WorldWideScience

Sample records for bioassay surface chemistry

  1. Acarine attractants: Chemoreception, bioassay, chemistry and control.

    Science.gov (United States)

    Carr, Ann L; Roe, Michael

    2016-07-01

    The Acari are of significant economic importance in crop production and human and animal health. Acaricides are essential for the control of these pests, but at the same time, the number of available pesticides is limited, especially for applications in animal production. The Acari consist of two major groups, the mites that demonstrate a wide variety of life strategies, i.e., herbivory, predation and ectoparasitism, and ticks which have evolved obligatory hematophagy. The major sites of chemoreception in the acarines are the chelicerae, palps and tarsi on the forelegs. A unifying name, the "foretarsal sensory organ" (FSO), is proposed for the first time in this review for the sensory site on the forelegs of all acarines. The FSO has multiple sensory functions including olfaction, gustation, and heat detection. Preliminary transcriptomic data in ticks suggest that chemoreception in the FSO is achieved by a different mechanism from insects. There are a variety of laboratory and field bioassay methods that have been developed for the identification and characterization of attractants but minimal techniques for electrophysiology studies. Over the past three to four decades, significant progress has been made in the chemistry and analysis of function for acarine attractants in mites and ticks. In mites, attractants include aggregation, immature female, female sex and alarm pheromones; in ticks, the attraction-aggregation-attachment, assembly and sex pheromones; in mites and ticks host kairomones and plant allomones; and in mites, fungal allomones. There are still large gaps in our knowledge of chemical communication in the acarines compared to insects, especially relative to acarine pheromones, and more so for mites than ticks. However, the use of lure-and-kill and lure-enhanced biocontrol strategies has been investigated for tick and mite control, respectively, with significant environmental advantages which warrant further study.

  2. Surface chemistry

    CERN Document Server

    Desai, KR

    2008-01-01

    The surface Chemistry of a material as a whole is crucially dependent upon the Nature and type of surfaces exposed on crystallites. It is therefore vitally important to independently Study different, well - defined surfaces through surface analytical techniques. In addition to composition and structure of surface, the subject also provides information on dynamic light scattering, micro emulsions, colloid Stability control and nanostructures. The present book endeavour to bring before the reader that the understanding and exploitation of Solid state phenomena depended largely on the ability to

  3. Surface chemistry essentials

    CERN Document Server

    Birdi, K S

    2013-01-01

    Surface chemistry plays an important role in everyday life, as the basis for many phenomena as well as technological applications. Common examples range from soap bubbles, foam, and raindrops to cosmetics, paint, adhesives, and pharmaceuticals. Additional areas that rely on surface chemistry include modern nanotechnology, medical diagnostics, and drug delivery. There is extensive literature on this subject, but most chemistry books only devote one or two chapters to it. Surface Chemistry Essentials fills a need for a reference that brings together the fundamental aspects of surface chemistry w

  4. Impact of surface chemistry

    OpenAIRE

    2010-01-01

    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.

  5. Bioassays as one of the Green Chemistry tools for assessing environmental quality: A review.

    Science.gov (United States)

    Wieczerzak, M; Namieśnik, J; Kudłak, B

    2016-09-01

    For centuries, mankind has contributed to irreversible environmental changes, but due to the modern science of recent decades, scientists are able to assess the scale of this impact. The introduction of laws and standards to ensure environmental cleanliness requires comprehensive environmental monitoring, which should also meet the requirements of Green Chemistry. The broad spectrum of Green Chemistry principle applications should also include all of the techniques and methods of pollutant analysis and environmental monitoring. The classical methods of chemical analyses do not always match the twelve principles of Green Chemistry, and they are often expensive and employ toxic and environmentally unfriendly solvents in large quantities. These solvents can generate hazardous and toxic waste while consuming large volumes of resources. Therefore, there is a need to develop reliable techniques that would not only meet the requirements of Green Analytical Chemistry, but they could also complement and sometimes provide an alternative to conventional classical analytical methods. These alternatives may be found in bioassays. Commercially available certified bioassays often come in the form of ready-to-use toxkits, and they are easy to use and relatively inexpensive in comparison with certain conventional analytical methods. The aim of this study is to provide evidence that bioassays can be a complementary alternative to classical methods of analysis and can fulfil Green Analytical Chemistry criteria. The test organisms discussed in this work include single-celled organisms, such as cell lines, fungi (yeast), and bacteria, and multicellular organisms, such as invertebrate and vertebrate animals and plants.

  6. Ecological quality assessment of Dutch surface waters using a new bioassay with the cladoceran Chydorus sphaericus

    NARCIS (Netherlands)

    Pieters, B.J.; Bosman-Meijerman, D.; Steenbergen, E.; van den Brandhof, E.J.; van Beelen, P.; van der Grinten, E.; Verweij, W.; Kraak, M.H.S.

    2008-01-01

    Routine chemical monitoring gives insight in the presence of contaminants in surface waters, but not in their joint ecological effects. Therefore ecological water quality is assessed with bioassays. Recently, a new bioassay using the chydorid Chydorus sphaericus has been developed. Working with smal

  7. Organic chemistry on solid surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Zhen; Zaera, Francisco [Department of Chemistry, University of California, Riverside, CA 92521 (United States)

    2006-07-15

    Chemistry on solid surfaces is central to many areas of practical interest such as heterogeneous catalysis, tribology, electrochemistry, and materials processing. With the development of many surface-sensitive analytical techniques in the past decades, great advances have been possible in our understanding of such surface chemistry at the molecular level. Earlier studies with model systems, single crystals in particular, have provided rich information about the adsorption and reaction kinetics of simple inorganic molecules. More recently, the same approach has been expanded to the study of the surface chemistry of relatively complex organic molecules, in large measure in connection with the selective synthesis of fine chemicals and pharmaceuticals. In this report, the chemical reactions of organic molecules and fragments on solid surfaces, mainly on single crystals of metals but also on crystals of metal oxides, carbides, nitrides, phosphides, sulfides and semiconductors as well as on more complex models such as bimetallics, alloys, and supported particles, are reviewed. A scheme borrowed from the organometallic and organic chemistry literature is followed in which key examples of representative reactions are cited first, and general reactivity trends in terms of both the reactants and the nature of the surface are then identified to highlight important mechanistic details. An attempt has been made to emphasize recent advances, but key earlier examples are cited as needed. Finally, correlations between surface and organometallic and organic chemistry, the relevance of surface reactions to applied catalysis and materials functionalization, and some promising future directions in this area are briefly discussed. (author)

  8. Surface chemistry theory and applications

    CERN Document Server

    Bikerman, J J

    2013-01-01

    Surface Chemistry Theory and Applications focuses on liquid-gas, liquid-liquid, solid-gas, solid-liquid, and solid-solid surfaces. The book first offers information on liquid-gas surfaces, including surface tension, measurement of surface tension, rate of capillarity rise, capillary attraction, bubble pressure and pore size, and surface tension and temperature. The text then ponders on liquid-liquid and solid-gas surfaces. Discussions focus on surface energy of solids, surface roughness and cleanness, adsorption of gases and vapors, adsorption hysteresis, interfacial tension, and interfacial t

  9. Surface Chemistry in Nanoscale Materials

    Directory of Open Access Journals (Sweden)

    Alex V. Hamza

    2009-12-01

    Full Text Available Although surfaces or, more precisely, the surface atomic and electronic structure, determine the way materials interact with their environment, the influence of surface chemistry on the bulk of the material is generally considered to be small. However, in the case of high surface area materials such as nanoporous solids, surface properties can start to dominate the overall material behavior. This allows one to create new materials with physical and chemical properties that are no longer determined by the bulk material, but by their nanoscale architectures. Here, we discuss several examples, ranging from nanoporous gold to surface engineered carbon aerogels that demonstrate the tuneability of nanoporous solids for sustainable energy applications.

  10. Surface chemistry in three dimensions

    DEFF Research Database (Denmark)

    Bollinger, Mikkel; Jacobsen, Karsten Wedel; Nørskov, Jens Kehlet

    2000-01-01

    the usual single surface ('2D') process because indirect adsorbate-adsorbate interactions in the transition state are absent in the '3D' case. The prospects for STM-induced single molecule chemistry and for '3D' catalysts are discussed. (C) 2000 Elsevier Science B.V. All rights reserved....

  11. Integrated assessment of runoff from livestock farming operations: analytical chemistry, in vitro bioassays, and in vivo fish exposures

    Science.gov (United States)

    Cavallin, Jenna E.; Durhan, Elizabeth J.; Evans, Nicola; Jensen, Kathleen M.; Kahl, Michael D.; Kolpin, Dana W.; Kolodziej, Edward P.; Foreman, William T.; LaLone, Carlie A.; Makynen, Elizabeth A.; Seidl, Sara M.; Thomas, Linnea M.; Villeneuve, Daniel L.; Weberg, Matthew A.; Wilson, Vickie S.; Ankley, Gerald T.

    2014-01-01

    Animal waste from livestock farming operations can contain varying levels of natural and synthetic androgens and/or estrogens, which can contaminate surrounding waterways. In the present study, surface stream water was collected from 6 basins containing livestock farming operations. Aqueous concentrations of 12 hormones were determined via chemical analyses. Relative androgenic and estrogenic activity was measured using in vitro cell assays (MDA-kb2 and T47D-Kbluc assays, respectively). In parallel, 48-h static-renewal in vivo exposures were conducted to examine potential endocrine-disrupting effects in fathead minnows. Mature fish were exposed to surface water dilutions (0%, 25%, 50%, and 100%) and 10-ng/L of 17α-ethynylestradiol or 50-ng/L of 17β-trenbolone as positive controls. Hepatic expression of vitellogenin and estrogen receptor α mRNA, gonadal ex vivo testosterone and 17β-estradiol production, and plasma vitellogenin concentrations were examined. Potentially estrogenic and androgenic steroids were detected at low nanogram per liter concentrations. In vitro estrogenic activity was detected in all samples, whereas androgenic activity was detected in only 1 sample. In vivo exposures to the surface water had no significant dose-dependent effect on any of the biological endpoints, with the exception of increased male testosterone production in 1 exposure. The present study, which combines analytical chemistry measurements, in vitro bioassays, and in vivo fish exposures, highlights the integrated value and future use of a combination of techniques to obtain a comprehensive characterization of an environmental chemical mixture. 

  12. Surface chemistry in photodissociation regions

    CERN Document Server

    Esplugues, G B; Meijerink, R; Spaans, M; Caselli, P

    2016-01-01

    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. 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. 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. 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 d...

  13. Programming Surface Chemistry with Engineered Cells.

    Science.gov (United States)

    Zhang, Ruihua; Heyde, Keith C; Scott, Felicia Y; Paek, Sung-Ho; Ruder, Warren C

    2016-09-16

    We have developed synthetic gene networks that enable engineered cells to selectively program surface chemistry. E. coli were engineered to upregulate biotin synthase, and therefore biotin synthesis, upon biochemical induction. Additionally, two different functionalized surfaces were developed that utilized binding between biotin and streptavidin to regulate enzyme assembly on programmable surfaces. When combined, the interactions between engineered cells and surfaces demonstrated that synthetic biology can be used to engineer cells that selectively control and modify molecular assembly by exploiting surface chemistry. Our system is highly modular and has the potential to influence fields ranging from tissue engineering to drug development and delivery.

  14. Chemistry of the Burning Surface

    Science.gov (United States)

    1993-10-12

    control voltage of the Pt filament is highly terial. This chemistry cannot be extracted by slowly heat- sensitive to the thermochemistry of the thin...azines. the residues formed at teach iernperature ’)ascd ýucli as melon, arc known to be thcriaalLv -.) tile absorhanice value ot ouhgaseous prod

  15. Switching surface chemistry with supramolecular machines.

    Energy Technology Data Exchange (ETDEWEB)

    Dunbar, Timothy D.; Kelly, Michael James; Jeppesen, Jan O. (University of California, Los Angeles, CA); Bunker, Bruce Conrad; Matzke, Carolyn M.; Stoddart, J. Fraser; Huber, Dale L.; Kushmerick, James G.; Flood, Amar H. (University of California, Los Angeles, CA); Perkins, Julie (University of California, Los Angeles, CA); Cao, Jianguo (University of California, Los Angeles, CA)

    2005-07-01

    Tethered supramolecular machines represent a new class of active self-assembled monolayers in which molecular configurations can be reversibly programmed using electrochemical stimuli. We are using these machines to address the chemistry of substrate surfaces for integrated microfluidic systems. Interactions between the tethered tetracationic cyclophane host cyclobis(paraquat-p-phenylene) and dissolved {pi}-electron-rich guest molecules, such as tetrathiafulvalene, have been reversibly switched by oxidative electrochemistry. The results demonstrate that surface-bound supramolecular machines can be programmed to adsorb or release appropriately designed solution species for manipulating surface chemistry.

  16. Controlled surface chemistries and quantitative cell response

    Science.gov (United States)

    Plant, Anne L.

    2002-03-01

    Living cells experience a large number of signaling cues from their extracellular matrix. As a result of these inputs, a variety of intracellular signaling pathways are apparently initiated simultaneously. The vast array of alternative responses that result from the integration of these inputs suggests that it may be reasonable to look for cellular response not as an 'on' or 'off' condition but as a distribution of responses. A difficult challenge is to determine whether variations in responses from individual cells arise from the complexity of intracellular signals or are due to variations in the cell culture environment. By controlling surface chemistry so that every cell 'sees' the same chemical and physical environment, we can begin to assess how the distribution of cell response is affected strictly by changes in the chemistry of the cell culture surface. Using the gene for green fluorescent protein linked to the gene for the promoter of the extracellular matrix protein, tenascin, we can easily probe the end product in a signaling pathway that is purported to be linked to surface protein chemistry and to cell shape. Cell response to well-controlled, well-characterized, and highly reproducible surfaces prepared using soft lithography techniques are compared with more conventional ways of preparing extracellular matrix proteins for cell culture. Using fluorescence microscopy and image analysis of populations of cells on these surfaces, we probe quantitatively the relationship between surface chemistry, cell shape and variations in gene expression endpoint.

  17. Surface chemistry driven actuation in nanoporous gold

    Energy Technology Data Exchange (ETDEWEB)

    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.

  18. The Plasma Chemistry of Polymer Surfaces

    CERN Document Server

    Friedrich, Jö

    2012-01-01

    This book illustrates plasma properties, polymer characteristics, surface specifics, and how to purposefully combine plasma and polymer chemistry. In so doing, it covers plasma polymerization, surface functionalization, etching, crosslinking, and deposition of monotype functional-group-bearing plasma polymers. It explains different techniques and plasma types, such as pressure-pulsed, remote, low-wattage plasmas and plasma polymerization in liquids. Finally, among the numerous applications discussed are plasmas for chemical synthesis, industrial processes or the modification of membranes and p

  19. Introduction to Applied Colloid and Surface Chemistry

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios; Kiil, Søren

    Colloid and Surface Chemistry is a subject of immense importance and implications both to our everyday life and numerous industrial sectors, ranging from coatings and materials to medicine and biotechnology. How do detergents really clean? (Why can’t we just use water ?) Why is milk “milky” Why do...... we use eggs so often for making sauces ? Can we deliver drugs in better and controlled ways? Coating industries wish to manufacture improved coatings e.g. for providing corrosion resistance, which are also environmentally friendly i.e. less based on organic solvents and if possible exclusively......, to the benefit of both the environment and our pocket. Cosmetics is also big business! Creams, lotions and other personal care products are really just complex emulsions. All of the above can be explained by the principles and methods of colloid and surface chemistry. A course on this topic is truly valuable...

  20. Chip-Scale Bioassays Based on Surface-Enhanced Raman Scattering: Fundamentals and Applications

    Energy Technology Data Exchange (ETDEWEB)

    Hye-Young Park

    2005-12-17

    This work explores the development and application of chip-scale bioassays based on surface-enhanced Raman scattering (SERS) for high throughput and high sensitivity analysis of biomolecules. The size effect of gold nanoparticles on the intensity of SERS is first presented. A sandwich immunoassay was performed using Raman-labeled immunogold nanoparticles with various sizes. The SERS responses were correlated to particle densities, which were obtained by atomic force microscopy (AFM). The response of individual particles was also investigated using Raman-microscope and an array of gold islands on a silicon substrate. The location and the size of individual particles were mapped using AFM. The next study describes a low-level detection of Escherichia coli 0157:H7 and simulants of biological warfare agents in a sandwich immunoassay format using SERS labels, which have been termed Extrinsic Raman labels (ERLs). A new ERL scheme based on a mixed monolayer is also introduced. The mixed monolayer ERLs were created by covering the gold nanoparticles with a mixture of two thiolates, one thiolate for covalently binding antibody to the particle and the other thiolate for producing a strong Raman signal. An assay platform based on mixed self-assembled monolayers (SAMs) on gold is then presented. The mixed SAMs were prepared from dithiobis(succinimidyl undecanoate) (DSU) to covalently bind antibodies on gold substrate and oligo(ethylene glycol)-terminated thiol to prevent nonspecific adsorption of antibodies. After the mixed SAMs surfaces, formed from various mole fraction of DSU were incubated with antibodies, AFM was used to image individual antibodies on the surface. The final study presents a collaborative work on the single molecule adsorption of YOYO-I labeled {lambda}-DNA at compositionally patterned SAMs using total internal reflection fluorescence microscopy. The role of solution pH, {lambda}-DNA concentration, and domain size was investigated. This work also revealed

  1. Chip-Scale Bioassays Based on Surface-Enhanced Raman Scattering: Fundamentals and Applications

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hye-Young [Iowa State Univ., Ames, IA (United States)

    2005-01-01

    This work explores the development and application of chip-scale bioassays based on surface-enhanced Raman scattering (SERS) for high throughput and high sensitivity analysis of biomolecules. The size effect of gold nanoparticles on the intensity of SERS is first presented. A sandwich immunoassay was performed using Raman-labeled immunogold nanoparticles with various sizes. The SERS responses were correlated to particle densities, which were obtained by atomic force microscopy (AFM). The response of individual particles was also investigated using Raman-microscope and an array of gold islands on a silicon substrate. The location and the size of individual particles were mapped using AFM. The next study describes a low-level detection of Escherichia coli 0157:H7 and simulants of biological warfare agents in a sandwich immunoassay format using SERS labels, which have been termed Extrinsic Raman labels (ERLs). A new ERL scheme based on a mixed monolayer is also introduced. The mixed monolayer ERLs were created by covering the gold nanoparticles with a mixture of two thiolates, one thiolate for covalently binding antibody to the particle and the other thiolate for producing a strong Raman signal. An assay platform based on mixed self-assembled monolayers (SAMs) on gold is then presented. The mixed SAMs were prepared from dithiobis(succinimidyl undecanoate) (DSU) to covalently bind antibodies on gold substrate and oligo(ethylene glycol)-terminated thiol to prevent nonspecific adsorption of antibodies. After the mixed SAMs surfaces, formed from various mole fraction of DSU were incubated with antibodies, AFM was used to image individual antibodies on the surface. The final study presents a collaborative work on the single molecule adsorption of YOYO-I labeled {lambda}-DNA at compositionally patterned SAMs using total internal reflection fluorescence microscopy. The role of solution pH, {lambda}-DNA concentration, and domain size was investigated. This work also revealed

  2. Surface chemistry of carbon dioxide revisited

    Science.gov (United States)

    Taifan, William; Boily, Jean-François; Baltrusaitis, Jonas

    2016-12-01

    This review discusses modern developments in CO2 surface chemistry by focusing on the work published since the original review by H.J. Freund and M.W. Roberts two decades ago (Surface Science Reports 25 (1996) 225-273). It includes relevant fundamentals pertaining to the topics covered in that earlier review, such as conventional metal and metal oxide surfaces and CO2 interactions thereon. While UHV spectroscopy has routinely been applied for CO2 gas-solid interface analysis, the present work goes further by describing surface-CO2 interactions under elevated CO2 pressure on non-oxide surfaces, such as zeolites, sulfides, carbides and nitrides. Furthermore, it describes additional salient in situ techniques relevant to the resolution of the interfacial chemistry of CO2, notably infrared spectroscopy and state-of-the-art theoretical methods, currently used in the resolution of solid and soluble carbonate species in liquid-water vapor, liquid-solid and liquid-liquid interfaces. These techniques are directly relevant to fundamental, natural and technological settings, such as heterogeneous and environmental catalysis and CO2 sequestration.

  3. Exploring the distance between nitrogen and phosphorus limitation in mesotrophic surface waters using a sensitive bioassay

    Science.gov (United States)

    Hrustić, Enis; Lignell, Risto; Riebesell, Ulf; Frede Thingstad, Tron

    2017-01-01

    The balance in microbial net consumption of nitrogen and phosphorus was investigated in samples collected in two mesotrophic coastal environments: the Baltic Sea (Tvärminne field station) and the North Sea (Espegrend field station). For this, we have refined a bioassay based on the response in alkaline phosphatase activity (APA) over a matrix of combinations in nitrogen and phosphorus additions. This assay not only provides information on which element (N or P) is the primary limiting nutrient, but also gives a quantitative estimate for the excess of the secondary limiting element (P+ or N+, respectively), as well as the ratio of balanced net consumption of added N and P over short timescales (days). As expected for a Baltic Sea late spring-early summer situation, the Tvärminne assays (n = 5) indicated N limitation with an average P+ = 0.30 ± 0.10 µM-P, when incubated for 4 days. For short incubations (1-2 days), the Espegrend assays indicated P limitation, but the shape of the response surface changed with incubation time, resulting in a drift in parameter estimates toward N limitation. Extrapolating back to zero incubation time gave P limitation with N+ ≈ 0.9 µM-N. The N : P ratio (molar) of nutrient net consumption varied considerably between investigated locations: from 2.3 ± 0.4 in the Tvärminne samples to 13 ± 5 and 32 ± 3 in two samples from Espegrend. Our assays included samples from mesocosm acidification experiments, but statistically significant effects of ocean acidification were not found by this method.

