface in laboratory air, in nitrogen gas, or in degassed mineral oil with and without an additive while not exposing specimen surface to any other environment. The various additives examined contained sulfur, phosphorus, chlorine, or oleic acid. The sulfur-containing additive exhibited the highest hardness and smallest dislocation patterns evidencing plastic deformation; the chlorine-containing additive exhibited the lowest hardness and largest dislocation patterns evidencing plastic deformation. Hydrocarbon and chloride (MgCl2) films formed on the magnesium oxide surface. A chloride film was responsible for the lowest measured hardness.

  2. Ion-Surface Collisions in Mass Spectrometry: Where Analytical Chemistry Meets Surface Science

    SciTech Connect

    Laskin, Julia

    2015-02-01

    This article presents a personal perspective regarding the development of key concepts in understanding hyperthermal collisions of polyatomic ions with surfaces as a unique tool for mass spectrometry applications. In particular, this article provides a historic overview of studies focused on understanding the phenomena underlying surface-induced dissociation (SID) and mass-selected deposition of complex ions on surfaces. Fast energy transfer in ion-surface collisions makes SID especially advantageous for structural characterization of large complex molecules, such as peptides, proteins, and protein complexes. Soft, dissociative, and reactive landing of mass-selected ions provide the basis for preparatory mass spectrometry. These techniques enable precisely controlled deposition of ions on surfaces for a variety of applications. This perspective article shows how basic concepts developed in the 1920s and 1970s have evolved to advance promising mass-spectrometry-based applications.

  3. Surface chemistry of Ti6Al4V components fabricated using selective laser melting for biomedical applications.

    PubMed

    Vaithilingam, Jayasheelan; Prina, Elisabetta; Goodridge, Ruth D; Hague, Richard J M; Edmondson, Steve; Rose, Felicity R A J; Christie, Steven D R

    2016-10-01

    Selective laser melting (SLM) has previously been shown to be a viable method for fabricating biomedical implants; however, the surface chemistry of SLM fabricated parts is poorly understood. In this study, X-ray photoelectron spectroscopy (XPS) was used to determine the surface chemistries of (a) SLM as-fabricated (SLM-AF) Ti6Al4V and (b) SLM fabricated and mechanically polished (SLM-MP) Ti6Al4V samples and compared with (c) traditionally manufactured (forged) and mechanically polished Ti6Al4V samples. The SLM-AF surface was observed to be porous with an average surface roughness (Ra) of 17.6±3.7μm. The surface chemistry of the SLM-AF was significantly different to the FGD-MP surface with respect to elemental distribution and their existence on the outermost surface. Sintered particles on the SLM-AF surface were observed to affect depth profiling of the sample due to a shadowing effect during argon ion sputtering. Surface heterogeneity was observed for all three surfaces; however, vanadium was witnessed only on the mechanically polished (SLM-MP and FGD-MP) surfaces. The direct and indirect 3T3 cell cytotoxicity studies revealed that the cells were viable on the SLM fabricated Ti6Al4V parts. The varied surface chemistry of the SLM-AF and SLM-MP did not influence the cell behaviour. PMID:27287125

  4. Surface layer ozone and nitric oxides in the Arctic: The inuence of boundary layer dynamics, snowpack chemistry, surface exchanges, and seasonality

    NASA Astrophysics Data System (ADS)

    Van Dam, Brie A.

    The snowpack is a region of active chemistry. Aqueous chemistry in a quasi-liquid layer on snow grains and gas-phase chemical reactions in snow interstitial air can lead to the production or destruction of important trace gases. Physical transport parameters such as wind pumping and diffusion affect the vertical distribution of gases within the snowpack. The resulting emission or uptake of trace gases at the atmosphere-snowpack interface can have significant in uence on the chemistry of the lower atmosphere. In this work the dynamic interactions between the snowpack and atmosphere are examined from multiple perspectives. The primary focus is on ozone (O3) and nitrogen oxides (NOx) in the Arctic, a region undergoing widespread environmental change. To investigate an ice-sheet location with year round snow cover, data from a two-year campaign at Summit, Greenland are implemented. At Summit this study examines (1) the processes contributing to vigorous chemistry in snow interstitial air, and (2) the role of the boundary layer over snow in determining surface layer NOx. Physical and chemical processes are shown to contribute to distinct seasonal and diurnal cycles of O3, NO, and NO2 in the snowpack. Boundary layer depths estimated from sonic anemometer turbulence quantities are used alongside sodar-derived values to show that the depth of the stable to weakly stable boundary layer at Summit was not a primary factor in determining NO x in early summer. Motivated by observations of an increase in the length of the snow-free season in the Arctic in recent decades, data from a one-year experiment at the seasonally-snow covered location of Toolik Lake, AK are also incorporated. This study shows the first observations of springtime ozone depletion events at a location over 200 km from the coast in the Arctic. FLEXPART analysis is used to illustrate that these inland events are linked to transport conditions. Lastly at this location, eddy-covariance O3 uxes were calculated to

  5. Investigating the stability of surface nanobubbles

    NASA Astrophysics Data System (ADS)

    Berkelaar, Robin; Dietrich, Erik; Kooij, Stefan; Zandvliet, Harold; Lohse, Detlef

    2014-03-01

    The primary attribute of interest of surface nanobubbles is their unusual stability and a number of theories trying to explain this have been put forward. Interestingly, the actual dissolution of nanobubbles is a topic that did not receive a lot of attention yet. We applied different experimental procedures in which gaseous nanobubbles should dissolve, according to the theories. In method A, the nanobubbles were exposed to a flow of degassed water for 96 hours. In method B, the ambient pressure was lowered in order to degas the liquid and the nanobubble-like objects. In method C, the liquid was evaporated and the geometry of the nanobubbles was indirectly studied in micrometers thick water films. The effects of these three methods on the stability of nanobubbles will be discussed.

  6. Surface chemistry and friction behavior of the silicon carbide (0001) surface at temperatures to 1500 deg C

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Buckley, D. H.

    1981-01-01

    X-ray photoelectron and Auger electron spectroscopy analyses and friction studies were conducted with a silicon carbide (0001) surface in contact with iron at various temperatures to 1200 or 1500 C in a vacuum of 10 to the minus 8th power Pa. The results indicate that there is a significant temperature influence on both the surface chemistry and friction properties of silicon carbide. The principal contaminant of adsorbed amorphous carbon on the silicon carbide surface in the as received state is removed by simply heating to 400 C. Above 400 C, graphite and carbide type carbine are the primary species on the silicon carbide surface, in addition to silicon. The coefficients of friction of polycrystalline iron sliding against a single crystal silicon carbide (0001) surface were high at temperatures to 800 C. Similar coefficients of friction were obtained at room temperature after the silicon carbide was preheated at various temperatures up 800 C. When the friction experiments were conducted above 800 C or when the specimens were preheated to above 800 C, the coefficients of friction were dramatically lower. At 800 C the silicon and carbide type carbon are at a maximum intensity in the XPS spectra. With increasing temperature above 800 C, the concentration of the graphite increases rapidly on the surface, whereas those of the carbide type carbon and silicon decrease rapidly.

  7. Spatial and Temporal Variability of Surface Snow Accumulation and Snow Chemistry at East Antarctic Ice Sheet

    NASA Astrophysics Data System (ADS)

    Motoyama, H.; Ito, K.; Hirabayashi, M.

    2014-12-01

    Snow stakes along the traverse routes have been observed for long term monitoring program 'the variation of ice sheet surface mass balance' from the 1960's by the Japanese Antarctic Research Expedition in Shirase glacier drainage basin, East Antarctica. During the traverse route between coastal S16 point (69 02'S, 40 03'E, 580m a.s.l.) to inland Dome Fuji (77 22'S, 39 42'E, 3,810m a.s.l.), the snow stake observations every 2 km have been carried out from 1993. Yearly net snow accumulations from S16 to Dome Fuji were calculated. Heavy, modern and light snow events were observed. They were different in way accumulating spatial pattern depending on places. The yearly accumulation rates were compared with seasonal change of AAO-index (SAM). As a result, yearly accumulation rate and AAO-index showed the positive correlation.Surface snow samplings were conducted every 10km along the traverse route. Generally, the snow surface features are classified into three regions. (1) the coastal region: smooth surface, high snow accumulation (2) the katabatic slope region: rough sastrugi surface and smooth glazed surface(3) the high plateau region: smooth surface, little snow accumulation The chemistry of surface snow changes from the coast to inland. Furthermore, the chemical properties of snow are different for each surface at the same area. We can classify the surface snow with fresh drifting snow, deposited drift snow, soft and hard surface snow, sustrugi, surface hoar and so on. The value of each isotope ration and ion concentration greatly varied. Sometimes, snow might deposit thick equally. But the deposited snow was redistributed by the wind. When the snowstorm occurred, the blowing snow started to deposit in a certain opportunity. As for it, the area was not the uniform. It is necessary to discuss inhomogeneity of the depositional condition quantitatively.

  8. Interfacial Atmospheric Chemistry: Quantum Chemical Calculations on the Mechanism of Protonation and Oligomerization of Isoprene on Aqueous Surfaces

    NASA Astrophysics Data System (ADS)

    Mishra, H.; Colussi, A. J.; Enami, S.; Nielsen, R. J.; Hoffmann, M. R.; Goddard, W. A.

    2012-12-01

    It has become increasingly apparent that atmospheric chemistry involves more than gas-phase reactions. Key processes, such as the decay of NO2 in urban plumes and the associated daytime formation of HONO, and the rapid chemistries observed in and over forest canopies at nighttime defy explanation by conventional atmospheric chemistry mechanisms. We have recently reported experimental results on several gas-liquid reactions of atmospheric interest, such as the facile protonation of gaseous isoprene on mildly acidic (pH < 4) water. Although interfacial proton transfers, such as the one involved in the protonation of gaseous isoprene, also participate in cloud and ocean acidification, bioenergetics coupling, 'on-water' catalysis, self-assembly and molecular recognition, little is known about the molecular mechanisms of such reactions. Herein we apply quantum mechanics to investigate how biogenic or anthropogenic olefins may get protonated and undergo oligomerization at the air-water interface by performing model calculations on small water clusters carrying an excess proton as surrogates for the surface of mildly acidic water as sensed by gaseous isoprene (ISO). We find that ISO binds weakly to the surface of water and accepts a proton from H+(H2O)3, leading to ISOH+ via a proton transfer hindered by a ΔG1‡ = 5.6 kcal mol-1 kinetic barrier. Subsequently, another ISO attaches loosely to this ensemble, before being attacked by the ISOH+. This process, which represents the first step of the cationic polymerization of ISO, is hindered by a similar ΔG2‡ = 5.7 kcal mol-1 barrier. Our theoretical results are consistent with experimental (~ 10-4) uptake coefficients for ISO measured on acidic water.

  9. National Surface Water Survey: Western Lake Survey (Phase 1 - synoptic chemistry) quality assurance plan

    SciTech Connect

    Silverstein, M.E.; Drouse, S.K.; Engels, J.L.; Faber, M.L.; Mitchell-Hall, T.E.

    1987-06-01

    The purpose of the National Surface Water Survey of the National Acid Precipitation Assessment Program is to evaluate the present water chemistry of lakes and streams, to determine the status of certain biotic resources, and to select regionally representative surface waters for a long-term monitoring program to study changes in aquatic resources. The Western Lake Survey is part of the National Surface Water Survey. The U.S. Environmental Protection Agency requires that data-collection activities be based on a program that ensures that the resulting data are of known quality and are suitable for their intended purpose. This quality assurance plan describes in detail the quality-assurance requirements and procedures that are unique to the Western Lake Survey - Phase I.

  10. Effects of extreme pressure additive chemistry on rolling element bearing surface durability

    SciTech Connect

    Evans, Ryan D.; Nixon, H. P.; Darragh, Craig V.; Howe, Jane Y; Coffey, Dorothy W

    2007-01-01

    Lubricant additives have been known to affect rolling element bearing surface durability for many years. Tapered roller bearings were used in fatigue testing of lubricants formulated with gear oil type additive systems. These systems have sulfur- and phosphoruscontaining compounds used for gear protection as well as bearing lubrication. Several variations of a commercially available base additive formulation were tested having modified sulfur components. The variations represent a range of ''active'' extreme pressure (EP) chemistries. The bearing fatigue test results were compared with respect to EP formulation and test conditions. Inner ring near-surface material in selected test bearings was evaluated on two scales: the micrometer scale using optical metallography and the nanometer scale using transmission electron microscopy (TEM). Focused-ion beam (FIB) techniques were used for TEM specimen preparation. Imaging and chemical analysis of the bearing samples revealed near-surface material and tribofilm characteristics. These results are discussed with respect to the relative fatigue lives.

  11. Nanoporous Anodic Alumina Platforms: Engineered Surface Chemistry and Structure for Optical Sensing Applications

    PubMed Central

    Kumeria, Tushar; Santos, Abel; Losic, Dusan

    2014-01-01

    Electrochemical anodization of pure aluminum enables the growth of highly ordered nanoporous anodic alumina (NAA) structures. This has made NAA one of the most popular nanomaterials with applications including molecular separation, catalysis, photonics, optoelectronics, sensing, drug delivery, and template synthesis. Over the past decades, the ability to engineer the structure and surface chemistry of NAA and its optical properties has led to the establishment of distinctive photonic structures that can be explored for developing low-cost, portable, rapid-response and highly sensitive sensing devices in combination with surface plasmon resonance (SPR) and reflective interference spectroscopy (RIfS) techniques. This review article highlights the recent advances on fabrication, surface modification and structural engineering of NAA and its application and performance as a platform for SPR- and RIfS-based sensing and biosensing devices. PMID:25004150

  12. Relationships between precipitation and surface water chemistry in three Carolina bays

    SciTech Connect

    Monegue, R.L.; Jagoe, C.H.

    1995-12-31

    Carolina Bays are shallow freshwater wetlands, the only naturally occurring lentic systems on the southeastern coastal plain. Bays are breeding sites for many amphibian species, but data on precipitation/surface water relationships and long-term chemical trends are lacking. Such data are essential to interpret major fluctuations in amphibian populations. Surface water and bulk precipitation were sampled bi-weekly for over two years at three bays along a 25 km transect on the Savannah River Site in South Carolina. Precipitation chemistry was similar at all sites; average pH was 4.56, and the major ions were H{sup +} (30.8 % of total), and SO{sub 4} (50.3% of total). H{sup +} was positively correlated with SO{sub 4}, suggesting the importance of anthropogenic acids to precipitation chemistry. All three bays, Rainbow Bay (RB), Thunder Bay (TB), and Ellenton Bay (EB), contained soft (specific conductivity 5--90 {micro}S/cm), acidic water (pH 4.0--5.9) with DOM from 4--40 mg/L. The major cation for RB, TB, and EB, respectively, was: Mg (30.8 % of total); Na (27% of total); and Ca (34.2% of total). DOM was the major anion for all bays, and SO{sub 4} represented 13 to 28 % of total anions. H{sup +} was not correlated to DOM or SO, in RB; H{sup +} was positively correlated to DOM and SO{sub 4} in TB, and negatively correlated to DOM and SO{sub 4} in EB. Different biogeochemical processes probably control pH and other chemical variables in each bay. While surface water H{sup +} was not directly correlated with precipitation H{sup +}, NO{sub 3}, or SO{sub 4}, precipitation and shallow groundwater are dominant water sources for these bays. Atmospheric inputs of anthropogenic acids and other chemicals are important factors influencing bay chemistry.

  13. The influence of the surface chemistry of silver nanoparticles on cell death

    NASA Astrophysics Data System (ADS)

    Sur, Ilknur; Altunbek, Mine; Kahraman, Mehmet; Culha, Mustafa

    2012-09-01

    The influence of the surface chemistry of silver nanoparticles (AgNPs) on p53 mediated cell death was evaluated using human dermal fibroblast (HDF) and lung cancer (A549) cells. The citrate reduced AgNPs (C-AgNPs) were modified with either lactose (L-AgNPs) or a 12-base long oligonucleotide (O-AgNPs). Both unmodified and modified AgNPs showed increased concentration and time dependent cytotoxicity and genotoxicity causing an increased p53 up-regulation within 6 h and led to apoptotic or necrotic cell deaths. The C-AgNPs induced more cytotoxicity and cellular DNA damage than the surface modified AgNPs. Modifying the C-AgNPs with lactose or the oligonucleotide reduced both necrotic and apoptotic cell deaths in the HDF cells. The C-AgNPs caused an insignificant necrosis in A549 cells whereas the modified AgNPs caused necrosis and apoptosis in both cell types. Compared to the O-AgNPs, the L-AgNPs triggered more cellular DNA damage, which led to up-regulation of p53 gene inducing apoptosis in A549 cells compared to HDF cells. This suggests that the different surface chemistries of the AgNPs cause different cellular responses that may be important not only for their use in medicine but also for reducing their toxicity.

  14. Lidar measurements from space for tropospheric chemistry investigations: Summary of workshop overview presentation

    NASA Technical Reports Server (NTRS)

    Browell, Edward V.

    1987-01-01

    Over the past decade, NASA has played a lead role in defining the scientific objectives and technology requirements for spaceborne lidar investigations of the atmosphere. An assessment of the potential for conducting lidar measurements from space for investigations that pertain specifically to tropospheric chemistry is presented. A description of potential lidar measurement techniques is given, and the scientific requirements for tropospheric chemistry are reviewed. The current status of airborne lidar measurements of aerosols, O3, and H2O is discussed, and a brief description of the evolution of lidar technology to space is given. Also, the measurement of tropospheric gases with a spaceborne lidar system is evaluated for a wide range of gas species. From this general assessment, it appears feasible to measure aerosols, H2O, O3, NH3, CO, CH4, NO2, atmospheric pressure and temperature, and wind with a lidar from space provided that the appropriate laser and receiver technology is available. For the mid-1990's, it is expected that lidar technology will be available for the measurement of aerosols, H2O, and O3 from a space platform.

  15. Changes in surface chemistry of silicon carbide (0001) surface with temperature and their effect on friction

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Buckley, D. H.

    1980-01-01

    Friction studies were conducted with a silicon carbide (0001) surface contacting polycrystalline iron. The surface of silicon carbide was pretreated: (1) by bombarding it with argon ions for 30 minutes at a pressure of 1.3 pascals; (2) by heating it at 800 C for 3 hours in vacuum at a pressure of 10 to the minus eighth power pascal; or (3) by heating it at 1500 C for 3 hours in a vacuum of 10 to the minus eighth power pascal. Auger emission spectroscopy was used to determine the presence of silicon and carbon and the form of the carbon. The surfaces of silicon carbide bombarded with argon ions or preheated to 800 C revealed the main Si peak and a carbide type of C peak in the Auger spectra. The surfaces preheated to 1500 C revealed only a graphite type of C peak in the Auger spectra, and the Si peak had diminished to a barely perceptible amount. The surfaces of silicon carbide preheated to 800 C gave a 1.5 to 3 times higher coefficient of friction than did the surfaces of silicon carbide preheated to 1500 C. The coefficient of friction was lower in the 11(-2)0 direction than in the 10(-1)0 direction; that is, it was lower in the preferred crystallographic slip direction.

  16. Investigating asteroid surface thermal inertias with NEOWISE

    NASA Astrophysics Data System (ADS)

    Nugent, C.; Mainzer, A.; Masiero, J.; Lysek, M.; Grav, T.; Bauer, J.; Cutri, R.; Wright, E.

    2014-07-01

    NEOWISE, the asteroid-hunting mission that employs the Wide-field Infrared Survey Explorer (WISE) spacecraft, has observed over 150,000 minor planets over four infrared wavelength bands (Mainzer et al. 2011). Several of these asteroids have also been observed by radar, and have associated shapes and spin states (e.g., Busch et al. 2011, see current list maintained by L. Benner at http://echo.jpl.nasa.gov/˜lance/shapes/ asteroid_shapes.html). We combine these datasets via thermophysical modeling, a technique that combines 3-D asteroid shapes, a model of heat transport, and infrared observations to determine the thermal inertia of an asteroid (e.g., Leyrat et al. 2011). Thermal inertia measurements can constrain regolith composition and density, which can be linked to collisional history and dynamical evolution. Measurements of thermal conductivity and heat capacity (components of thermal inertia), can refine predictions of the Yarkovsky drift, a non-gravitational force that can change asteroid orbits (Bottke et al. 2006). We present thermal inertia measurements derived from the NEOWISE dataset, such as surface thermal inertia measurements of 2008 EV5 (see figure).

  17. Characterization of peptide immobilization on an acetylene terminated surface via click chemistry

    NASA Astrophysics Data System (ADS)

    Shamsi, Fahimeh; Coster, Hans; Jolliffe, Katrina A.