  4. Surface chemistry and mineralogy. [of planet Mars

    Science.gov (United States)

    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.

  5. Bioassay Laboratory

    Data.gov (United States)

    Federal Laboratory Consortium — The Bioassay Laboratory is an accredited laboratory capable of conducting standardized and innovative environmental testing in the area of aquatic ecotoxicology. The...

  6. Ferroelectric based catalysis: Switchable surface chemistry

    Science.gov (United States)

    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.

  7. Surface Chemistry and Spectroscopy of Chromium in Inorganic Oxides

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Wachs, I.E.; Schoonheydt, R.A.

    1996-01-01

    Focuses on the surface chemistry and spectroscopy of chromium in inorganic oxides. Characterization of the molecular structures of chromium; Mechanics of hydrogenation-dehydrogenation reactions; Mobility and reactivity on oxidic surfaces.

  8. The 2007 Nobel Prize in Chemistry for surface chemistry: understanding nanoscale phenomena at surfaces.

    Science.gov (United States)

    Bowker, Michael

    2007-11-01

    The 2007 Nobel Prize in Chemistry was awarded to Gerhard Ertl for his seminal work in the area of surface science, particularly at the gas-solid interface. Although Ertl began his career at a time when the term "nanotechnology" was not yet known, his contributions to the field have paved the way for many future scientists in this area and led to a deeper understanding of catalysis and other surface-specific processes at the nanoscale. Here, we summarize the scientific developments that guided early progress in surface science, and we explore the major advancements in Ertl's career, including his work on adsorption and oxidation of small molecules on metal surfaces. Significant contributions of other key scientists to this rich area are also presented.

  9. Bioassay-guided extraction of crude fucose-containing sulphated polysaccharides from Sargassum fusiforme with response surface methodology

    Science.gov (United States)

    Fu, Zhifei; Li, Haihua; Liu, Hongbing; Hu, Shuman; Li, Yueying; Wang, Mengxue; Guan, Huashi

    2016-06-01

    The response surface methodology (RSM) combined with bioassays was employed to optimize the extraction process of crude fucose-containing sulphated polysaccharides (cFCSP) from Sargassum fusiforme. The central composite design (CCD) was used with four variables, five levels, and four responses. The four variables were pH value of hydrochloric acid solution, extraction temperature (°C), ratio of liquid to raw material (mL g-1), and extraction time (h), respectively. Chemical and bioassay indices were used in combination as the response parameters, which included the yield of cFCSP, fucose content, proliferation rate of spleen cells, and lipopolysaccharide-induced proliferation of splenocytes. The experimental data were fitted to a second-order polynomial equation using multiple regression analysis, and examined using the appropriate statistical methods. The best extraction conditions were as follows: the pH value of hydrochloric acid solution was 3.50; the extraction temperature was 100°C; the ratio of liquid to raw material was 15.00 mL g-1 and the extraction time was 2.50 h. The experimental yield was close to the predicted from the model. The extract could promote spleen lymphocyte proliferation, especially the lipopolysaccharide-induced lymphocyte proliferation in vitro, which suggested that its immunomodulatory effect on B lymphocytes. Therefore, cFCSP extracted from S. fusiforme could be utilized as an immunostimulant in functional foods and pharmaceutical industry in future.

  10. Assessing sediment hazard through a weight of evidence approach with bioindicator organisms: a practical model to elaborate data from sediment chemistry, bioavailability, biomarkers and ecotoxicological bioassays.

    Science.gov (United States)

    Piva, Francesco; Ciaprini, Francesco; Onorati, Fulvio; Benedetti, Maura; Fattorini, Daniele; Ausili, Antonella; Regoli, Francesco

    2011-04-01

    Quality assessments are crucial to all activities related to removal and management of sediments. Following a multidisciplinary, weight of evidence approach, a new model is presented here for comprehensive assessment of hazards associated to polluted sediments. The lines of evidence considered were sediment chemistry, assessment of bioavailability, sub-lethal effects on biomarkers, and ecotoxicological bioassays. A conceptual and software-assisted model was developed with logical flow-charts elaborating results from each line of evidence on the basis of several chemical and biological parameters, normative guidelines or scientific evidence; the data are thus summarized into four specific synthetic indices, before their integration into an overall sediment hazard evaluation. This model was validated using European eels (Anguilla anguilla) as the bioindicator species, exposed under laboratory conditions to sediments from an industrial site, and caged under field conditions in two harbour areas. The concentrations of aliphatic hydrocarbons, polycyclic aromatic hydrocarbons and trace metals were much higher in the industrial compared to harbour sediments, and accordingly the bioaccumulation in liver and gills of exposed eels showed marked differences between conditions seen. Among biomarkers, significant variations were observed for cytochrome P450-related responses, oxidative stress biomarkers, lysosomal stability and genotoxic effects; the overall elaboration of these data, as those of standard ecotoxicological bioassays with bacteria, algae and copepods, confirmed a higher level of biological hazard for industrial sediments. Based on comparisons with expert judgment, the model presented efficiently discriminates between the various conditions, both as individual modules and as an integrated final evaluation, and it appears to be a powerful tool to support more complex processes of environmental risk assessment.

  11. Covalent-Bond Formation via On-Surface Chemistry.

    Science.gov (United States)

    Held, Philipp Alexander; Fuchs, Harald; Studer, Armido

    2017-01-18

    In this Review article pioneering work and recent achievements in the emerging research area of on-surface chemistry is discussed. On-surface chemistry, sometimes also called two-dimensional chemistry, shows great potential for bottom-up preparation of defined nanostructures. In contrast to traditional organic synthesis, where reactions are generally conducted in well-defined reaction flasks in solution, on-surface chemistry is performed in the cavity of a scanning probe microscope on a metal crystal under ultrahigh vacuum conditions. The metal first acts as a platform for self-assembly of the organic building blocks and in many cases it also acts as a catalyst for the given chemical transformation. Products and hence success of the reaction are directly analyzed by scanning probe microscopy. This Review provides a general overview of this chemistry highlighting advantages and disadvantages as compared to traditional reaction setups. The second part of the Review then focuses on reactions that have been successfully conducted as on-surface processes. On-surface Ullmann and Glaser couplings are addressed. In addition, cyclodehydrogenation reactions and cycloadditions are discussed and reactions involving the carbonyl functionality are highlighted. Finally, the first examples of sequential on-surface chemistry are considered in which two different functionalities are chemoselectively addressed. The Review gives an overview for experts working in the area but also offers a starting point to non-experts to enter into this exciting new interdisciplinary research field.

  12. Detection of multiple hormonal activities in wastewater effluents and surface water, using a panel of steroid receptor CALUX bioassays.

    Science.gov (United States)

    Van der Linden, Sander C; Heringa, Minne B; Man, Hai-Yen; Sonneveld, Edwin; Puijker, Leo M; Brouwer, Abraham; Van der Burg, Bart

    2008-08-01

    It is generally known that there are compounds present in the aquatic environment that can disturb endocrine processes, for example via interaction with the endogenous hormone receptors. Most research so far has focused on compounds that bind to the estrogen and/or androgen receptor, but ligands for other hormone receptors might also be present. In this study, a newly completed panel of human cell derived CALUX reporter gene bioassays was utilized to test water extracts for estrogen (ER), as well as androgen (AR), progesterone (PR), and glucocorticoid (GR) receptor mediated transactivation activity. Effluents from industry, hospital, and municipal sewage treatment plants, as well as tap water and different sources of surface water were tested. The CALUX reporter gene panel showed high sensitivity and specificity to known agonists, enabling discrimination between different receptor based endocrine responses present in the aquatic environment. Our results clearly showed the presence of agonistic activity on the ER, as well as on the AR, PR, and GR in the raw and wastewater and surface water extracts. However, no hormone receptor-mediated transactivation was detected in the drinking water or in the blank water. The levels of estrogenic activity were 0.2-0.5 ng E2-equiv/L for surface water and 0.4-1.0 ng E2-equiv/L for municipal effluents, which was consistent with previous studies. Surprisingly, the other hormonal activities were found to be present in similar or much higher levels. Most notably, glucocorticoid-like activity was detected in all samples, at surprisingly high levels ranging from 0.39-1.3 ng Dex-equiv/L in surface water and 11-243 ng Dex-equiv/L in effluents. When regarding the fact that dexamethasone in the GR CALUX bioassay is a factor 12 more potent than the natural hormone cortisol, results expressed as cortisol equivalents would range up to 2900 ng cortisol equiv/L. Further studies are needed to establish the identity of the active compounds and to

  13. Gas Plasma Surface Chemistry for Biological Assays.

    Science.gov (United States)

    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.

  14. Fundamentals of Chemistry at Surfaces and Beyond

    Science.gov (United States)

    2013-09-23

    Physics Club , Westridge High School, Pasadena, CA, 2012 Lecture: Electron Transfers and Other Reactions in Chemistry, Baku State University, Azerbaijan...of the Vibrational Mode of an Adatom-Substrate System Under a Resonant Laser Field,” Phys. Rev. B, 78, 125303 (2008). 9P. Guyot-Sionnest, P. Dumas , Y...Under a Resonant Laser Field,” Phys. Rev. B, 78, 125303 (2008). 9P. Guyot-Sionnest, P. Dumas , Y. J. Chabal, “Lifetime of an adsorbate-substrate

  15. Surface chemistry and tribology of MEMS.

    Science.gov (United States)

    Maboudian, Roya; Carraro, Carlo

    2004-01-01

    The microscopic length scale and high surface-to-volume ratio, characteristic of microelectro-mechanical systems (MEMS), dictate that surface properties are of paramount importance. This review deals with the effects of surface chemical treatments on tribological properties (adhesion, friction, and wear) of MEMS devices. After a brief review of materials and processes that are utilized in MEMS technology, the relevant tribological and chemical issues are discussed. Various MEMS microinstruments are discussed, which are commonly employed to perform adhesion, friction, and wear measurements. The effects of different surface treatments on the reported tribological properties are discussed.

  16. Chemistry - Toward efficient hydrogen production at surfaces

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Christensen, Claus H.

    2006-01-01

    Calculations are providing a molecular picture of hydrogen production on catalytic surfaces and within enzymes, knowledge that may guide the design of new, more efficient catalysts for the hydrogen economy.......Calculations are providing a molecular picture of hydrogen production on catalytic surfaces and within enzymes, knowledge that may guide the design of new, more efficient catalysts for the hydrogen economy....

  17. Heterogeneous Chemistry on the Ice Surfaces

    Science.gov (United States)

    Klán, P.; Heger, D.; Ray, D.; Krausko, J.; Lisitsyn, L.; Neděla, V.

    2012-04-01

    The porous nature of ice surfaces, especially of snow crystals, allows for adsorption of volatile and semivolatile organic compounds. Contrary to frozen aqueous solutions, in which the impurities reside in a 3-dimensional cage (micropockets), contaminant molecules located on a snow grain surface at low concentrations can be visualized in terms of a 2-dimensional cage. Low concentrations of snow contaminants and the complexity the system are a great challenge to those who want to study the physical and chemical processes occurring in natural snow. We investigated the surface coverage of artificial snow grains by organic contaminants in relation to their surface self-association, diffusion, and chemical reactions, such as radical recombination, ozonolysis, or redox processes. Our studies have revealed that hydrophobic organic molecules can be located on the surface of snow grains in associations rather than as isolated species even at very low concentrations. The results from investigations on photochemistry of ice surface contaminants in the absence or presence of semiconductor nanoparticles or humic acids, using various study techniques, including fluorimetry or scanning electron microscopy, will be presented.

  18. Chemistry in the near-surface atmosphere at Ganymede

    Science.gov (United States)

    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. Quantification of air plasma chemistry for surface disinfection

    Science.gov (United States)

    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.

  20. Organic chemistry on Titan: Surface interactions

    Science.gov (United States)

    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.

  1. Metal-Free Click Chemistry Reactions on Surfaces

    NARCIS (Netherlands)

    Escorihuela, J.; Marcelis, A.T.M.; Zuilhof, H.

    2015-01-01

    In the last decade, interest in the functionalization of surfaces and materials has increased dramatically. In this regard, click chemistry deserves a central focus because of its mild reaction conditions, high efficiency, and easy post-treatment. Among such novel click reactions, those that do not

  2. Density functional theory in surface chemistry and catalysis

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Abild-Pedersen, Frank; Studt, Felix

    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...

  3. Density Functional Theory in Surface Chemistry and Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    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.

  4. Architecture and Surface Chemistry of Compound Nanoclusters

    Science.gov (United States)

    2012-08-01

    size. Surface enhanced Raman spectroscopy on silver nanorods substrates were undertaken to determine the structure of the Co4O4(CH3CN)6 species...potential new applications is the controlled synthesis of desired nanoparticles with favorable composition and stability. Our research project explores new...macroscopic synthesis of cluster materials, and new synthetic experiments employing ligand-coating strategies have been initiated using a “laser ablation

  5. Theoretical Insights into C1 Surface Chemistry

    Science.gov (United States)

    Neurock, Matthew

    2008-03-01

    Reforming and partial oxidation of methane as well as other C1 fuels are important processes in the production of hydrogen and synthesis gas and will likely play important roles future energy strategies. Herein we use theory and simulation to examine the reactivity of methane, methanol and dimethyl ether with CO2, H2O, or O2 over supported transition metals. We systematically probe the elementary C-H bond activation as well as the oxidation pathways involved in both reforming as the oxidation of methane and other C1 intermediates over well defined transition metal surfaces, metal alloys and metal nanoparticles. The calculations demonstrate well-established trends in C-H bond activation as the result of changes in the metal, the activating molecule (methane, methanol, and DME) as well as the reaction conditions. The reaction conditions ultimately dictate the surface coverage of carbon and oxygen which have important consequences on the surface reactivity. The theoretical and simulation results are compared with well defined experiments carried out at Berkeley over supported particles.

  6. Detection of estrogenic potency in wastewater and surface water with three in vitro bioassays.

    Science.gov (United States)

    Murk, Albertinka J; Legler, Juliette; van Lipzig, Marola M H; Meerman, John H N; Belfroid, Angelique C; Spenkelink, Albertus; van der Burg, Bart; Rijs, Gerard B J; Vethaak, Dick

    2002-01-01

    A study was performed to optimize sample preparation and application of three in vitro assays for measuring estrogenic potency in environmental extracts. The three assays applied were an estrogen receptor (ER)-binding assay and two reporter gene effect assays: a yeast estrogen screen (YES) and the ER-mediated chemically activated luciferase gene expression (ER-CALUX) assay. All assays were able to detect estrogenicity, but the amounts of material needed for the assays differed greatly between the three assays (ER-binding assay > YES > ER-CALUX). In addition, in the ER-binding assay, both agonists and antagonists give an estrogenic response, resulting in higher estradiol equivalency (EEQ) levels than both the ER-CALUX and the YES assay for the same samples. The EEQs found in wastewater treatment plants (WTPs) with the ER-CALUX assay were in the range of 4 to 440 and 0.11 to 59 pmol/L for influent and effluent, respectively. Water extracts from four large rivers had levels ranging from 0.25 to 1.72 pmol/L. Extracts from suspended matter and sludge contained estrogenic potency of 0.26 to 2.49 and 1.6 to 41 pmol EEQ/g dry weight, respectively. In WTPs, the average reduction of estrogenic potency in effluent compared to influent was 90 to 95% in municipal WTPs and about 50% in industrial WTPs. In influent, 30% of the ER-CALUX activity could not be explained by the calculated potencies based on chemical analysis of a number of known (xeno)estrogens; in effluent the unexplained fraction was 80%. These first results of analyzing estrogenic potency in WTP water and surface water in The Netherlands indicate that further studies are warranted to investigate the actual risks for aquatic systems.

  7. Heterogeneous catalytic materials solid state chemistry, surface chemistry and catalytic behaviour

    CERN Document Server

    Busca, Guido

    2014-01-01

    Heterogeneous Catalytic Materials discusses experimental methods and the latest developments in three areas of research: heterogeneous catalysis; surface chemistry; and the chemistry of catalysts. Catalytic materials are those solids that allow the chemical reaction to occur efficiently and cost-effectively. This book provides you with all necessary information to synthesize, characterize, and relate the properties of a catalyst to its behavior, enabling you to select the appropriate catalyst for the process and reactor system. Oxides (used both as catalysts and as supports for cata

  8. Smart Surface Chemistries of Conducting Polymers

    DEFF Research Database (Denmark)

    Lind, Johan Ulrik

    In this thesis we investigate post-polymerization covalent modifications of poly(3,4-dioxythiophene (PEDOT)-type conducting polymers. The aim of the modifications is to gain specific control of the interaction between the material and living mammalian cells. The use of “click-chemistry” to modify...... film substrates. Complementing these findings, we introduce a novel technique for fabricating surface chemical gradients on PEDOT-N3 substrates. The technique is based on applying “electro-click chemistry” to locally induce covalent modifications. Further supplementing these results, we develop......-ethylene-glycol-coatings of the conducting polymer substrates. These coatings render the substrates resistant to protein adsorption. Hence, the choice of solvent is found to be a key parameter for achieving functional post-polymerization modifications of PEDOT-N3. The methods developed in this thesis are highly generic, and can therefore...

  9. Magmatic and fragmentation controls on volcanic ash surface chemistry

    Science.gov (United States)

    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

  10. Probing Surface Chemistry at the Nanoscale Level

    Science.gov (United States)

    Rene-Boisneuf, Laetitia

    Studies various nanostructured materials have gained considerable interest within the past several decades. This novel class of materials has opened up a new realm of possibilities, both for the fundamental comprehension of matter, but also for innovative applications. The size-dependent effect observed for these systems often lies in their interaction with the surrounding environment and understanding such interactions is the pivotal point for the investigations undertaken in this thesis. Three families of nanoparticles are analyzed: semiconductor quantum dots, metallic silver nanoparticles and rare-earth oxide nanomaterials. The radical scavenging ability of cerium oxide nanoparticles (CeO 2) is quite controversial since they have been labeled as both oxidizing and antioxidant species for biological systems. Here, both aqueous and organic stabilized nanoparticles are examined in straightforward systems containing only one reactive oxygen species to ensure a controlled release. The apparent absence of their direct radical scavenging ability is demonstrated despite the ease at which CeO2 nanoparticles generate stable surface Ce 3+ clusters, which is used to explain the redox activity of these nanomaterials. On the contrary, CeO2 nanoparticles are shown to have an indirect scavenging effect in Fenton reactions by annihilating the reactivity of Fe 2+ salts. Cadmium selenide quantum dots (CdSe QD) constitute another highly appealing family of nanocolloids in part due to their tunable, size-dependent luminescence across the visible spectrum. The effect of elemental sulfur treatment is investigated to overcome one of the main drawbacks of CdSe QD: low fluorescence quantum yield. Herein, we report a constant and reproducible quantum yield of 15%. The effect of sulfur surface treatment is also assessed following the growth of a silica shell, as well as the response towards a solution quencher (4-amino-TEMPO). The sulfur treated QD is also tested for interaction with

  11. Susceptibility of cat fleas (Siphonaptera: Pulicidae) to fipronil and imidacloprid using adult and larval bioassays.

    Science.gov (United States)

    Rust, M K; Vetter, R; Denholm, I; Blagburn, B; Williamson, M S; Kopp, S; Coleman, G; Hostetler, J; Davis, W; Mencke, N; Rees, R; Foit, S; Tetzner, K

    2014-05-01

    The monitoring of the susceptibility offleas to insecticides has typically been conducted by exposing adults on treated surfaces. Other methods such as topical applications of insecticides to adults and larval bioassays on treated rearing media have been developed. Unfortunately, baseline responses of susceptible strains of cat flea, Ctenocephalides felis (Bouchè), except for imidacloprid, have not been determined for all on-animal therapies and new classes of chemistry now being used. However, the relationship between adult and larval bioassays of fleas has not been previously investigated. The adult and larval bioassays of fipronil and imidacloprid were compared for both field-collected isolates and laboratory strains. Adult topical bioassays of fipronil and imidacloprid to laboratory strains and field-collected isolates demonstrated that LD50s of fipronil and imidacloprid ranged from 0.11 to 0.40 nanograms per flea and 0.02 to 0.18 nanograms per flea, respectively. Resistance ratios for fipronil and imidacloprid ranged from 0.11 to 2.21. Based on the larval bioassay published for imidacloprid, a larval bioassay was established for fipronil and reported in this article. The ranges of the LC50s of fipronil and imidacloprid in the larval rearing media were 0.07-0.16 and 0.11-0.21 ppm, respectively. Resistance ratios for adult and larval bioassays ranged from 0.11 to 2.2 and 0.58 to 1.75, respectively. Both adult and larval bioassays provided similar patterns for fipronil and imidacloprid. Although the adult bioassays permitted a more precise dosage applied, the larval bioassays allowed for testing isolates without the need to maintain on synthetic or natural hosts.