    2011-10-01

    Peptide (A-A-A-A-G-G-G-E-R-G-D)1A: Alanine; D: Glutamic acid; E: Aspartic acid; G: Glycine; R: Arginine. conjugated surfaces were prepared on silicon surfaces through click chemistry. The amino acid sequence RGD is the cellular attachment site of a large number of extracellular matrices such as blood and cell surface proteins. Recent research has focused on developing RGD peptides which mimic cell adhesion proteins and integrins [1,2].The steps involved the formation of an alkyne-terminated monolayer on Si(111), followed by linking the peptide to 4-azidophenyl isothiocyanate via a specific and gentle reaction. This was followed by the attachment of the azido peptide to the surface-bound alkynes using the Cu (I)-catalyzed Huisgen 1,3-dipolar cycloaddition reaction. The surface structures of the alkyne terminated monolayer and the attached peptide were characterized using high resolution impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared (ATR-FTIR) Spectroscopy. EIS characterization revealed the alkyne layer and the hydrophobic and polar regions of the attached peptide. XPS analysis showed a high surface coverage of the peptide on the silicon substrates and this was confirmed by FTIR.Our results confirmed a specific covalent attachment of the peptide on the silicon surfaces. This approach offers a versatile, experimentally simple, method for the specific attachment of peptide ligands. This approach would have applications for cell attachment and biosensors.

  18. Surface Modification of Polydivinylbenzene Microspheres with a Fluorinated Glycopolymer Using Thiol-Halogen Click Chemistry.

    PubMed

    Song, Wentao; Granville, Anthony M

    2016-01-01

    Distillation-precipitation polymerization of divinylbenzene was applied to obtain uniform-sized polymeric microspheres. The microspheres were then modified with polypentafluorostyrene chains utilizing surface-initiated atom transfer radical polymerization techniques. The hydrophobic fluoropolymer-coated microsphere was then converted to a hydrophilic biopolymer by performing thiol-halogen click chemistry between polypentafluorostyrene and 1-thio-β-D-glucose sodium salt. The semi-fluorinated glycopolymer showed good binding ability with Concanavalin A as determined by confocal microscopy and turbidity experiments. PMID:26537469

  19. Multifunctionality of organometallic quinonoid metal complexes: surface chemistry, coordination polymers, and catalysts.

    PubMed

    Kim, Sang Bok; Pike, Robert D; Sweigart, Dwight A

    2013-11-19

    Quinonoid metal complexes have potential applications in surface chemistry, coordination polymers, and catalysts. Although quinonoid manganese tricarbonyl complexes have been used as secondary building units (SBUs) in the formation of novel metal-organometallic coordination networks and polymers, the potentially wider applications of these versatile linkers have not yet been recognized. In this Account, we focus on these diverse new applications of quinonoid metal complexes, and report on the variety of quinonoid metal complexes that we have synthesized. Through the use of [(η(6)-hydroquinone)Mn(CO)3](+), we are able to modify the surface of Fe3O4 and FePt nanoparticles (NPs). This process occurs either by the replacement of oleylamine with neutral [(η(5)-semiquinone)Mn(CO)3] at the NP surface, or by the binding of anionic [(η(4)-quinone)Mn(CO)3](-) upon further deprotonation of [(η(5)-semiquinone)Mn(CO)3] at the NP surface. We have demonstrated chemistry at the intersection of surface-modified NPs and coordination polymers through the growth of organometallic coordination polymers onto the surface modified Fe3O4 NPs. The resulting magnetic NP/organometallic coordination polymer hybrid material exhibited both the unique superparamagnetic behavior associated with Fe3O4 NPs and the paramagnetism attributable to the metal nodes, depending upon the magnetic range examined. By the use of functionalized [(η(5)-semiquinone)Mn(CO)3] complexes, we attained the formation of an organometallic monolayer on the surface of highly ordered pyrolitic graphite (HOPG). The resulting organometallic monolayer was not simply a random array of manganese atoms on the surface, but rather consisted of an alternating "up and down" spatial arrangement of Mn atoms extending from the HOPG surface due to hydrogen bonding of the quinonoid complexes. We also showed that the topology of metal atoms on the surface could be controlled through the use of quinonoid metal complexes. A quinonoid

  20. Heterogeneous chemistry and reaction dynamics of the atmospheric oxidants, O3, NO3, and OH, on organic surfaces.

    PubMed

    Chapleski, Robert C; Zhang, Yafen; Troya, Diego; Morris, John R

    2016-07-01

    Heterogeneous chemistry of the most important atmospheric oxidants, O3, NO3, and OH, plays a central role in regulating atmospheric gas concentrations, processing aerosols, and aging materials. Recent experimental and computational studies have begun to reveal the detailed reaction mechanisms and kinetics for gas-phase O3, NO3, and OH when they impinge on organic surfaces. Through new research approaches that merge the fields of traditional surface science with atmospheric chemistry, researchers are developing an understanding for how surface structure and functionality affect interfacial chemistry with this class of highly oxidizing pollutants. Together with future research initiatives, these studies will provide a more complete description of atmospheric chemistry and help others more accurately predict the properties of aerosols, the environmental impact of interfacial oxidation, and the concentrations of tropospheric gases. PMID:26555710

  1. Surface structure and chemistry of Pt/Cu/Pt(1 1 1) near surface alloy model catalyst in CO

    NASA Astrophysics Data System (ADS)

    Zeng, Shibi; Nguyen, Luan; Cheng, Fang; Liu, Lacheng; Yu, Ying; Tao, Franklin (Feng)

    2014-11-01

    Near surface alloy (NSA) model catalyst Pt/Cu/Pt(1 1 1) was prepared on Pt(1 1 1) through a controlled vapor deposition of Cu atoms. Different coordination environments of Pt atoms of the topmost Pt layer with the underneath Cu atoms in the subsurface result in different local electronic structures of surface Pt atoms. Surface structure and chemistry of the NAS model catalyst in Torr pressure of CO were studied with high pressure scanning tunneling microscopy (HP-STM) and ambient pressure X-ray photoelectron spectroscopy (AP-XPS). In Torr pressure of CO, the topmost Pt layer of Pt/Cu/Pt(1 1 1) is restructured to thin nanoclusters with size of about 1 nm. Photoemission feature of O 1s of CO on Pt/Cu/Pt(1 1 1) suggests CO adsorbed on both edge and surface of these formed nanoclusters. This surface is active for CO oxidation. Atomic layers of carbon are formed on Pt/Cu/Pt(1 1 1) at 573 K in 2 Torr of CO.

  2. A pinch of salt is all it takes: chemistry at the frozen water surface.

    PubMed

    Kahan, Tara F; Wren, Sumi N; Donaldson, D James

    2014-05-20

    Chemical interactions at the air-ice interface are of great importance to local atmospheric chemistry but also to the concentrations of pollutants deposited onto natural snow and ice. However, the study of such processes has been hampered by the lack of general, surface-specific probes. Even seemingly basic chemical properties, such as the local concentration of chemical compounds, or the pH at the interface, have required the application of assumptions about solute distributions in frozen media. The measurements that have been reported have tended for the most part to focus on entire ice or snow samples, rather than strictly the frozen interface with the atmosphere. We have used glancing-angle laser spectroscopy to interrogate the air-ice interface; this has yielded several insights into the chemical interactions there. The linear fluorescence and Raman spectra thus measured have the advantage of easy interpretability; careful experimentation can limit their probe depth to that which is relevant to atmospheric heterogeneous processes. We have used these techniques to show that the environment at the interface between air and freshwater ice surfaces is distinct from that at the interface between air and liquid water. Acids such as HCl that adsorb to ice surfaces from the gas phase result in significantly different pH responses than those at liquid water surfaces. Further, the solvation of aromatic species is suppressed at freshwater ice surfaces compared with that at liquid water surfaces, leading to extensive self-association of aromatics at ice surfaces. Photolysis kinetics of these species are much faster than at liquid water surfaces; this can sometimes (but not always) be explained by red shifts in the absorption spectra of self-associated aromatics increasing the extent to which solar radiation is absorbed. The environment presented by frozen saltwater surfaces, in contrast, appears to be reasonably well-described by liquid water. The extent of hydrogen

  3. Laboratory investigations of the role of the grain surface in astrochemical models.

    PubMed

    Brown, Wendy A; Viti, Serena; Wolff, Angela J; Bolina, Amandeep S

    2006-01-01

    The rich chemistry often detected in star forming regions is now recognized to be a consequence of solid-state astrochemistry and the thermal desorption of its products. In recent experimental studies, desorption of a range of ices from a gold surface was investigated using temperature programmed desorption (TPD). These data were then used in astrochemical models. In this paper we investigate the sensitivity of these models to the inclusion of TPD data obtained from different surfaces (simulating different dust grains) and different thicknesses of the icy mantles. Detailed laboratory TPD studies of the desorption of ices from a highly oriented pyrolytic graphite (HOPG) surface have been performed. Desorption temperatures and kinetic parameters have been determined directly from the TPD data and have been used to determine the expected desorption temperature for the ices from grain surfaces. The results of these experiments have been incorporated into astrochemical models of high mass star forming regions and have then been compared with the results of previous experiments. From this comparison, we are able to determine whether the nature and composition of the grain surface is important in dictating the chemistry that occurs in star forming regions. PMID:17191445

  4. Theoretical investigation of gas-surface interactions

    NASA Technical Reports Server (NTRS)

    Dyall, Kenneth G.

    1992-01-01

    The investigation into the appearance of intruder states from the negative continuum when some of the two-electron integrals were omitted was completed. The work shows that, provided all integrals involving core contracted functions in an atomic general contraction are included, or that the core functions are radially localized, meaningful results are obtained and intruder states do not appear. In the area of program development, the Dirac-Hartree-Fock (DHF) program for closed-shell polyatomic molecules was extended to permit Kramers-restricted open-shell DHF calculations with one electron in an open shell or one hole in a closed shell, or state-averaged DHF calculations over several particle or hole doublet states. One application of the open-shell code was to the KO molecule. Another major area of program development is the transformation of integrals from the scalar basis in which they are generated to the 2-spinor basis employed in parts of the DHF program, and hence to supermatrix form. Particularly concerning the omission of small component integrals, and with increase in availability of disk space, it is now possible to consider transforming the integrals. The use of ordered integrals, either in the scalar basis or in the 2-spinor basis, would considerably speed up the construction of the Fock matrix, and even more so if supermatrices were constructed. A considerable amount of effort was spent on analyzing the integral ordering and tranformation for the DHF program. The work of assessing the reliability of the relativistic effective core potentials (RECPs) was continued with calculation of the group IV monoxides. The perturbation of the metal atom provided by oxygen is expected to be larger than that provided by hydrogen and thus provide a better test of the qualification of the RECPs. Calculations on some platinum hydrides were carried out at nonrelativistic (NR), perturbation theory (PT) and DHF levels. Reprints of four papers describing this work are

  5. Laboratory Investigations of Heterogeneous Chemistry Important to Ozone Depletion in the Stratosphere

    NASA Astrophysics Data System (ADS)

    Zhang, Renyi

    Results of laboratory investigations of heterogeneous chemistry important to ozone depletion in the stratosphere are presented. Thermodynamic properties (such as melting points, enthalpies of fusion, etc.) for acids which are present in the stratosphere (HCl, HNO_3 , and H_2SO_4 ) are studied using laboratory-assembled apparatus of electrical conductivity and differential thermal analysis and using a commercial differential scanning calorimeter (DSC). Vapor pressures and infrared spectra of liquid and supercooled solutions, and of liquid-solid and solid -solid coexistence mixtures for the HCl/H_2 O and H_2SO_4 /H_2O binary systems are investigated. Equilibrium constants and standard enthalpies of formation for the pure crystalline hydrates of those acids as well as their corresponding liquid compositions are determined from the vapor pressure and calorimetric data. A theoretical approach, which allows determination of vapor pressures for two adjacent hydrates in thermodynamic equilibrium and for the coexistence systems involving a hydrate and ice in a binary system, is presented in terms of chemical equilibrium principles and compared with the experimental data for thermodynamic consistence. Vapor pressures of HNO_3 and HCl over H_2SO_4 /HNO_3/H_2 O and H_2SO_4 /HCl/H_2O solutions as well as over H_2SO_4/HNO _3/HCl/H_2O solutions are also measured in order to predict incorporation of stratospheric acids into the background sulfate aerosols. From the data, the Henry's law solubility constants for those systems are determined and the equilibrium compositions of aqueous stratospheric aerosols are predicted as a function of ambient temperature and mixing ratios of H_2 O and HNO_3. The results indicate that at the low temperatures characteristic of the stratosphere at high latitudes in the winter and spring, the HNO_3 content reaches levels of the order of 10% wt in the background sulfate aerosols. The results also reveal that the amount of dissolved HCl in the

  6. Chemistry of bimetallic and alloy surfaces. Progress report, June 1, 1990--November 30, 1991

    SciTech Connect

    Koel, B.E.

    1991-10-18

    In the first funding period, we continued our work on elucidating the underlying principles that govern chemical reactions occurring on bimetallic and alloy surfaces. Our goal is to aid in the atomic level explanation of the reactivity and selectivity of alloy and bimetallic cluster catalysts and to provide a fundamental basis for the design of new catalysts with improved performance. Our approach is to use a battery of surface science methods to obtain fundamental data on the thermochemistry and kinetics of the adsorption and reaction of molecules on extensively characterized, single-crystal bimetallic surfaces. We measure changes in chemisorption bond strengths, adsorption site distributions, and hydrocarbon fragment stability and reactivity and correlate these results with the geometric and electronic structure of the metal atoms on the surface. Often, our aim is to carefully design experiments that isolate the several factors (e.g., ensemble and ligand effects) that control surface chemistry and catalysis on bimetallic and alloy surfaces in order to better understand the importance of each contribution. Some of the highlights and noteworthy accomplishments made during the first period of this grant are given.

  7. CHEMICAL MODELING OF INFRARED DARK CLOUDS: THE ROLE OF SURFACE CHEMISTRY

    SciTech Connect

    Vasyunina, T.; Vasyunin, A. I.; Herbst, Eric; Linz, H.

    2012-06-01

    We simulate the chemistry of infrared dark clouds (IRDCs) with a model in which the physical conditions are homogeneous and time independent. The chemistry is solved as a function of time with three networks: one purely gas phase, one that includes accretion and desorption, and one, the complete gas-grain network, that includes surface chemistry in addition. We compare our results with observed molecular abundances for two representative IRDCs-IRDC013.90-1 and IRDC321.73-1-using the molecular species N{sub 2}H{sup +}, HC{sub 3}N, HNC, HCO{sup +}, HCN, C{sub 2}H, NH{sub 3}, and CS. IRDC013.90-1 is a cold IRDC, with a temperature below 20 K, while IRDC321.73-1 is somewhat warmer, in the range 20-30 K. We find that the complete gas-grain model fits the data very well, but that the goodness of fit is not sharply peaked at a particular temperature. Surface processes are important for the explanation of the high gas-phase abundance of N{sub 2}H{sup +} in IRDC321.73-1. The general success of the zero-dimensional model in reproducing single-dish observations of our limited sample of eight species shows that it is probably sufficient for an explanation of this type of data. To build and justify more complicated models, including spatial temperature and density structure, contraction, and heating, we require high-resolution interferometric data.

  8. Comparative Experimental Investigation of Titan's Atmospheric Chemistry Driven by Solar EUV Radiation and Energetic Electron Precipitation

    NASA Astrophysics Data System (ADS)

    Imanaka, Hiroshi; Lavvas, P.; Yelle, R. V.; Smith, M. A.

    2010-10-01

    The observations by the Cassini Ion Neutral Mass Spectrometer (INMS) and the Cassini Plasma Spectrometer (CAPS) clearly demonstrate the importance of complex organic chemistry in the upper atmosphere of Titan; a complex coupling of neutral and ion chemistry for organic aerosol generation induced by EUV photons and Saturn's magnetospheric charged particles. To understand the dominant energy source for aerosol formation and its formation chemistry, we comparatively investigate the chemical mechanism in N2/CH4 gas mixtures resulting from EUV-VUV synchrotron radiation (50-150 nm) and tunable mono-energetic electron beam irradiation (5 eV - 2000 eV). These excitation energy sources cover the dominant energy source available in Titan's upper atmosphere. Our previous study of the EUV-VUV photolysis of N2/CH4 gas mixtures revealed the unique role of nitrogen photoionization in the catalytic formation of complex hydrocarbons and in the major nitrogen fixation process in Titan's upper atmosphere (Imanaka and Smith, 2007, 2009, 2010). However, relative roles of ion-molecule reactions and radical/neutral reactions in such complex chemistry remain to be determined. We characterized the electron energy distribution by conducting the Langmuir probe measurements. Degradation of the primary photoelectron from N2 photoionization at 20.6 eV photons is clearly observed, and the electron density rapidly decreases down to 109-10 cm-3, which suggests the complex coupling of ion-molecular reactions and dissociative ion-electron recombination reactions for the observed development of complex organic molecules. The electron beam irradiation experiments at energy larger than 200 eV shows distinct gaseous product distribution with nitrogenated gaseous species from those with EUV irradiation products. The generation of secondary electrons and multiple inelastic collisions of fast electrons might increases the nitrogen fixation efficiency. The much less stringent spin selection rules could

  9. Investigating the Impact of Adding an Environmental Focus to a Developmental Chemistry Course

    ERIC Educational Resources Information Center

    Robelia, Beth; McNeill, Kristopher; Wammer, Kristine; Lawrenz, Frances

    2010-01-01

    This study explores how adding environmental perspectives to a developmental chemistry course affected student learning of both general chemistry and environmental chemistry concepts. In addition to measuring learning changes, changes in students' environmental attitudes and behaviors were also measured. A pretest-posttest design measured…

  10. Gene expression profiling and mechanism study of neural stem cells response to surface chemistry

    PubMed Central

    Wang, Ying; Yao, Shenglian; Meng, Qingyuan; Yu, Xiaolong; Wang, Xiumei; Cui, Fuzhai

    2014-01-01

    To declare the mechanisms of neural stem cells (NSCs) in response to material surface chemistry, NSCs were exposed to the self-assemble monolayers of alkanethiolates on gold surfaces terminated with amine (NH2), hydroxyl (OH) and methyl (CH3) for analysis. The morphological responses of NSCs were recorded; the gene expression profilings were detected by genechips; the gene expressions data of NSCs responded to different chemical groups were declared through the gene ontology term and pathway analyses. It showed that cells behaved dissimilar on the three chemical groups, the adhesion, proliferation and migration were easier on the NH2 and OH groups; the gene expressions of NSCs were induced differently, either, involved in several functional processes and signaling pathways. CH3 group induced genes enriched much in chemistry reactions and death processes, whereas many genes of cellular nucleotide metabolism were down-regulated. NH2 group induced NSCs to express many genes of receptors on membrane, and participated in cellular signal transduction of cell adhesion and interactions, or associated with axon growth. OH group was similar to NH2 group to induce the membrane response, but it also down regulated metabolism of cells. Therefore, it declared the chemical groups affected NSCs through inner way and the NH2, OH and CH3 groups triggered the cellular gene expression in different signaling pathways. PMID:26816623

  11. Thermal chemistry of the Cu-KI5 atomic layer deposition precursor on a copper surface

    SciTech Connect

    Ma, Qiang; Zaera, Francisco

    2015-01-01

    The thermal chemistry of a Cu(I) ketoiminate complex, Cu-KI5, resulting from the modification of the known Air Products CupraSelect{sup ®} copper CVD precursor Cu(hfac)(tmvs) designed to tether the two ligands via an isopropoxide linker, was studied under ultrahigh vacuum on a Cu(110) single-crystal surface by using a combination of temperature programmed desorption (TPD) and x-ray photoelectron spectroscopy. Adsorption at low temperatures was determined to take place via the displacement of the vinyl ligand by the surface. Molecular desorption was seen at 210 K, and the evolution of Cu(II)-KI5{sub 2} was established to take place at 280 K, presumably from a disproportionation reaction that also leads to the deposition of Cu(0). Other sets of desorption products were seen at 150, 250, and 430 K, all containing copper atoms and small organic moieties with molecular masses below 100 amu. The latter TPD peak in particular indicates significant fragmentation of the ligands, likely at the C–N bond that holds the vinylsilane-isopropoxide moiety tethered to the ketoimine fragment, and possibly also at the union between the vinylsilane and the alkoxide linker. The 430 K temperature measured for this chemistry may set an upper limit for clean Cu film deposition, but since reactivity on the surface was also found to be inhibited at higher surface coverages, it may be delayed to higher temperatures under atomic layer deposition conditions.

  12. Stability of carbon fiber surface chemistry under temperature and its influence on interfacial adhesion with polymer matrices

    SciTech Connect

    Vautard, Frederic; Grappe, Hippolyte A; Ozcan, Soydan

    2013-01-01

    The thermal stability of the surface chemistry of a surface treated carbon fiber was investigated by X-ray Photoelectron Spectroscopy. Within a range of temperatures from room temperature to 400 C, the only surface functionalities that decomposed were carboxylic acids and dangling nitrogen containing functionalities like amines, amides or nitriles. Significant amounts of water were desorbed as well. This study enabled the testing of the coherence our the fitting of the C(1s), O(1s) and N(1s) peaks. Particularly, when considering the fitting of in the O(1s) peak, carboxylic acids were shown to be included in a single component peak centered at a binding energy of 532.1 eV. The reaction of the carbon fiber surface and an acrylate resin at high temperature, because of the decomposition of carboxylic acids, was highlighted by Differential Scanning Calorimetry. The thermal history of the composite material during its manufacture appeared to be a major influence on the nature of the interactions generated at the fiber-matrix interface and the resulting mechanical properties.