  12. Surface Chemistry and Properties of Oxides as Catalyst Supports

    Energy Technology Data Exchange (ETDEWEB)

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

    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. Engineered microtopographies and surface chemistries direct cell attachment and function

    Science.gov (United States)

    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

  14. Surface Chemistry of Nano-Structured Mixed Metal Oxide Films

    Science.gov (United States)

    2012-12-11

    Low Temperature Synthesis and Characterization of Nanocrystalline Titanium Carbide with Tunable Porous Architectures, Chemistry of Materials, (01...of the C–H bond to form carboxyl, both of which decompose via a COd 2 intermediate to evolve CO2 and H2. High surface area, porous titanium carbide films...characterization of nanocrystalline titanium carbide with tunable porous architectures” Chem. Mater. 22, 319-329 (2010). http://dx.doi.org/10.1021/cm902184m 3

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

    Science.gov (United States)

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

    2016-03-14

    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.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  18. The impact of surface chemistry modification on macrophage polarisation.

    Science.gov (United States)

    Rostam, Hassan M; Singh, Sonali; Salazar, Fabian; Magennis, Peter; Hook, Andrew; Singh, Taranjit; Vrana, Nihal E; Alexander, Morgan R; Ghaemmaghami, Amir M

    2016-11-01

    Macrophages are innate immune cells that have a central role in combating infection and maintaining tissue homeostasis. They exhibit remarkable plasticity in response to environmental cues. At either end of a broad activation spectrum are pro-inflammatory (M1) and anti-inflammatory (M2) macrophages with distinct functional and phenotypical characteristics. Macrophages also play a crucial role in orchestrating immune responses to biomaterials used in the fabrication of implantable devices and drug delivery systems. To assess the impact of different surface chemistries on macrophage polarisation, human monocytes were cultured for 6 days on untreated hydrophobic polystyrene (PS) and hydrophilic O2 plasma-etched polystyrene (O2-PS40) surfaces. Our data clearly show that monocytes cultured on the hydrophilic O2-PS40 surface are polarised towards an M1-like phenotype, as evidenced by significantly higher expression of the pro-inflammatory transcription factors STAT1 and IRF5. By comparison, monocytes cultured on the hydrophobic PS surface exhibited an M2-like phenotype with high expression of mannose receptor (MR) and production of the anti-inflammatory cytokines IL-10 and CCL18. While the molecular basis of such different patterns of cell differentiation is yet to be fully elucidated, we hypothesise that it is due to the adsorption of different biomolecules on these surface chemistries. Indeed our surface characterisation data show quantitative and qualitative differences between the protein layers on the O2-PS40 surface compared to PS surface which could be responsible for the observed differential macrophage polarisation on each surface.

  19. The role of "inert" surface chemistry in marine biofouling prevention.

    Science.gov (United States)

    Rosenhahn, Axel; Schilp, Sören; Kreuzer, Hans Jürgen; Grunze, Michael

    2010-05-01

    The settlement and colonization of marine organisms on submerged man-made surfaces is a major economic problem for many marine industries. The most apparent detrimental effects of biofouling are increased fuel consumption of ships, clogging of membranes and heat exchangers, disabled underwater sensors, and growth of biofoulers in aquaculture systems. The presently common-but environmentally very problematic-way to deal with marine biofouling is to incorporate biocides, which use biocidal products in the surface coatings to kill the colonizing organisms, into the surface coatings. Since the implementation of the International Maritime Organization Treaty on biocides in 2008, the use of tributyltin (TBT) is restricted and thus environmentally benign but effective surface coatings are required. In this short review, we summarize the different strategies which are pursued in academia and industry to better understand the mechanisms of biofouling and to develop strategies which can be used for industrial products. Our focus will be on chemically "inert" model surface coatings, in particular oligo- and poly(ethylene glycol) (OEG and PEG) functionalized surface films. The reasons for choosing this class of chemistry as an example are three-fold: Firstly, experiments on spore settlement on OEG and PEG coatings help to understand the mechanism of non-fouling of highly hydrated interfaces; secondly, these studies defy the common assumption that surface hydrophilicity-as measured by water contact angles-is an unambiguous and predictive tool to determine the fouling behavior on the surface; and thirdly, choosing this system is a good example for "interfacial systems chemistry": it connects the behavior of unicellular marine organisms with the antifouling properties of a hydrated surface coating with structural and electronic properties as derived from ab initio quantum mechanical calculations using the electronic wave functions of oxygen, hydrogen, and carbon. This short

  20. Controlling Multivalent Binding through Surface Chemistry: Model Study on Streptavidin

    Science.gov (United States)

    2017-01-01

    Although multivalent binding to surfaces is an important tool in nanotechnology, quantitative information about the residual valency and orientation of surface-bound molecules is missing. To address these questions, we study streptavidin (SAv) binding to commonly used biotinylated surfaces such as supported lipid bilayers (SLBs) and self-assembled monolayers (SAMs). Stability and kinetics of SAv binding are characterized by quartz crystal microbalance with dissipation monitoring, while the residual valency of immobilized SAv is quantified using spectroscopic ellipsometry by monitoring binding of biotinylated probes. Purpose-designed SAv constructs having controlled valencies (mono-, di-, trivalent in terms of biotin-binding sites) are studied to rationalize the results obtained on regular (tetravalent) SAv. We find that divalent interaction of SAv with biotinylated surfaces is a strict requirement for stable immobilization, while monovalent attachment is reversible and, in the case of SLBs, leads to the extraction of biotinylated lipids from the bilayer. The surface density and lateral mobility of biotin, and the SAv surface coverage are all found to influence the average orientation and residual valency of SAv on a biotinylated surface. We demonstrate how the residual valency can be adjusted to one or two biotin binding sites per immobilized SAv by choosing appropriate surface chemistry. The obtained results provide means for the rational design of surface-confined supramolecular architectures involving specific biointeractions at tunable valency. This knowledge can be used for the development of well-defined bioactive coatings, biosensors and biomimetic model systems. PMID:28234007

  1. Genotoxic and mutagenic effects of polluted surface water in the midwestern region of Brazil using animal and plant bioassays

    Directory of Open Access Journals (Sweden)

    Priscila Leocádia Rosa Dourado

    Full Text Available Abstract This study aimed to evaluate DNA damage in animal and plant cells exposed to water from the Água Boa stream (Dourados, Mato Grosso do Sul, Brazil by using bioassays, and to identify the chemical compounds in the water to determine the water quality in the area. Through the cytotoxicity bioassay with Allium cepa, using micronucleus test, and comet assay, using Astyanax altiparanae fish, the results indicated that biological samples were genetically altered. Micronuclei were observed in erythrocytes of A. altiparanae after exposure to water from locations close to industrial waste discharge. The highest DNA damage observed with the comet assay in fish occurred with the exposure to water from locations where the presence of metals (Cu, Pb, Cd, Ni was high, indicating the possibility of genotoxic effects of these compounds. Thus, these results reinforce the importance of conducting genotoxicity tests for developing management plans to improve water quality, and indicate the need for waste management before domestic and industrial effluents are released into the rivers and streams.

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

    Directory of Open Access Journals (Sweden)

    E. D. Sofen

    2015-07-01

    Full Text Available 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.

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

    Science.gov (United States)

    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.

  4. Modulation of human osteoblasts by metal surface chemistry.

    Science.gov (United States)

    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.

  5. Surface chemistry interventions to control boiler tube fouling - Part II

    Energy Technology Data Exchange (ETDEWEB)

    Turner, C.W.; Guzonas, D.A.; Klimas, S.J

    2004-06-15

    This is the third in a series of reports from an investigation co-funded by the Electric Power Research Institute (EPRI) and by Atomic Energy of Canada Limited (AECL) into the effectiveness of alternative amines for controlling the rate of tube-bundle fouling under steam generator (SG) operating conditions. The objectives of this investigation are to determine whether the fouling rate depends on the amine used for pH control, to identify those factors that influence the effectiveness, and use this information to optimize the selection of an amine for chemistry control and deposit control in the steam cycle and steam generator, respectively. Work to date has demonstrated that the rate of particle deposition under steam generator operating conditions is strongly influenced by surface chemistry (Turner et al., 1997; Turner et al., 1999). This dependence upon surface chemistry is illustrated by the difference between the deposition rates measured for hematite and magnetite, and by the dependence of the particle deposition rate on the amine used for pH control. Deposition rates of hematite were found to be more than 10 times greater than those for magnetite under similar test conditions (Turner et al., 1997). At 270{sup o}C and pH{sub T} 6.2, the surfaces of hematite and magnetite are predicted to be positively charged and negatively charged, respectively (Shoonen, 1994). Measurements of the point of zero charge (PZC) of magnetite at temperatures from 25{sup o}C to 290{sup o}C by Wesolowski et al. (1999) have confirmed that magnetite is negatively charged at the stated conditions. A PZC of 4.2 was measured for Alloy 600 at 25{sup o}C (Balakrishnan and Turner, un-published results), and its surface is expected to remain negatively charged for alkaline chemistry over the temperature range of interest. Therefore, there will be a repulsive force between the surfaces of magnetite particles and Alloy 600 at 270{sup o}C and pH{sub T} 6.2 that is absent for hematite particles

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

    Science.gov (United States)

    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)

  7. Carbon dioxide chemistry on the surface of Titan

    Science.gov (United States)

    Hodyss, Robert; Piao, Sophie; Malaska, Michael; Cable, Morgan

    2016-10-01

    Titan possesses many of the basic elements of habitability, including a rich organic chemistry. However, the thick atmosphere of Titan shields the surface from radiation, which makes the incorporation of oxygen into organic compounds difficult, due to a reducing environment and low temperatures that slow chemical reactions. These obstacles may be overcome by impacts or cryovolcanic heating of ice, which would mix organics with liquid water and allow chemical reactions that can incorporate oxygen. However, reactions involving oxygen can occur on Titan without invoking such unusual conditions. We show that the reaction of carbon dioxide with amines can lead to oxygenated organics at Titan's surface without the need for external energy input, via the carbamation reaction: R-NH2 + CO2 → R-NH-COOH. Using a combination of micro-Raman spectroscopy and UHV FTIR spectroscopy, we examine the reaction products and kinetics of the carbamation reaction for a variety of primary and secondary amines. We have observed carbamic acid formation in mixtures of methylamine, ethylamine and dibutylamine with CO2 at cryogenic temperatures. This indicates that both primary and secondary amines can undergo carbamation at low temperatures. Reaction was observed with methylamine as low as 40 K, and with ethylamine at 100 K, demonstrating that carbamation is fast at Titan surface temperatures. We will present data on the kinetics of the carbamation reaction for a variety of amines, as well as estimates of the quantity of carbamic acids that may be produced on Titan's surface and in the atmosphere.

  8. Surface chemistry and physics of III/V compound semiconductors

    Science.gov (United States)

    Fu, Qiang

    The surface chemistry of gallium arsenide and indium phosphide has been investigated using infrared spectroscopy (IR), scanning tunneling microscopy (STM), and ab initio molecular cluster calculations. The work presented here provides the first theoretical framework for studying the reaction sites on compound semiconductor surfaces. These sites consist of dimers and threefold-coordinated atoms in the second layer. Stable clusters of gallium arsenide, i.e., GaxAsyHz, where x, y = 4, 5 and z = 11, 13, are those in which the arsenic dangling bonds are filled, while the gallium dangling bonds are empty. By contrast, stable clusters of indium phosphide, i.e., InxPyHz, where x, y = 4, 5 and z = 10, 11, 13, are those in which the phosphorous dangling bonds are either filled or half filled, and the indium dangling bonds are empty. The most important contribution of this work is the discovery of a new surface structure, the InP (001)-(2 x 1). The InP (2 x 1) is terminated with a complete layer of phosphorous dimers with a half-filled dangling bond on every other phosphorous atom. The half-filled orbital violate the electron counting model [Pashley, Phys. Rev. B 1989, 40, 10481], and indicate that many more reconstructions are possible on these surfaces than was originally thought. Excellent agreement is achieved between the molecular cluster calculations and the measured vibrational frequencies of adsorbed hydrogen and arsine on gallium arsenide and indium phosphide (001) surfaces. On both GaAs and InP, mono-hydrogen and di-hydrogen bonds are formed with the three-coordinate, group V atoms and dimers. Conversely, electron deficient bridging hydrides are produced on the group III dimers. These latter species occur in isolated or coupled structures involving two or three metal atoms. In addition, we have elucidated the kinetics and mechanism of arsine decomposition on gallium-rich GaAs (001). The combination of STM, IR, and ab initio molecular cluster calculations provides a

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

    Science.gov (United States)

    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.

  10. Assessing toxicity of copper, cadmium and chromium levels relevant to discharge limits of industrial effluents into inland surface waters using common onion, Allium cepa bioassay.

    Science.gov (United States)

    Hemachandra, Chamini K; Pathiratne, Asoka

    2015-02-01

    Toxicity of copper, cadmium and chromium relevant to established tolerance limits for the discharge of industrial effluents into inland surface waters was evaluated by Allium cepa bioassay. The roots of A. cepa bulbs exposed to Cu(2+) (3 mg L(-1)) individually or in mixtures with Cd(2+) (0.1 mg L(-1)) or/and Cr(6+) (0.1 mg L(-1)) exhibited the highest growth inhibition, mitotic index depression and nuclear abnormalities. Root tip cells exposed to Cr(6+) or Cd(2+) alone or in mixture displayed significant chromosomal aberrations in comparison to the controls. EC50s for root growth inhibition followed the order Cu(2+) < Cd(2+) < Cr(6+) indicating greater toxicity of copper. The results show that the industrial effluent discharge regulatory limits for these metals need to be reviewed considering potential cyto-genotoxicity to biological systems.

  11. Exploring silicon surface chemistry with spectroscopy and microscopy

    Science.gov (United States)

    Zheng, Fan

    Recent technology advances have pushed the development of silicon devices to their physical performance limits. An alternative way to keep Moore's law valid and avoid the physical limits of today's magnetic memory is to combine molecules with the silicon. Molecules possess degrees of freedom that traditional silicon devices lack, such as rotation, conformation, oxidation states, spontaneous dipole moment, and discrete energy levels. Cleverly taking advantage of these properties may lead to next generation devices that are more powerful and efficient than today's silicon devices. To realize such an ambitious goal, it is necessary to understand the surface chemistry of silicon, i.e., the adsorption, reaction, and disorder phenomena of molecules at the surface. Spectroscopy and microscopy are two complementary methods to study surface chemistry and provide insight into mechanisms for next generation silicon devices. In this thesis, the major spectroscopy method used is Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. To make full use of this technique, a new model is introduced in order to disentangle the concepts of disorder and orientation, both of which are provided by a NEXAFS measurement. The disorder information is obtained by introducing a disorder parameter sigma, whose magnitude directly measures the spread of the orientation angle around its average. This model clarifies some long existing controversial interpretations of NEXAFS measurements and provides insights into disorder-related physical properties. The second emphasis of this thesis is the development of molecular nanostructures where one-dimensional molecular arrays with strong dipole moments are formed on the Si(111) 5x2-Au surface. Scanning Tunneling Microscopy (STM) is used to characterize these nanostructures. The study shows that upward versus downward orientations of the dipole moment of the molecules can be distinguished by STM barrier height imaging. Such structures could be a

  12. Rational design of surface/interface chemistry for quantitative in vivo monitoring of brain chemistry.

    Science.gov (United States)

    Zhang, Meining; Yu, Ping; Mao, Lanqun

    2012-04-17

    To understand the molecular basis of brain functions, researchers would like to be able to quantitatively monitor the levels of neurochemicals in the extracellular fluid in vivo. However, the chemical and physiological complexity of the central nervous system (CNS) presents challenges for the development of these analytical methods. This Account describes the rational design and careful construction of electrodes and nanoparticles with specific surface/interface chemistry for quantitative in vivo monitoring of brain chemistry. We used the redox nature of neurochemicals at the electrode/electrolyte interface to establish a basis for monitoring specific neurochemicals. Carbon nanotubes provide an electrode/electrolyte interface for the selective oxidation of ascorbate, and we have developed both in vivo voltammetry and an online electrochemical detecting system for continuously monitoring this molecule in the CNS. Although Ca(2+) and Mg(2+) are involved in a number of neurochemical signaling processes, they are still difficult to detect in the CNS. These divalent cations can enhance electrocatalytic oxidation of NADH at an electrode modified with toluidine blue O. We used this property to develop online electrochemical detection systems for simultaneous measurements of Ca(2+) and Mg(2+) and for continuous selective monitoring of Mg(2+) in the CNS. We have also harnessed biological schemes for neurosensing in the brain to design other monitoring systems. By taking advantage of the distinct reaction properties of dopamine (DA), we have developed a nonoxidative mechanism for DA sensing and a system that can potentially be used for continuously sensing of DA release. Using "artificial peroxidase" (Prussian blue) to replace a natural peroxidase (horseradish peroxidase, HRP), our online system can simultaneously detect basal levels of glucose and lactate. By substituting oxidases with dehydrogenases, we have used enzyme-based biosensing schemes to develop a physiologically

  13. The interfacial chemistry of organic materials on commercial glass surfaces

    Science.gov (United States)

    Banerjee, Joy

    The hydrolytic stability of glass is dependent on its composition. Glasses are exposed to water during their processing and in many applications; therefore, their surface or interface with other materials must withstand hydrolytic attack. Multi-component silicate glasses are widely used but have been the least studied. In coatings-based applications, these glasses come in contact with organosilanes and organic molecules where the adsorption may be affected by surface water. For example, the influence of glass composition on the wet strength of a glass/polymer composite material is unclear, but it is presumed to be driven by the hydrolytic stability of the interfacial chemistry. Organosilanes are critical for increasing the performance of composite materials in humid environments but the precise manner by which the improvement occurs has not been verified. The current school of thought is that the application of silane coatings on a multi-component glass surface transforms the chemically heterogeneous surface into a homogenous and hydrolytically stable surface. In this study, multi-component silicate glass surfaces were silanized by both aqueous and non-aqueous methods. The effect of glass composition and surface hydration on silane coverage was quantified by X-ray Photoelectron Spectroscopy (XPS) analysis. The monolayer-level adsorption results showed that the low-sodium content glasses had greater coverage than a high-sodium content glass in dry conditions in contrast to an equivalent coverage in wet conditions. The hydrolytically-stable coverage on multi-component silicate glass surfaces by both silanization methods was found to be sub-monolayer. A thin film model in conjunction with XPS and Infrared Spectroscopy was used to probe the interfacial region of a fiberglass insulation material containing a sodium-rich multi-component silicate glass and an acrylate resin binder. Upon the application of the aqueous binder, the leaching of sodium from the glass promoted

  14. Coupling of Ligands to the Liposome Surface by Click Chemistry.

    Science.gov (United States)

    Spanedda, Maria Vittoria; De Giorgi, Marcella; Hassane, Fatouma Saïd; Schuber, Francis; Bourel-Bonnet, Line; Frisch, Benoît

    2017-01-01

    Click chemistry represents a new bioconjugation strategy that can be used to conveniently attach various ligands to the surface of preformed liposomes. This efficient and chemoselective reaction involves a Cu(I)-catalyzed azide-alkyne cycloaddition which can be performed under mild experimental conditions in aqueous media. Here we describe the application of a model click reaction to the conjugation, in a single step, of unprotected α-1-thiomannosyl ligands, functionalized with an azide group, to liposomes containing a terminal alkyne-functionalized lipid anchor. Excellent coupling yields have been obtained in the presence of bathophenanthroline disulfonate, a water soluble copper-ion chelator, acting as a catalyst. No vesicle leakage is triggered by this conjugation reaction and the coupled mannose ligands are exposed at the surface of the liposomes. The major limitation of Cu(I)-catalyzed click reactions is that this conjugation is restricted to liposomes made of saturated (phospho)lipids. To circumvent that constraint, an example of alternative copper-free azide-alkyne click reaction has been developed. Molecular tools and results are presented here.

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

    Science.gov (United States)

    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.

  16. Surface Chemistry and Growth of Large Molecules in Protoplanetary Disks

    Science.gov (United States)

    Walsh, Catherine; Aikawa, Yuri; Herbst, Eric; Millar, Tom; Widicus Weaver, Susanna; Nomura, Hideko

    Protoplanetary disks are vital objects in star and planet formation, possessing all the material - dust, gas, and ice - which may form a planetary system orbiting the new star. To date, a handful of small and relatively simple molecules have been observed in nearby disks reflecting the limitations of existing telescopes. However, in the era of ALMA, the Atacama Large Millimeter/Submillimeter Array, we expect the molecular inventory of protoplanetary disks to significantly increase. Of particular interest are so-called complex organic molecules (COMs) which are thought to be necessary precursors to molecules important for prebiotic chemistry, such as, amino acids. The formation of COMs remains one of the puzzles of astrochemistry. Under the physical conditions in interstellar and circumstellar environments, COMs do not have efficient gas-phase routes to formation. Instead, they are postulated to form via association reactions on and within ice mantles on the the surfaces of dust grains and released to the gas phase via either thermal desorption (sublimation) or desorpton triggered by the absorption of UV radiation (photodesorption). In this presentation, I will discuss the synthesis of COMs in protoplanetary disks to investigate the potential origin of complex molecules in planetary systems. I will present results from exploratory models of a protoplanetary disk around a low-mass star including a large grain-surface chemical network to model the formation of large complex organic molecules. I will compare the resulting abundances of COMs in the gas phase and in the solid phase with existing observations towards nearby low-mass star-disk systems and comets, respectively. I will also discuss how the formation of COMs is influenced by the birth environment of the young stellar system.