  13. Osteoinductive activity of insulin-functionalized cell culture surfaces obtained using diazonium chemistry

    NASA Astrophysics Data System (ADS)

    Mikulska, Anna; Filipowska, Joanna; Osyczka, Anna; Nowakowska, Maria; Szczubiałka, Krzysztof

    2014-12-01

    Polymeric surfaces suitable for cell culture (DR/Pec) were constructed from diazoresin (DR) and pectin (Pec) in a form of ultrathin films using the layer-by-layer (LbL) technique. The surfaces were functionalized with insulin using diazonium chemistry. Such functionalized surfaces were used to culture human mesenchymal stem cells (hMSCs) to assess their suitability for bone tissue engineering and regeneration. The activity of insulin immobilized on the surfaces (DR/Pec/Ins) was compared to that of insulin dissolved in the culture medium. Human MSC grown on insulin-immobilized DR/Pec surfaces displayed increased proliferation and higher osteogenic activity. The latter was determined by means of alkaline phosphatase (ALP) activity, which increases at early stages of osteoblasts differentiation. Insulin dissolved in the culture medium did not stimulate cell proliferation and its osteogenic activity was significantly lower. Addition of recombinant human bone morphogenetic protein 2 (rhBMP-2) to the culture medium further increased ALP activity in hMSCs indicating additive osteogenic action of immobilized insulin and rhBMP-2

  14. Osteoinductive activity of insulin-functionalized cell culture surfaces obtained using diazonium chemistry

    PubMed Central

    Mikulska, Anna; Filipowska, Joanna; Osyczka, Anna M.; Nowakowska, Maria; Szczubiałka, Krzysztof

    2015-01-01

    Polymeric surfaces suitable for cell culture (DR/Pec) were constructed from diazoresin (DR) and pectin (Pec) in a form of ultrathin films using the layer-by-layer (LbL) technique. The surfaces were functionalized with insulin using diazonium chemistry. Such functionalized surfaces were used to culture human mesenchymal stem cells (hMSCs) to assess their suitability for bone tissue engineering and regeneration. The activity of insulin immobilized on the surfaces (DR/Pec/Ins) was compared to that of insulin dissolved in the culture medium. Human MSC grown on insulin-immobilized DR/Pec surfaces displayed increased proliferation and higher osteogenic activity. The latter was determined by means of alkaline phosphatase (ALP) activity, which increases at early stages of osteoblasts differentiation. Insulin dissolved in the culture medium did not stimulate cell proliferation and its osteogenic activity was significantly lower. Addition of recombinant human bone morphogenetic protein 2 (rhBMP-2) to the culture medium further increased ALP activity in hMSCs indicating additive osteogenic action of immobilized insulin and rhBMP-2. PMID:25629028

  15. MIR station atmospheric chemistry investigations: numerical simulation of the future space experiments

    NASA Astrophysics Data System (ADS)

    Timofeyev, Yuriy M.

    1995-12-01

    Regular, long-term, g1obalscale measurements of atmospheric minor gaseous and aerosol composition (MGAC) by means ofdifferent instruments (PHOENIX, OZONE-MIR, ISTOK-1, DOPI) are planned on board the SPECTR and PRIRODA modules of the Space Station MIR during 1995-1998. The main characteristics of these devices are given. The principal goals of the space experiments are: investigations of the spatial and temporal MGAC variations, comparisons of different space-borne atmospheric chemistry sensors and their intercalibration, validation of the space MGAC measurements using different ground-based station and aircraft data, and studies of the molecular absorption in the atmosphere aimed to enhance an accuracy of radiative transfer atmospheric models. Special attention is . devoted to radiative transfer model (line-mixing, line-shift, line-narrowing, Non-LTE effects). The numerical estimations of the errors of the MGAC vertical profile retrievals using different device data are carried out.

  16. Characterizing Surface Acidic Sites in Mesoporous-Silica-Supported Tungsten Oxide Catalysts Using Solid State NMR and Quantum Chemistry Calculations

    SciTech Connect

    Hu, Jian Z.; Kwak, Ja Hun; Wang, Yong; Hu, Mary Y.; Turcu, Romulus VF; Peden, Charles HF

    2011-10-18

    The acidic sites in dispersed tungsten oxide supported on SBA-15 mesoporous silica were investigated using a combination of pyridine titration, both fast-, and slow-MAS {sup 15}N NMR, static {sup 2}H NMR, and quantum chemistry calculations. It is found that the bridged acidic -OH groups in surface adsorbed tungsten dimers (i.e., W-OH-W) are the Broensted acid sites. The unusually strong acidity of these Broensted acid sites is confirmed by quantum chemistry calculations. In contrast, terminal W-OH sites are very stable and only weakly acidic as are terminal Si-OH sites. Furthermore, molecular interactions between pyridine molecules and the dimer Broensted and terminal W-OH sites for dispersed tungsten oxide species is strong. This results in restricted molecular motion for the interacting pyridine molecules even at room temperature, i.e., a reorientation mainly about the molecular 2-fold axis. This restricted reorientation makes it possible to estimate the relative ratio of the Broensted (tungsten dimer) to the weakly acidic terminal W-OH sites in the catalyst using the slow-MAS {sup 1}H-{sup 15}N CP PASS method.

  17. Patterned porous silicon photonic crystals with modular surface chemistry for spatial control of neural stem cell differentiation.

    PubMed

    Huang, Tiffany H; Pei, Yi; Zhang, Douglas; Li, Yanfen; Kilian, Kristopher A

    2016-06-01

    We present a strategy to spatially define regions of gold and nanostructured silicon photonics, each with materials-specific surface chemistry, for azide-alkyne cycloaddition of different bioactive peptides. Neural stem cells are spatially directed to undergo neurogenesis and astrogenesis as a function of both surface properties and peptide identity. PMID:27173986

  18. Using a Dialogical Approach to Examine Peer Feedback During Chemistry Investigative Task Discussion

    NASA Astrophysics Data System (ADS)

    Gan Joo Seng, Mark; Hill, Mary

    2014-10-01

    Peer feedback is an inherent feature of classroom collaborative learning. Students invariably turn to their peers for feedback when carrying out an investigative task, and this feedback is usually implicit, unstructured and may positively or negatively influence students' learning when they work on a task. This study explored the characteristics of verbal peer feedback during a collaborative investigative chemistry task involving New Zealand Year 13 students. During the planning stage of the students' investigation, the discussions of five pairs of students were recorded and then transcribed. Analysis of transcribed verbal data focused on interactions that involved peer feedback along two dimensions, interactive/non-interactive and dialogic/authoritative (Mortimer and Scott, 2003). The findings indicated that although students adopted a predominantly interactive/authoritative communicative approach, with peer feedback as confirmation or evaluation, they are also capable of a more interactive/dialogic exchange, characterised by elaborative peer feedback. We discuss how this dialogic perspective on peer feedback provides an alternative approach to the analysis and study of student-student interactions during science investigations. The findings should be interpreted in light of the limitations in terms of sample size, grouping and specificity of the coding scheme. Implications for teacher practice are discussed in relation to facilitating peer feedback discourse in the science classroom.

  19. Investigation of the effect of chemistry models on the numerical predictions of the supersonic combustion of hydrogen

    SciTech Connect

    Kumaran, K.; Babu, V.

    2009-04-15

    In this numerical study, the influence of chemistry models on the predictions of supersonic combustion in a model combustor is investigated. To this end, 3D, compressible, turbulent, reacting flow calculations with a detailed chemistry model (with 37 reactions and 9 species) and the Spalart-Allmaras turbulence model have been carried out. These results are compared with earlier results obtained using single step chemistry. Hydrogen is used as the fuel and three fuel injection schemes, namely, strut, staged (i.e., strut and wall) and wall injection, are considered to evaluate the impact of the chemistry models on the flow field predictions. Predictions of the mass fractions of major species, minor species, dimensionless stagnation temperature, dimensionless static pressure rise and thrust percentage along the combustor length are presented and discussed. Overall performance metrics such as mixing efficiency and combustion efficiency are used to draw inferences on the nature (whether mixing- or kinetic-controlled) and the completeness of the combustion process. The predicted values of the dimensionless wall static pressure are compared with experimental data reported in the literature. The calculations show that multi step chemistry predicts higher and more wide spread heat release than what is predicted by single step chemistry. In addition, it is also shown that multi step chemistry predicts intricate details of the combustion process such as the ignition distance and induction distance. (author)

  20. Hot-electron-mediated surface chemistry: toward electronic control of catalytic activity.

    PubMed

    Park, Jeong Young; Kim, Sun Mi; Lee, Hyosun; Nedrygailov, Ievgen I

    2015-08-18

    Energy dissipation at surfaces and interfaces is mediated by excitation of elementary processes, including phonons and electronic excitation, once external energy is deposited to the surface during exothermic chemical processes. Nonadiabatic electronic excitation in exothermic catalytic reactions results in the flow of energetic electrons with an energy of 1-3 eV when chemical energy is converted to electron flow on a short (femtosecond) time scale before atomic vibration adiabatically dissipates the energy (in picoseconds). These energetic electrons that are not in thermal equilibrium with the metal atoms are called "hot electrons". The detection of hot electron flow under atomic or molecular processes and understanding its role in chemical reactions have been major topics in surface chemistry. Recent studies have demonstrated electronic excitation produced during atomic or molecular processes on surfaces, and the influence of hot electrons on atomic and molecular processes. We outline research efforts aimed at identification of the intrinsic relation between the flow of hot electrons and catalytic reactions. We show various strategies for detection and use of hot electrons generated by the energy dissipation processes in surface chemical reactions and photon absorption. A Schottky barrier localized at the metal-oxide interface of either catalytic nanodiodes or hybrid nanocatalysts allows hot electrons to irreversibly transport through the interface. We show that the chemicurrent, composed of hot electrons excited by the surface reaction of CO oxidation or hydrogen oxidation, correlates well with the turnover rate measured separately by gas chromatography. Furthermore, we show that hot electron flows generated on a gold thin film by photon absorption (or internal photoemission) can be amplified by localized surface plasmon resonance. The influence of hot charge carriers on the chemistry at the metal-oxide interface are discussed for the cases of Au, Ag, and Pt

  1. Untangling the Chemical Evolution of Titan's Atmosphere and Surface -- From Homogeneous to Heterogeneous Chemistry

    SciTech Connect

    Kaiser, Ralf I.; Maksyutenko, Pavlo; Ennis, Courtney; Zhang, Fangtong; Gu, Xibin; Krishtal, Sergey P.; Mebel, Alexander M.; Kostko, Oleg; Ahmed, Musahid

    2010-03-16

    The arrival of the Cassini-Huygens probe at Saturn's moon Titan - the only Solar System body besides Earth and Venus with a solid surface and a thick atmosphere with a pressure of 1.4 atm at surface level - in 2004 opened up a new chapter in the history of Solar System exploration. The mission revealed Titan as a world with striking Earth-like landscapes involving hydrocarbon lakes and seas as well as sand dunes and lava-like features interspersed with craters and icy mountains of hitherto unknown chemical composition. The discovery of a dynamic atmosphere and active weather system illustrates further the similarities between Titan and Earth. The aerosol-based haze layers, which give Titan its orange-brownish color, are not only Titan's most prominent optically visible features, but also play a crucial role in determining Titan's thermal structure and chemistry. These smog-like haze layers are thought to be very similar to those that were present in Earth's atmosphere before life developed more than 3.8 billion years ago, absorbing the destructive ultraviolet radiation from the Sun, thus acting as 'prebiotic ozone' to preserve astrobiologically important molecules on Titan. Compared to Earth, Titan's low surface temperature of 94 K and the absence of liquid water preclude the evolution of biological chemistry as we know it. Exactly because of these low temperatures, Titan provides us with a unique prebiotic 'atmospheric laboratory' yielding vital clues - at the frozen stage - on the likely chemical composition of the atmosphere of the primitive Earth. However, the underlying chemical processes, which initiate the haze formation from simple molecules, have been not understood well to date.

  2. Surface Chemistry of Nanoscale Mineralized Collagen Regulates Periodontal Ligament Stem Cell Fate.

    PubMed

    Fu, Yu; Liu, Shuai; Cui, Sheng-Jie; Kou, Xiao-Xing; Wang, Xue-Dong; Liu, Xiao-Mo; Sun, Yue; Wang, Gao-Nan; Liu, Yan; Zhou, Yan-Heng

    2016-06-29

    The interplay between stem cells and their extracellular microenvironment is of critical importance to the stem cell-based therapeutics in regenerative medicine. Mineralized collagen is the main component of bone extracellular matrix, but the effect of interfacial properties of mineralized collagen on subsequent cellular behaviors is unclear. This study examined the role of surface chemistry of nanoscale mineralized collagen on human periodontal ligament stem cell (hPDLSC) fate decisions. The intrafibrillarly mineralized collagen (IMC), fabricated by a biomimetic bottom-up approach, showed a bonelike hierarchy with nanohydroxyapatites (HAs) periodically embedded within fibrils. The infrared spectrum of the IMC showed the presence of phosphate, carbonate, amide I and II bands; and infrared mapping displayed uniform and higher spatial distribution of mineralization in the IMC. However, the distribution of the phosphate group differed far from that of the amide I group in the extrafibrillarly mineralized collagen (EMC), in which flowerlike HA clusters randomly depositing around the surface of the fibrils. Moreover, a large quantity of extrafibrillar HAs covered up the C═O stretch and N-H in-plane bend, resulting in substantial reduction of amide I and II bands. Cell experiments demonstrated that the hPDLSCs seeded on the IMC exhibited a highly branched, osteoblast-like polygonal shape with extended pseudopodia and thick stress fiber formation; while cells on the EMC displayed a spindle shape with less branch points and thin actin fibril formation. Furthermore, the biocompatibility of EMC was much lower than that of IMC. Interestingly, even without osteogenic induction, mRNA levels of major osteogenic differentiation genes were highly expressed in the IMC during cultivation time. These data suggest that the IMC with a similar nanotopography and surface chemistry to natural mineralized collagen directs hPDLSCs toward osteoblast differentiation, providing a promising

  3. Formation of host-guest complexes on gold surface investigated by surface-enhanced IR absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Inokuchi, Yoshiya; Mizuuchi, Takahiro; Ebata, Takayuki; Ikeda, Toshiaki; Haino, Takeharu; Kimura, Tetsunari; Guo, Hao; Furutani, Yuji

    2014-01-01

    We apply surface-enhanced infrared absorption (SEIRA) spectroscopy to host-guest complexes in liquid phase to examine the structural change in the complex formation. Two thiol derivatives of 18-crown-6 (18C6) are chemisorbed on a gold surface, and aqueous solutions of MCl salts (M = Li, Na, K, Rb, and Cs) are put to form M+·18C6 complexes. Infrared spectra of these complexes in the 900-2000 cm-1 region are obtained by SEIRA spectroscopy. The observed IR spectra show noticeable peaks due to the complex formation, demonstrating that SEIRA spectroscopy will be a powerful method to investigate the structure of host-guest complexes in supramolecular chemistry.

  4. SURFACE CHEMISTRY INFLUENCE CANCER KILLING EFFECT OF TiO2 NANOPARTICLES

    PubMed Central

    Thevenot, Paul; Cho, Jai; Wavhal, Dattatray; Timmons, Richard B.; Tang, Liping

    2008-01-01

    Photocatalyzed TiO2 nanoparticles have been shown to eradicate cancer cells. However the required in situ introduction of UV light limits the use of such a therapy in patients. In the present study, the non-photocatalyic anti-cancer effect of surface functionalized TiO2 was examined. Nanoparticles bearing -OH, -NH2, or –COOH surface groups, were tested for their effect on in vitro survival of several cancer and control cell lines. The cells tested included B16F10 melanoma, Lewis lung carcinoma (LLC), JHU prostate cancer cells, and 3T3 fibroblasts. Cell viability was observed to depend on particle concentrations, cell types, and surface chemistry. Specifically, -NH2 and -OH groups exhibited significantly higher toxicity than -COOH. Microscopic and spectrophotometric studies revealed nanoparticle-mediated cell membrane disruption leading to cell death. The results suggest that functionalized TiO2, and presumably other nanoparticles, may be surface engineered for targeted cancer therapy. PMID:18502186

  5. The Influence of Surface Topography and Surface Chemistry on the Anti-Adhesive Performance of Nanoporous Monoliths.

    PubMed

    Eichler-Volf, Anna; Xue, Longjian; Dornberg, Gregor; Chen, He; Kovalev, Alexander; Enke, Dirk; Wang, Yong; Gorb, Elena V; Gorb, Stanislav N; Steinhart, Martin

    2016-08-31

    We designed spongy monoliths allowing liquid delivery to their surfaces through continuous nanopore systems (mean pore diameter ∼40 nm). These nanoporous monoliths were flat or patterned with microspherical structures a few tens of microns in diameter, and their surfaces consisted of aprotic polymer or of TiO2 coatings. Liquid may reduce adhesion forces FAd; possible reasons include screening of solid-solid interactions and poroelastic effects. Softening-induced deformation of flat polymeric monoliths upon contact formation in the presence of liquids enhanced the work of separation WSe. On flat TiO2-coated monoliths, WSe was smaller under wet conditions than under dry conditions, possibly because of liquid-induced screening of solid-solid interactions. Under dry conditions, WSe is larger on flat TiO2-coated monoliths than on flat monoliths with a polymeric surface. However, under wet conditions, liquid-induced softening results in larger WSe on flat monoliths with a polymeric surface than on flat monoliths with an oxidic surface. Monolithic microsphere arrays show antiadhesive properties; FAd and WSe are reduced by at least 1 order of magnitude as compared to flat nanoporous counterparts. On nanoporous monolithic microsphere arrays, capillarity (WSe is larger under wet than under dry conditions) and solid-solid interactions (WSe is larger on oxide than on polymer) dominate contact mechanics. Thus, the microsphere topography reduces the impact of softening-induced surface deformation and screening of solid-solid interactions associated with liquid supply. Overall, simple modifications of surface topography and chemistry combined with delivery of liquid to the contact interface allow adjusting WSe and FAd over at least 1 order of magnitude. Adhesion management with spongy monoliths exploiting deployment (or drainage) of interfacial liquids as well as induction or prevention of liquid-induced softening of the monoliths may pave the way for the design of artificial

  6. Chemistry in disks. IV. Benchmarking gas-grain chemical models with surface reactions

    NASA Astrophysics Data System (ADS)

    Semenov, D.; Hersant, F.; Wakelam, V.; Dutrey, A.; Chapillon, E.; Guilloteau, St.; Henning, Th.; Launhardt, R.; Piétu, V.; Schreyer, K.

    2010-11-01

    Context. We describe and benchmark two sophisticated chemical models developed by the Heidelberg and Bordeaux astrochemistry groups. Aims: The main goal of this study is to elaborate on a few well-described tests for state-of-the-art astrochemical codes covering a range of physical conditions and chemical processes, in particular those aimed at constraining current and future interferometric observations of protoplanetary disks. Methods: We considered three physical models: a cold molecular cloud core, a hot core, and an outer region of a T Tauri disk. Our chemical network (for both models) is based on the original gas-phase osu_03_2008 ratefile and includes gas-grain interactions and a set of surface reactions for the H-, O-, C-, S-, and N-bearing molecules. The benchmarking was performed with the increasing complexity of the considered processes: (1) the pure gas-phase chemistry, (2) the gas-phase chemistry with accretion and desorption, and (3) the full gas-grain model with surface reactions. The chemical evolution is modeled within 109 years using atomic initial abundances with heavily depleted metals and hydrogen in its molecular form. Results: The time-dependent abundances calculated with the two chemical models are essentially the same for all considered physical cases and for all species, including the most complex polyatomic ions and organic molecules. This result, however, required a lot of effort to make all necessary details consistent through the model runs, e.g., definition of the gas particle density, density of grain surface sites, or the strength and shape of the UV radiation field. Conclusions: The reference models and the benchmark setup, along with the two chemical codes and resulting time-dependent abundances are made publicly available on the internet. This will facilitate and ease the development of other astrochemical models and provide nonspecialists with a detailed description of the model ingredients and requirements to analyze the cosmic

  7. An Ab Initio Approach Towards Engineering Fischer-Tropsch Surface Chemistry

    SciTech Connect

    Matthew Neurock

    2006-09-11

    One of the greatest societal challenges over the next decade is the production of cheap, renewable energy for the 10 billion people that inhabit the earth. This will require the development of various energy sources which will likely include fuels derived from methane, coal, and biomass and alternatives sources such as solar, wind and nuclear energy. One approach will be to synthesize gasoline and other fuels from simpler hydrocarbons such as CO derived from methane or other U.S. based sources such as coal. Syngas (CO and H{sub 2}) can be readily converted into higher molecular weight hydrocarbons through Fischer-Tropsch synthesis. Fischer-Tropsch (FT) synthesis involves the adsorption and the activation of CO and H{sub 2}, the subsequent propagation steps including hydrogenation and carbon-carbon coupling, followed by chain termination reactions. The current commercial catalysts are supported Co and Co-alloys particles. This project set out with the following objectives in mind: (1) understand the reaction mechanisms that control FT kinetics, (2) predict how the intrinsic metal-adsorbate bond affects the sequence of elementary steps in FT, (3) establish the effects of the reaction environment on catalytic activity and selectivity, (4) construct a first-principles based algorithm that can incorporate the detailed atomic surface structure and simulate the kinetics for the myriad of elementary pathways that make up FT chemistry, and (5) suggest a set of optimal features such as alloy composition and spatial configuration, oxide support, distribution of defect sites. As part of this effort we devoted a significant portion of time to develop an ab initio based kinetic Monte Carlo simulation which can be used to follow FT surface chemistry over different transition metal and alloy surfaces defined by the user. Over the life of this program, we have used theory and have developed and applied stochastic Monte Carlo simulations in order to establish the fundamental

  8. Surface chemistry of InP ridge structures etched in Cl{sub 2}-based plasma analyzed with angular XPS

    SciTech Connect

    Bouchoule, Sophie Cambril, Edmond; Guilet, Stephane; Chanson, Romain; Pageau, Arnaud; Rhallabi, Ahmed; Cardinaud, Christophe

    2015-09-15

    Two x-ray photoelectron spectroscopy configurations are proposed to analyze the surface chemistry of micron-scale InP ridge structures etched in chlorine-based inductively coupled plasma (ICP). Either a classical or a grazing configuration allows to retrieve information about the surface chemistry of the bottom surface and sidewalls of the etched features. The procedure is used to study the stoichiometry of the etched surface as a function of ridge aspect ratio for Cl{sub 2}/Ar and Cl{sub 2}/H{sub 2} plasma chemistries. The results show that the bottom surface and the etched sidewalls are P-rich, and indicate that the P-enrichment mechanism is rather chemically driven. Results also evidence that adding H{sub 2} to Cl{sub 2} does not necessarily leads to a more balanced surface stoichiometry. This is in contrast with recent experimental results obtained with the HBr ICP chemistry for which fairly stoichiometric surfaces have been obtained.

  9. Aqueous reactive species induced by a surface air discharge: Heterogeneous mass transfer and liquid chemistry pathways

    NASA Astrophysics Data System (ADS)

    Liu, D. X.; Liu, Z. C.; Chen, C.; Yang, A. J.; Li, D.; Rong, M. Z.; Chen, H. L.; Kong, M. G.

    2016-04-01

    Plasma-liquid interaction is a critical area of plasma science and a knowledge bottleneck for many promising applications. In this paper, the interaction between a surface air discharge and its downstream sample of deionized water is studied with a system-level computational model, which has previously reached good agreement with experimental results. Our computational results reveal that the plasma-induced aqueous species are mainly H+, nitrate, nitrite, H2O2 and O3. In addition, various short-lived aqueous species are also induced, regardless whether they are generated in the gas phase first. The production/loss pathways for aqueous species are quantified for an air gap width ranging from 0.1 to 2 cm, of which heterogeneous mass transfer and liquid chemistry are found to play a dominant role. The short-lived reactive oxygen species (ROS) and reactive nitrogen species (RNS) are strongly coupled in liquid-phase reactions: NO3 is an important precursor for short-lived ROS, and in turn OH, O2‑ and HO2 play a crucial role for the production of short-lived RNS. Also, heterogeneous mass transfer depends strongly on the air gap width, resulting in two distinct scenarios separated by a critical air gap of 0.5 cm. The liquid chemistry is significantly different in these two scenarios.

  10. Aqueous reactive species induced by a surface air discharge: Heterogeneous mass transfer and liquid chemistry pathways.

    PubMed

    Liu, D X; Liu, Z C; Chen, C; Yang, A J; Li, D; Rong, M Z; Chen, H L; Kong, M G

    2016-01-01

    Plasma-liquid interaction is a critical area of plasma science and a knowledge bottleneck for many promising applications. In this paper, the interaction between a surface air discharge and its downstream sample of deionized water is studied with a system-level computational model, which has previously reached good agreement with experimental results. Our computational results reveal that the plasma-induced aqueous species are mainly H(+), nitrate, nitrite, H2O2 and O3. In addition, various short-lived aqueous species are also induced, regardless whether they are generated in the gas phase first. The production/loss pathways for aqueous species are quantified for an air gap width ranging from 0.1 to 2 cm, of which heterogeneous mass transfer and liquid chemistry are found to play a dominant role. The short-lived reactive oxygen species (ROS) and reactive nitrogen species (RNS) are strongly coupled in liquid-phase reactions: NO3 is an important precursor for short-lived ROS, and in turn OH, O2(-) and HO2 play a crucial role for the production of short-lived RNS. Also, heterogeneous mass transfer depends strongly on the air gap width, resulting in two distinct scenarios separated by a critical air gap of 0.5 cm. The liquid chemistry is significantly different in these two scenarios. PMID:27033381

  11. Aqueous reactive species induced by a surface air discharge: Heterogeneous mass transfer and liquid chemistry pathways

    PubMed Central

    Liu, D. X.; Liu, Z. C.; Chen, C.; Yang, A. J.; Li, D.; Rong, M. Z.; Chen, H. L.; Kong, M. G.

    2016-01-01

    Plasma-liquid interaction is a critical area of plasma science and a knowledge bottleneck for many promising applications. In this paper, the interaction between a surface air discharge and its downstream sample of deionized water is studied with a system-level computational model, which has previously reached good agreement with experimental results. Our computational results reveal that the plasma-induced aqueous species are mainly H+, nitrate, nitrite, H2O2 and O3. In addition, various short-lived aqueous species are also induced, regardless whether they are generated in the gas phase first. The production/loss pathways for aqueous species are quantified for an air gap width ranging from 0.1 to 2 cm, of which heterogeneous mass transfer and liquid chemistry are found to play a dominant role. The short-lived reactive oxygen species (ROS) and reactive nitrogen species (RNS) are strongly coupled in liquid-phase reactions: NO3 is an important precursor for short-lived ROS, and in turn OH, O2− and HO2 play a crucial role for the production of short-lived RNS. Also, heterogeneous mass transfer depends strongly on the air gap width, resulting in two distinct scenarios separated by a critical air gap of 0.5 cm. The liquid chemistry is significantly different in these two scenarios. PMID:27033381

  12. A theoretical investigation of the (0001) covellite surfaces.

    PubMed

    Gaspari, Roberto; Manna, Liberato; Cavalli, Andrea

    2014-07-28

    We report on the properties of the (0001) covellites surfaces, which we investigate by periodic slab density functional theory calculations. The absolute surface energies have been computed for all bulk terminations, showing that surfaces terminated by the flat CuS layer are associated with the lowest surface energy. Cleavage is predicted to occur across the [0001] interlayer Cu-S bond. The surfaces obtained by lowest energy cleavage are analyzed in terms of the atomic vertical relaxation, workfunction, and surface band structure. Our study predicts the presence of a shallow pz-derived surface state located 0.26 eV below the Fermi level, which is set to play an important role in the surface reactivity of covellite. PMID:25084932

  13. A theoretical investigation of the (0001) covellite surfaces

    SciTech Connect

    Gaspari, Roberto; Manna, Liberato; Cavalli, Andrea

    2014-07-28

    We report on the properties of the (0001) covellites surfaces, which we investigate by periodic slab density functional theory calculations. The absolute surface energies have been computed for all bulk terminations, showing that surfaces terminated by the flat CuS layer are associated with the lowest surface energy. Cleavage is predicted to occur across the [0001] interlayer Cu–S bond. The surfaces obtained by lowest energy cleavage are analyzed in terms of the atomic vertical relaxation, workfunction, and surface band structure. Our study predicts the presence of a shallow p{sub z}-derived surface state located 0.26 eV below the Fermi level, which is set to play an important role in the surface reactivity of covellite.

  14. New insights into the chemistry of imidodiphosphinates from investigations of tellurium-centered systems.

    PubMed

    Chivers, Tristram; Ritch, Jamie S; Robertson, Stuart D; Konu, Jari; Tuononen, Heikki M

    2010-08-17

    Dichalcogenido-imidodiphosphinates, [N(PR(2)E)(2)](-) (R = alkyl, aryl), are chelating ligands that readily form cyclic complexes with main group metals, transition metals, lanthanides, and actinides. Since their discovery in the early 1960s, researchers have studied the structural chemistry of the resulting metal complexes (where E = O, S, Se) extensively and identified a variety of potential applications, including as NMR shift reagents, luminescent complexes in photonic devices, or single-source precursors for metal sulfides or selenides. In 2002, a suitable synthesis of the tellurium analogs [N(PR(2)Te)(2)](-) was developed. In this Account, we describe comprehensive investigations of the chemistry of these tellurium-centered anions, and related mixed chalcogen systems, which have revealed unanticipated features of their fundamental structure and reactivity. An exhaustive examination of previously unrecognized redox behavior has uncovered a variety of novel dimeric arrangements of these ligands, as well as an extensive series of cyclic cations. In combination with calculations using density functional theory, these new structural frameworks have provided new insights into the nature of chalcogen-chalcogen bonding. Studies of metal complexes of the ditellurido ligands [N(PR(2)Te)(2)](-) have revealed unprecedented structural and reaction chemistry. The large tellurium donor sites confer greater flexibility, which can lead to unique structures in which the tellurium-centered ligand bridges two metal centers. The relatively weak P-Te bonds facilitate metal-insertion reactions (intramolecular oxidative-addition) to give new metal-tellurium ring systems for some group 11 and 13 metals. Metal tellurides have potential applications as low band gap semiconductor materials in solar cells, thermoelectric devices, and in telecommunications. Practically, some of these telluride ligands could be applied in these industries. For example, certain metal complexes of the

  15. High school students' enactment of chemistry knowing in open-entry laboratory investigations

    NASA Astrophysics Data System (ADS)

    Pilane, Sentsetsa M.

    2003-10-01

    This study is an exploration of student meaning making in a non-traditional, high activity, hands-on grade 12 high school chemistry setting. The study focused on a sequence of three "open-entry" laboratory investigations (i.e., iodine clock reaction, pop-can cell and electroplating). These open-entry laboratory investigations were designed to be flexible and to take place in settings where students could make an impact. Students were responsible for devising their own problem and entry strategy, for making decisions about what reagents to use, what variables to manipulate, and how to proceed to develop the problem to a resolution acceptable to them and to the teacher. To explore students' meaning making in open-entry laboratory settings, their interactions were video taped and samples of their written laboratory reports were collected from time to time. Students were also requested to write reflective notes on their experiences of each investigation, some students were interviewed at the end of the course. This thesis consists of accounts and interpretations of what students did and said as they made meaning in these open-entry, hands-on laboratory investigations. The research uses an enactivist perspective to explore the meanings emerging from the study. From an enactivist view, cognition is seen as perceptually guided action in which a knower brings forth a world of significance with others. Enactivism suggests that students do not only express their knowing in what they say or write but also in their actions with others within this learning community. The research revealed that meaning making in these circumstances was highly complex. It involved systematic trial and error at various levels within the multiple iterative feedback loops. Students' interactions in this setting were mediated by the culture of chemistry which is embodied in the practices of the discipline. With students having to make decisions with every action, their meaning making was not only

  16. Metal plasma immersion ion implantation and deposition (MePIIID) on screw-shaped titanium implant: The effects of ion source, ion dose and acceleration voltage on surface chemistry and morphology.

    PubMed

    Kang, Byung-Soo; Sul, Young-Taeg; Jeong, Yongsoo; Byon, Eungsun; Kim, Jong-Kuk; Cho, Suyeon; Oh, Se-Jung; Albrektsson, Tomas

    2011-07-01

    The present study investigated the effect of metal plasma immersion ion implantation and deposition (MePIIID) process parameters, i.e., plasma sources of magnesium and calcium, ion dose, and acceleration voltage on the surface chemistry and morphology of screw-type titanium implants that have been most widely used for osseointegrated implants. It is found that irrespective of plasma ion source, surface topography and roughness showed no differences at the nanometer level; that atom concentrations increased with ion dose but decreased with acceleration voltage. Data obtained from X-ray photoelectron spectroscopy and auger electron spectroscopy suggested that MePIIID process produces 'intermixed' layer of cathodic arc deposition and plasma immersion ion implantation. The MePIIID process may create desired bioactive surface chemistry of dental and orthopaedic implants by tailoring ion and plasma sources and thus enable investigations of the effect of the surface chemistry on bone response. PMID:21334957

  17. Investigation of Atmospheric Chemistry in the Tropical UTLS with NASA's Global Hawk UAS during ATTREX

    NASA Astrophysics Data System (ADS)

    Stutz, J.; Atlas, E. L.; Cheung, R.; Chipperfield, M.; Colosimo, S. F.; Deutschmann, T.; Daube, B. C.; Gao, R. S.; Elkins, J. W.; Fahey, D. W.; Feng, W.; Hossaini, R.; Navarro, M. A.; Pittman, J. V.; Raecke, R.; Scalone, L.; Spolaor, M.; Tricoli, U.; Thornberry, T. D.; Tsai, J. Y.; Werner, B.; Wofsy, S. C.; Pfeilsticker, K.

    2015-12-01

    Bromine species play an important role in ozone chemistry in the tropical upper troposphere / lower stratosphere (UTLS). The tropical UTLS also serves as a gate to the stratosphere, and the vertical transport of organic and inorganic bromine species is an important source of halogens that impact stratospheric ozone chemistry. An accurate quantification of the sources, sinks, and chemical transformation of bromine species is thus crucial to the understanding of the bromine and ozone budget in the UTLS and the stratosphere. However, the investigation of the composition of the tropical UTLS is challenging, as the altitude of this region of 15 - 20 km requires high-altitude aircraft, or balloons. In recent years a new aircraft has become available to penetrate into this region: NASA's Global Hawk (GH) Unmanned Aircraft System (UAS). The GH has a ceiling altitude of 20 km and a 24h endurance with a full complement of scientific experiments. The GH provides a new and exciting platform that allows unique insights into atmospheric processes in the UTLS. Here we present observations of CH4, BrO, NO2, and ozone made on-board the GH during the 2011, 2013, and 2014 Airborne Tropical TRopopause EXperiment (ATTREX) in the pacific tropical UTLS. We will discuss the details of UV-vis remote sensing measurements of BrO and NO2 by the UCLA/HD limb scanning Differential Optical Absorption Spectroscopy instrument. We also present observations of organic bromine species from the University of Miami's Whole Air Sampler, in-situ ozone measurement by NOAA, and CH4 measurements by the Harvard Picarro instrument and the NOAA UCATS gas chromatograph. Methods to determine vertical trace gas profiles through aircraft maneuvers and by scanning the mini-DOAS telescope in viewing elevation will be discussed. The combination of the observations with calculations using the TOMCAT/SLIMCAT 3-D model allows quantification and interpretation of the bromine and ozone budget in the UTLS.

  18. Influence of surface chemistry on the structural organization of monomolecular protein layers adsorbed to functionalized aqueous interfaces.

    PubMed Central

    Lösche, M; Piepenstock, M; Diederich, A; Grünewald, T; Kjaer, K; Vaknin, D

    1993-01-01

    The molecular organization of streptavidin (SA) bound to aqueous surface monolayers of biotin-functionalized lipids and binary lipid mixtures has been investigated with neutron reflectivity and electron and fluorescence microscopy. The substitution of deuterons (2H) for protons (1H), both in subphase water molecules and in the alkyl chains of the lipid surface monolayer, was utilized to determine the interface structure on the molecular length scale. In all cases studied, the protein forms monomolecular layers underneath the interface with thickness values of approximately 40 A. A systematic dependence of the structural properties of such self-assembled SA monolayers on the surface chemistry was observed: the lateral protein density depends on the length of the spacer connecting the biotin moiety and its hydrophobic anchor. The hydration of the lipid head groups in the protein-bound state depends on the dipole moment density at the interface. Images FIGURE 1 FIGURE 2 FIGURE 3 FIGURE 5 FIGURE 11 FIGURE 12 FIGURE A1 PMID:8298041

  19. Surface chemistry but not aspect ratio mediates the biological toxicity of gold nanorods in vitro and in vivo

    PubMed Central

    Wan, Jiali; Wang, Jia-Hong; Liu, Ting; Xie, Zhixiong; Yu, Xue-Feng; Li, Wenhua

    2015-01-01

    Gold nanorods are a promising nanoscale material in clinical diagnosis and treatment. The physicochemical properties of GNRs, including size, shape and surface features, are crucial factors affecting their cytotoxicity. In this study, we investigated the effects of different aspect ratios and surface modifications on the cytotoxicity and cellular uptake of GNRs in cultured cells and in mice. The results indicated that the surface chemistry but not the aspect ratio of GNRs mediates their biological toxicity. CTAB-GNRs with various aspect ratios had similar abilities to induce cell apoptosis and autophagy by damaging mitochondria and activating intracellular reactive oxygen species (ROS). However, GNRs coated with CTAB/PSS, CTAB/PAH, CTAB/PSS/PAH or CTAB/PAH/PSS displayed low toxicity and did not induce cell death. CTAB/PAH-coated GNRs caused minimally abnormal cell morphology compared with CTAB/PSS and CTAB/PSS/PAH coated GNRs. Moreover, the intravenous injection of CTAB/PAH GNRs enabled the GNRs to reach tumor tissues through blood circulation in animals and remained stable, with a longer half-life compared to the other GNRs. Therefore, our results demonstrated that further coating can prevent cytotoxicity and cell death upon CTAB-coated GNR administration, similar to changing the GNR aspect ratio and CTAB/PAH coated GNRs show superior biological properties with better biocompatibility and minimal cytotoxicity. PMID:26096816

  20. Surface chemistry but not aspect ratio mediates the biological toxicity of gold nanorods in vitro and in vivo.

    PubMed

    Wan, Jiali; Wang, Jia-Hong; Liu, Ting; Xie, Zhixiong; Yu, Xue-Feng; Li, Wenhua

    2015-01-01

    Gold nanorods are a promising nanoscale material in clinical diagnosis and treatment. The physicochemical properties of GNRs, including size, shape and surface features, are crucial factors affecting their cytotoxicity. In this study, we investigated the effects of different aspect ratios and surface modifications on the cytotoxicity and cellular uptake of GNRs in cultured cells and in mice. The results indicated that the surface chemistry but not the aspect ratio of GNRs mediates their biological toxicity. CTAB-GNRs with various aspect ratios had similar abilities to induce cell apoptosis and autophagy by damaging mitochondria and activating intracellular reactive oxygen species (ROS). However, GNRs coated with CTAB/PSS, CTAB/PAH, CTAB/PSS/PAH or CTAB/PAH/PSS displayed low toxicity and did not induce cell death. CTAB/PAH-coated GNRs caused minimally abnormal cell morphology compared with CTAB/PSS and CTAB/PSS/PAH coated GNRs. Moreover, the intravenous injection of CTAB/PAH GNRs enabled the GNRs to reach tumor tissues through blood circulation in animals and remained stable, with a longer half-life compared to the other GNRs. Therefore, our results demonstrated that further coating can prevent cytotoxicity and cell death upon CTAB-coated GNR administration, similar to changing the GNR aspect ratio and CTAB/PAH coated GNRs show superior biological properties with better biocompatibility and minimal cytotoxicity. PMID:26096816

  1. Correlation between the surface chemistry and the atmospheric corrosion of AZ31, AZ80 and AZ91D magnesium alloys

    NASA Astrophysics Data System (ADS)

    Feliu, S., Jr.; Pardo, A.; Merino, M. C.; Coy, A. E.; Viejo, F.; Arrabal, R.

    2009-01-01

    X-ray photoelectron spectroscopy (XPS) was used in order to investigate the correlation between the surface chemistry and the atmospheric corrosion of AZ31, AZ80 and AZ91D magnesium alloys exposed to 98% relative humidity at 50 °C. Commercially pure magnesium, used as the reference material, revealed MgO, Mg(OH) 2 and tracers of magnesium carbonate in the air-formed film. For the AZ80 and AZ91D alloys, the amount of magnesium carbonate formed on the surface reached similar values to those of MgO and Mg(OH) 2. A linear relation between the amount of magnesium carbonate formed on the surface and the subsequent corrosion behaviour in the humid environment was found. The AZ80 alloy revealed the highest amount of magnesium carbonate in the air-formed film and the highest atmospheric corrosion resistance, even higher than the AZ91D alloy, indicating that aluminium distribution in the alloy microstructure influenced the amount of magnesium carbonate formed.

  2. Macrophage Serum-Based Adhesion to Plasma-Processed Surface Chemistry is Distinct from That Exhibited by Fibroblasts.

    PubMed

    Godek, Marisha L; Malkov, Galiya Sh; Fisher, Ellen R; Grainger, David W

    2006-08-15

    Plasma-polymerized films deposited from AlAm, HxAm, NVP, NVFA, AA and FC were compared to TCPS and PS surfaces in supporting cellular attachment, viability, and proliferation in serum-based culture in vitro for extended periods of time (>7 d). Surface patterns were created using multi-step depositions with physical masks. Cell adhesion in the presence of serum was compared for (monocyte-) macrophage and fibroblast cell lines. Cellular response was tracked over time, reporting adhesive behavior, proliferative rates, and morphological changes as a function of surface chemistry. Micropatterned surfaces containing different surface chemistries and functional groups (e.g. -NH(2), -COOH, -CF(3)) produced differential cell adhesive patterns for NIH 3T3 fibroblasts compared to J774A.1, RAW 264.7 or IC-21 (monocyte-) macrophage cell types. Significantly, macrophage adhesion is substantial on surfaces where fibroblasts do not adhere under identical culture conditions. PMID:17417668

  3. Macrophage Serum-Based Adhesion to Plasma-Processed Surface Chemistry is Distinct from That Exhibited by Fibroblasts

    PubMed Central

    Godek, Marisha L.; Malkov, Galiya Sh.; Fisher, Ellen R.; Grainger, David W.