  17. Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons

    Science.gov (United States)

    Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A.; Wäckerlin, Aneliia; Meyer, Ernst

    2017-01-01

    Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect – oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level. PMID:28327642

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

    Science.gov (United States)

    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…

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

    Science.gov (United States)

    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.

  20. Surface-Enhanced Raman Spectroscopy Based Quantitative Bioassay on Aptamer-Functionalized Nanopillars Using Large-Area Raman Mapping

    DEFF Research Database (Denmark)

    Yang, Jaeyoung; Palla, Mirko; Bosco, Filippo;

    2013-01-01

    Surface-enhanced Raman spectroscopy (SERS) has been used in a variety of biological applications due to its high sensitivity and specificity. Here, we report a SERS-based biosensing approach for quantitative detection of biomolecules. A SERS substrate bearing gold-decorated silicon nanopillars is...

  1. Pyridine coordination chemistry for molecular assemblies on surfaces.

    Science.gov (United States)

    de Ruiter, Graham; Lahav, Michal; van der Boom, Milko E

    2014-12-16

    CONSPECTUS: Since the first description of coordination complexes, many types of metal-ligand interactions have creatively been used in the chemical sciences. The rich coordination chemistry of pyridine-type ligands has contributed significantly to the incorporation of diverse metal ions into functional materials. Here we discuss molecular assemblies (MAs) formed with a variety of pyridine-type compounds and a metal containing cross-linker (e.g., PdCl2(PhCN2)). These MAs are formed using Layer-by-Layer (LbL) deposition from solution that allows for precise fitting of the assembly properties through molecular programming. The position of each component can be controlled by altering the assembly sequence, while the degree of intermolecular interactions can be varied by the level of π-conjugation and the availability of metal coordination sites. By setting the structural parameters (e.g., bond angles, number of coordination sites, geometry) of the ligand, control over MA structure was achieved, resulting in surface-confined metal-organic networks and oligomers. Unlike MAs that are constructed with organic ligands, MAs with polypyridyl complexes of ruthenium, osmium, and cobalt are active participants in their own formation and amplify the growth of the incoming molecular layer. Such a self-propagating behavior for molecular systems is rare, and the mechanism of their formation will be discussed. These exponentially growing MAs are capable of storing metal salts that can be used during the buildup of additional molecular layers. Various parameters influencing the film growth mechanism will be presented, including (i) the number of binding sites and geometry of the organic ligands, (ii) the metal and the structure of the polypyridyl complexes, (iii) the influence of the metal cross-linker (e.g., second or third row transition metals), and (iv) the deposition conditions. By systematic variation of these parameters, switching between linear and exponential growth could

  2. Study on adverse impact of e-waste disassembly on surface sediment in East China by chemical analysis and bioassays

    Energy Technology Data Exchange (ETDEWEB)

    Chen Lei; Zhang Congkai; Chen Yingxu [Inst. of Environmental Science and Techn., Zhejiang Univ., Hangzhou (China); Key Lab. of Non-point Source Pollution Control, Ministry of Agriculture, Zhejiang Univ., Hangzhou (China); Yu Chunna [Centre for Biomedicine and Health, Hangzhou Normal Univ., Hangzhou (China); Shen Chaofeng [Inst. of Environmental Science and Techn., Zhejiang Univ., Hangzhou (China); Key Lab. for Water Pollution Control and Environmental Safety, Hangzhou, ZJ (China); Liu Lei; Shen Kaili [Inst. of Environmental Science and Techn., Zhejiang Univ., Hangzhou (China); Tang Xianjin [Key Lab. of Non-point Source Pollution Control, Ministry of Agriculture, Zhejiang Univ., Hangzhou (China)

    2010-04-15

    Purpose: The primitive recycling of electronic waste (e-waste) in developing countries is causing serious environmental pollution. The objective of this study was to determine the contamination and toxicity of surface sediment of Nanguan River, which runs through the e-waste recycling area of Taizhou, East China. Materials and methods Surface sediments were collected from Nanguan River, including one from the control site, four near the household workshops, and two near the industrial parks. Levels of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and heavy metals/metalloid (Ni, Pb, Cd, Cr, Zn, Cu, Hg, and As), which are most widely detected in e-waste contaminated surroundings, were determined. Acute toxicity and genetic toxicity were evaluated by luminescence inhibition assay in luminescent bacterium Vibrio qingaiensis sp. nov. (Q67) and Vicia faba roots tip micronucleus assay, respectively. Results and discussion The surface sediment has been seriously contaminated by PCBs, PAHs, and heavy metals/metalloid due to the e-waste disassembly process. Significant acute and genetic toxicity of the sediments presented a big threat to the aquatic life and human health through food chain, as the river is an extent water source for local residents. Conclusions The environmental issue of e-waste recycling is emergent and measures should be taken to mitigate the adverse impacts of e-waste disassembly. (orig.)

  3. A surface-chemistry study of barium ferrite nanoplates with DBSa-modified surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Lisjak, Darja, E-mail: darja.lisjak@ijs.si [Jožef Stefan Institute, Ljubljana (Slovenia); Ovtar, Simona; Kovač, Janez [Jožef Stefan Institute, Ljubljana (Slovenia); Gregoratti, Luca; Aleman, Belen; Amati, Matteo [Elettra – Sincrotrone Trieste S.C.p.A. di interesse nazionale, Trieste (Italy); Fanetti, Mattia [University of Nova Gorica, Nova Gorica (Slovenia); Istituto Officina dei Materiali CNR, Area Science Park, Trieste (Italy); Makovec, Darko [Jožef Stefan Institute, Ljubljana (Slovenia)

    2014-06-01

    Barium ferrite (BaFe{sub 12}O{sub 19}) is a ferrimagnetic oxide with a high magnetocrystalline anisotropy that can be exploited in magnetically aligned ceramics or films for self-biased magnetic applications. Magnetic alignment of the films can be achieved by the directed assembly of barium ferrite nanoplates. In this investigation the nanoplates were synthesized hydrothermally and suspended in 1-butanol using dodecylbenzene sulphonic acid (DBSa) as a surfactant. They were then deposited in an electric or magnetic field on flat substrates and exhibited a significant preferential alignment in the plane of the substrate, allowing a differentiation between the analysis of their basal and side planes using scanning photoelectron microscopy with a lateral resolution down to 100 nm. The surface chemistry of the nanoplates was additionally studied with X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry. For a comparison, bare barium ferrite nanoplates were also analyzed after decomposing the DBSa at 460 °C. The deviation of the surface chemistry from the stoichiometric composition was observed and the adsorption of the DBSa molecules on the nanoplates was confirmed with all three methods. Different types of bonding (physi- or chemisorption) were possible and considered with respect to the assembly of the barium ferrite nanoplates into anisotropic magnetic films.

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

    Science.gov (United States)

    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.

  5. Surface chemistry of hierarchical nanosprings for sensing and catalysis

    Science.gov (United States)

    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

  6. On-Surface Synthesis by Click Chemistry Investigated by STM and XPS

    DEFF Research Database (Denmark)

    Vadapoo, Sundar Raja

    2014-01-01

    such as molecular electronics and surface functionalization. In this thesis, a well-defined click chemistry approach is followed, with the study of azide-alkyne cycloaddition on Cu(111) surface in UHV environment. A successful achievement of the click reaction product via on-surface synthesis has been shown, which...

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

    Energy Technology Data Exchange (ETDEWEB)

    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)

  8. Fenton Redox Chemistry: Arsenite Oxidation by Metallic Surfaces

    NARCIS (Netherlands)

    Borges Freitas, S.C.; Van Halem, D.; Badruzzaman, A.B.M.; Van der Meer, W.G.J.

    2014-01-01

    Pre-oxidation of As(III) is necessary in arsenic removal processes in order to increase its efficiency. Therefore, the Fenton Redox Chemistry is defined by catalytic activation of H2O2 and currently common used for its redox oxidative properties. In this study the effect of H2O2 production catalysed

  9. Surface Chemistry of CWAs for Decon Enabling Sciences

    Science.gov (United States)

    2014-11-04

    John T. Yates, John R. Morris. Mechanistic Studies of Hydrogen Dissociation and Spillover on Au/TiO2, The Journal of Physical Chemistry C, (11...reservoir is composed of a custom cartridge, which can be loaded with the liquid (typically 10-30 µL for semi- volatile compounds). The cartridge is mounted

  10. Desorption of 1,3,5-Trichlorobenzene from Multi-Walled Carbon Nanotubes: Impact of Solution Chemistry and Surface Chemistry

    Directory of Open Access Journals (Sweden)

    Sheikh Uddin

    2013-05-01

    Full Text Available The strong affinity of carbon nanotubes (CNTs to environmental contaminants has raised serious concern that CNTs may function as a carrier of environmental pollutants and lead to contamination in places where the environmental pollutants are not expected. However, this concern will not be realized until the contaminants are desorbed from CNTs. It is well recognized that the desorption of environmental pollutants from pre-laden CNTs varies with the environmental conditions, such as the solution pH and ionic strength. However, comprehensive investigation on the influence of solution chemistry on the desorption process has not been carried out, even though numerous investigations have been conducted to investigate the impact of solution chemistry on the adsorption of environmental pollutants on CNTs. The main objective of this study was to determine the influence of solution chemistry (e.g., pH, ionic strength and surface functionalization on the desorption of preloaded 1,3,5-trichlorobenzene (1,3,5-TCB from multi-walled carbon nanotubes (MWNTs. The results suggested that higher pH, ionic strength and natural organic matter in solution generally led to higher desorption of 1,3,5-TCB from MWNTs. However, the extent of change varied at different values of the tested parameters (e.g., pH 7. In addition, the impact of these parameters varied with MWNTs possessing different surface functional groups, suggesting that surface functionalization could considerably alter the environmental behaviors and impact of MWNTs.

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

    Science.gov (United States)

    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.

  12. Structure, Bonding and Surface Chemistry of Metal Oxide Nanoclusters

    Science.gov (United States)

    2015-06-23

    spectroscopy, complemented by computational quantum chemistry. Recent experiments have investigated the carbonyl complexes of Ti, Zr, Hf , Sc, Y and...16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT unlimited 18. NUMBER OF PAGES 9 19a. NAME OF RESPONSIBLE PERSON Michael A. Duncan a...information. 15. SUBJECT TERMS. Key words or phrases identifying major concepts in the report. 16. SECURITY CLASSIFICATION. Enter security classification in

  13. Complex Surface Concentration Gradients by Stenciled "Electro Click Chemistry"

    DEFF Research Database (Denmark)

    Hansen, Thomas Steen; Lind, Johan Ulrik; Daugaard, Anders Egede;

    2010-01-01

    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...... active ligands including cell binding peptides are patterned in gradients by this method without losing their biological function or the conductivity of the polymer....

  14. Detection of Tetrodotoxins in Puffer Fish by a Self-Assembled Monolayer-Based Immunoassay and Comparison with Surface Plasmon Resonance, LC-MS/MS, and Mouse Bioassay.

    Science.gov (United States)

    Reverté, Laia; de la Iglesia, Pablo; del Río, Vanessa; Campbell, Katrina; Elliott, Christopher T; Kawatsu, Kentaro; Katikou, Panagiota; Diogène, Jorge; Campàs, Mònica

    2015-11-03

    The increasing occurrence of puffer fish containing tetrodotoxin (TTX) in the Mediterranean could represent a major food safety risk for European consumers and threaten the fishing industry. The work presented herein describes the development of a new enzyme linked immunosorbent assay (mELISA) based on the immobilization of TTX through dithiol monolayers self-assembled on maleimide plates, which provides an ordered and oriented antigen immobilization and favors the antigen-antibody affinity interaction. The mELISA was found to have a limit of detection (LOD) of TTX of 0.23 mg/kg of puffer fish matrix. The mELISA and a surface plasmon resonance (SPR) immunosensor previously developed were employed to establish the cross-reactivity factors (CRFs) of 5,6,11-trideoxy-TTX, 5,11-deoxy-TTX, 11-nor-TTX-6-ol, and 5,6,11-trideoxy-4-anhydro-TTX, as well as to determine TTX equivalent contents in puffer fish samples. Results obtained by both immunochemical tools were correlated (R(2) = 0.977). The puffer fish samples were also analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS), and the corresponding CRFs were applied to the individual TTX contents. Results provided by the immunochemical tools, when compared with those obtained by LC-MS/MS, showed a good degree of correlation (R(2) = 0.991 and 0.979 for mELISA and SPR, respectively). The mouse bioassay (MBA) slightly overestimated the CRF adjusted TTX content of samples when compared with the data obtained from the other techniques. The mELISA has been demonstrated to be fit for the purpose for screening samples in monitoring programs and in research activities.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  17. 3D Printed Potential and Free Energy Surfaces for Teaching Fundamental Concepts in Physical Chemistry

    Science.gov (United States)

    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…

  18. Switchable Surface Wettability by Using Boronic Ester Chemistry.

    Science.gov (United States)

    Taleb, Sabri; Noyer, Elisabeth; Godeau, Guilhem; Darmanin, Thierry; Guittard, Frédéric

    2016-01-18

    Here, we report for the first time the use of a boronic ester as an efficient tool for reversible surface post-functionalization. The boronic ester bond allows surfaces to be reversibly switched from hydrophilic to hydrophobic. Based on the well-known boronic acid/glycol affinity, this strategy offers the opportunity to play with surface hydrophobic properties by adding various boronic acids onto substrates bearing glycol groups. The post-functionalization can then be reversed to regenerate the starting glycol surface. This pathway allows for the preparation of various switchable surfaces for a large range of applications in biosensors, liquid transportation, and separation membranes.

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

    Directory of Open Access Journals (Sweden)

    Marta Galbiati

    2015-05-01

    Full Text Available 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.

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

    Science.gov (United States)

    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.

  1. Micropatterning of Functional Conductive Polymers with Multiple Surface Chemistries in Register

    DEFF Research Database (Denmark)

    Lind, Johan Ulrik; Acikgöz, Canet; Daugaard, Anders Egede;

    2012-01-01

    A versatile procedure is presented for fast and efficient micropatterning of multiple types of covalently bound surface chemistry in perfect register on and between conductive polymer microcircuits. The micropatterning principle is applied to several types of native and functionalized PEDOT (poly(3......,4-ethylenedioxythiophene)) thin films. The method is based on contacting PEDOT-type thin films with a micropatterned agarose stamp containing an oxidant (aqueous hypochlorite) and applying a nonionic detergent. Where contacted, PEDOT not only loses its conductance but is entirely removed, thereby locally revealing...... the underlying substrate. Surface analysis showed that the substrate surface chemistry was fully exposed and not affected by the treatment. Click chemistry could thus be applied to selectively modify re-exposed alkyne and azide functional groups of functionalized polystyrene substrates. The versatility...

  2. The surface chemistry of metal-oxygen interactions

    DEFF Research Database (Denmark)

    Stokbro, Kurt; Baroni, Stefano

    1997-01-01

    We report on a computational study of the clean and oxygen-covered Rh(110) surface, based on density-functional theory within the local-density approximation. We have used plane-wave basis sets and Vanderbilt ultra-soft pseudopotentials. For the clean surface, we present results for the equilibrium...

  3. Geochemistry and Organic Chemistry on the Surface of Titan

    Science.gov (United States)

    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.

  4. Adsorption of atrazine on hemp stem-based activated carbons with different surface chemistry

    OpenAIRE

    Lupul, Iwona; Yperman, Jan; Carleer, Robert; Gryglewicz, Grazyna

    2015-01-01

    Surface-modified hemp stem-based activated carbons (HACs) were prepared and used for the adsorption of atrazine from aqueous solution, and their adsorption performance was examined. A series of HACs were prepared by potassium hydroxide activation of hemp stems, followed by subsequent modification by thermal annealing, oxidation with nitric acid and amination. The resultant HACs differed in surface chemistry, while possessing similar porous structure. The surface group characteristics were exa...

  5. Surface chemistry interventions to control boiler tube fouling

    Energy Technology Data Exchange (ETDEWEB)

    Turner, C.W.; Guzonas, D.A.; Klimas, S.J

    2000-06-01

    The adsorption of ammonia, morpholine, ethanolamine, and dimethylamine onto the surfaces of colloidal magnetite and hematite was measured at 25{sup o}C. The effect of the adsorption on the surface potential was quantified by measuring the resulting shift in the isoelectric point of the corrosion products and by the direct measurement of the surface interaction force between the corrosion products and Inconel 600. These measurements have served to support the hypothesis that adsorption of amine affects the magnetite deposition rate by lowering the force of repulsion between magnetite and the surface of Inconel 600. The deposition rate of hematite increased as the oxygen concentration increased. A mechanism to account for enhanced deposition rates at high mixture qualities (> 0.35) has been identified and shown to predict behaviour that is consistent with both experimental and plant data. As a result of this investigation, several criteria are proposed to reduce the extent of corrosion product deposition on the tube bundle. Low hematite deposition is favoured by a low concentration of dissolved oxygen, and low magnetite deposition is favoured by choosing an amine for pH control that has little tendency to adsorb onto the surface of magnetite. To minimize adsorption the amine should have a high base strength and a large 'footprint' on the surface of magnetite. To prevent enhanced deposition at high mixture qualities, it is proposed that a modified amine be used that will reduce the surface tension or the elasticity of the steam-water interface or both.

  6. First-order chemistry in the surface-flux layer

    DEFF Research Database (Denmark)

    Kristensen, L.; Andersen, C.E.; Ejsing Jørgensen, Hans

    1997-01-01

    We have discussed the behavior of a non-conserved scalar in the stationary, horizontally homogeneous, neutral surface-flux layer and, on the basis of conventional second-order closure, derived analytic expressions for flux and for mean concentration of a gas, subjected to a first-order removal...... process, The analytic flux solution showed a clear deviation from the constant flux, characterizing a conserved scalar in the surface-flux layer. It decreases with height and is reduced by an order of magnitude of the surface flux at a height equal to about the typical mean distance a molecule can travel...

  7. Chemistry and material science at the cell surface

    Directory of Open Access Journals (Sweden)

    Weian Zhao

    2010-04-01

    Full Text Available Cell surfaces are fertile ground for chemists and material scientists to manipulate or augment cell functions and phenotypes. This not only helps to answer basic biology questions but also has diagnostic and therapeutic applications. In this review, we summarize the most recent advances in the engineering of the cell surface. In particular, we focus on the potential applications of surface engineered cells for 1 targeting cells to desirable sites in cell therapy, 2 programming assembly of cells for tissue engineering, 3 bioimaging and sensing, and ultimately 4 manipulating cell biology.

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

    Science.gov (United States)

    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.

  9. From helical to planar chirality by on-surface chemistry.

    Science.gov (United States)

    Stetsovych, Oleksandr; Švec, Martin; Vacek, Jaroslav; Chocholoušová, Jana Vacek; Jančařík, Andrej; Rybáček, Jiří; Kosmider, Krzysztof; Stará, Irena G; Jelínek, Pavel; Starý, Ivo

    2017-03-01

    The chirality of molecular structures is paramount in many phenomena, including enantioselective reactions, molecular self-assembly, biological processes and light or electron-spin polarization. Flat prochiral molecules, which are achiral in the gas phase or solution, can exhibit adsorption-induced chirality when deposited on surfaces. The whole array of such molecular adsorbates is naturally racemic as spontaneous global mirror-symmetry breaking is disfavoured. Here we demonstrate a chemical method of obtaining flat prochiral molecules adsorbed on the solid achiral surface in such a way that a specific adsorbate handedness globally dominates. An optically pure helical precursor is flattened in a cascade of on-surface reactions, which enables chirality transfer. The individual reaction products are identified by high-resolution scanning-probe microscopy. The ultimate formation of globally non-racemic assemblies of flat molecules through stereocontrolled on-surface synthesis allows for chirality to be expressed in as yet unexplored types of organic-inorganic chiral interfaces.

  10. From helical to planar chirality by on-surface chemistry

    Science.gov (United States)

    Stetsovych, Oleksandr; Švec, Martin; Vacek, Jaroslav; Chocholoušová, Jana Vacek; Jančařík, Andrej; Rybáček, Jiří; Kosmider, Krzysztof; Stará, Irena G.; Jelínek, Pavel; Starý, Ivo

    2016-11-01

    The chirality of molecular structures is paramount in many phenomena, including enantioselective reactions, molecular self-assembly, biological processes and light or electron-spin polarization. Flat prochiral molecules, which are achiral in the gas phase or solution, can exhibit adsorption-induced chirality when deposited on surfaces. The whole array of such molecular adsorbates is naturally racemic as spontaneous global mirror-symmetry breaking is disfavoured. Here we demonstrate a chemical method of obtaining flat prochiral molecules adsorbed on the solid achiral surface in such a way that a specific adsorbate handedness globally dominates. An optically pure helical precursor is flattened in a cascade of on-surface reactions, which enables chirality transfer. The individual reaction products are identified by high-resolution scanning-probe microscopy. The ultimate formation of globally non-racemic assemblies of flat molecules through stereocontrolled on-surface synthesis allows for chirality to be expressed in as yet unexplored types of organic-inorganic chiral interfaces.

  11. Reaction kinetics of fluorite in flow systems and surface chemistry

    Institute of Scientific and Technical Information of China (English)

    张荣华; 胡书敏

    1996-01-01

    The kinetic experiments of fluorite in water-HCl solution in an open-flow system at the temperatures ≤100℃ reveal that the variation of flow rate (U) can change the reaction rate orders from 0 to 2 or higher. In the far from equilibrium systems, the dissolution rates of fluorite in aqueous solutions have a zero order.The reaction rates are controlled by pH values of input solutions. In fact, the reaction rates are related to the concentrations of the active sites occupied by H+ on fluorite surface [SOH]. X-ray photospectroscopy observations on fluorite surface before and after reaction indicate that surface chemical processes control the reaction rates: Cl- cations attach on and enter into surface of fluorite besides H+ when fluorites react with HCl solutions, which affect the reaction rates.

  12. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing, E-mail: shisq@nwu.edu.cn; Gong, Yongkuan

    2016-11-15

    Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH{sub 2}) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

  13. EFFECT OF HYPERCROSSLINKED RESINS SURFACE CHEMISTRY ON THEADSORPTION OF PHENOL FROM AQUEOUS SOLUTION

    Institute of Scientific and Technical Information of China (English)

    Guan-hua Meng; Ai-min Lia; Wei-ben Yang; Fu-qiang Liu; Quan-xing Zhang

    2006-01-01

    Two hypercrosslinked resins with similar physical characters but different surface chemistry were synthesized and used to remove phenol from aqueous solutions. The FTIR spectra, elemental analysis and the Boehm titration were used to characterize the chemical properties of the resins. The adsorption experiments were carried out using the bottle-point technique, and the effects of the surface chemistry on the adsorption were discussed. The adsorption data fit well with the Freundlich model, indicating the heterogeneity of the resins surface. It could be seen from the experimental results that the adsorption capacity increased with the increase in the total surface concentration of oxygen-containing groups. The pH dependence and the effects of ionic strength were also discussed. The kinetic adsorption data fit well with the pseudo-second order model, and the results showed that the surface oxygen-containing groups have little effect on the adsorption rate.

  14. Water Powered Bioassay System

    Science.gov (United States)

    2004-06-01

    capillary micropump 27 Figure 30: Slow dripping/separation of a droplet from a capillary 4.1.5 Micro Osmotic Pumping Nano Droplet...stored and delivered fluidic pressure and, with a combination of pumps and valves, formed the basic micro fluidic processing unit. The addition of...System, Microvalve, Micro -Accumulator, Micro Dialysis Needle, Bioassay System, Water Activated, Micro Osmotic Pump 16. PRICE CODE 17. SECURITY

  15. Mussel-Inspired Surface Chemistry for Multifunctional Coatings

    Science.gov (United States)

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

    2007-10-01

    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.

  16. Surface Physics and Chemistry of Electrical Contact Phenomena.

    Science.gov (United States)

    1982-09-24

    EVOLUIONS Fig. 2. Electrical contact resistances and coefficients of friction vs. number of slip ring revolutions under 1 atm of wet CO2 and a 30 A brush...number is in actual contact. However, the results especially at 50 A clearly point towards melting temperatures. Further, the ’AD-A12 2 i SURFACE

  17. Surface chemistry and rheology of polysulfobetaine-coated silica.

    Science.gov (United States)

    Starck, Pierre; Mosse, Wade K J; Nicholas, Nathan J; Spiniello, Marisa; Tyrrell, Johanna; Nelson, Andrew; Qiao, Greg G; Ducker, William A

    2007-07-03

    We have measured the viscosity of suspensions of colloidal silica particles (d = 300 nm) and the properties of silica surfaces in solutions of a polymer consisting of zwitterionic monomer groups, poly(sulfobetaine methacrylate), polySBMA. This polymer has potential use in modifying surface properties because the polymer is net uncharged and therefore does not generate double-layer forces. The solubility of the polymer can be controlled and varies from poor to good by the addition of sodium chloride salt. Ellipsometry was used to demonstrate that polySBMA adsorbs to silica and exhibits an increase in surface excess at lower salt concentration, which is consistent with a smaller area per molecule at low salt concentration. Neutron reflectivity measurements show that the adsorbed polymer has a thickness of about 3.7 nm and is highly hydrated. The polymer can be used to exercise considerable control over suspension rheology. When silica particles are not completely covered in polymer, the suspension produces a highly viscous gel. Atomic force microscopy was used to show this is caused by bridging of polymer between the particles. At higher surface coverage, the polymer can produce either a high or very low viscosity slurry depending on the sodium chloride concentration. At high salt concentration, the suspension is stable, and the viscosity is lower. This is probably because the entrainment of many small ions renders the polymer film highly hydrophilic, producing repulsive surface forces and lubricating the flow of particles. At low salt concentrations, the polymer is barely soluble and more densely adsorbed. This produces less stable and more viscous solutions, which we attribute to attractive interactions between the adsorbed polymer layers.

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

    Science.gov (United States)

    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. Surface Geometry and Chemistry of Hydrothermally Synthesized Single Crystal Thorium Dioxide

    Science.gov (United States)

    2015-03-01

    THORIUM DIOXIDE THESIS Presented to the Faculty Department of Engineering Physics Graduate School of Engineering and Management Air Force...UNLIMITED. AFIT-ENP-MS-15-M-87 SURFACE GEOMETRY AND CHEMISTRY OF HYDROTHERMALLY SYNTHESIZED SINGLE CRYSTAL THORIUM DIOXIDE Scott W. Key...51 21. As-grown thorium dioxide adhesion force and graphite adhesion force. .................. 52 22. Adhesion plot of indium and gold on

  20. Functional monolayers on oxide-free silicon surfaces via thiol–ene click chemistry

    NARCIS (Netherlands)

    Caipa Campos, Mabel A.; Paulusse, Jos M.J.; Zuilhof, Han

    2010-01-01

    Thiol–ene click chemistry was used for the attachment of a variety of functional molecules onto oxide-free Si(111) surfaces using very mild conditions; the efficient nature of this coupling strategy allowed for successful light-induced micropatterning and thus provides a novel route towards biofunct

  1. Facile modification of silica substrates provides a platform for direct-writing surface click chemistry.

    Science.gov (United States)

    Oberhansl, Sabine; Hirtz, Michael; Lagunas, Anna; Eritja, Ramon; Martinez, Elena; Fuchs, Harald; Samitier, Josep

    2012-02-20

    Please click here: a facile two-step functionalization strategy for silicon oxide-based substrates generates a stable platform for surface click chemistry via direct writing. The suitability of the obtained substrates is proven by patterning with two different direct-writing techniques and three different molecules.

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

    NARCIS (Netherlands)

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

    2012-01-01

    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 mod

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

    Energy Technology Data Exchange (ETDEWEB)

    Bertozzi, C.R. [Univ. of California, Berkeley, CA (United States)]|[Lawrence Berkeley National Lab., CA (United States)

    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.

  4. Atomic scale characterization and surface chemistry of metal modified titanate nanotubes and nanowires

    Science.gov (United States)

    Kukovecz, Ákos; Kordás, Krisztián; Kiss, János; Kónya, Zoltán

    2016-10-01

    Titanates are salts of polytitanic acid that can be synthesized as nanostructures in a great variety concerning crystallinity, morphology, size, metal content and surface chemistry. Titanate nanotubes (open-ended hollow cylinders measuring up to 200 nm in length and 15 nm in outer diameter) and nanowires (solid, elongated rectangular blocks with length up to 1500 nm and 30-60 nm diameter) are the most widespread representatives of the titanate nanomaterial family. This review covers the properties and applications of these two materials from the surface science point of view. Dielectric, vibrational, electron and X-ray spectroscopic results are comprehensively discussed first, then surface modification methods including covalent functionalization, ion exchange and metal loading are covered. The versatile surface chemistry of one-dimensional titanates renders them excellent candidates for heterogeneous catalytic, photocatalytic, photovoltaic and energy storage applications, therefore, these fields are also reviewed.

  5. High-temperature vesuvianite: crystal chemistry and surface considerations

    Science.gov (United States)

    Elmi, Chiara; Brigatti, Maria Franca; Pasquali, Luca; Montecchi, Monica; Laurora, Angela; Malferrari, Daniele; Nannarone, Stefano

    2011-06-01

    A multi-methodical approach has been applied for characterizing the bulk and surface crystal chemical features of a high-temperature vesuvianite crystal from skarns of Mount Somma-Vesuvius Volcano (Naples, Italy). Vesuvianite belongs to the space group P4/ nnc with unit cell parameters a = 15.633(1) Å, c = 11.834(1) Å and chemical formula (Ca18.858 Na0.028 Ba0.004 K0.006 Sr0.005 □0.098)19.000 (Al8.813 Ti0.037 Mg2.954 Mn0.008 Fe{0.114/2+} Fe{1.375/3+} Cr0.008 B0.202)13.511 Si18.000(O0.261 F0.940 OH7.799)9.000. Structure refinement, which converges at R = 0.0328, demonstrates a strong positional disorder down the fourfold axes, indicating that the Y1 site is split into two positions (Y1A and Y1B) alternatively occupied. However, because of X4 proximity to Y1B and Y1A, X4 cannot be occupied if Y1B or Y1A are. Overall Y1 occupancy (Y1A + Y1B) reaches approximately 0.5, as common in vesuvianite and occupancy of Y1B site is extremely limited. Moreover, T1 position, limitedly occupied, accommodates the excess of cations generally related to Y position. A small quantity (0.202 apfu) of boron is sited at the T2 site that, like T1, is poorly occupied. The determination of the amount of each element on the (100) vesuvianite surface, obtained through X-ray photoelectron spectroscopy high-resolution spectra in the region of the Si2p, Al2p, Mg1s, and Ca2p core levels, evidences that a greater amount of aluminum and a smaller amount of calcium characterize the surface with respect to the bulk. Although both of these features require further investigation, we may consider the Al increase can be related to preferential orientation of Al-rich sites on the (100) plane. Furthermore, the surface structure of vesuvianite suggests that Al, Ca, and Mg cations maintain coordination features at the surface similar to the bulk. Silica, however, while presenting fourfold coordination, shows also a [1]-fold small coordinated component at binding energy 99.85 eV, due to broken Si-O bonds at

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

    Science.gov (United States)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Greczynski, G. [Thin Film Physics Division, Department of Physics (IFM), Linköping University, SE-581 83 Linköping (Sweden); Materials Chemistry, RWTH Aachen University, Kopernikusstr. 10, D-52074 Aachen (Germany); Mráz, S.; Schneider, J. M. [Materials Chemistry, RWTH Aachen University, Kopernikusstr. 10, D-52074 Aachen (Germany); Hultman, L. [Thin Film Physics Division, Department of Physics (IFM), Linköping University, SE-581 83 Linköping (Sweden)

    2016-01-25

    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 T{sub v}, each affecting the surface chemistry, are addressed. It is demonstrated for the TiN model materials system that T{sub v} 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.

  8. Engineering of Surface Chemistry for Enhanced Sensitivity in Nanoporous Interferometric Sensing Platforms.

    Science.gov (United States)

    Law, Cheryl Suwen; Sylvia, Georgina M; Nemati, Madieh; Yu, Jingxian; Losic, Dusan; Abell, Andrew D; Santos, Abel

    2017-03-15

    We explore new approaches to engineering the surface chemistry of interferometric sensing platforms based on nanoporous anodic alumina (NAA) and reflectometric interference spectroscopy (RIfS). Two surface engineering strategies are presented, namely (i) selective chemical functionalization of the inner surface of NAA pores with amine-terminated thiol molecules and (ii) selective chemical functionalization of the top surface of NAA with dithiol molecules. The strong molecular interaction of Au(3+) ions with thiol-containing functional molecules of alkane chain or peptide character provides a model sensing system with which to assess the sensitivity of these NAA platforms by both molecular feature and surface engineering. Changes in the effective optical thickness of the functionalized NAA photonic films (i.e., sensing principle), in response to gold ions, are monitored in real-time by RIfS. 6-Amino-1-hexanethiol (inner surface) and 1,6-hexanedithiol (top surface), the most sensitive functional molecules from approaches i and ii, respectively, were combined into a third sensing strategy whereby the NAA platforms are functionalized on both the top and inner surfaces concurrently. Engineering of the surface according to this approach resulted in an additive enhancement in sensitivity of up to 5-fold compared to previously reported systems. This study advances the rational engineering of surface chemistry for interferometric sensing on nanoporous platforms with potential applications for real-time monitoring of multiple analytes in dynamic environments.

  9. Bioassays Based on Molecular Nanomechanics

    Directory of Open Access Journals (Sweden)

    Arun Majumdar

    2002-01-01

    Full Text Available Recent experiments have shown that when specific biomolecular interactions are confined to one surface of a microcantilever beam, changes in intermolecular nanomechanical forces provide sufficient differential torque to bend the cantilever beam. This has been used to detect single base pair mismatches during DNA hybridization, as well as prostate specific antigen (PSA at concentrations and conditions that are clinically relevant for prostate cancer diagnosis. Since cantilever motion originates from free energy change induced by specific biomolecular binding, this technique is now offering a common platform for label-free quantitative analysis of protein-protein binding, DNA hybridization DNA-protein interactions, and in general receptor-ligand interactions. Current work is focused on developing “universal microarrays” of microcantilever beams for high-throughput multiplexed bioassays.

  10. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    Science.gov (United States)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing; Gong, Yongkuan

    2016-11-01

    Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH2) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such zwitterion modified PP surface.

  11. Using advanced surface complexation models for modelling soil chemistry under forests: Solling forest, Germany.

    Science.gov (United States)

    Bonten, Luc T C; Groenenberg, Jan E; Meesenburg, Henning; de Vries, Wim

    2011-10-01

    Various dynamic soil chemistry models have been developed to gain insight into impacts of atmospheric deposition of sulphur, nitrogen and other elements on soil and soil solution chemistry. Sorption parameters for anions and cations are generally calibrated for each site, which hampers extrapolation in space and time. On the other hand, recently developed surface complexation models (SCMs) have been successful in predicting ion sorption for static systems using generic parameter sets. This study reports the inclusion of an assemblage of these SCMs in the dynamic soil chemistry model SMARTml and applies this model to a spruce forest site in Solling Germany. Parameters for SCMs were taken from generic datasets and not calibrated. Nevertheless, modelling results for major elements matched observations well. Further, trace metals were included in the model, also using the existing framework of SCMs. The model predicted sorption for most trace elements well.

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

    Science.gov (United States)

    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.

  13. Surface Chemistry of Aluminium Alloy Slid against Steel Lubricated by Organic Friction Modifier in Hydrocarbon Oil

    Directory of Open Access Journals (Sweden)

    Ichiro Minami

    2012-01-01

    Full Text Available The lubrication mechanism of aluminium alloy slid against steel was investigated from the standpoint of surface chemistry. Low friction and low wear were observed using glycerol mono-olate in a hydrocarbon as lubricant. Increase in the silicon content in the aluminium alloy during rubbing was observed by surface analyses using (1 Auger electron spectroscopy, (2 scanning electron microscopy along with energy dispersive X-ray spectroscopy, and (3 X-ray photoelectron spectroscopy. Mild removal of the passive state (aluminium oxide from the uppermost surface by the additive during the running-in process was proposed as the lubrication mechanism. The importance of additive chemistry that improves the running-in process was pointed out.

  14. Surface chemistry of black phosphorus under a controlled oxidative environment

    Science.gov (United States)

    Luo, Wei; Zemlyanov, Dmitry Y.; Milligan, Cory A.; Du, Yuchen; Yang, Lingming; Wu, Yanqing; Ye, Peide D.

    2016-10-01

    Black phosphorus (BP), the bulk counterpart of monolayer phosphorene, is a relatively stable phosphorus allotrope at room temperature. However, monolayer phosphorene and ultra-thin BP layers degrade in ambient atmosphere. In this paper, we report the investigation of BP oxidation and discuss the reaction mechanism based on the x-ray photoelectron spectroscopy (XPS) data. The kinetics of BP oxidation was examined under various well-controlled conditions, namely in 5% O2/Ar, 2.3% H2O/Ar, and 5% O2 and 2.3% H2O/Ar. At room temperature, the BP surface is demonstrated not to be oxidized at a high oxidation rate in 5% O2/Ar nor in 2.3% H2O/Ar, according to XPS, with the thickness of the oxidized phosphorus layer <5 Å for 5 h. On the other hand, in the O2/H2O mixture, a 30 Å thickness oxide layer was detected already after 2 h of the treatment. This result points to a synergetic effect of water and oxygen in the BP oxidation. The oxidation effect was also studied in applications to the electrical measurements of BP field-effect transistors (FETs) with or without passivation. The electrical performance of BP FETs with atomic layer deposition (ALD) dielectric passivation or h-BN passivation formed in a glove-box environment are also presented.

  15. Surface chemistry regulates the sensitivity and tolerability of osteoblasts to various magnitudes of fluid shear stress.

    Science.gov (United States)

    Li, Yan; Wang, Jinfeng; Xing, Juan; Wang, Yuanliang; Luo, Yanfeng

    2016-12-01

    Scaffolds provide a physical support for osteoblasts and act as the medium to transfer mechanical stimuli to cells. To verify our hypothesis that the surface chemistry of scaffolds regulates the perception of cells to mechanical stimuli, the sensitivity and tolerability of osteoblasts to fluid shear stress (FSS) of various magnitudes (5, 12, 20 dynes/cm(2) ) were investigated on various surface chemistries (-OH, -CH3 , -NH2 ), and their follow-up effects on cell proliferation and differentiation were examined as well. The sensitivity was characterized by the release of adenosine triphosphate (ATP), nitric oxide (NO) and prostaglandin E2 (PGE2 ) while the tolerability was by cellular membrane integrity. The cell proliferation was characterized by S-phase cell fraction and the differentiation by ALP activity and ECM expression (fibronectin and type I collagen). As revealed, osteoblasts demonstrated higher sensitivity and lower tolerability on OH and CH3 surfaces, yet lower sensitivity and higher tolerability on NH2 surfaces. Observations on the focal adhesion formation, F-actin organization and cellular orientation before and after FSS exposure suggest that the potential mechanism lies in the differential control of F-actin organization and focal adhesion formation by surface chemistry, which further divergently mediates the sensitivity and tolerability of ROBs to FSS and the follow-up cell proliferation and differentiation. These findings are essentially valuable for design/selection of desirable surface chemistry to orchestrate with FSS stimuli, inducing appropriate cell responses and promoting bone formation. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2978-2991, 2016.

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

    Directory of Open Access Journals (Sweden)

    NL Davison

    2015-06-01

    Full Text Available 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  18. Enabling organosilicon chemistries on inert polymer surfaces with a vapor-deposited silica layer.

    Science.gov (United States)

    Anderson, A; Ashurst, W R

    2009-10-06

    Given the large surface area-to-volume ratios commonly encountered in microfluidics applications, the ability to engineer the chemical properties of surfaces encountered in these applications is critically important. However, as various polymers are rapidly replacing glass and silicon as the chosen materials for microfluidics devices, the ability to easily modify the surface chemistry has been diminished by the relatively inert nature of some commonly employed polymer surfaces, such as poly(methyl methacrylate) (PMMA), polystyrene, and polydimethylsiloxane (PDMS). This paper describes the low-temperature, vapor-phase deposition of robust silica layers to PMMA, polystyrene, and PDMS surfaces, which enables the functionalization of these surfaces by standard organosilane chemistries. Attenuated total reflection infrared spectroscopy, contact angle goniometry, ellipsometry, and atomic force microscopy are used to characterize the silica layers that form on these surfaces. Aqueous immersion experiments indicate that the silica layer has excellent stability in aqueous environments, which is a prerequisite for microfluidics applications, but for PMMA surfaces, low adhesion of the silica layer to the underlying substrate is problematic. For PDMS substrates, the presence of the silica layer helps to slow the process of hydrophobic recovery, which is an additional advantage.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2015-09-04

    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.

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

    Science.gov (United States)

    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.

  2. Role of nanoparticle size, shape and surface chemistry in oral drug delivery.

    Science.gov (United States)

    Banerjee, Amrita; Qi, Jianping; Gogoi, Rohan; Wong, Jessica; Mitragotri, Samir

    2016-09-28

    Nanoparticles find intriguing applications in oral drug delivery since they present a large surface area for interactions with the gastrointestinal tract and can be modified in various ways to address the barriers associated with oral delivery. The size, shape and surface chemistry of nanoparticles can greatly impact cellular uptake and efficacy of the treatment. However, the interplay between particle size, shape and surface chemistry has not been well investigated especially for oral drug delivery. To this end, we prepared sphere-, rod- and disc-shaped nanoparticles and conjugated them with targeting ligands to study the influence of size, shape and surface chemistry on their uptake and transport across intestinal cells. A triple co-culture model of intestinal cells was utilized to more closely mimic the intestinal epithelium. Results demonstrated higher cellular uptake of rod-shaped nanoparticles in the co-culture compared to spheres regardless of the presence of active targeting moieties. Transport of nanorods across the intestinal co-culture was also significantly higher than spheres. The findings indicate that nanoparticle-mediated oral drug delivery can be potentially improved with departure from spherical shape which has been traditionally utilized for the design of nanoparticles. We believe that understanding the role of nanoparticle geometry in intestinal uptake and transport will bring forth a paradigm shift in nanoparticle engineering for oral delivery and non-spherical nanoparticles should be further investigated and considered for oral delivery of therapeutic drugs and diagnostic materials.