    2007-01-01

    Summary Plasma-polymerized films deposited from AlAm, HxAm, NVP, NVFA, AA and FC were compared to TCPS and PS surfaces in supporting cellular attachment, viability, and proliferation in serum-based culture in vitro for extended periods of time (>7 d). Surface patterns were created using multi-step depositions with physical masks. Cell adhesion in the presence of serum was compared for (monocyte-) macrophage and fibroblast cell lines. Cellular response was tracked over time, reporting adhesive behavior, proliferative rates, and morphological changes as a function of surface chemistry. Micropatterned surfaces containing different surface chemistries and functional groups (e.g. –NH2, –COOH, –CF3) produced differential cell adhesive patterns for NIH 3T3 fibroblasts compared to J774A.1, RAW 264.7 or IC-21 (monocyte-) macrophage cell types. Significantly, macrophage adhesion is substantial on surfaces where fibroblasts do not adhere under identical culture conditions. PMID:17417668

  4. Surface chemistry improvement of 100mm GaSb for advanced space based applications

    NASA Astrophysics Data System (ADS)

    Allen, L. P.; Flint, J. P.; Meshew, G.; Trevethan, J.; Furlong, M. J.; Martinez, B.; Mobray, A.

    2012-01-01

    As size requirements and pixel viabilities for infrared focal plane arrays (IRFPAs) continue to increase, resolution and sensitivity requirements for high performance advanced imaging systems must meet or surpass stringent demands. Strain layer superlattice (SLS) grown by molecular beam epitaxy (MBE) on 100mm GaSb has necessitated changes in crystal processing and finishing parameters. Device layer growth typically requires a thin (2-5 nm) and highly desorbable surface oxide on very flat substrates for successful MBE. This study compares the ability for rapid pre-epi desoprtion of three different chemo-mechanical (CMP) finishes on 100mm n:GaSb: CMP-1 with sequential double side polished (DSP), CMP-2 with sequential DSP, and CMP-2 with simultaneous double side polished (S-DSP). X-ray photoelectron spectroscopy (XPS) reveals the improvement from a CMP-1 (Ga-oxide rich) to CMP-2 (Sb-oxide rich) surface. No difference in surface chemistry was found between the CMP-2 of the sequential vs. simultaneous DSP. Tropel flatness measurements of the 100mm n:GaSb substrates show that both DSP and SDSP substrate batches yield excellent (<5μm) wafer warp. However, initial studies have shown a more consistent wafer flatness with use of the simultaneous-DSP process. MBE growth on the Sb-rich surface was examined by high resolution XRD and resulted in a 64.7A periodicity and excellent FWHM (~20 arcsec) which verified the GaSb surface finish effectiveness. The resultant surface finish and flatness may provide a benefit for larger diameter GaSb IRFPA applications.

  5. The Materials Chemistry of Atomic Oxygen with Applications to Anisotropic Etching of Submicron Structures in Microelectronics and the Surface Chemistry Engineering of Porous Solids

    NASA Technical Reports Server (NTRS)

    Koontz, Steve L.; Leger, Lubert J.; Wu, Corina; Cross, Jon B.; Jurgensen, Charles W.

    1994-01-01

    Neutral atomic oxygen is the most abundant component of the ionospheric plasma in the low Earth orbit environment (LEO; 200 to 700 kilometers altitude) and can produce significant degradation of some spacecraft materials. In order to produce a more complete understanding of the materials chemistry of atomic oxygen, the chemistry and physics of O-atom interactions with materials were determined in three radically different environments: (1) The Space Shuttle cargo bay in low Earth orbit (the EOIM-3 space flight experiment), (2) a high-velocity neutral atom beam system (HVAB) at Los Alamos National Laboratory (LANL), and (3) a microwave-plasma flowing-discharge system at JSC. The Space Shuttle and the high velocity atom beam systems produce atom-surface collision energies ranging from 0.1 to 7 eV (hyperthermal atoms) under high-vacuum conditions, while the flowing discharge system produces a 0.065 eV surface collision energy at a total pressure of 2 Torr. Data obtained in the three different O-atom environments referred to above show that the rate of O-atom reaction with polymeric materials is strongly dependent on atom kinetic energy, obeying a reactive scattering law which suggests that atom kinetic energy is directly available for overcoming activation barriers in the reaction. General relationships between polymer reactivity with O atoms and polymer composition and molecular structure have been determined. In addition, vacuum ultraviolet photochemical effects have been shown to dominate the reaction of O atoms with fluorocarbon polymers. Finally, studies of the materials chemistry of O atoms have produced results which may be of interest to technologists outside the aerospace industry. Atomic oxygen 'spin-off' or 'dual use' technologies in the areas of anisotropic etching in microelectronic materials and device processing, as well as surface chemistry engineering of porous solid materials are described.

  6. Modification of ilmenite surface chemistry for enhancing surfactants adsorption and bubble attachment.

    PubMed

    Fan, Xianfeng; Waters, Kristian E; Rowson, Neil A; Parker, David J

    2009-01-01

    In this study, microwave irradiation is used to modify ilmenite surface chemistry to enhance the adsorption of surfactants and the air bubble attachment. The results indicate that microwave irradiation can increase ilmenite flotation recovery by 20%. A positron emission particle tracking technique is used to study the dynamic behaviour of ilmenite particles in a Denver cell. The data shows that the poor flotation recovery of ilmenite is not only due to the reduce probability of ilmenite being captured by air bubbles, but also the short residence time of the particles remaining in the froth phase. The ilmenite particles can be frequently captured by air bubbles, but dropped to the bulk liquid from the froth phase, normally over 15 s. Microwave irradiation changes the ilmenite flow pattern in the Denver cell. The average time of ilmenite remaining in froth phase is increased from 11.5 to 29.1 s. PMID:18950784

  7. Controls on surface water chemistry in the upper Merced River basin, Yosemite National Park, California

    USGS Publications Warehouse

    Clow, D.W.; Mast, M.A.; Campbell, D.H.

    1996-01-01

    Surface water draining granitic bedrock in Yosemite National Park exhibits considerable variability in chemical composition, despite the relative homogeneity of bedrock chemistry. Other geological factors, including the jointing and distribution of glacial till, appear to exert strong controls on water composition. Chemical data from three surface water surveys in the upper Merced River basin conducted in August 1981, June 1988 and August 1991 were analysed and compared with mapped geological, hydrological and topographic features to identify the solute sources and processes that control water chemistry within the basin during baseflow. Water at most of the sampling sites was dilute, with alkalinities ranging from 26 to 77 ??equiv. 1-1. Alkalinity was much higher in two subcatchments, however, ranging from 51 to 302 ??equiv. 1-1. Base cations and silica were also significantly higher in these two catchments than in the rest of the watershed. Concentrations of weathering products in surface water were correlated to the fraction of each subcatchment underlain by surficial material, which is mostly glacial till. Silicate mineral weathering is the dominant control on concentrations of alkalinity, silica and base cations, and ratios of these constituents in surface water reflect the composition of local bedrock, Chloride concentrations in surface water samples varied widely, ranging from <1 to 96 ??equiv. 1-1. The annual volume-weighted mean chloride concentration in the Merced River at the Happy Isles gauge from 1968 to 1990 was 26 ??equiv. 1-1, which was five times higher than in atmospheric deposition (4-5 ??equiv. 1-1), suggesting that a source of chloride exists within the watershed. Saline groundwater springs, whose locations are probably controlled by vertical jointing in the bedrock, are the most likely source of the chloride. Sulphate concentrations varied much less than most other solutes, ranging from 3 to 14 ??equiv. 1-1. Concentrations of sulphate in

  8. Friction and surface chemistry of some ferrous-base metallic glasses

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Buckley, D. H.

    1982-01-01

    The friction properties of some ferrous-base metallic glasses were measured both in argon and in vacuum to a temperature of 350 C. The alloy surfaces were also analyzed with X-ray photoelectron spectroscopy to identify the compounds and elements present on the surface. The results of the investigation indicate that even when the surfaces of the amorphous alloys, or metallic glasses, are atomically clean, bulk contaminants such as boric oxide and silicon dioxide diffuse to the surfaces. Friction measurements in both argon and vacuum indicate that the alloys exhibit higher coefficients of friction in the crystalline state than they do in the amorphous state.

  9. Surface chemistry and optical property of TiO{sub 2} thin films treated by low-pressure plasma

    SciTech Connect

    Dhayal, Marshal Jun, Jin; Gu, Hal Bon; Hee Park, Kyung

    2007-10-15

    The low temperature RF plasma treatment was used to control the surface chemistry and optical property of TiO{sub 2} thin films deposited by RF magnetron sputtering with a very good uniformity at 300 deg. C substrate heating temperature. The XRD pattern indicates the crystalline structure of the film could be associated to amorphous structure of TiO{sub 2} in thin film. The plasma treatment of TiO{sub 2} film can increase the proportion of Ti{sup 3+} in Ti2p and decrease in carbon atoms as alcohol/ether group in C1s at the surface. The optical transmittance of the film was enhanced by 50% after the plasma treatment. The surface structure and morphology remain the same for untreated and low-pressure plasma-treated films. Therefore, increase in the optical transmission could be due to change in surface chemistry and surface cleaning by plasma treatment. - Graphical abstract: The surface chemistry and surface states of TiO{sub 2} films was modified using low-pressure RF plasma treatment. The surface roughness and crystalline structure remain unchanged for low-pressure plasma-treated films. There was an increase in the Ti{sup 3+} surface states of Ti2p at the surface and this can be useful to increase the photocatalytic activities of TiO{sub 2} films. The proportion of carbon atoms as carboxyl group in C1s was also increased after plasma treatment. All the plasma-treated films show a higher optical transmittance when untreated and it was increased when the power was increased. The increase in the optical transmission could be due to surface cleaning of films by plasma treatment and possibly due to change in the surface chemistry.

  10. A review of the sources of uncertainties in atmospheric mercury modeling II. Mercury surface and heterogeneous chemistry - A missing link

    NASA Astrophysics Data System (ADS)

    Subir, Mahamud; Ariya, Parisa A.; Dastoor, Ashu P.

    2012-01-01

    Despite direct and indirect evidence suggesting that heterogeneous surfaces potentially play a key role in mercury chemistry, there is little known about mercury reactions and equilibrium processes that take place at atmospherically relevant surfaces. The lack of knowledge of mercury surface chemistry is a major gap for adequate modeling of mercury cycling. In part I of this review, we assessed the sources of uncertainty associated with existing kinetic parameters. In this part, we present evidence that supports surface-mercury interactions in the ecosystem elucidating the importance of heterogeneous and interfacial chemistry from a fundamental viewpoint. Consequently, we draw attention to the chemical processes that are missing and/or are inadequately incorporated in the atmospheric mercury models and highlight some of the recent advances in this field. We reveal that adsorption equilibrium of mercury species, most of which are not well characterized, to natural surfaces such as atmospheric particles and air/water interface are not known. Gas-liquid partitioning of mercury and its compounds are not adequately implemented. Equilibrium constants for aqueous phase complex formation with dissolved organic matters and formation of possible solid mercury clusters and nanoparticles are not considered in the global models. Potential heterogeneous mercury reduction reactions that can be important in mercury cycling require further evaluation which includes characterizing the influence of surfaces on mercury chemistry. The implementation of chemical processes for which information is available but not currently included in the models bears the potential of greatly reducing the uncertainties that are currently present in the models.

  11. Investigation of differential surface removal due to electropolishing at JLab

    SciTech Connect

    Marhauser, Frank; Folkie, James; Reece, Charles

    2015-09-01

    Surface chemistry carried out for Superconducting Radio Frequency (SRF) cavities such as Buffered Chemical Polishing (BCP) and Electropolishing (EP) aims to uniformly remove the internal surface of a cavity along the entire structure and within each cell from equator to iris in order to obtain an equally etched surface. A uniform removal, however, is not readily achievable due to the complex fluid flow and varying temperatures of the acid mixture, which can lead to differential etching. This needs to be considered when envisaging a certain surface damage removal throughout the interior. The process-specific differential etching influences the target frequency set at the manufacturing stage as well as the field flatness and length of the as-built cavity. We report on analyses of JLab's present EP system using experimental data for six nine-cell cavities that have been processed recently in the frame of the LCLS-II high-Q development plan. In conjunction with numerical simulations, the differential etching and the impact on field flatness is assessed.

  12. Quantum Chemistry in Nanoscale Environments: Insights on Surface-Enhanced Raman Scattering and Organic Photovoltaics

    NASA Astrophysics Data System (ADS)

    Olivares-Amaya, Roberto

    The understanding of molecular effects in nanoscale environments is becoming increasingly relevant for various emerging fields. These include spectroscopy for molecular identification as well as in finding molecules for energy harvesting. Theoretical quantum chemistry has been increasingly useful to address these phenomena to yield an understanding of these effects. In the first part of this dissertation, we study the chemical effect of surface-enhanced Raman scattering (SERS). We use quantum chemistry simulations to study the metal-molecule interactions present in these systems. We find that the excitations that provide a chemical enhancement contain a mixed contribution from the metal and the molecule. Moreover, using atomistic studies we propose an additional source of enhancement, where a transition metal dopant surface could provide an additional enhancement. We also develop methods to study the electrostatic effects of molecules in metallic environments. We study the importance of image-charge effects, as well as field-bias to molecules interacting with perfect conductors. The atomistic modeling and the electrostatic approximation enable us to study the effects of the metal interacting with the molecule in a complementary fashion, which provides a better understanding of the complex effects present in SERS. In the second part of this dissertation, we present the Harvard Clean Energy Project, a high-throughput approach for a large-scale computational screening and design of organic photovoltaic materials. We create molecular libraries to search for candidates structures and use quantum chemistry, machine learning and cheminformatics methods to characterize these systems and find structure-property relations. The scale of this study requires an equally large computational resource. We rely on distributed volunteer computing to obtain these properties. In the third part of this dissertation we present our work related to the acceleration of electronic structure

  13. Morphology of cerium oxide surfaces in an oxidzing enviroment:a first-principles investigation

    NASA Astrophysics Data System (ADS)

    Fronzi, Marco; Soon, Aloysius; Stampfl, Catherine; Delley, Bernard; Traversa, Enrico

    2007-03-01

    A good understanding of the stability and chemistry of CeO2 surfaces is crucial for a better designing of solid oxide fuel cells. As the first step, we use DFT [1] to study the structural and electronic ground state properties of bulk CeO2. various surface termination of the low-index surface of CeO2 are then investigated, namely the stoichiometric, metal- and oxygen- rich terminations, and defected surfaces. Using the concept of ab initio atomistic thermodynamics&[tilde;2], we calculate the surface free energy phase diagram. This allows us to identify and predict stable, and potentally catalytically important, structures. There is an evidence to suggest an interesting morphological change in the surface structures with varying oxygen concentration. Reaction pathways for methane oxidation on low energy cerium oxide surfaces are being investigated and will be reported.[1] Formulated in the DMol^3 code; B. Delley, J. Chem. Phys. 92, 508 (1990);ibid. 113, 7756 (2000).[2] K. Reuter, C. Stampfl and M. Scheffler, in Handbook of Materials Modeling, Volume 1, Fundamental Models and Methods, Sidney Yip (Ed)(2005).

  14. Combined experiment and theory approach in surface chemistry: Stairway to heaven?

    NASA Astrophysics Data System (ADS)

    Exner, Kai S.; Heß, Franziska; Over, Herbert; Seitsonen, Ari Paavo

    2015-10-01

    In this perspective we discuss how an intimate interaction of experiments with theory is able to deepen our insight into the catalytic reaction system on the molecular level. This strategy is illustrated by discussing various examples from our own research of surface chemistry and model catalysis. The particular examples were carefully chosen to balance the specific strength of both approaches - theory and experiment - and emphasize the benefit of this combined approach. We start with the determination of complex surface structures, where diffraction techniques in combination with theory are clear-cut. The promoter action of alkali metals in heterogeneous catalysis is rationalized with theory and experiment for the case of CO coadsorption. Predictive power of theory is limited as demonstrated with the apparent activity of chlorinated TiO2(110) in the oxidation of HCl: Even if we know all elementary reaction steps of a catalytic reaction mechanism, the overall kinetics may remain elusive and require the application kinetic Monte Carlo simulations. Catalysts are not always stable under reaction conditions and may chemically transform as discussed for the CO oxidation reaction over ruthenium. Under oxidizing reaction conditions ruthenium transforms into RuO2, a process which is hardly understood on the molecular level. Lastly we focus on electrochemical reactions. Here theory is clearly ahead since spectroscopic methods are not available to resolve the processes at the electrode surface.

  15. Surface chemistry gradients on silicone elastomers for high-throughput modulation of cell-adhesive interfaces.

    PubMed

    Mohan, Greeshma; Gallant, Nathan D

    2015-06-01

    Combinatorial and high-throughput approaches to screening cell responses to material properties accelerate the speed of discovery and facilitate the identification of cell instructive cues or trends that may be missed by discrete sampling. However, these technologies have not yet been widely applied to materials with tissue-like stiffness. The fabrication of monotonically varying surface chemistry gradients on polydimethylsiloxane, an elastic biomaterial, and the influence of these engineered surfaces on protein adsorption and adherent cell morphology were explored in this study. Crosslinked networks of polydimethylsiloxane were functionalized with a hydrophobic self-assembled monolayer and then modified by spatiotemporally regulated ultraviolet ozonolysis to obtain gradients of oxygenated species ranging from ∼10° to ∼100° in water contact angle. Automated microscopy and image analysis of fibroblast cell morphology revealed a strong correlation between cell spreading and hydrophobicity. However, structural and functional analysis of the fibronectin interface indicated a proportional increase in cell spreading with adsorption, but a biphasic relationship with fibronectin conformation, underscoring the complexity of the adhesive interface. This work demonstrates the development of an elastomer surface modification platform that can be extended to future combinatorial studies of biological responses to chemical and mechanical material properties. PMID:25294744

  16. Global distribution and surface activity of macromolecules in offline simulations of marine organic chemistry

    DOE PAGESBeta

    Ogunro, Oluwaseun O.; Burrows, Susannah M.; Elliott, Scott; Frossard, Amanda A.; Hoffman, Forrest M.; Letscher, Robert T.; Moore, J. Keith; Russell, Lynn M.; Wang, Shanlin; Wingenter, Oliver W.

    2015-10-13

    Here, organic macromolecules constitute high percentage components of remote sea spray. They enter the atmosphere through adsorption onto bubbles followed by bursting at the ocean surface, and go on to influence the chemistry of the fine mode aerosol. We present a global estimate of mixed-layer organic macromolecular distributions, driven by offline marine systems model output. The approach permits estimation of oceanic concentrations and bubble film surface coverages for several classes of organic compound. Mixed layer levels are computed from the output of a global ocean biogeochemistry model by relating the macromolecules to standard biogeochemical tracers. Steady state is assumed formore » labile forms, and for longer-lived components we rely on ratios to existing transported variables. Adsorption is then represented through conventional Langmuir isotherms, with equilibria deduced from laboratory analogs. Open water concentrations locally exceed one micromolar carbon for the total of protein, polysaccharide and refractory heteropolycondensate. The shorter-lived lipids remain confined to regions of strong biological activity. Results are evaluated against available measurements for all compound types, and agreement is generally quite reasonable. Global distributions are further estimated for both fractional coverage of bubble films at the air-water interface and the two-dimensional concentration excess. Overall, we show that macromolecular mapping provides a novel tool for the comprehension of oceanic surfactant distributions. Results may prove useful in planning field experiments and assessing the potential response of surface chemical behaviors to global change.« less

  17. Global distribution and surface activity of macromolecules in offline simulations of marine organic chemistry

    SciTech Connect

    Ogunro, Oluwaseun O.; Burrows, Susannah M.; Elliott, Scott; Frossard, Amanda A.; Hoffman, Forrest M.; Letscher, Robert T.; Moore, J. Keith; Russell, Lynn M.; Wang, Shanlin; Wingenter, Oliver W.

    2015-10-13

    Here, organic macromolecules constitute high percentage components of remote sea spray. They enter the atmosphere through adsorption onto bubbles followed by bursting at the ocean surface, and go on to influence the chemistry of the fine mode aerosol. We present a global estimate of mixed-layer organic macromolecular distributions, driven by offline marine systems model output. The approach permits estimation of oceanic concentrations and bubble film surface coverages for several classes of organic compound. Mixed layer levels are computed from the output of a global ocean biogeochemistry model by relating the macromolecules to standard biogeochemical tracers. Steady state is assumed for labile forms, and for longer-lived components we rely on ratios to existing transported variables. Adsorption is then represented through conventional Langmuir isotherms, with equilibria deduced from laboratory analogs. Open water concentrations locally exceed one micromolar carbon for the total of protein, polysaccharide and refractory heteropolycondensate. The shorter-lived lipids remain confined to regions of strong biological activity. Results are evaluated against available measurements for all compound types, and agreement is generally quite reasonable. Global distributions are further estimated for both fractional coverage of bubble films at the air-water interface and the two-dimensional concentration excess. Overall, we show that macromolecular mapping provides a novel tool for the comprehension of oceanic surfactant distributions. Results may prove useful in planning field experiments and assessing the potential response of surface chemical behaviors to global change.