  3. Oxygen concentration control of dopamine-induced high uniformity surface coating chemistry.

    Science.gov (United States)

    Kim, Hyo Won; McCloskey, Bryan D; Choi, Tae Hwan; Lee, Changho; Kim, Min-Joung; Freeman, Benny D; Park, Ho Bum

    2013-01-23

    Material surface engineering has attracted great interest in important applications, including electronics, biomedicine, and membranes. More recently, dopamine has been widely exploited in solution-based chemistry to direct facile surface modification. However, unsolved questions remain about the chemical identity of the final products, their deposition kinetics and their binding mechanism. In particular, the dopamine oxidation reaction kinetics is a key to improving surface modification efficiency. Here, we demonstrate that high O(2) concentrations in the dopamine solution lead to highly homogeneous, thin layer deposition on any material surfaces via accelerated reaction kinetics, elucidated by Le Chatelier's principle toward dopamine oxidation steps in a Michael-addition reaction. As a result, highly uniform, ultra-smooth modified surfaces are achieved in much shorter deposition times. This finding provides new insights into the effect of reaction kinetics and molecular geometry on the uniformity of modifications for surface engineering techniques.

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

    Science.gov (United States)

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

    2015-03-01

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  8. Surface Chemistry and Structural Effects in the Stress Corrosion of Glass and Ceramic Materials

    Science.gov (United States)

    1988-09-15

    the strength and fatigue characteristics of ZBLAN (zirconium barium-lanthanum-aluminum-sodium fluoride) optical glass fiber obtained from British...Surface Chemistry and Structural Effects in the Stress Corrosion of Glass and Ceramic Materlals 12. PERSONAL AUTHOR(S) Carlo G. Pantano 13a. TYPE OF...fluorozirconate glasses . °. DTICS ELEC T E DEC 09 I 20. DISTRIBUTION/ AVAILABILITY OF ABSTRACT 21.-A% RACT SECURITY CLASSIFICATION [BUNCLASSIFIED/UNLIMITED

  9. Deuteration and evolution in the massive star formation process: the role of surface chemistry

    OpenAIRE

    Fontani, F.; Busquet, G.; Palau, Aina; Caselli, P.; Van, A; Sanchez-Monge; Tan, J. C.; Audard, M.

    2014-01-01

    An ever growing number of observational and theoretical evidence suggests that the deuterated fraction (column density ratio between a species containing D and its hydrogenated counterpart, Dfrac) is an evolutionary indicator both in the low- and the high-mass star formation process. However, the role of surface chemistry in these studies has not been quantified from an observational point of view. In order to compare how the deuterated fractions of species formed only in the gas and partiall...

  10. Surface chemistry allows for abiotic precipitation of dolomite at low temperature

    OpenAIRE

    Roberts, Jennifer A.; Kenward, Paul A.; Fowle, David A.; Goldstein, Robert H.; Luis A. González; Moore, David S.

    2013-01-01

    Abundant in the geologic record, but scarce in modern environments below 50 °C, the mineral dolomite is used to interpret ancient fluid chemistry, paleotemperature, and is a major hydrocarbon reservoir rock. Because laboratory synthesis of abiotic dolomite had been unsuccessful, chemical mechanisms for precipitation are poorly constrained, and limit interpretations of its occurrence. Here we report the abiotic synthesis of dolomite at 25 °C, and demonstrate that carboxylated surfaces on organ...

  11. BIOASSAY VESSEL FAILURE ANALYSIS

    Energy Technology Data Exchange (ETDEWEB)

    Vormelker, P

    2008-09-22

    Two high-pressure bioassay vessels failed at the Savannah River Site during a microwave heating process for biosample testing. Improper installation of the thermal shield in the first failure caused the vessel to burst during microwave heating. The second vessel failure is attributed to overpressurization during a test run. Vessel failure appeared to initiate in the mold parting line, the thinnest cross-section of the octagonal vessel. No material flaws were found in the vessel that would impair its structural performance. Content weight should be minimized to reduce operating temperature and pressure. Outer vessel life is dependent on actual temperature exposure. Since thermal aging of the vessels can be detrimental to their performance, it was recommended that the vessels be used for a limited number of cycles to be determined by additional testing.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  14. Effects of wood fiber surface chemistry on strength of wood–plastic composites

    Energy Technology Data Exchange (ETDEWEB)

    Migneault, Sébastien, E-mail: sebastien.migneault@uqat.ca [University of Quebec in Abitibi-Temiscamingue (UQAT), 445 boulevard de l’Université, Rouyn-Noranda, Québec J9X 5E4 (Canada); Koubaa, Ahmed, E-mail: ahmed.koubaa@uqat.ca [UQAT (Canada); Perré, Patrick, E-mail: patrick.perre@ecp.fr [École centrale de Paris, Grande Voie des Vignes, F-92 295 Chatenay-Malabry Cedex (France); Riedl, Bernard, E-mail: Bernard.Riedl@sbf.ulaval.ca [Université Laval, 2425 rue de la Terrasse, Québec City, Québec G1V 0A6 (Canada)

    2015-07-15

    Highlights: • Infrared spectroscopy and X-ray photoelectron spectroscopy analyses showed variations of surface chemical characteristics according to fiber origin. • Surface chemical characteristics of fibers could partly explain the differences in mechanical properties of the wood–plastic composites. • Fibers with carbohydrate rich surface led to stronger wood–plastic composites because the coupling between the matrix and fibers using coupling agent is achieved with polar sites mostly available on carbohydrates. • Conversely, lignin or extractives rich surface do not have oxidized functions for the esterification reaction with coupling agent and thus led to wood–plastic composites with lower mechanical properties. • Other factors such as mechanical interlocking and fiber morphology interfere with the effects of fiber surface chemistry. - Abstract: 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

  15. Examining metal nanoparticle surface chemistry using hollow-core, photonic-crystal, fiber-assisted SERS.

    Science.gov (United States)

    Eftekhari, Fatemeh; Lee, Anna; Kumacheva, Eugenia; Helmy, Amr S

    2012-02-15

    In this Letter, we demonstrate the efficacy of hollow core photonic crystal fibers (HCPCFs) as a surface-enhanced Raman spectroscopy (SERS) platform for investigating the ligand exchange process on the surface of gold nanoparticles. Raman measurements carried out using this platform show the capability to monitor minute amounts of surface ligands on gold nanoparticles used as an SERS substrate. The SERS signal from an HCPCF exhibits a tenfold enhancement compared to that in a direct sampling scheme using a cuvette. Using exchange of cytotoxic cetyltrimethylammonium bromide with α-methoxy-ω-mercaptopoly(ethylene glycol) on the surface of gold nanorods as an exemplary system, we show the feasibility of using HCPCF SERS to monitor the change in surface chemistry of nanoparticles.

  16. Efficient Functionalization of Oxide-Free Silicon(111) Surfaces: Thiol–yne versus Thiol–ene Click Chemistry

    NARCIS (Netherlands)

    Bhairamadgi, N.S.; Gangarapu, S.; Caipa Campos, M.A.; Paulusse, J.M.J.; Rijn, van C.J.M.; Zuilhof, H.

    2013-01-01

    Thiol-yne click (TYC) chemistry was utilized as a copper-free click reaction for the modification of alkyne-terminated monolayers on oxide-free Si(111) surfaces, and the results were compared with the analogous thiol–ene click (TEC) chemistry. A wide range of thiols such as 9-fluorenylmethoxy-carbon

  17. Efficient Functionalization of Oxide-Free Silicon(111) Surfaces: Thiol-yne versus Thiol-ene Click Chemistry

    NARCIS (Netherlands)

    Bhairamadgi, N.S.; Gangarapu, S.; Caipa Campos, M.A.; Paulusse, J.M.J.; Rijn, van C.J.M.; Zuilhof, H.

    2013-01-01

    Thiol-yne click (TYC) chemistry was utilized as a copper-free click reaction for the modification of alkyne-terminated monolayers on oxide-free Si(111) surfaces, and the results were compared with the analogous thiol–ene click (TEC) chemistry. A wide range of thiols such as 9-fluorenylmethoxy-carbon

  18. Impact of Surface Chemistry on Grain Boundary Induced Intrinsic Stress Evolution during Polycrystalline Thin Film Growth

    Science.gov (United States)

    Qi, Y.; Sheldon, B. W.; Guo, H.; Xiao, X.; Kothari, A. K.

    2009-02-01

    First principles calculations were integrated with cohesive zone and growth chemistry models to demonstrate that adsorbed species can significantly alter stresses associated with grain boundary formation during polycrystalline film growth. Using diamond growth as an example, the results show that lower substrate temperatures increase the hydrogen content at the surface, which reduces tensile stress, widens the grain boundary separations, and permits additional atom insertions that can induce compressive stress. More generally, this work demonstrates that surface heteroatoms can lead to behavior which is not readily described by existing models of intrinsic stress evolution.

  19. Clathrin to Lipid Raft-Endocytosis via Controlled Surface Chemistry and Efficient Perinuclear Targeting of Nanoparticle.

    Science.gov (United States)

    Chakraborty, Atanu; Jana, Nikhil R

    2015-09-17

    Nanoparticle interacts with live cells depending on their surface chemistry, enters into cell via endocytosis, and is commonly trafficked to an endosome/lysozome that restricts subcellular targeting options. Here we show that nanoparticle surface chemistry can be tuned to alter their cell uptake mechanism and subcellular trafficking. Quantum dot based nanoprobes of 20-30 nm hydrodynamic diameters have been synthesized with tunable surface charge (between +15 mV to -25 mV) and lipophilicity to influence their cellular uptake processes and subcellular trafficking. It is observed that cationic nanoprobe electrostatically interacts with cell membrane and enters into cell via clathrin-mediated endocytosis. At lower surface charge (between +10 mV to -10 mV), the electrostatic interaction with cell membrane becomes weaker, and additional lipid raft endocytosis is initiated. If a lipophilic functional group is introduced on a weakly anionic nanoparticle surface, the uptake mechanism shifts to predominant lipid raft-mediated endocytosis. In particular, the zwitterionic-lipophilic nanoprobe has the unique advantage as it weakly interacts with anionic cell membrane, migrates toward lipid rafts for interaction through lipophilic functional group, and induces lipid raft-mediated endocytosis. While predominate or partial clathrin-mediated entry traffics most of the nanoprobes to lysozome, predominate lipid raft-mediated entry traffics them to perinuclear region, particularly to the Golgi apparatus. This finding would guide in designing appropriate nanoprobe for subcellular targeting and delivery.

  20. Bioadhesion of mussels and geckos: Molecular mechanics, surface chemistry, and nanoadhesives

    Science.gov (United States)

    Lee, Haeshin

    The adhesive strategies of living creatures are diverse, ranging from temporary to permanent adhesions with various functions such as locomotion, self-defense, communication, colony formation, and so on. The classic example of temporary adhesion is the gecko, which is known for its ability to walk along vertical and even inverted surfaces; this remarkable adhesion arises from the interfacial weak interactions of van der Waals and capillary forces. In contrast, a celerbrated example of permanent adhesion is found in marine mussels which secrete protein adhesives that function in aqueous environments without mechanical failure against turbulent conditions on the seashore. In addition, mussel adhesives stick to virtually all inorganic and organic surfaces. However, most commonly used man-made adhesives lack such unique adhesion properties compared to their natural counterparts. For example, many commercial adhesives quickly lose their adhesive strength when exposed to solvents, particularly water. The first part of this thesis focused on adhesion mechanics of mussels at a single-molecule level, in which the adhesive molecule showed surprisingly strong yet reversible adhesion on inorganic surfaces but exhibited irreversible covalent bond formation on organic surfaces. Strong and reversible adhesion on mucin surfaces was found, indicating potential application for drug delivery via mucus layers. Next, inspired by the mussel's versatile adhesion on a wide variety of material surfaces, a material-independent surface modification chemistry called 'polydopamine coating' is described. This concept was subsequently adapted to develop a surface-independent polymeric primer for layer-by-layer assembly of multifunctional coatings. Finally, a new bio-hybrid adhesive 'geckel' was developed by the functional combination of adhesion strategies of geckos and mussels. The new bio-inspired adhesive and material-independent surface chemistry can revolutionize the research areas such as

  1. Wettability and surface chemistry of crystalline and amorphous forms of a poorly water soluble drug.

    Science.gov (United States)

    Puri, Vibha; Dantuluri, Ajay K; Kumar, Mahesh; Karar, N; Bansal, Arvind K

    2010-05-12

    The present study compares energetics of wetting behavior of crystalline and amorphous forms of a poorly water soluble drug, celecoxib (CLB) and attempts to correlate it to their surface molecular environment. Wettability and surface free energy were determined using sessile drop contact angle technique and water vapor sorption energetics was measured by adsorption calorimetry. The surface chemistry was elucidated by X-ray photoelectron spectroscopy (XPS) and crystallographic evaluation. The two solid forms displayed distinctly different wetting with various probe liquids and in vitro dissolution media. The crystalline form surface primarily exhibited dispersive surface energy (47.3mJ/m(2)), while the amorphous form had a slightly reduced dispersive (45.2mJ/m(2)) and a small additional polar (4.8mJ/m(2)) surface energy. Calorimetric measurements, revealed the amorphous form to possess a noticeably high differential heat of absorption, suggesting hydrogen bond interactions between its polar energetic sites and water molecules. Conversely, the crystalline CLB form was found to be inert to water vapor sorption. The relatively higher surface polarity of the amorphous form could be linked to its greater oxygen-to-fluorine surface concentration ratio of 1.27 (cf. 0.62 for crystalline CLB), as determined by XPS. The crystallographic studies of the preferred cleavage plane (020) of crystalline CLB further supported its higher hydrophobicity. In conclusion, the crystalline and amorphous forms of CLB exhibited disparate surface milieu, which in turn can have implications on the surface mediated events.

  2. Experimental studies of lithium-based surface chemistry for fusion plasma-facing materials applications

    Energy Technology Data Exchange (ETDEWEB)

    Allain, J.P., E-mail: allain@purdue.ed [Purdue University, West Lafayette, 400 Central Drive, IN 47907 (United States); Rokusek, D.L.; Harilal, S.S. [Purdue University, West Lafayette, 400 Central Drive, IN 47907 (United States); Nieto-Perez, M. [CICATA-IPN, Cerro Blanco 141 Cimatario, Queretaro, QRO 76090 (Mexico); Skinner, C.H.; Kugel, H.W. [Princeton Plasma Physics Laboratory, Princeton, NJ 08543 (United States); Heim, B. [Purdue University, West Lafayette, 400 Central Drive, IN 47907 (United States); Kaita, R.; Majeski, R. [Princeton Plasma Physics Laboratory, Princeton, NJ 08543 (United States)

    2009-06-15

    Lithium has enhanced the operational performance of fusion devices such as: TFTR, CDX-U, FTU, T-11 M, and NSTX. Lithium in the solid and liquid state has been studied extensively in laboratory experiments including its erosion and hydrogen-retaining properties. Reductions in physical sputtering up to 40-60% have been measured for deuterated solid and liquid lithium surfaces. Computational modeling indicates that up to a 1:1 deuterium volumetric retention in lithium is possible. This paper presents the results of systematic in situ laboratory experimental studies on the surface chemistry evolution of ATJ graphite under lithium deposition. Results are compared to post-mortem analysis of similar lithium surface coatings on graphite exposed to deuterium discharge plasmas in NSTX. Lithium coatings on plasma-facing components in NSTX have shown substantial reduction of hydrogenic recycling. Questions remain on the role lithium surface chemistry on a graphite substrate has on particle sputtering (physical and chemical) as well as hydrogen isotope recycling. This is particularly due to the lack of in situ measurements of plasma-surface interactions in tokamaks such as NSTX. Results suggest that the lithium bonding state on ATJ graphite is lithium peroxide and with sufficient exposure to ambient air conditions, lithium carbonate is generated. Correlation between both results is used to assess the role of lithium chemistry on the state of lithium bonding and implications on hydrogen pumping and lithium sputtering. In addition, reduction of factors between 10 and 30 reduction in physical sputtering from lithiated graphite compared to pure lithium or carbon is also measured.

  3. Probing the effect of surface chemistry on the electrical properties of ultrathin gold nanowire sensors.

    Science.gov (United States)

    Kisner, Alexandre; Heggen, Marc; Mayer, Dirk; Simon, Ulrich; Offenhäusser, Andreas; Mourzina, Yulia

    2014-05-21

    Ultrathin metal nanowires are ultimately analytical tools that can be used to survey the interfacial properties of the functional groups of organic molecules immobilized on nanoelectrodes. The high ratio of surface to bulk atoms makes such ultrathin nanowires extremely electrically sensitive to adsorbates and their charge and/or polarity, although little is known about the nature of surface chemistry interactions on metallic ultrathin nanowires. Here we report the first studies about the effect of functional groups of short-chain alkanethiol molecules on the electrical resistance of ultrathin gold nanowires. We fabricated ultrathin nanowire electrical sensors based on chemiresistors using conventional microfabrication techniques, so that the contact areas were passivated to leave only the surface of the nanowires exposed to the environment. By immobilizing alkanethiol molecules with head groups such as -CH3, -NH2 and -COOH on gold nanowires, we examined how the charge proximity due to protonation/deprotonation of the functional groups affects the resistance of the sensors. Electrical measurements in air and in water only indicate that beyond the gold-sulfur moiety interactions, the interfacial charge due to the acid-base chemistry of the functional groups of the molecules has a significant impact on the electrical resistance of the wires. Our data demonstrate that the degree of dissociation of the corresponding functional groups plays a major role in enhancing the surface-sensitive resistivity of the nanowires. These results stress the importance of recognizing the effect of protonation/deprotonation of the surface chemistry on the resulting electrical sensitivity of ultrathin metal nanowires and the applicability of such sensors for studying interfacial properties using electrodes of comparable size to the electrochemical double layer.

  4. New Concept of C–H and C–C Bond Activation via Surface Organometallic Chemistry

    KAUST Repository

    Samantaray, Manoja

    2015-08-18

    In this chapter we describe the recent applications of well-defined oxidesupported metal alkyls/alkylidenes/alkylidynes and hydrides of group IV, V, and VI transition metals in the field of C–H and C–C bond activation. The activation of ubiquitous C–H and C–C bonds of paraffin is a long-standing challenge because of intrinsic low reactivity. There are many concepts derived from surface organometallic chemistry (SOMC): surface organometallic fragments are always intermediates in heterogeneous catalysis. The study of their synthesis and reactivity is a way to rationalize mechanism of heterogeneous catalysis and to achieve structure activity relationship. By surface organometallic chemistry one can enter any catalytic center by a reaction intermediate leading in fine to single site catalysts. With surface organometallic chemistry one can coordinate to the metal which can play a role in different elementary steps leading for example to C–H activation and Olefin metathesis. Because of the development of SOMC there is a lot of space for the improvement of homogeneous catalysis. After the 1997 discovery of alkane metathesis using silica-supported tantalum hydride by Basset et al. at low temperature (150ºC) the focus in this area was shifted to the discovery of more and more challenging surface complexes active in the application of C–H and C–C bond activation. Here we describe the evolution of well-defined metathesis catalyst with time as well as the effect of support on catalysis. We also describe here which metal–ligand combinations are responsible for a variety of C–H and C–C bond activation.

  5. Surface chemistry of Ti6Al4V components fabricated using selective laser melting for biomedical applications

    Energy Technology Data Exchange (ETDEWEB)

    Vaithilingam, Jayasheelan, E-mail: Jayasheelan.Vaithilingam@nottingham.ac.uk [Additive Manufacturing and 3D Printing Research Group, EPSRC Centre for Innovative Manufacturing in Additive Manufacturing, School of Engineering, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Prina, Elisabetta [School of Pharmacy, Centre for Biomolecular Sciences, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Goodridge, Ruth D.; Hague, Richard J.M. [Additive Manufacturing and 3D Printing Research Group, EPSRC Centre for Innovative Manufacturing in Additive Manufacturing, School of Engineering, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Edmondson, Steve [School of Materials, The University of Manchester, Manchester M13 9PL (United Kingdom); Rose, Felicity R.A.J. [School of Pharmacy, Centre for Biomolecular Sciences, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Christie, Steven D.R. [Department of Chemistry, Loughborough University, Loughborough LE11 3TU (United Kingdom)

    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 ± 3.7 μm. 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. - Highlights: • Surface chemistry of selective laser melted (SLM) Ti6Al4V parts was compared with conventionally forged Ti6Al4V parts. • The surface elemental compositions of the SLM as-fabricated surfaces were significantly different to the forged surface. • Surface oxide-layer of the SLM as-fabricated was thicker than the polished SLM surfaces and the forged Ti6Al4V surfaces.