  18. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

    NASA Astrophysics Data System (ADS)

    Sych, N. V.; Trofymenko, S. I.; Poddubnaya, O. I.; Tsyba, M. M.; Sapsay, V. I.; Klymchuk, D. O.; Puziy, A. M.

    2012-11-01

    Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 °C using varied ratio of impregnation (RI). Porous structure of carbons was characterized by nitrogen adsorption and scanning electron microscopy. Surface chemistry was studied by IR and potentiometric titration method. It has been shown that porosity development was peaked at RI = 1.0 (SBET = 2081 m2/g, Vtot = 1.1 cm3/g), while maximum amount of acid surface groups was observed at RI = 1.25. Acid surface groups of phosphoric acid activated carbons from corncob includes phosphate and strongly acidic carboxylic (pK = 2.0-2.6), weakly acidic carboxylic (pK = 4.7-5.0), enol/lactone (pK = 6.7-7.4; 8.8-9.4) and phenol (pK = 10.1-10.7). Corncob derived carbons showed high adsorption capacity to copper, especially at low pH. Maximum adsorption of methylene blue and iodine was observed for carbon with most developed porosity (RI = 1.0).

  19. Specific activity of polypyrrole nanoparticulate immunoreagents: comparison of surface chemistry and immobilization options.

    PubMed

    Pope, M R; Armes, S P; Tarcha, P J

    1996-01-01

    Polypyrrole-based colloids with differing surface chemistries were compared with respect to the specific activity of immobilized antibody. Monoclonal antibody to the alpha subunit of human chorionic gonadotropin (hCG) was modified by incorporation of cystamine into the Fc-carbohydrate, followed by reduction with dithiothreitol resulting in the generation of 4.5 free thiols per IgG. The reduced IgG was added to clean, unmodified and surface-modified polypyrrole colloids. Functionalized colloids included carboxylate-modified polypyrrole, poly[pyrrole-co-1-(2-carboxyethyl) pyrrole]-silica composite, and amine forms of the carboxylated colloids. The amine-functionalized colloids were subsequently treated with sulfosuccinimidyl 4-(N-maleimidomethyl)cyclohexane-1-carboxylate to provide thiol-reactive maleimide surface groups. Following the conjugation of IgG to the colloids, bound and soluble antibody activity was quantitated using a sequentially competitive immunoassay for hCG, based on an automated commercial hCG kit. The results indicated that all forms of polypyrrole retained the equivalence of between 12 and 33 micrograms of IgG activity/mg of colloidal solids, relative to the unmodified soluble IgG. PMID:8853457

  20. DNA damage response to different surface chemistry of silver nanoparticles in mammalian cells

    SciTech Connect

    Ahamed, Maqusood; Karns, Michael; Goodson, Michael; Rowe, John; Hussain, Saber M.; Schlager, John J.

    2008-12-15

    Silver nanoparticles (Ag NPs) have recently received much attention for their possible applications in biotechnology and life sciences. Ag NPs are of interest to defense and engineering programs for new material applications as well as for commercial purposes as an antimicrobial. However, little is known about the genotoxicity of Ag NPs following exposure to mammalian cells. This study was undertaken to examine the DNA damage response to polysaccharide surface functionalized (coated) and non-functionalized (uncoated) Ag NPs in two types of mammalian cells; mouse embryonic stem (mES) cells and mouse embryonic fibroblasts (MEF). Both types of Ag NPs up-regulated the cell cycle checkpoint protein p53 and DNA damage repair proteins Rad51 and phosphorylated-H2AX expression. Furthermore both of them induced cell death as measured by the annexin V protein expression and MTT assay. Our observations also suggested that the different surface chemistry of Ag NPs induce different DNA damage response: coated Ag NPs exhibited more severe damage than uncoated Ag NPs. The results suggest that polysaccharide coated particles are more individually distributed while agglomeration of the uncoated particles limits the surface area availability and access to membrane bound organelles.

  1. Neutron reflectivity study of substrate surface chemistry effects on supported phospholipid bilayer formation on (1120) sapphire.

    SciTech Connect

    Oleson, Timothy A.; Sahai, Nita; Wesolowski, David J; Dura, Joseph A; Majkrzak, Charles F; Giuffre, Anthony J.

    2012-01-01

    Oxide-supported phospholipid bilayers (SPBs) used as biomimetric membranes are significant for a broad range of applications including improvement of biomedical devices and biosensors, and in understanding biomineralization processes and the possible role of mineral surfaces in the evolution of pre-biotic membranes. Continuous-coverage and/or stacjed SPBs retain properties (e.,g. fluidity) more similar to native biological membranes, which is desirable for most applications. Using neutron reflectivity, we examined face coverage and potential stacking of dipalmitoylphosphatidylcholine (DPPC) bilayers on the (1120) face of sapphire (a-Al2O3). Nearly full bilayers were formed at low to neutral pH, when the sapphire surface is positively charged, and at low ionic strength (l=15 mM NaCl). Coverage decreased at higher pH, close to the isoelectric point of sapphire, and also at high I>210mM, or with addition of 2mM Ca2+. The latter two effects are additive, suggesting that Ca2+ mitigates the effect of higher I. These trends agree with previous results for phospholipid adsorption on a-Al2O3 particles determined by adsorption isotherms and on single-crystal (1010) sapphire by atomic force microscopy, suggesting consistency of oxide surface chemistry-dependent effects across experimental techniques.

  2. Surface Chemistry, Microstructure, and Tribological Properties of Cubic Boron Nitride Films

    NASA Technical Reports Server (NTRS)

    Watanabe, Shuichi; Wheeler, Donald R.; Abel, Phillip B.; Street, Kenneth W.; Miyoshi, Kazuhisa; Murakawa, Masao; Miyake, Shojiro

    1998-01-01

    This report deals with the surface chemistry, microstructure, bonding state, morphology, and friction and wear properties of cubic boron nitride (c-BN) films that were synthesized by magnetically enhanced plasma ion plating. Several analytical techniques - x-ray photoelectron spectroscopy, transmission electron microscopy and electron diffraction, Fourier transform infrared spectroscopy, atomic force microscopy, and surface profilometry - were used to characterize the films. Sliding friction experiments using a ball-on-disk configuration were conducted for the c-BN films in sliding contact with 440C stainless-steel balls at room temperature in ultrahigh vacuum (pressure, 10(exp -6), in ambient air, and under water lubrication. Results indicate that the boron-to-nitrogen ratio on the surface of the as-deposited c-BN film is greater than 1 and that not all the boron is present as boron nitride but a small percentage is present as an oxide. Both in air and under water lubrication, the c-BN film in sliding contact with steel showed a low wear rate, whereas a high wear rate was observed in vacuum. In air and under water lubrication, c-BN exhibited wear resistance superior to that of amorphous boron nitride, titanium nitride, and titanium carbide.

  3. Algal Biomass Constituent Analysis: Method Uncertainties and Investigation of the Underlying Measuring Chemistries

    SciTech Connect

    Laurens, L. M. L.; Dempster, T. A.; Jones, H. D. T.; Wolfrum, E. J.; Van Wychen, S.; McAllister, J. S. P.; Rencenberger, M.; Parchert, K. J.; Gloe, L. M.

    2012-02-21

    Algal biomass compositional analysis data form the basis of a large number of techno-economic process analysis models that are used to investigate and compare different processes in algal biofuels production. However, the analytical methods used to generate these data are far from standardized. This work investigated the applicability of common methods for rapid chemical analysis of biomass samples with respect to accuracy and precision. This study measured lipids, protein, carbohydrates, ash, and moisture of a single algal biomass sample at 3 institutions by 8 independent researchers over 12 separate workdays. Results show statistically significant differences in the results from a given analytical method among laboratories but not between analysts at individual laboratories, suggesting consistent training is a critical issue for empirical analytical methods. Significantly different results from multiple lipid and protein measurements were found to be due to different measurement chemistries. We identified a set of compositional analysis procedures that are in best agreement with data obtained by more advanced analytical procedures. The methods described here and used for the round robin experiment do not require specialized instrumentation, and with detailed analytical documentation, the differences between laboratories can be markedly reduced.

  4. Benzenethiol chemistry on the Ni(111) surface: The influence of coadsorbed species

    SciTech Connect

    Kane, S.M.; Rufael, T.S.; Gland, J.L.; Huntley, D.R.

    1996-10-01

    The effect of several coadsorbed species on the reactions of benzenethiol on the Ni(111) surface has been characterized. On the clean surface, benzenethiol is adsorbed as phenylthiolate with an orientation tilted form the surface normal, and hydrogenolysis to form benzene at 260 K is the primary reaction. H{sub 2} preadsorption onto the surface affects reaction selectivity at submonolayer coverages. Higher thiol coverages show no change in hydrogenolysis kinetics, either under either UHV conditions as measured by isothermal TPD or at H{sub 2} pressures up to 7X10{sup {minus}3} torr (measured by FYNES). HREELS indicates that coadsorbed hydrogen induces a change in the orientation of the phenylthiolate. Coadsorbed oxygen is shown to remove surface hydrogen by water formation and broadens the benzene desorption state. A novel reaction between coadsorbed methanethiol and benzethiol to form toluene, and the role of surface hydrogen and oxygen on this reaction, have been investigated.

  5. Surface chemistry features in the hot water processing of Utah tar sand

    SciTech Connect

    Misra, M.; Aguilar, R.; Miller, J.D.

    1981-01-01

    The hot water processing of Utah tar sand involves two important steps in the process sequence, phase disengagement (digestion) and phase separation (flotation). Inasmuch as phase separation is accomplished by flotation, the hydrophobic/hydrophilic balance at the surface of the bitumen droplets was studied in conjunction with the system's solution chemistry and the results correlated with the flotation response. Contact angle measurements of solvent extracted bitumen revealed a moderate hydrophobic character; however, air bubble attachment at the surface of bitumen obtained from a hot water concentrate was difficult and required long induction times. These results suggest that the phase separation by flotation is dependent on air bubble entrapment by bitumen droplets rather than attachment due to surface hydrophobicity. In addition, identification of surface functional groups and components solubilized during hot water digestion was attempted using IR and NMR spectra. Strong absorption peaks at 1708 cm/sup -1/, and 2855 cm/sup -1/ for the solubilized components together with NMR spectra indicate the presence of dissolved paraffinic carboxylates, the amount of which increased as the digestion pH was increased. Potentiometric titration of the water soluble constituents indicated an acid dissociation constant of pK/sub a/ approx. = 5 which would be expected for such carboxylate species. This phenomenon appears to account, in part, for the polar bitumen surface and the hydrophilic character of the digested bitumen. These and other results indicate that phase disengagement during digestion and bitumen hydrophobicity may be mutually exclusive effects and reinforce the notion that flotation separation is achieved by entrapment of air bubbles in the viscous bitumen droplets. 10 figures.

  6. Plant surface reactions: an opportunistic ozone defence mechanism impacting atmospheric chemistry

    NASA Astrophysics Data System (ADS)

    Jud, W.; Fischer, L.; Canaval, E.; Wohlfahrt, G.; Tissier, A.; Hansel, A.

    2016-01-01

    Elevated tropospheric ozone concentrations are considered a toxic threat to plants, responsible for global crop losses with associated economic costs of several billion dollars per year. Plant injuries have been linked to the uptake of ozone through stomatal pores and oxidative damage of the internal leaf tissue. But a striking question remains: can surface reactions limit the stomatal uptake of ozone and therefore reduce its detrimental effects to plants?In this laboratory study we could show that semi-volatile organic compounds exuded by the glandular trichomes of different Nicotiana tabacum varieties are an efficient ozone sink at the plant surface. In our experiments, different diterpenoid compounds were responsible for a strongly variety-dependent ozone uptake of plants under dark conditions, when stomatal pores are almost closed. Surface reactions of ozone were accompanied by a prompt release of oxygenated volatile organic compounds, which could be linked to the corresponding precursor compounds: ozonolysis cis-abienol (C20H34O) - a diterpenoid with two exocyclic double bonds - caused emissions of formaldehyde (HCHO) and methyl vinyl ketone (C4H6O). The ring-structured cembratrien-diols (C20H34O2) with three endocyclic double bonds need at least two ozonolysis steps to form volatile carbonyls such as 4-oxopentanal (C5H8O2), which we could observe in the gas phase, too.Fluid dynamic calculations were used to model ozone distribution in the diffusion-limited leaf boundary layer under daylight conditions. In the case of an ozone-reactive leaf surface, ozone gradients in the vicinity of stomatal pores are changed in such a way that the ozone flux through the open stomata is strongly reduced.Our results show that unsaturated semi-volatile compounds at the plant surface should be considered as a source of oxygenated volatile organic compounds, impacting gas phase chemistry, as well as efficient ozone sink improving the ozone tolerance of plants.

  7. Investigating Art Objects through Collaborative Student Research Projects in an Undergraduate Chemistry and Art Course

    ERIC Educational Resources Information Center

    Wells, Gary; Haaf, Michael

    2013-01-01

    Inspired in part by Chemistry Collaborations, Workshops, and Community of Scholars workshops, the Chemistry and Art course offered at Ithaca College is team-taught by a chemist and an art historian, underscoring the complementary nature of the two disciplines. The course, populated primarily by nonscience majors, highlights the importance of using…

  8. An Investigation into the Relationship between Academic Risk Taking and Chemistry Laboratory Anxiety in Turkey

    ERIC Educational Resources Information Center

    Öner Sünkür, Meral

    2015-01-01

    This study evaluates the relationship between academic risk taking and chemistry laboratory anxiety using a relational scanning model. The research sample consisted of 127 undergraduate students (sophomores, juniors and seniors) in the Chemistry Teaching Department at Dicle University. This research was done in the spring semester of the 2012 to…

  9. Investigating Affective Experiences in the Undergraduate Chemistry Laboratory: Students' Perceptions of Control and Responsibility

    ERIC Educational Resources Information Center

    Galloway, Kelli R.; Malakpa, Zoebedeh; Bretz, Stacey Lowery

    2016-01-01

    Meaningful learning requires the integration of cognitive and affective learning with the psychomotor, i.e., hands-on learning. The undergraduate chemistry laboratory is an ideal place for meaningful learning to occur. However, accurately characterizing students' affective experiences in the chemistry laboratory can be a very difficult task. While…

  10. Factors Influencing Student Prerequisite Preparation for and Subsequent Performance in College Chemistry Two: A Statistical Investigation

    ERIC Educational Resources Information Center

    Easter, David C.

    2010-01-01

    For students entering Chemistry Two following a Chemistry One course, an assessment exam was given and the results were evaluated in combination with other variables to develop a predictive model that forecasts student achievement in the course. Variables considered in the analysis included student major, GPA, classification (student standing:…

  11. Is Mathematics to Blame? An Investigation into High School Students' Difficulty in Performing Calculations in Chemistry

    ERIC Educational Resources Information Center

    Scott, Fraser J.

    2012-01-01

    Mathematical ability is a major contributory factor to the success of a student in any science course. This paper aims to determine the source of the difficulty that students often find when performing calculations in chemistry. Through the design and analysis of a set of chemistry questions and analogous mathematics questions, set in a Standard…

  12. Investigation of UV Laser Triggered, Nanosecond, Surface Flashover Switches

    SciTech Connect

    Nunnally, W C; Neurath, R; Holmes, C; Sampayan, S; Caporaso, G

    2003-06-03

    Triggered, multi-channel, surface discharges or surface flashover switching have been investigated as a low inductance, low pulse rate switch for conducting large currents. This paper discusses the investigation of UV (355 nm) laser triggered, single channel, low inductance, ns closure and sub-ns jitter switches for applications in switching high dielectric constant, compact pulse forming lines into accelerator loads. The experimental arrangement for evaluating the switch performance and for measuring the high field dielectric constant of the pulse forming lines is presented. Experimental results of delay and jitter measurements versus optical energy on the flashover surface and dc electric field charge.

  13. Investigating Titan's Atmospheric Chemistry at Low Temperature in Support of the NASA Cassini Mission

    NASA Technical Reports Server (NTRS)

    Sciamma-O'Brien, Ella; Salama, Farid

    2013-01-01

    Titan's atmosphere, composed mainly of N2 and CH4, is the siege of a complex chemistry induced by solar UV radiation and electron bombardment from Saturn's magnetosphere. This organic chemistry occurs at temperatures lower than 200 K and leads to the production of heavy molecules and subsequently solid aerosols that form the orange haze surrounding Titan. The Titan Haze Simulation (THS) experiment has been developed on the COSMIC simulation chamber at NASA Ames in order to study the different steps of Titan's atmospheric chemistry at low temperature and to provide laboratory data in support for Cassini data analysis. The chemistry is simulated by plasma in the stream of a supersonic expansion. With this unique design, the gas mixture is adiabatically cooled to Titan-like temperature (approx. 150 K) before inducing the chemistry by plasma discharge. Different gas mixtures containing N2, CH4, and the first products of the N2,-CH4 chemistry (C2H2, C2H4, C6H6...) but also heavier molecules such as PAHs or nitrogen containing PAHs can be injected. Both the gas phase and solid phase products resulting from the plasma-induced chemistry can be monitored and analyzed. Here we present the results of recent gas phase and solid phase studies that highlight the chemical growth evolution when injecting heavier hydrocarbon trace elements in the initial N2-CH4 mixture. Due to the short residence time of the gas in the plasma discharge, only the first steps of the chemistry have time to occur in a N2-CH4 discharge. However by adding acetylene and benzene to the initial N2-CH4 mixture, we can study the intermediate steps of Titan's atmospheric chemistry as well as specific chemical pathways. These results show the uniqueness of the THS experiment to help understand the first and intermediate steps of Titan fs atmospheric chemistry as well as specific chemical pathways leading to Titan fs haze formation.

  14. Infrared spectroscopy and surface chemistry of beta-Ga(2)O(3) nanoribbons.

    PubMed

    Bermudez, V M; Prokes, S M

    2007-12-01

    The structure and surface chemistry of crystalline beta-Ga2O3 nanoribbons (NRs), deposited in a thin layer on various metallic and dielectric substrates (mainly on Au), have been characterized using vibrational spectroscopy. The results have been analyzed with the aid of a previous ab initio theoretical model for the beta-Ga2O3 surface structure. Raman spectra and normal-incidence infrared (IR) transmission data show little if any difference from corresponding results for bulk single crystals. For a layer formed on a metallic substrate, IR reflection-absorption spectroscopy (IRRAS) shows longitudinal-optic (LO) modes that are red-shifted by approximately 37 cm-1 relative to those of a bulk crystal. Evidence is also seen for a bonding interaction at the Ga2O3/Au interface following heating in room air. Polarization-modulated IRRAS has been used to study the adsorption of pyridine under steady-state conditions in ambient pressures as high as approximately 5 Torr. The characteristic nu19b and nu8a modes of adsorbed pyridine exhibit little or no shift from the corresponding gas-phase values. This indicates that the surface is only weakly acidic, consistent with the theoretical prediction that singly unsaturated octahedral Ga sites are the only reactive cation sites on the NR surface. However, evidence for adsorption at defect sites is seen in the form of more strongly shifted modes that saturate in intensity at low pyridine coverage. The effect of H atoms, formed by thermal cracking of H2, has also been studied. No Ga-H or O-H bonds are observed on the pristine NR surface. This suggests that the previously reported presence of such species on Ga2O3 powders heated in H2 is a result of a partial reduction of the oxide surface. The heat of adsorption of atomic H on the pristine beta-Ga2O3(100) surface at 0 K is computed to be -1.79 eV per H at saturation (average of Ga-H and O-H sites), whereas a value of +0.45 eV per H is found for the dissociative adsorption of H2. This

  15. Evaluation of the Effectiveness of Surfactants and Denaturants to Elute and Denature Adsorbed Protein on Different Surface Chemistries.

    PubMed

    Thyparambil, Aby A; Wei, Yang; Latour, Robert A

    2015-11-01

    The elution and/or denaturation of proteins from material surfaces by chemical excipients such as surfactants and denaturants is important for numerous applications including medical implant reprocessing, bioanalyses, and biodefense. The objective of this study was to develop and apply methods to quantitatively assess how surface chemistry and adsorption conditions influence the effectiveness of three commonly used surfactants (sodium dodecyl sulfate, n-octyl-β-d-glucoside, and 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate) and two denaturants (guanidium hydrochloride and urea) to elute protein (hen egg white lysozyme and bovine pancreatic ribonuclease A) from three different surface chemistries (silica glass, poly(methyl methacrylate), and high-density polyethylene). The structure and bioactivity of residual protein on the surface following elution were characterized using circular dichroism spectropolarimetry and enzyme assays to assess the extent of protein denaturation. Our results indicate that the denaturants were generally more effective than the surfactants in removing the adsorbed proteins from each type of surface. Also, the denaturing capacity of these excipients on the residual proteins on the surfaces was distinctly different from their influence on the proteins in solution and was unique for each of the adsorption conditions. Taken altogether, these results reveal that the effectiveness of surfactants and denaturants to elute and denature adsorbed protein is significantly influenced by surface chemistry and the conditions from which the protein was adsorbed. These results provide a basis for the selection, design, and further development of chemical agents for protein elution and surface decontamination. PMID:26449787

  16. Short-term inactivation rates of selected Gram-positive and Gram-negative bacteria attached to metal oxide mineral surfaces: role of solution and surface chemistry.

    PubMed

    Asadishad, Bahareh; Ghoshal, Subhasis; Tufenkji, Nathalie

    2013-06-01

    Metal oxides such as ferric or aluminum oxides can play an important role in the retention of bacteria in granular aquatic environments; however, their role in bacterial inactivation is not well understood. Herein, we examined the role of water chemistry and surface chemistry on the short-term inactivation rates of three bacteria when adhered to surfaces. To evaluate the role of water chemistry on the inactivation of attached bacteria, the loss in membrane integrity of bacteria attached to an iron oxide (Fe2O3) surface was measured over a range of water ionic strengths of either monovalent or divalent salts in the absence of a growth substrate. The influence of surface chemistry on the inactivation of attached bacteria was examined by measuring the loss in membrane integrity of cells attached to three surfaces (SiO2, Fe2O3, and Al2O3) at a specific water chemistry (10 mM KCl). Bacteria were allowed to attach onto the SiO2 or metal oxide coated slides mounted in a parallel-plate flow cell, and their inactivation rate (loss in membrane integrity) was measured directly without removing the cells from the surface and without disturbing the system. X-ray photoelectron spectroscopy analysis revealed a high correlation between the amounts of C-metal or O-metal bonds and the corresponding bacterial inactivation rates for each surface. Finally, for all three surfaces, a consistent increase in inactivation rate was observed with the type of bacterium in the order: Enterococcus faecalis, Escherichia coli O157:H7, and Escherichia coli D21f2. PMID:23679056

  17. Aqueous and surface chemistry of calcium-metal hydroxides in high pH environments

    SciTech Connect

    Cocke, D.L.; Mollah, M.Y.A.; Hess, T.R.; Lin, T.C.

    1997-08-01

    There is considerable interest in the chemistry associated with hazardous waste treatment by cement. The hydration of Portland cement is retarded in presence of zinc, cadmium and lead ions. Mixed hydroxides of calcium, zinc, cadmium and lead have been recently identified in the high pH environments of hydrating cement. FTIR, XRD, SEM, and SPM have been used to characterize these systems. A chemical equilibrium model of the early hydration of a zinc-doped cement/water system, Na-K-Ca-ZnH-SO{sub 4}-OH-Zn(OH){sub 2}-Zn(OH){sub 3}-Zn(OH){sub 4}-H{sub 2}O, has been developed to better understand the mechanism of the surface formation of calcium hydroxyzincate (CHZ). The model is based on Pitzer`s semi-empirical method for calculation of ion-activity coefficients at high ionic strength. The Pitzer parameters for Na{sup +}-Zn{sup 2+}, Na{sup +}-Zn{sup 2+}-SO{sub 4}{sup 2{minus}} and K{sup +}-Zn(OH){sub 4}{sup 2{minus}} have been evaluated, and the results successfully predict the equilibria (solubilities) of Na{sub 2}SO{sub 4}-ZnSO{sub 4}-H{sub 2}O, NaOH-Zn(OH){sub 2}-H{sub 2}O and KOH-ZnO-H{sub 2}O systems. The chemical model clearly demonstrates that the formation of CHZ on the calcium-silica-hydrate (C-S-H) surface is critically controlled by the Ca{sup 2+} ion concentration as well as pH of the pore water system. The results of this study suggest that the growth of CHZ is preceded by surface complex formation. Sequential charge control and sequential structure development have been used to discuss the surface selectivity of these compounds and their control of cement hydration.

  18. Fracture mechanics and surface chemistry studies of fatigue crack growth in an aluminum alloy

    NASA Astrophysics Data System (ADS)

    Wei, R. P.; Pao, P. S.; Hart, R. G.; Weir, T. W.; Simmons, G. W.

    1980-12-01

    Fracture mechanics and surface chemistry studies were carried out to develop further understanding of the influence of water vapor on fatigue crack growth in aluminum alloys. The room temperature fatigue crack growth response was determined for 2219-T851 aluminum alloy exposed to water vapor at pressures from 1 to 30 Pa over a range of stress intensity factors ( K). Data were also obtained in vacuum (at < 0.50 μPa), and dehumidified argon. The test results showed that, at a frequency of 5 Hz, the rate of crack growth is essentially unaffected by water vapor until a threshold pressure is reached. Above this threshold, the rates increased, reaching a maximum within one order of magnitude increase in vapor pressure. This maximum crack growth rate is equal to that obtained in air (40 to 60 pct relative humidity), distilled water and 3.5 pct NaCl solution on the same material. Parallel studies of the reactions of water vapor with fresh alloy surfaces (produced either by in situ impact fracture or by ion etching) were made by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The extent of surface reaction was monitored by changes in the oxygen AES and XPS signals. Correlation between the fatigue crack growth response and the surface reaction kinetics has been made, and is consistent with a transport-limited model for crack growth. The results also suggest that enhancement of fatigue crack growth by water vapor in the aluminum alloys occurs through a “hydrogen embrittle ment” mechanism.

  19. Atomic-scale theoretical investigations of compound semiconductor surfaces

    NASA Astrophysics Data System (ADS)

    Srivastava, G. P.

    2005-05-01

    Atomic-scale theoretical investigations of clean and covered low-index surfaces of compound semiconductors are presented. Particular emphasis is laid on the role of the electron counting rule (ECR) in governing plausible surface reconstructions. Trends are presented for the characeristic tilt of the topmost atomic layer and the highest localised phonon mode on nonpolar III-V(1 1 0) surfaces, including III-nitride compounds. Reconstructions and electronic properties of polar surfaces are explained in terms of dimer formation on (0 0 1), and trimer and/or chain formation on (1 1 1) faces. It is pointed out that some surface reconstructions stabilise as a result of a balance between the ECR and minimization of adsorbate-induced local distortion. This is demonstrated for the long-range ordered reconstruction on the Sb:GaAs(1 1 1)B surface.

  20. Toxicological assessment of kretek cigarettes Part 4: mechanistic investigations, smoke chemistry and in vitro toxicity.

    PubMed

    Roemer, E; Dempsey, R; Lawless-Pyne, J; Lukman, S; Evans, A Deger; Trelles-Sticken, E; Wittke, S; Schorp, M K

    2014-12-01

    The smoke chemistry and in vitro toxicity of mainstream smoke (MS) was investigated in American-blended cigarettes with or without the addition of 2.5%, 5% or 10% eugenol to the tobacco and in Indonesian-blended cigarettes with and without the addition of cloves, cloves extracted with hot ethanol, and extracted cloves replenished with eugenol or clove oil. The addition of eugenol reduced the concentration of nearly all toxicants measured in MS as well as the in vitro cytotoxicity of the gas/vapor phase. Reductions were also seen in bacterial mutagenicity of the total particulate matter (TPM) assessed by the Ames Assay. The addition of extracted cloves led to increases and decreases of toxicant concentrations in MS. Replenishment with eugenol or clove oil decreased the toxicant concentrations; with most smoke constituent concentrations reduced below the concentration found in tobacco-only cigarettes. Cytotoxicity of the TPM was not affected by the clove preparations. However, GVP cytotoxicity was reduced (untreated cloves showing the highest reductions). Mutagenicity of TPM was decreased by the clove preparations. Mechanisms for the reductions, (up to 40%), are most likely due to dilution effects by eugenol, changed burning characteristics of the tobacco, and free radical scavenging by eugenol. PMID:25455230

  1. The Role of Grain Surface Reactions in the Chemistry of Star Forming Regions

    NASA Technical Reports Server (NTRS)

    Kress, M. E.; Tielens, A. G. G. M.; Roberge, W. G.

    1998-01-01

    The importance of reactions at the surfaces of dust grains has long been recognized to be one of the two main chemical processes that form molecules in cold, dark interstellar clouds where simple, saturated (fully-hydrogenated) molecules such as H2 water, methanol, H2CO, H2S, ammonia and CH4 are present in quantities far too high to be consistent with their extremely low gas phase formation rates. In cold dark regions of interstellar space, dust grains provide a substrate onto which gas-phase species can accrete and react. Grains provide a "third body" or a sink for the energy released in the exothermic reactions that form chemical bonds. In essence, the surfaces of dust grains open up alternative reaction pathways to form observed molecules whose abundances cannot be explained with gas-phase chemistry alone. This concept is taken one step further in this work: instead of merely acting as a substrate onto which radicals and molecules may physically adsorb, some grains may actively participate in the reaction itself, forming chemical bonds with the accreting species. Until recently, surface chemical reactions had not been thought to be important in warm circumstellar media because adspecies rapidly desorb from grains at very low temperatures; thus, the residence times of molecules and radicals on the surface of grains at all but the lowest temperatures are far too short to allow these reactions to occur. However, if the adspecies could adsorb more strongly, via a true chemical bond with surfaces of some dust grains, then grain surface reactions will play an important role in warm circumstellar regions as well. In this work, the surface-catalyzed reaction CO + 3 H2 yields CH4 + H2O is studied in the context that it may be very effective at converting the inorganic molecule CO into the simplest organic compound, methane. H2 and CO are the most abundant molecules in space, and the reaction converting them to methane, while kinetically inhibited in the gas phase under

  2. Evolution of interfacial intercalation chemistry on epitaxial graphene/SiC by surface enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Ferralis, Nicola; Carraro, Carlo

    2014-11-01

    A rapid and facile evaluation of the effects of physical and chemical processes on the interfacial layer between epitaxial graphene monolayers on SiC(0 0 0 1) surfaces is essential for applications in electronics, photonics, and optoelectronics. Here, the evolution of the atomic scale epitaxial graphene-buffer-layer-SiC interface through hydrogen intercalation, thermal annealings, UV-ozone etching and oxygen exposure is studied by means of single microparticle mediated surface enhanced Raman spectroscopy (smSERS). The evolution of the interfacial chemistry in the buffer layer is monitored through the Raman band at 2132 cm-1 corresponding to the Sisbnd H stretch mode. Graphene quality is monitored directly by the selectively enhanced Raman signal of graphene compared to the SiC substrate signal. Through smSERS, a simultaneous correlation between optimized hydrogen intercalation in epitaxial graphene/SiC and an increase in graphene quality is uncovered. Following UV-ozone treatment, a fully hydrogen passivated interface is retained, while a moderate degradation in the quality of the hydrogen intercalated quasi-freestanding graphene is observed. While hydrogen intercalated defect free quasi-freestanding graphene is expected to be robust upon UV-ozone, thermal annealing, and oxygen exposure, ozonolytic reactivity at the edges of H-intercalated defected graphene results in enhanced amorphization of the quasi-freestanding (compared to non-intercalated) graphene, leading ultimately to its complete etching.

  3. The evolution of the surface of the mineral schreibersite in prebiotic chemistry.

    PubMed

    La Cruz, Nikita L; Qasim, Danna; Abbott-Lyon, Heather; Pirim, Claire; McKee, Aaron D; Orlando, Thomas; Gull, Maheen; Lindsay, Danny; Pasek, Matthew A

    2016-07-27

    We present a study of the reactions of the meteoritic mineral schreibersite (Fe,Ni)3P, focusing primarily on surface chemistry and prebiotic phosphorylation. In this work, a synthetic analogue of the mineral was synthesized by mixing stoichiometric proportions of elemental iron, nickel and phosphorus and heating in a tube furnace at 820 °C for approximately 235 hours under argon or under vacuum, a modification of the method of Skála and Drábek (2002). Once synthesized, the schreibersite was characterized to confirm the identity of the product as well as to elucidate the oxidation processes affecting the surface. In addition to characterization of the solid product, this schreibersite was reacted with water or with organic solutes in a choline chloride-urea deep eutectic mixture, to constrain potential prebiotic products. Major inorganic solutes produced by reaction of water include orthophosphate, phosphite, pyrophosphate and hypophosphate consistent with prior work on Fe3P corrosion. Additionally, schreibersite corrodes in water and dries down to form a deep eutectic solution, generating phosphorylated products, in this case phosphocholine, using this synthesized schreibersite. PMID:27157087

  4. Preparation and application of a novel electrochemical sensing material based on surface chemistry of polyhydroquinone.

    PubMed

    Dang, Xueping; Wang, Yingkai; Hu, Chengguo; Huang, Jianlin; Chen, Huaixia; Wang, Shengfu; Hu, Shengshui

    2014-07-01

    A new analogue of polydopamine (PDA), i.e., polyhydroquinone (PH2Q), was polymerized and its surface chemistry was studied by different ways of characterization. PH2Q was produced by the self-polymerization of H2Q mediated by dissolved oxygen, and the self-polymerization process was strongly dependent on the type and the pH value of the buffer solutions. PH2Q can not only achieve surface hydrophilization of different substrates like polyethylene terephthalate (PET) film, graphite strip, C12SH/Au and wax slice, but also possess several unique properties like reversible adsorption, good solubility and low cost. These properties made PH2Q an ideal polymeric modifier for the noncovalent functionalization of some nanomaterials. By simply grinding with PH2Q, pristine multi-walled carbon nanotubes (MWNTs) can be readily dispersed in water with high solubility and good stability. The resulting MWNT-PH2Q composite exhibited excellent electrochemical performance, which was employed for the simultaneous determination of dopamine (DA) and uric acid (UA). PMID:24857459

  5. Surface functionalization of two-dimensional metal chalcogenides by Lewis acid–base chemistry

    NASA Astrophysics Data System (ADS)

    Lei, Sidong; Wang, Xifan; Li, Bo; Kang, Jiahao; He, Yongmin; George, Antony; Ge, Liehui; Gong, Yongji; Dong, Pei; Jin, Zehua; Brunetto, Gustavo; Chen, Weibing; Lin, Zuan-Tao; Baines, Robert; Galvão, Douglas S.; Lou, Jun; Barrera, Enrique; Banerjee, Kaustav; Vajtai, Robert; Ajayan, Pulickel

    2016-05-01

    Precise control of the electronic surface states of two-dimensional (2D) materials could improve their versatility and widen their applicability in electronics and sensing. To this end, chemical surface functionalization has been used to adjust the electronic properties of 2D materials. So far, however, chemical functionalization has relied on lattice defects and physisorption methods that inevitably modify the topological characteristics of the atomic layers. Here we make use of the lone pair electrons found in most of 2D metal chalcogenides and report a functionalization method via a Lewis acid–base reaction that does not alter the host structure. Atomic layers of n-type InSe react with Ti4+ to form planar p-type [Ti4+n(InSe)] coordination complexes. Using this strategy, we fabricate planar p–n junctions on 2D InSe with improved rectification and photovoltaic properties, without requiring heterostructure growth procedures or device fabrication processes. We also show that this functionalization approach works with other Lewis acids (such as B3+, Al3+ and Sn4+) and can be applied to other 2D materials (for example MoS2, MoSe2). Finally, we show that it is possible to use Lewis acid–base chemistry as a bridge to connect molecules to 2D atomic layers and fabricate a proof-of-principle dye-sensitized photosensing device.

  6. Surface functionalization of two-dimensional metal chalcogenides by Lewis acid-base chemistry.

    PubMed

    Lei, Sidong; Wang, Xifan; Li, Bo; Kang, Jiahao; He, Yongmin; George, Antony; Ge, Liehui; Gong, Yongji; Dong, Pei; Jin, Zehua; Brunetto, Gustavo; Chen, Weibing; Lin, Zuan-Tao; Baines, Robert; Galvão, Douglas S; Lou, Jun; Barrera, Enrique; Banerjee, Kaustav; Vajtai, Robert; Ajayan, Pulickel

    2016-05-01

    Precise control of the electronic surface states of two-dimensional (2D) materials could improve their versatility and widen their applicability in electronics and sensing. To this end, chemical surface functionalization has been used to adjust the electronic properties of 2D materials. So far, however, chemical functionalization has relied on lattice defects and physisorption methods that inevitably modify the topological characteristics of the atomic layers. Here we make use of the lone pair electrons found in most of 2D metal chalcogenides and report a functionalization method via a Lewis acid-base reaction that does not alter the host structure. Atomic layers of n-type InSe react with Ti(4+) to form planar p-type [Ti(4+)n(InSe)] coordination complexes. Using this strategy, we fabricate planar p-n junctions on 2D InSe with improved rectification and photovoltaic properties, without requiring heterostructure growth procedures or device fabrication processes. We also show that this functionalization approach works with other Lewis acids (such as B(3+), Al(3+) and Sn(4+)) and can be applied to other 2D materials (for example MoS2, MoSe2). Finally, we show that it is possible to use Lewis acid-base chemistry as a bridge to connect molecules to 2D atomic layers and fabricate a proof-of-principle dye-sensitized photosensing device. PMID:26828848

  7. Surface chemistry of coated lithium manganese nickel oxide thin film cathodes studied by XPS

    SciTech Connect

    Baggetto, Loic; Dudney, Nancy J; Veith, Gabriel M

    2013-01-01

    The effect of coating high voltage LiMn1.5Ni0.5O4 spinel cathode thin films with three metal oxide thin layers is discussed. The changes in surface chemistry of the electrodes are measured by X-ray photoelectron spectroscopy. ZnO is found to decompose during the first charge whereas Al2O3 and ZrO2 are stable for more than 100 cycles. ZrO2, however, importantly limits the available Li storage capacity of the electrochemical reaction due to poorer kinetics. Al2O3 offers the best results in term of capacity retention. Upon cycling, the evidence of a signal at 75.4 eV in the Al2p binding energy spectrum indicates the partial conversion of Al2O3 into Al2O2F2. Moreover, the continuous formation of PEO , esters and LixPOyFz compounds on the surface of the electrodes is found for all coating materials.

  8. Succinimidyl Ester Surface Chemistry: Implications of the Competition between Aminolysis and Hydrolysis on Covalent Protein Immobilization

    PubMed Central

    2015-01-01

    N-Hydroxysuccinimide (NHS) ester terminal groups are commonly used to covalently couple amine-containing biomolecules (e.g., proteins and peptides) to surfaces via amide linkages. This one-step aminolysis is often performed in buffered aqueous solutions near physiological pH (pH 6 to pH 9). Under these conditions, the hydrolysis of the ester group competes with the amidization process, potentially degrading the efficiency of the coupling chemistry. The work herein examines the efficiency of covalent protein immobilization in borate buffer (50 mM, pH 8.50) using the thiolate monolayer formed by the chemisorption of dithiobis (succinimidyl propionate) (DSP) on gold films. The structure and reactivity of these adlayers are assessed via infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), electrochemical reductive desorption, and contact angle measurements. The hydrolysis of the DSP-based monolayer is proposed to follow a reaction mechanism with an initial nucleation step, in contrast to a simple pseudo first-order reaction rate law for the entire reaction, indicating a strong dependence of the interfacial reaction on the packing and presence of defects in the adlayer. This interpretation is used in the subsequent analysis of IR-ERS kinetic plots which give a heterogeneous aminolysis rate constant, ka, that is over 3 orders of magnitude lower than that of the heterogeneous hydrolysis rate constant, kh. More importantly, a projection of these heterogeneous kinetic rates to protein immobilization suggests that under coupling conditions in which low protein concentrations and buffers of near physiological pH are used, proteins are more likely physically adsorbed rather than covalently linked. This result is paramount for biosensors that use NHS chemistry for protein immobilization due to effects that may arise from noncovalently linked proteins. PMID:25317495

  9. Comparison of surface water chemistry and weathering effects of two lake basins in the Changtang Nature Reserve, China.