  6. Surface chemistry for molecular layer deposition of organic and hybrid organic-inorganic polymers.

    Science.gov (United States)

    George, Steven M; Yoon, Byunghoon; Dameron, Arrelaine A

    2009-04-21

    The fabrication of many devices in modern technology requires techniques for growing thin films. As devices miniaturize, manufacturers will need to control thin film growth at the atomic level. Because many devices have challenging morphologies, thin films must be able to coat conformally on structures with high aspect ratios. Techniques based on atomic layer deposition (ALD), a special type of chemical vapor deposition, allow for the growth of ultra-thin and conformal films of inorganic materials using sequential, self-limiting reactions. Molecular layer deposition (MLD) methods extend this strategy to include organic and hybrid organic-inorganic polymeric materials. In this Account, we provide an overview of the surface chemistry for the MLD of organic and hybrid organic-inorganic polymers and examine a variety of surface chemistry strategies for growing polymer thin films. Previously, surface chemistry for the MLD of organic polymers such as polyamides and polyimides has used two-step AB reaction cycles using homo-bifunctional reactants. However, these reagents can react twice and eliminate active sites on the growing polymer surface. To avoid this problem, we can employ alternative precursors for MLD based on hetero-bifunctional reactants and ring-opening reactions. We can also use surface activation or protected chemical functional groups. In addition, we can combine the reactants for ALD and MLD to grow hybrid organic-inorganic polymers that should display interesting properties. For example, using trimethylaluminum (TMA) and various diols as reactants, we can achieve the MLD of alucone organic-inorganic polymers. We can alter the chemical and physical properties of these organic-inorganic polymers by varying the organic constituent in the diol or blending the alucone MLD films with purely inorganic ALD films to build a nanocomposite or nanolaminate. The combination of ALD and MLD reactants enlarges the number of possible sequential self-limiting surface

  7. Protein Adsorption to Surface Chemistry and Crystal Structure Modification of Titanium Surfaces

    Directory of Open Access Journals (Sweden)

    Ryo Jimbo

    2010-07-01

    Full Text Available Objectives: To observe the early adsorption of extracellular matrix and blood plasma proteins to magnesium-incorporated titanium oxide surfaces, which has shown superior bone response in animal models.Material and Methods: Commercially pure titanium discs were blasted with titanium dioxide (TiO2 particles (control, and for the test group, TiO2 blasted discs were further processed with a micro-arc oxidation method (test. Surface morphology was investigated by scanning electron microscopy, surface topography by optic interferometry, characterization by X-ray photoelectron spectroscopy (XPS, and by X-ray diffraction (XRD analysis. The adsorption of 3 different proteins (fibronectin, albumin, and collagen type I was investigated by an immunoblotting technique.Results: The test surface showed a porous structure, whereas the control surface showed a typical TiO2 blasted structure. XPS data revealed magnesium-incorporation to the anodic oxide film of the surface. There was no difference in surface roughness between the control and test surfaces. For the protein adsorption test, the amount of albumin was significantly higher on the control surface whereas the amount of fibronectin was significantly higher on the test surface. Although there was no significant difference, the test surface had a tendency to adsorb more collagen type I.Conclusions: The magnesium-incorporated anodized surface showed significantly higher fibronectin adsorption and lower albumin adsorption than the blasted surface. These results may be one of the reasons for the excellent bone response previously observed in animal studies.

  8. Surface chemistry influences cancer killing effect of TiO2 nanoparticles.

    Science.gov (United States)

    Thevenot, Paul; Cho, Jai; Wavhal, Dattatray; Timmons, Richard B; Tang, Liping

    2008-09-01

    Photocatalyzed titanium dioxide (TiO2) nanoparticles have been shown to eradicate cancer cells. However, the required in situ introduction of ultraviolet light limits the use of such a therapy in humans. In the present study the nonphotocatalytic anticancer effect of surface-functionalized TiO2 was examined. Nanoparticles bearing -OH, -NH(2), 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, JHU prostate cancer cells, and 3T3 fibroblasts. Cell viability was observed to depend on particle concentrations, cell types, and surface chemistry. Specifically, -NH(2) and -OH groups showed 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, can be surface-engineered for targeted cancer therapy.

  9. Control and Characterization of Titanium Dioxide Morphology: Applications in Surface Organometallic Chemistry

    KAUST Repository

    Jeantelot, Gabriel

    2014-05-01

    Surface Organometallic Chemistry leads to the combination of the high activity and specificity of homogeneous catalysts with the recoverability and practicality of heterogeneous catalysts. Most metal complexes used in this chemistry are grafted on metal oxide supports such as amorphous silica (SiO2) and γ-alumina (Al2O3). In this thesis, we sought to enable the use of titania (TiO2) as a new support for single-site well-defined grafting of metal complexes. This was achieved by synthesizing a special type of anatase-TiO2, bearing a high density of identical hydroxyl groups, through hydrothermal synthesis then post-treatment under high vacuum followed by oxygen flow, and characterized by several analytical techniques including X-ray diffraction, transmission electron microscopy, infrared spectroscopy and nuclear magnetic resonance. Finally, as a proof of concept, the grafting of vanadium oxychloride (VOCl3) was successfully attempted.

  10. Heterogeneous chemistry and reaction dynamics of the atmospheric oxidants, O3, NO3, and OH, on organic surfaces

    OpenAIRE

    Chapleski, Robert C.; Zhang, Yafen; Troya, Diego; Morris, John R.

    2015-01-01

    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, research...

  11. Impact of plasma chemistry versus titanium surface topography on osteoblast orientation.

    Science.gov (United States)

    Rebl, Henrike; Finke, Birgit; Lange, Regina; Weltmann, Klaus-Dieter; Nebe, J Barbara

    2012-10-01

    Topographical and chemical modifications of biomaterial surfaces both influence tissue physiology, but unfortunately little knowledge exists as to their combined effect. There are many indications that rough surfaces positively influence osteoblast behavior. Having determined previously that a positively charged, smooth titanium surface boosts osteoblast adhesion, we wanted to investigate the combined effects of topography and chemistry and elucidate which of these properties is dominant. Polished, machined and corundum-blasted titanium of increasing microroughness was additionally coated with plasma-polymerized allylamine (PPAAm). Collagen I was then immobilized using polyethylene glycol diacid and glutar dialdehyde. On all PPAAm-modified surfaces (i) adhesion of human MG-63 osteoblastic cells increased significantly in combination with roughness, (ii) cells resemble the underlying structure and melt with the surface, and (iii) cells overcome the restrictions of a grooved surface and spread out over a large area as indicated by actin staining. Interestingly, the cellular effects of the plasma-chemical surface modification are predominant over surface topography, especially in the initial phase. Collagen I, although it is the gold standard, does not improve surface adhesion features comparably.

  12. Do organic surface films on sea salt aerosols influence atmospheric chemistry? ─ a model study

    Directory of Open Access Journals (Sweden)

    R. von Glasow

    2007-11-01

    Full Text Available Organic material from the ocean's surface can be incorporated into sea salt aerosol particles often producing a surface film on the aerosol. Such an organic coating can reduce the mass transfer between the gas phase and the aerosol phase influencing sea salt chemistry in the marine atmosphere. To investigate these effects and their importance for the marine boundary layer (MBL we used the one-dimensional numerical model MISTRA. We considered the uncertainties regarding the magnitude of uptake reduction, the concentrations of organic compounds in sea salt aerosols and the oxidation rate of the organics to analyse the possible influence of organic surfactants on gas and liquid phase chemistry with a special focus on halogen chemistry. By assuming destruction rates for the organic coating based on laboratory measurements we get a rapid destruction of the organic monolayer within the first meters of the MBL. Larger organic initial concentrations lead to a longer lifetime of the coating but lead also to an unrealistically strong decrease of O3 concentrations as the organic film is destroyed by reaction with O3. The lifetime of the film is increased by assuming smaller reactive uptake coefficients for O3 or by assuming that a part of the organic surfactants react with OH. With regard to tropospheric chemistry we found that gas phase concentrations for chlorine and bromine species decreased due to the decreased mass transfer between gas phase and aerosol phase. Aqueous phase chlorine concentrations also decreased but aqueous phase bromine concentrations increased. Differences for gas phase concentrations are in general smaller than for liquid phase concentrations. The effect on gas phase NO2 or NO is very small (reduction less than 5% whereas liquid phase NO2 concentrations increased in some cases by nearly 100%. We list suggestions for further laboratory studies which are needed for improved model studies.

  13. Surface chemistry dependent "switch" regulates the trafficking and therapeutic performance of drug-loaded carbon nanotubes.

    Science.gov (United States)

    Das, Manasmita; Singh, Raman Preet; Datir, Satyajit R; Jain, Sanyog

    2013-04-17

    The present study explores the possibility of exploiting surface functionality as one of the key regulators for modulating the intracellular trafficking and therapeutic performance of drug loaded carbon nanotubes (CNTs). In line with that approach, a series of biofunctionalized multiwalled carbon nanotubes (f-CNTs 1-6) decorated with various functional molecules including antifouling polymer (PEG), tumor recognition modules (folic acid/hyaluronic acid/estradiol), and fluorophores (rhodamine B isothiocyanate/Alexa Fluor) were synthesized. By loading different anticancer agents (methotrexate (MTX), doxorubicin (DOX), and paclitaxel (PTX)) onto each functionalized CNT preparation, we tried to elucidate how the surface functional molecules associated with each f-CNT influence their therapeutic potential. We observed that antiproliferative or apoptotic activity of drug-loaded CNTs critically depends on their mechanistic pathway of cellular internalization and intracellular trafficking, which in turn had an intimate rapport with their surface chemistry. To our knowledge, for the first time, we have embarked on the possibility of using a surface chemistry dependent "switch" to remote-control the second and third order targeting of chemotherapeutic agents supramolecularly complexed/adsorbed on CNTs, which in turn is expected to benefit the development of futuristic nanobots for cancer theranostics.

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

    Science.gov (United States)

    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

  15. Fabrication of a platform to isolate the influences of surface nanotopography from chemistry on bacterial attachment and growth.

    Science.gov (United States)

    Pegalajar-Jurado, Adoracion; Easton, Christopher D; Crawford, Russell J; McArthur, Sally L

    2015-03-26

    Billions of dollars are spent annually worldwide to combat the adverse effects of bacterial attachment and biofilm formation in industries as varied as maritime, food, and health. While advances in the fabrication of antifouling surfaces have been reported recently, a number of the essential aspects responsible for the formation of biofilms remain unresolved, including the important initial stages of bacterial attachment to a substrate surface. The reduction of bacterial attachment to surfaces is a key concept in the prevention or minimization of biofilm formation. The chemical and physical characteristics of both the substrate and bacteria are important in understanding the attachment process, but substrate modification is likely the most practical route to enable the extent of bacterial attachment taking place to be effectively controlled. The microtopography and chemistry of the surface are known to influence bacterial attachment. The role of surface chemistry versus nanotopography and their interplay, however, remain unclear. Most methods used for imparting nanotopographical patterns onto a surface also induce changes in the surface chemistry and vice versa. In this study, the authors combine colloidal lithography and plasma polymerization to fabricate homogeneous, reproducible, and periodic nanotopographies with a controllable surface chemistry. The attachment of Escherichia coli bacteria onto carboxyl (plasma polymerized acrylic acid, ppAAc) and hydrocarbon (plasma polymerized octadiene, ppOct) rich plasma polymer films on either flat or colloidal array surfaces revealed that the surface chemistry plays a critical role in bacterial attachment, whereas the effect of surface nanotopography on the bacterial attachment appears to be more difficult to define. This platform represents a promising approach to allow a greater understanding of the role that surface chemistry and nanotopography play on bacterial attachment and the subsequent biofouling of the surface.

  16. Surface chemistry of Ti6Al4V components fabricated using selective laser melting for biomedical applications.

    Science.gov (United States)

    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.

  17. Saturn Magnetospheric Impact on Surface Molecular Chemistry and Astrobiological Potential of Enceladus

    Science.gov (United States)

    Cooper, P. D.; Cooper, J. F.; Sittler, E. C.; Burger, M. H.; Sturner, S. J.; Rymer, A. M.

    2008-12-01

    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 H2O2 at the surface in this region and less directly by substantial presence of CO2, 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, H2O neutrals dominating the emitted plume gas return to the surface mostly as H3O+ 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.

  18. Effect of chitosan and cationic starch on the surface chemistry properties of bagasse paper.

    Science.gov (United States)

    Ashori, Alireza; Cordeiro, Nereida; Faria, Marisa; Hamzeh, Yahya

    2013-07-01

    The use of non-wood fibers in the paper industry has been an economical and environmental necessity. The application of dry-strength agents has been a successful method to enhance the strength properties of paper. The experimental results evidencing the potential of chitosan and cationic starch utilization in bagasse paper subjected to hot water pre-extraction has been presented in this paper. The research analyzes the surface properties alterations due to these dry-strength agents. Inverse gas chromatography was used to evaluate the properties of surface chemistry of the papers namely the surface energy, active sites, surface area as well as the acidic/basic character. The results of the study revealed that the handsheets process causes surface arrangement and orientation of chemical groups, which induce a more hydrophobic and basic surface. The acid-base surface characteristics after the addition of dry-strength agents were the same as the bagasse handsheets with and without hot water pre-extraction. The results showed that the dry-strength agent acts as a protecting film or glaze on the surfaces of bagasse paper handsheets.

  19. Heterogeneous chemistry and reaction dynamics of the atmospheric oxidants, O3, NO3, and OH, on organic surfaces.

    Science.gov (United States)

    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.

  20. Influence of mineral oil and additives on microhardness and surface chemistry of magnesium oxide (001) surface

    Science.gov (United States)

    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.

  1. Anti-fouling chemistry of chiral monolayers: enhancing biofilm resistance on racemic surface.

    Science.gov (United States)

    Bandyopadhyay, Debjyoti; Prashar, Deepali; Luk, Yan-Yeung

    2011-05-17

    This work reports the resistance to protein adsorption and bacterial biofilm formation by chiral monolayers of polyol-terminated alkanethiols surrounding micrometer-sized patterns of methyl-terminated alkanethiols on gold films. We discover that patterned surfaces surrounded by chiral polyol monolayers can distinguish different stages of biofilm formation. After inoculation on the surfaces, bacteria first reversibly attached on the chiral polyol monolayers. Over time, the bacteria detached from the polyol surfaces, and attached on the hydrophobic micropatterns to form biofilms. Interestingly, while both enantiomers of gulitol- and mannonamide-terminated monolayer resisted adsorption of proteins (bovine serum albumin, lysozyme, and fibrinogen) and confined biofilms formed on the micropatterns, the monolayers formed by the racemic mixture of either pair of enantiomers exhibited stronger antifouling chemistry against both protein adsorption and biofilm formation than monolayers formed by one enantiomer alone. These results reveal the different chemistries that separate the different stages of biofilm formation, and the stereochemical influence on resisting biofoulings at a molecular-level.

  2. The influence of the surface chemistry of silver nanoparticles on cell death.

    Science.gov (United States)

    Sur, Ilknur; Altunbek, Mine; Kahraman, Mehmet; Culha, Mustafa

    2012-09-21

    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.

  3. The role of aragonite matrix surface chemistry on the chondrogenic differentiation of mesenchymal stem cells.

    Science.gov (United States)

    Gross-Aviv, Talia; Vago, Razi

    2009-02-01

    In the present research we study the effects of surface chemistry of an aragonite crystalline biomatrix on the chondrogenesis of mesenchymal stem cells (MSCs). An aragonite matrix obtained from the coral Porites lutea and a gold-coated P. lutea matrix were seeded with MSCs, with and without the addition of growth factors (GFs). Scanning electron microscopy, histochemical staining, immunofluorescence, biochemical analyses and quantitative polymerase chain reaction showed that the chemistry of the matrix influenced the differentiation process of the MSCs. The calcium carbonate composition of the coral promoted osteogenesis, while impeding cell-material contact (by gold coating) altered the differentiation lineage of MSCs towards chondrogenic fate. Supplementation of the culture medium with GFs intensified the influence of the surface composition on the differentiation of MSCs, and the synergistic effect of the biomatrix surface composition and the GFs induced chondrogenesis and facilitated maintenance of the chondrocyte phenotype. Therefore, we suggest that scaffolding material candidates for tissue engineering should be examined for their effects on the MSCs differentiation process and their effect on signal transduction events in the cells.

  4. Chemically active colloids near osmotic-responsive walls with surface-chemistry gradients

    Science.gov (United States)

    Popescu, M. N.; Uspal, W. E.; Dietrich, S.

    2017-04-01

    Chemically active colloids move by creating gradients in the composition of the surrounding solution and by exploiting the differences in their interactions with the various molecular species in solution. If such particles move near boundaries, e.g. the walls of the container confining the suspension, gradients in the composition of the solution are also created along the wall. This give rise to chemi-osmosis (via the interactions of the wall with the molecular species forming the solution), which drives flows coupling back to the colloid and thus influences its motility. Employing an approximate ‘point-particle’ analysis, we show analytically that—owing to this kind of induced active response (chemi-osmosis) of the wall—such chemically active colloids can align with, and follow, gradients in the surface chemistry of the wall. In this sense, these artificial ‘swimmers’ exhibit a primitive form of thigmotaxis with the meaning of sensing the proximity of a (not necessarily discontinuous) physical change in the environment. We show that the alignment with the surface-chemistry gradient is generic for chemically active colloids as long as they exhibit motility in an unbounded fluid, i.e. this phenomenon does not depend on the exact details of the propulsion mechanism. The results are discussed in the context of simple models of chemical activity, corresponding to Janus particles with ‘source’ chemical reactions on one half of the surface and either ‘inert’ or ‘sink’ reactions over the other half.

  5. Surface chemistry manipulation of gold nanorods preserves optical properties for bio-imaging applications

    Energy Technology Data Exchange (ETDEWEB)

    Polito, Anthony B.; Maurer-Gardner, Elizabeth I.; Hussain, Saber M., E-mail: saber.hussain@us.af.mil [Air Force Research Laboratory, Molecular Bioeffects Branch, Bioeffects Division, Human Effectiveness Directorate (United States)

    2015-12-15

    Due to their anisotropic shape, gold nanorods (GNRs) possess a number of advantages for biosystem use including, enhanced surface area and tunable optical properties within the near-infrared (NIR) region. However, cetyl trimethylammonium bromide-related cytotoxicity, overall poor cellular uptake following surface chemistry modifications, and loss of NIR optical properties due to material intracellular aggregation in combination remain as obstacles for nanobased biomedical GNR applications. In this article, we report that tannic acid-coated 11-mercaptoundecyl trimethylammonium bromide (MTAB) GNRs (MTAB-TA) show no significant decrease in either in vitro cell viability or stress activation after exposures to A549 human alveolar epithelial cells. In addition, MTAB-TA GNRs demonstrate a substantial level of cellular uptake while displaying a unique intracellular clustering pattern. This clustering pattern significantly reduces intracellular aggregation, preserving the GNRs NIR optical properties, vital for biomedical imaging applications. These results demonstrate how surface chemistry modifications enhance biocompatibility, allow for higher rate of internalization with low intracellular aggregation of MTAB-TA GNRs, and identify them as prime candidates for use in nanobased bio-imaging applications.Graphical Abstract.

  6. The influence of the surface chemistry of silver nanoparticles on cell death

    Science.gov (United States)

    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.

  7. Multifunctionality of organometallic quinonoid metal complexes: surface chemistry, coordination polymers, and catalysts.

    Science.gov (United States)

    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

  8. Self-Restoration of Superhydrophobicity on Shape Memory Polymer Arrays with Both Crushed Microstructure and Damaged Surface Chemistry.

    Science.gov (United States)

    Lv, Tong; Cheng, Zhongjun; Zhang, Enshuang; Kang, Hongjun; Liu, Yuyan; Jiang, Lei

    2017-01-01

    Recently, self-healing superhydrophobic surfaces have become a new research focus due to their recoverable wetting performances and wide applications. However, until now, on almost all reported surfaces, only one factor (surface chemistry or microstructure) can be restored. In this paper, a new superhydrophobic surface with self-healing ability in both crushed microstructure and damaged surface chemistry is prepared by creating lotus-leaves-like microstructure on the epoxy shape memory polymer (SMP). Through a simple heating process, the crushed surface microstructure, the damaged surface chemistry, and the surface superhydrophobicity that are destroyed under the external pressure and/or O2 plasma action can be recovered, demonstrating that the obtained superhydrophobic surface has a good self-healing ability in both of the two factors that govern the surface wettability. The special self-healing ability is ascribed to the good shape memory effect of the polymer and the reorganization effect of surface molecules. This paper reports the first use of SMP material to demonstrate the self-healing ability of surface superhydrophobicity, which opens up some new perspectives in designing self-healing superhydrophobic surfaces. Given the properties of this surface, it could be used in many applications, such as self-cleaning coatings, microfluidic devices, and biodetection.

  9. A pinch of salt is all it takes: chemistry at the frozen water surface.

    Science.gov (United States)

    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

  10. Simple coupling chemistry linking carboxyl-containing organic molecules to silicon oxide surfaces under acidic conditions.