    PubMed

    Wang, Rui; Liu, Zhaofei; Jiang, Liguang; Yao, Zhijun; Wang, Junbo; Ju, Jianting

    2016-03-01

    The geochemistry of natural waters in the Changtang Nature Reserve, northern Tibet, can help us understand the geology of catchments, and provide additional insight in surface processes that influence water chemistry such as rock weathering on the Qinghai-Tibet Plateau. However, severe natural conditions are responsible for a lack of scientific data for this area. This study represents the first investigation of the chemical composition of surface waters and weathering effects in two lake basins in the reserve (Lake Dogaicoring Qiangco and Lake Longwei Co). The results indicate that total dissolved solids (TDS) in the two lakes are significantly higher than in other gauged lakes on the Qinghai-Tibet Plateau, reaching 20-40g/L, and that TDS of the tectonic lake (Lake Dogaicoring Qiangco) is significantly higher than that of the barrier lake (Lake Longwei Co). Na(+) and Cl(-) are the dominant ions in the lake waters as well as in the glacier-fed lake inflows, with chemical compositions mainly affected by halite weathering. In contrast, ion contents of inflowing rivers fed by nearby runoff are lower and concentrations of dominant ions are not significant. Evaporite, silicate, and carbonate weathering has relatively equal effects on these rivers. Due to their limited scope, small streams near the lakes are less affected by carbonate than by silicate weathering. PMID:26969064

  10. Adsorption of dyes by ACs prepared from waste tyre reinforcing fibre. Effect of texture, surface chemistry and pH.

    PubMed

    Acevedo, Beatriz; Rocha, Raquel P; Pereira, Manuel F R; Figueiredo, José L; Barriocanal, Carmen

    2015-12-01

    This paper compares the importance of the texture and surface chemistry of waste tyre activated carbons in the adsorption of commercial dyes. The adsorption of two commercial dyes, Basic Astrazon Yellow 7GLL and Reactive Rifafix Red 3BN on activated carbons made up of reinforcing fibres from tyre waste and low-rank bituminous coal was studied. The surface chemistry of activated carbons was modified by means of HCl-HNO3 treatment in order to increase the number of functional groups. Moreover, the influence of the pH on the process was also studied, this factor being of great importance due to the amphoteric characteristics of activated carbons. The activated carbons made with reinforcing fibre and coal had the highest SBET, but the reinforcing fibre activated carbon samples had the highest mesopore volume. The texture of the activated carbons was not modified upon acid oxidation treatment, unlike their surface chemistry which underwent considerable modification. The activated carbons made with a mixture of reinforcing fibre and coal experienced the largest degree of oxidation, and so had more acid surface groups. The adsorption of reactive dye was governed by the mesoporous volume, whilst surface chemistry played only a secondary role. However, the surface chemistry of the activated carbons and dispersive interactions played a key role in the adsorption of the basic dye. The adsorption of the reactive dye was more favored in a solution of pH 2, whereas the basic dye was adsorbed more easily in a solution of pH 12. PMID:26295195

  11. Near-ambient pressure XPS of high-temperature surface chemistry in Sr2Co2O5 thin films

    DOE PAGESBeta

    Hong, Wesley T.; Stoerzinger, Kelsey; Crumlin, Ethan J.; Mutoro, Eva; Jeen, Hyoung Jeen; Lee, Ho Nyung; Shao-Horn, Yang

    2016-02-11

    Transition metal perovskite oxides are promising electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells, but a lack of fundamental understanding of oxide surfaces impedes the rational design of novel catalysts with improved device efficiencies. In particular, understanding the surface chemistry of oxides is essential for controlling both catalytic activity and long-term stability. Thus, elucidating the physical nature of species on perovskite surfaces and their catalytic enhancement would generate new insights in developing oxide electrocatalysts. In this article, we perform near-ambient pressure XPS of model brownmillerite Sr2Co2O5 (SCO) epitaxial thin films with different crystallographic orientations. Detailed analysis of themore » Co 2p spectra suggests that the films lose oxygen as a function of temperature. Moreover, deconvolution of the O 1s spectra shows distinct behavior for (114)-oriented SCO films compared to (001)-oriented SCO films, where an additional bulk oxygen species is observed. These findings indicate a change to a perovskite-like oxygen chemistry that occurs more easily in (114) SCO than (001) SCO, likely due to the orientation of oxygen vacancy channels out-of-plane with respect to the film surface. This difference in surface chemistry is responsible for the anisotropy of the oxygen surface exchange coefficient of SCO and may contribute to the enhanced ORR kinetics of La0.8Sr0.2CoO3-δ thin films by SCO surface particles observed previously.« less

  12. Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

    NASA Astrophysics Data System (ADS)

    González, J.; Chen, L. F.; Wang, J. A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J. L.

    2016-08-01

    A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H2O2 as oxidant. ODS activity was found to be proportional to the V5+/(V4+ + V5+) values of the catalysts, indicating that the surface vanadium pentoxide (V2O5) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V2O5) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V2O5/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

  13. Atomic Scale Imaging of the Electronic Structure and Chemistry of Graphene and Its Precursors on Metal Surfaces

    SciTech Connect

    Flynn, George W

    2015-02-16

    Executive Summary of Final Report for Award DE-FG02-88ER13937 Project Title: Atomic Scale Imaging of the Electronic Structure and Chemistry of Graphene and its Precursors on Metal Surfaces Applicant/Institution: Columbia University Principal Investigator: George W. Flynn Objectives: The objectives of this project were to reveal the mechanisms and reaction processes that solid carbon materials undergo when combining with gases such as oxygen, water vapor and hydrocarbons. This research was focused on fundamental chemical events taking place on single carbon sheets of graphene, a two-dimensional, polycyclic carbon material that possesses remarkable chemical and electronic properties. Ultimately, this work is related to the role of these materials in mediating the formation of polycyclic aromatic hydrocarbons (PAH’s), their reactions at interfaces, and the growth of soot particles. Our intent has been to contribute to a fundamental understanding of carbon chemistry and the mechanisms that control the formation of PAH’s, which eventually lead to the growth of undesirable particulates. We expect increased understanding of these basic chemical mechanisms to spur development of techniques for more efficient combustion of fossil fuels and to lead to a concomitant reduction in the production of undesirable solid carbon material. Project Description: Our work treated specifically the surface chemistry aspects of carbon reactions by using proximal probe (atomic scale imaging) techniques to study model systems of graphene that have many features in common with soot forming reactions of importance in combustion flames. Scanning tunneling microscopy (STM) is the main probe technique that we used to study the interfacial structure and chemistry of graphene, mainly because of its ability to elucidate surface structure and dynamics with molecular or even atomic resolution. Scanning tunneling spectroscopy (STS), which measures the local density of quantum states over a single

  14. Surface-Enhanced Resonance Raman Scattering and Visible Extinction Spectroscopy of Copper Chlorophyllin: An Upper Level Chemistry Experiment

    ERIC Educational Resources Information Center

    Schnitzer, Cheryl S.; Reim, Candace Lawson; Sirois, John J.; House, Paul G.

    2010-01-01

    Advanced chemistry students are introduced to surface-enhanced resonance Raman scattering (SERRS) by studying how sodium copper chlorophyllin (CuChl) adsorbs onto silver colloids (CuChl/Ag) as a function of pH. Using both SERRS and visible extinction spectroscopy, the extent of CuChl adsorption and colloidal aggregation are monitored. Initially at…

  15. Trends in Surface Water Chemistry in Acidified Areas in Europe and North America from 1990 to 2008

    EPA Science Inventory

    Acidification of lakes and rivers is still an environmental concern despite reduced emissions of acidifying compounds. We analyzed trends in surface water chemistry of 173 acid-sensitive sites from 12 regions in Europe and North America. In 11 of 12 regions, non-marine sulphate (...

  16. Investigating the effectiveness of implementing the Science Writing Heuristic on student performance in general chemistry

    NASA Astrophysics Data System (ADS)

    Poock, Jason Ray

    This research investigated the effectiveness at how the Science Writing Heuristic in the freshman chemistry laboratory for science and engineering majors at Iowa State University during the fall and spring semesters of the 2002--2003 academic year, was implemented. The Science Writing Heuristic (SWH) consists of two components, writing to learn strategies and conducting the laboratory session in a student-centered, guided-inquiry fashion. The writing component replaced the standard laboratory report with a series of questions that guided the students' critical thinking along the lines of scientific investigation. The writing process helped students construct knowledge. Also critical to the successful implementation of the SWH was conducting the laboratory experiments in a student-centered, guided-inquiry fashion. Through the SWH the students became engaged in meaningful scientific dialogue that promoted knowledge construction. For the SWH to be properly implemented, a classroom dynamic between the teacher and the students should be established. The teacher provides the framework within which the laboratory experiment is conducted and the students respond to that guidance by becoming engaged in the learning process. Results of the study showed that student scores improved when the teacher properly implemented the SWH, when the students responded positively to the implementation of the SWH, and when there was a proper classroom dynamic created between the teacher and the students. This study revealed that successful implementation of the SWH was beneficial to females and low ability students. This research also demonstrated a connection between the implementation of a learning strategy in the laboratory component of a course and the subsequent benefit in student performance in the lecture component of the course.

  17. INVESTIGATION OF FUEL CHEMISTRY AND BED PERFORMANCE IN A FLUIDIZED BED BLACK LIQUOR STEAM REFORMER

    SciTech Connect

    Kevin Whitty

    2003-12-01

    The University of Utah project ''Investigation of Fuel Chemistry and Bed Performance in a Fluidized Bed Black Liquor Steam Reformer'' (DOE award number DE-FC26-02NT41490) was developed in response to a solicitation for projects to provide technical support for black liquor and biomass gasification. The primary focus of the project is to provide support for a DOE-sponsored demonstration of MTCI's black liquor steam reforming technology at Georgia-Pacific's paper mill in Big Island, Virginia. A more overarching goal is to improve the understanding of phenomena that take place during low temperature black liquor gasification. This is achieved through five complementary technical tasks: (1) construction of a fluidized bed black liquor gasification test system, (2) investigation of bed performance, (3) evaluation of product gas quality, (4) black liquor conversion analysis and modeling and (5) computational modeling of the Big Island gasifier. Four experimental devices have been constructed under this project. The largest facility, which is the heart of the experimental effort, is a pressurized fluidized bed gasification test system. The system is designed to be able to reproduce conditions near the black liquor injectors in the Big Island steam reformer, so the behavior of black liquor pyrolysis and char gasification can be quantified in a representative environment. The gasification test system comprises five subsystems: steam generation and superheating, black liquor feed, fluidized bed reactor, afterburner for syngas combustion and a flue gas cooler/condenser. The three-story system is located at University of Utah's Industrial Combustion and Gasification Research Facility, and all resources there are available to support the research.

  18. Surface chemistry of the atomic layer deposition of metals and group III oxides

    NASA Astrophysics Data System (ADS)

    Goldstein, David Nathan

    Atomic Layer Deposition (ALD) is a thin-film growth technique offering precise control of film thickness and the ability to coat high-aspect-ratio features such as trenches and nanopowders. Unlike other film growth techniques, ALD does not require harsh processing conditions and is not limited by line-of-sight deposition. Emerging applications for ALD materials include semiconductor devices, gas sensors, and water-diffusion barriers. The chemistry behind ALD involves understanding how the precursors interact with surfaces to deposit the desired material. All ALD precursors need to be stable on the substrate to ensure self-limiting behavior yet reactive enough to be easily removed with the second reagent. Recent precursor development has provided many volatile organometallic compounds for most of the periodic table. As the number of precursors increases, proper precursor choice becomes crucial. This is because the film properties, growth rates, and growth temperature vary widely between the precursors. Many of the above traits can be predicted with knowledge of the precursor reaction mechanisms. This thesis aims to link surface reaction mechanisms to observed growth and nucleation trends in metal and oxide ALD systems. The first portion of this thesis explores the mechanisms of two ALD oxide systems. First, I examine the mechanism of ALD alumina with ozone. Ozone is used as an oxidant in the semiconductor industry because the deposited Al 2O3 films possess better insulating properties and ozone is easier to purge from a vacuum system. FT-IR analysis reveals a complicated array of surface intermediates such as formate, carbonate, and methoxy groups that form during Al2O3 growth with ozone. Next, a new method to deposit thin films of Ga2O3 is introduced. Gallium oxide is a transparent conducting oxide that needs expensive solid precursors to be deposited by ALD. I show that trimethylgallium is a good high-temperature ALD precursor that deposits films of Ga2O 3 with

  19. Patterned porous silicon photonic crystals with modular surface chemistry for spatial control of neural stem cell differentiation

    NASA Astrophysics Data System (ADS)

    Huang, Tiffany H.; Pei, Yi; Zhang, Douglas; Li, Yanfen; Kilian, Kristopher A.

    2016-05-01

    We present a strategy to spatially define regions of gold and nanostructured silicon photonics, each with materials-specific surface chemistry, for azide-alkyne cycloaddition of different bioactive peptides. Neural stem cells are spatially directed to undergo neurogenesis and astrogenesis as a function of both surface properties and peptide identity.We present a strategy to spatially define regions of gold and nanostructured silicon photonics, each with materials-specific surface chemistry, for azide-alkyne cycloaddition of different bioactive peptides. Neural stem cells are spatially directed to undergo neurogenesis and astrogenesis as a function of both surface properties and peptide identity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08327c

  20. A UNIFIED MONTE CARLO TREATMENT OF GAS-GRAIN CHEMISTRY FOR LARGE REACTION NETWORKS. II. A MULTIPHASE GAS-SURFACE-LAYERED BULK MODEL

    SciTech Connect

    Vasyunin, A. I.; Herbst, Eric E-mail: eh2ef@virginia.edu

    2013-01-10

    The observed gas-phase molecular inventory of hot cores is believed to be significantly impacted by the products of chemistry in interstellar ices. In this study, we report the construction of a full macroscopic Monte Carlo model of both the gas-phase chemistry and the chemistry occurring in the icy mantles of interstellar grains. Our model treats icy grain mantles in a layer-by-layer manner, which incorporates laboratory data on ice desorption correctly. The ice treatment includes a distinction between a reactive ice surface and an inert bulk. The treatment also distinguishes between zeroth- and first-order desorption, and includes the entrapment of volatile species in more refractory ice mantles. We apply the model to the investigation of the chemistry in hot cores, in which a thick ice mantle built up during the previous cold phase of protostellar evolution undergoes surface reactions and is eventually evaporated. For the first time, the impact of a detailed multilayer approach to grain mantle formation on the warm-up chemistry is explored. The use of a multilayer ice structure has a mixed impact on the abundances of organic species formed during the warm-up phase. For example, the abundance of gaseous HCOOCH{sub 3} is lower in the multilayer model than in previous grain models that do not distinguish between layers (so-called two phase models). Other gaseous organic species formed in the warm-up phase are affected slightly. Finally, we find that the entrapment of volatile species in water ice can explain the two-jump behavior of H{sub 2}CO previously found in observations of protostars.

  1. LABORATORY AND COMPUTATIONAL INVESTIGATIONS OF THE ATMOSPHERIC CHEMISTRY OF KEY OXIDATION PRODUCTS CONTROLLING TROPOSPHERIC OZONE FORMATION

    EPA Science Inventory

    Major uncertainties remain in our ability to identify the key reactions and primary oxidation products of volatile hydrocarbons that contribute to ozone formation in the troposphere. To reduce these uncertainties, computational chemistry, mechanistic and process analysis techniqu...

  2. Effects of surface chemistry prepared by self-assembled monolayers on osteoblast behavior.

    PubMed

    Nakaoka, Ryusuke; Yamakoshi, Yoko; Isama, Kazuo; Tsuchiya, Toshie

    2010-08-01

    A surface of biomaterials is known to affect the behavior of cells after their adhesion on the surface, indicating that surface characteristics of biomaterials play an important role in cell adhesion, proliferation, and differentiation. To assess the effects of functional groups on biomaterial surface, normal human osteoblasts (NHOsts) were cultured on surfaces coated with self-assembled monolayers (SAMs) containing various functional groups, and the adhesion, proliferation, differentiation, and gap junctional intercellular communication (GJIC) of the NHOsts were investigated. In the case of SAM with terminal methyl groups (hydrophobic surface), NHOst adhesion and proliferation was less prevalent. In contrast, NHOsts were adhered well on SAMs with hydroxyl, carboxyl, amino, phosphate, and sulfate group, which are relatively hydrophilic, their proliferation and differentiation level were dependent on the type of functional groups. Especially, when they were cultured on either SAMs with phosphate or sulfate group, both their alkaline phosphate activity and the calcium deposition by them were enhanced more than those cultured on a collagen-coated dish. More interestingly, GJIC of NHOsts, which has been reported to play a role in cell differentiation as well as homeostasis of cells, were not significantly different among the SAM surfaces tested. These suggest that a specific functional group on a material surface can regulate NHOst adhesion, proliferation, and differentiation via cell-functional group interaction without influencing their homeostasis. PMID:20186768

  3. Theoretical Investigation of TI-Doped Zirconia Surfaces

    NASA Astrophysics Data System (ADS)

    Chauke, Hasani; Grau-Crespo, Ricardo; Ngoepe, Phuti; de Leeuw, Nora H.

    2010-03-01

    We use density functional theory calculations with Hubbard corrections (DFT+U) to investigate the electronic and redox properties of Ti-substituted zirconia (111) surfaces. It is found that titanium dopants are more likely to segregate at the surface than to migrate to the zirconia bulk. The formation energy of oxygen vacancies decreases substantially in titanium-substituted surfaces with respect to undoped surfaces. If an O vacancy is created around an isolated Ti dopant, a Ti^4+ -> Ti^2+ reduction takes place, while if the vacancy is created in the vicinity of a pair of dopants, each Ti atom adopts a 3+ oxidation state, with additional decrease in the vacancy formation energy. We investigate in detail the relevant distribution of dopants and vacancies in the system, and discuss the implications of our results for some applications of zirconia-based ceramics.

  4. Nanocrystalline Sm{sub 0.5}Sr{sub 0.5}CoO{sub 3−δ} synthesized using a chelating route for use in IT-SOFC cathodes: Microstructure, surface chemistry and electrical conductivity

    SciTech Connect

    Scurtu, Rares; Somacescu, Simona; Calderon-Moreno, Jose Maria; Culita, Daniela; Bulimestru, Ion; Popa, Nelea; Gulea, Aurelian; Osiceanu, Petre

    2014-02-15

    Nanocrystalline Sm{sub 0.5}Sr{sub 0.5}CoO{sub 3−δ} powders were synthesized by a chelating route using different polyfunctional H{sub x}APC acids (APC=aminopolycarboxylate; x=3, 4, 5). Different homologous aminopolycarboxylic acids, namely nitrilotriacetic (H{sub 3}nta), ethylenediaminetetraacetic (H{sub 4}edta), 1,2-cyclohexanediaminetetracetic (H{sub 4}cdta) and diethylenetriaminepentaacetic (H{sub 5}dtpa) acid, were used as chelating agents to combine Sm, Sr, Co elements into a perovskite structure. The effects of the chelating agents on the crystalline structure, porosity, surface chemistry and electrical properties were investigated. The electrical properties of the perovskite-type materials emphasized that their conductivities in the temperature range of interest (600–800 °C) depend on the nature of the precursors as well as on the presence of a residual Co oxide phase as shown by XRD and XPS analysis. The surface chemistry and the surface stoichiometries were determined by XPS revealing a complex chemical behavior of Sr that exhibits a peculiar “surface phase” and “bulk phase” chemistry within the detected volume (<10 nm). - Graphical abstract: Synthesis of nanocrystalline Sm{sub 0.5}Sr{sub 0.5}CoO{sub 3−δ} powders by a chelating route and the investigation of the microstructure, surface chemistry and electrical properties. Display Omitted - Highlights: • Nanocrystalline Sm{sub 0.5}Sr{sub 0.5}CoO{sub 3−δ} obtained by a chelating synthesis route. • Cubic perovskite structures with crystallite sizes ∼23±2 nm. • The porous nature revealed by N{sub 2} adsorption/desorption (BET). • The surface chemistry and the surface stoichiometries highlighted by XPS. • A complex chemical behavior of Sr exhibits a peculiar “surface phase” and “bulk phase” chemistry.

  5. Surface Chemistry, Friction, and Wear Properties of Untreated and Laser-Annealed Surfaces of Pulsed-Laser-Deposited WS(sub 2) Coatings

    NASA Technical Reports Server (NTRS)

    Miyoshi, Kazuhisa; Wheeler, Donald R.; Zabinski, Jeffrey S.

    1996-01-01

    An investigation was conducted to examine the surface chemistry, friction, and wear behavior of untreated and annealed tungsten disulfide (WS2) coatings in sliding contact with a 6-mm-diameter 440C stainless-steel ball. The WS2 coatings and annealing were performed using the pulsed-laser-deposition technique. All sliding friction experiments were conducted with a load of 0.98 N (100 g), an average Hertzian contact pressure of 0.44 GPa, and a constant rotating speed of 120 rpm. The sliding velocity ranged from 31 to 107 mm/s because of the range of wear track radii involved in the experiments. The experiment was performed at room temperature in three environments: ultrahigh vacuum (vacuum pressure, 7X(exp -10) Pa), dry nitrogen (relative humidity, less than 1 percent), and humid air (relative humidity, 15 to 40 percent). Analytical techniques, including scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDX), x-ray photo electron spectroscopy (XPS), surface profilometry, and Vickers hardness testing, were used to characterize the tribological surfaces of WS2 coatings. The results of the investigation indicate that the laser annealing decreased the wear of a WS2 coating in an ultrahigh vacuum. The wear rate was reduced by a factor of 30. Thus, the laser annealing increased the wear life and resistance of the WS2 coating. The annealed WS 2 coating had a low coefficient of friction (less than O.1) and a low wear rate ((10(exp -7) mm(exp 3)/N-m)) both of which are favorable in an ultrahigh vacuum.

  6. The Martian Dust Cycle: Investigation of the Surface Lifting Component

    NASA Technical Reports Server (NTRS)

    Murphy, James R.; Bridger, Alison F. C.; Haberle, Robert M.

    1996-01-01

    We have investigated the nature of the annual cycle of suspended dust in the martian atmosphere. This has been undertaken to understand the dynamical processes responsible for lifting dust from the surface, locations where dust is preferentially lifted, and preferred sites for dust deposition upon the surface. Our efforts have involved carrying out a number of numerical simulations with the Ames Mars General Circulation Model (GCM) interactively coupled with an aerosol transport/ micro-physical model. The model generates an annual dust cycle similar to that observed. Various feedbacks are present in the atmosphere/ surface system which enter into the generation of the cycle. Several locations are primary surface sources of dust, while much of the remaining planet's surface acts a sink for suspended dust.

  7. Investigation of aluminum surface cleaning using cavitating fluid flow

    NASA Astrophysics Data System (ADS)

    Ralys, Aurimas; Striška, Vytautas; Mokšin, Vadim

    2013-12-01

    This paper investigates efficiency of specially designed atomizer used to spray water and cavitate microbubbles in water flow. Surface cleaning system was used to clean machined (grinded) aluminum surface from abrasive particles. It is established that cleaning efficiency depends