    Science.gov (United States)

    Schmidt, Sebastian W; Christ, Timo; Glockner, Christian; Beyer, Martin K; Clausen-Schaumann, Hauke

    2010-10-05

    The coupling chemistry of carboxymethylated amylose with organo-silanized silicon oxide surfaces at pH 7.4 and 2.0 was investigated using atomic force microscopy (AFM) based single-molecule force spectroscopy. At close to neutral pH, carbodiimide activation of a carboxylic acid affords formation of an amide bond with an amino surface linker. At pH 2.0, no activation with carbodiimide was required to anchor carboxymethylated amylose between an AFM tip and a glass substrate. At the same time, the mean bond rupture force f(r) dropped from 1.65 ± 0.37 nN at pH 7.4 to 1.39 ± 0.30 nN at pH 2.0 without carbodiimide, indicating that a different link to the surface can be formed at low pH. The coupling mechanism at pH 2.0 was elucidated by a series of experiments, in which the surface was functionalized with four different organosilanes, each containing characteristic functional groups. The results are rationalized with an acid-catalyzed ester condensation between a carboxyl group and a free, unreacted silanol group in the surface anchor or on the surface.

  11. A new combinatorial method for synthesizing, screening, and discovering antifouling surface chemistries.

    Science.gov (United States)

    Imbrogno, Joseph; Williams, Matthew D; Belfort, Georges

    2015-02-04

    A set of diverse monomers were synthesized using combinatorial chemistry and tested using our unique high-throughput screening platform. The versatility of our platform is exemplified by possible applications in reducing biological fouling on ship hulls, filtration membranes, and surgical instruments, to name a few. To demonstrate its efficacy, the novel monomers were graft-polymerized onto light sensitive poly(ether sulfone) (PES) membranes via atmospheric-pressure plasma polymerization. A diverse library was synthesized by reacting a common vinyl ester linker with a library of maleimides containing various different functional groups. This allowed us to produce a library of many different surfaces and graft them all using the same linker chemistry. The modified surfaces were then tested and screened for the best antiprotein adsorption (nonfouling) properties. Membranes, functionalized with carboxylic acid, zwitterionic, and ester groups, had the lowest protein adhesion compared with that of an unmodified control PES membrane after a static fouling test. After dynamic fouling, these same functionalities as well as a hydroxyl group exhibited the highest permeability. These monomers performed better than our best previously synthesized amide monomers as well as our best poly(ethylene glycol) monomers, which are known to have very high protein resistance. Hansen solubility parameters qualitatively predicted which monomers performed best, indicating favorable interactions with water molecules.

  12. Chemistry in Disks. IV. Benchmarking gas-grain chemical models with surface reactions

    CERN Document Server

    Semenov, D; Wakelam, V; Dutrey, A; Chapillon, E; Guilloteau, St; Henning, Th; Launhardt, R; Pietu, V; Schreyer, K

    2010-01-01

    Abridged: We detail and benchmark two sophisticated chemical models developed by the Heidelberg and Bordeaux astrochemistry groups. 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. We consider 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 is 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. Using atomic initial abundances ...

  13. Effect of pore size and surface chemistry of porous silica on CO2 adsorption

    Directory of Open Access Journals (Sweden)

    Thongthai Witoon

    2012-09-01

    Full Text Available In the present study, porous silica synthesized using sodium silicate as a low-cost raw material was selected as a CO2sorbent. The effects of pore size and amount of silanol content on CO2 adsorption capacity were investigated. The physicalproperties and surface chemistry (silanol content of the porous silica products were characterized by means of N2-physisorption, Fourier transform infrared spectroscopy and thermogravimetric analysis technique. The pore size of the poroussilica materials did not affect the equilibrium CO2 capacity; however the porous silica with large pore size could enhance thediffusion of CO2. The amount of silanol content was found to be a key factor for the CO2 adsorption capacity. A greater CO2adsorption capacity would be obtained with an increase of the silanol concentration on the surface of the porous silicamaterials.

  14. On the master equation approach to diffusive grain-surface chemistry: the H, O, CO system

    CERN Document Server

    Stantcheva, T; Herbst, E

    2002-01-01

    We have used the master equation approach to study a moderately complex network of diffusive reactions occurring on the surfaces of interstellar dust particles. This network is meant to apply to dense clouds in which a large portion of the gas-phase carbon has already been converted to carbon monoxide. Hydrogen atoms, oxygen atoms, and CO molecules are allowed to accrete onto dust particles and their chemistry is followed. The stable molecules produced are oxygen, hydrogen, water, carbon dioxide (CO2), formaldehyde (H2CO), and methanol (CH3OH). The surface abundances calculated via the master equation approach are in good agreement with those obtained via a Monte Carlo method but can differ considerably from those obtained with standard rate equations.

  15. Wet-electron Enhanced Surface Dissociative Electron Attachment Chemistry of Halocarbons

    Science.gov (United States)

    2011-03-14

    structure and exciton  properties of  anatase  and  rutile  TiO2.  Despite being a paradigm for  photocatalytic chemistry, the electronic structure of TiO2 had...OF: We investigated photocatalytic decomposition of organic compounds on rutile TiO2(110) single crystal surfaces in presence of near-UV light and O2... rutile TiO2(110) single crystal surfaces in presence of near-UV light and O2 by two-photon photoemission spectroscopy. We found that the irradiation

  16. The UV Surface Environment on Young Planets: Implications for Prebiotic Chemistry & Life on Other Worlds

    Science.gov (United States)

    Ranjan, Sukrit; Simons Collaboration on the Origin of Life, Harvard Origins of Life Initiative

    2017-01-01

    Understanding the origin of life (abiogenesis) on Earth is key to understanding how it might start elsewhere. Recent laboratory studies suggest UV light may have played a critical role in the synthesis of molecules relevant to abiogenesis (prebiotic chemistry), such as RNA. I show that UV light interacts with prebiotic chemistry in ways that may be sensitive to the spectral shape and overall amplitude of irradiation. I use radiative transfer models to constrain the UV environment on early Earth (3.9 Ga). I find that the surface UV is insensitive to much of the considerable uncertainty in the atmospheric state, enabling me to constrain the UV environment for prebiotic chemistry on early Earth. Some authors have suggested Mars as a venue for prebiotic chemistry. Therefore, I explore plausible UV spectral fluences on Mars at 3.9 Ga. I find that the early Martian UV environment is comparable to Earth’s under conventional assumptions about the atmosphere. However, if the atmosphere was dusty or SO2 levels were high, UV fluence would have been strongly suppressed. Intriguingly, despite overall attenuation of UV fluence, SO2 preferentially attenuates destructive FUV radiation over prebiotically-useful NUV radiation, meaning high-SO2 epochs may have been more clement for the origin of life. Better measurements of the spectral dependence of prebiotic photoprocesses are required to constrain this hypothesis. Finally, I calculate the UV fluence on planets orbiting M-dwarfs. I find that UV irradiation on such planets is low compared to Earth. Laboratory studies are required to understand whether prebiotic photoprocesses that worked on Earth can function on low-UV M-dwarf planets. My work 1) provides initial conditions for laboratory studies of prebiotic chemistry, 2) constrains the inhabitability of Mars and planets orbiting M-dwarfs, and 3) demonstrates the need for laboratory studies to characterize the impact of variations in irradiating intensity and spectral shape on

  17. Oxide/Water Interfaces: How the Surface Chemistry Modifies the Electronic Energy Alignment

    Science.gov (United States)

    Sprik, Michiel

    2014-03-01

    The minimum of the d-electron conduction band of an aqueous transition metal oxide electrode is typically no more than a few 100 mV away from the standard hydrogen electrode (SHE). Because of this favourable alignment of the electronic energy levels (near) metallic transition metal oxides with partly filled d bands can be used as electrocatalysts while the compounds with finite electronic gap can be used as photocatalysts. However, because of their ionic character, transition metal-oxide surfaces also show amphiphilic acid-base activity. At low pH the basic sites are protonated and at high pH the acidic sites deprotonated creating an electrical double layer with corresponding surface potential. The alignment of the electronic energy levels, and by implication their redox activity, is therefore pH dependent. In fact, even in absence of protonic surface charge, the coordination with water molecules is already capable of shifting the electronic energy levels of the oxide by 1 eV or more. Computation of the electronic energies in transition metal oxide electrodes requires therefore a detailed modeling of their aqueous surface chemistry. The solvation energy of the proton is the common energy reference for both redox potentials on the SHE scale and acidity constants (pKa). Computation of the H+ solvation energy is therefore a key component in a unified treatment of redox and acid-base chemistry. In this talk we outline the Density Functional Theory based Molecular Dynamics (DFTMD) method we have developed for this purpose. The central tool of our approach is a method for reversible insertion of protons in the aqueous part of the DFTMD model system. As an illustration we discuss the application to the rutile TiO2/water and MnO2/water interface.

  18. Thermal chemistry of copper acetamidinate atomic layer deposition precursors on silicon oxide surfaces studied by XPS

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Yunxi; Zaera, Francisco, E-mail: zaera@ucr.edu [Department of Chemistry, University of California, Riverside, California 92521 (United States)

    2016-01-15

    The thermal surface chemistry of copper(I)-N,N′-di-sec-butylacetamidinate, [Cu({sup s}Bu-amd)]{sub 2}, a metalorganic complex recently proposed for the chemical-based deposition of copper films, has been characterized on SiO{sub 2} films under ultrahigh vacuum conditions by x-ray photoelectron spectroscopy (XPS). Initial adsorption at cryogenic temperatures results in the oxidation of the copper centers with Cu 2p{sub 3/2} XPS binding energies close to those seen for a +2 oxidation state, an observation that the authors interpret as the result of the additional coordination of oxygen atoms from the surface to the Cu atoms of the molecular acetamidinate dimer. Either heating to 300 K or dosing the precursor directly at that temperature leads to the loss of one of its two ligands, presumably via hydrogenation/protonation with a hydrogen/proton from a silanol group, or following a similar reaction on a defect site. By approximately 500 K the Cu 2p{sub 3/2}, C 1s, and N 1s XPS data suggest that the remaining acetamidinate ligand is displaced from the copper center and bonds to the silicon oxide directly, after which temperatures above 900 K need to be reached to promote further (and only partial) decomposition of those organic moieties. It was also shown that the uptake of the Cu precursor is self-limiting at either 300 or 500 K, although the initial chemistry is somewhat different at the two temperatures, and that the nature of the substrate also defines reactivity, with the thin native silicon oxide layer always present on Si(100) surfaces being less reactive than thicker films grown by evaporation, presumably because of the lower density of surface nucleation sites.

  19. Constraints on the Early Terrestrial Surface UV Environment Relevant to Prebiotic Chemistry

    CERN Document Server

    Ranjan, Sukrit

    2016-01-01

    The UV environment is a key boundary condition for the origin of life. However, considerable uncertainty exists as to planetary conditions and hence surface UV at abiogenesis. Here, we present two-stream multi-layer clear-sky calculations of the UV surface radiance on Earth at 3.9 Ga to constrain the UV surface fluence as a function of albedo, solar zenith angle (SZA), and atmospheric composition. Variation in albedo and latitude (through SZA) can affect maximum photoreaction rates by a factor of >10.4; for the same atmosphere, photoreactions can proceed an order of magnitude faster at the equator of a snowball Earth than at the poles of a warmer world. Surface conditions are important considerations when computing prebiotic UV fluences. For climatically reasonable levels of CO2, fluence shortward of 189 nm is screened out, meaning that prebiotic chemistry is robustly shielded from variations in UV fluence due to solar flares or variability. Strong shielding from CO2 also means that the UV surface fluence is ...

  20. Surface chemistry and fundamental limitations on the plasma cleaning of metals

    Science.gov (United States)

    Dong, Bin; Driver, M. Sky; Emesh, Ismail; Shaviv, Roey; Kelber, Jeffry A.

    2016-10-01

    In-situ X-ray photoelectron spectroscopy (XPS) studies reveal that plasma cleaning of air-exposed Co or Cu transition metal surfaces results in the formation of a remnant C film 1-3 monolayers thick, which is not reduced upon extensive further plasma exposure. This effect is observed for H2 or NH3 plasma cleaning of Co, and He or NH3 plasma cleaning of Cu, and is observed with both inductively coupled (ICP) and capacitively-coupled plasma (CCP). Changes in C 1 s XPS spectra indicate that this remnant film formation is accompanied by the formation of carbidic C on Co and of graphitic C on Cu. This is in contrast to published work showing no such remnant carbidic/carbon layer after similar treatments of Si oxynitride surfaces. The observation of the remnant carbidic C film on Co and graphitic film on Cu, but not on silicon oxynitride (SiOxNy), regardless of plasma chemistry or type, indicates that this effect is due to plasma induced secondary electron emission from the metal surface, resulting in transformation of sp3 adventitious C to either a metal carbide or graphite. These results suggest fundamental limitations to plasma-based surface cleaning procedures on metal surfaces.

  1. Microscopic work function anisotropy and surface chemistry of 316L stainless steel using photoelectron emission microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Barrett, N., E-mail: nick.barrett@cea.fr [CEA, IRAMIS, SPEC, LENSIS, F-91191 Gif-sur-Yvette (France); Renault, O. [CEA, LETI, Minatec Campus, F-38054 Grenoble Cedex 09 (France); Lemaître, H. [Université de Cergy-Pontoise, Rue d’Eragny, Neuville sur Oise, 95 031 Cergy-Pontoise (France); Surface Dynamics Laboratory, Institut for Fysik og Astronomi Aarhus Universitet, Ny Munkegade 120, 8000 Aarhus C (Denmark); Bonnaillie, P. [CEA, DEN, DANS, DMN, SRMP, F-91191 Gif-sur-Yvette (France); Barcelo, F. [CEA, DEN, DANS, DMN, SRMA, LA2M, F-91191 Gif-sur-Yvette (France); Miserque, F. [CEA, DEN, DANS, DPC, SCCME, LECA, F-91191 Gif-sur-Yvette (France); Wang, M.; Corbel, C. [Laboratoire des Solides Irradis, Ecole Polytechnique, route de Saclay, F-91128 Palaiseau (France)

    2014-08-15

    Highlights: • PEEM and EBSD study of spatial variations in local work function of 316L steel. • Correlation between work function and crystal grain orientation at the surface of 316L steel. • Spatially resolved chemistry of residual oxide layer. - Abstract: We have studied the variation in the work function of the surface of sputtered cleaned 316L stainless steel with only a very thin residual oxide surface layer as a function of grain orientation using X-ray photoelectron emission microscopy (XPEEM) and Electron Backscattering Diffraction. The grains are mainly oriented [1 1 1] and [1 0 1]. Four distinct work function values spanning a 150 meV energy window are measured. Grains oriented [1 1 1] have a higher work function than those oriented [1 0 1]. From core level XPEEM we deduce that all grain surfaces are Cr enriched and Ni depleted whereas the Cr/Fe ratio is similar for all grains. The [1 1 1] oriented grains show evidence for a Cr{sub 2}O{sub 3} surface oxide and a higher concentration of defective oxygen sites.

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

    Science.gov (United States)

    Nady, Norhan

    2016-04-18

    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.

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

    Directory of Open Access Journals (Sweden)

    Norhan Nady

    2016-04-01

    Full Text Available 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.

  4. Surface Chemistry and Tribology of Copper Surfaces in Carbon Dioxide and Water Vapor Environments

    Science.gov (United States)

    2011-02-23

    progress). Simultaneous XAS and cyclic voltammetry of Cu in bicarbonate solutions under potentiostatic control at the Berkeley Synchrotron facility (Figure...bicarbonate ions that mimic the conditions of the wet brush-rotor contact. Electrochemical control of the surface by cyclic voltammetry makes it...the electrochemical modifications of Cu under potentiostat control and solution pH 3) Determine the loss of mass of Cu when in carbonate containing

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

    Energy Technology Data Exchange (ETDEWEB)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  7. Surface chemistry of InP ridge structures etched in Cl{sub 2}-based plasma analyzed with angular XPS

    Energy Technology Data Exchange (ETDEWEB)

    Bouchoule, Sophie, E-mail: sophie.bouchoule@lpn.cnrs.fr; Cambril, Edmond; Guilet, Stephane [Laboratoire de Photonique et Nanostructure (LPN)—UPR20, CNRS, Route de Nozay, 91460 Marcoussis (France); Chanson, Romain; Pageau, Arnaud; Rhallabi, Ahmed; Cardinaud, Christophe, E-mail: christophe.cardinaud@cnrs-imn.fr [Institut des matériaux Jean Rouxel (IMN), UMR6502, Université de Nantes, CNRS, 44322 Nantes (France)

    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.

  8. Surface Chemistry of Nanoscale Mineralized Collagen Regulates Periodontal Ligament Stem Cell Fate.

    Science.gov (United States)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  10. Surface chemistry and fundamental limitations on the plasma cleaning of metals

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Bin, E-mail: bindong@my.unt.edu [Department of Chemistry, University of North Texas, 1155 Union Circle 305070, Denton, TX, 76203 (United States); Driver, M. Sky, E-mail: Marcus.Driver@unt.edu [Department of Chemistry, University of North Texas, 1155 Union Circle 305070, Denton, TX, 76203 (United States); Emesh, Ismail, E-mail: Ismail_Emesh@amat.com [Applied Materials Inc., 3050 Bowers Ave, Santa Clara, CA, 95054 (United States); Shaviv, Roey, E-mail: Roey_Shaviv@amat.com [Applied Materials Inc., 3050 Bowers Ave, Santa Clara, CA, 95054 (United States); Kelber, Jeffry A., E-mail: Jeffry.Kelber@unt.edu [Department of Chemistry, University of North Texas, 1155 Union Circle 305070, Denton, TX, 76203 (United States)

    2016-10-30

    Highlights: • O{sub 2}-free plasma treatment of air-exposed Co or Cu surfaces yields remnant C layers inert to further plasma cleaning. • The formation of the remnant C layer is graphitic (Cu) or carbidic (Co). • The formation of a remnant C layer is linked to plasma cleaning of a metal surface. - Abstract: In-situ X-ray photoelectron spectroscopy (XPS) studies reveal that plasma cleaning of air-exposed Co or Cu transition metal surfaces results in the formation of a remnant C film 1–3 monolayers thick, which is not reduced upon extensive further plasma exposure. This effect is observed for H{sub 2} or NH{sub 3} plasma cleaning of Co, and He or NH{sub 3} plasma cleaning of Cu, and is observed with both inductively coupled (ICP) and capacitively-coupled plasma (CCP). Changes in C 1 s XPS spectra indicate that this remnant film formation is accompanied by the formation of carbidic C on Co and of graphitic C on Cu. This is in contrast to published work showing no such remnant carbidic/carbon layer after similar treatments of Si oxynitride surfaces. The observation of the remnant carbidic C film on Co and graphitic film on Cu, but not on silicon oxynitride (SiO{sub x}N{sub y}), regardless of plasma chemistry or type, indicates that this effect is due to plasma induced secondary electron emission from the metal surface, resulting in transformation of sp{sup 3} adventitious C to either a metal carbide or graphite. These results suggest fundamental limitations to plasma-based surface cleaning procedures on metal surfaces.

  11. Corrosion product layers on magnesium alloys AZ31 and AZ61: Surface chemistry and protective ability

    Energy Technology Data Exchange (ETDEWEB)

    Feliu, S., E-mail: sfeliu@cenim.csic.es; Llorente, I.

    2015-08-30

    Highlights: • Surface chemistry of the corrosion product layers on magnesium alloys. • Influence of the type of alloy on the carbonate surface enrichment. • Relation between surface composition and protection properties. - Abstract: This paper studies the chemical composition of the corrosion product layers formed on magnesium alloys AZ31 and AZ61 following immersion in 0.6 M NaCl, with a view to better understanding their protective action. Relative differences in the chemical nature of the layers were quantified by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive analysis of X-ray (EDX) and low-angle X-ray diffraction (XRD). Corrosion behavior was investigated by Electrochemical Impedance Spectroscopy (EIS) and hydrogen evolution measurement. An inhibitive effect from the corrosion product layers was observed from EIS, principally in the case of AZ31, as confirmed by hydrogen evolution tests. A link was found between carbonate enrichment observed by XPS in the surface of the corrosion product layer, concomitant with the increase in the protective properties observed by EIS.

  12. Aqueous reactive species induced by a surface air discharge: Heterogeneous mass transfer and liquid chemistry pathways

    Science.gov (United States)

    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

  13. Aqueous reactive species induced by a surface air discharge: Heterogeneous mass transfer and liquid chemistry pathways.

    Science.gov (United States)

    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.

  14. Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes

    Directory of Open Access Journals (Sweden)

    Nicola H. Perry

    2016-10-01

    Full Text Available Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic, and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I2CNER, Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance.

  15. Application of Multi-Species Microbial Bioassay to Assess the Effects of Engineered Nanoparticles in the Aquatic Environment: Potential of a Luminous Microbial Array for Toxicity Risk Assessment (LumiMARA on Testing for Surface-Coated Silver Nanoparticles

    Directory of Open Access Journals (Sweden)

    YounJung Jung

    2015-07-01

    Full Text Available Four different manufactured surface-coated silver nanoparticles (AgNPs with coating of citrate, tannic acid, polyethylene glycol, and branched polyethylenimine were used in this study. The toxicity of surface-coated AgNPs was evaluated by a luminous microbial array for toxicity risk assessment (LumiMARA using multi-species of luminescent bacteria. The salt stability of four different AgNPs was measured by UV absorbance at 400 nm wavelength, and different surface-charged AgNPs in combination with bacteria were observed using scanning electron microscopy (SEM. Both branched polyethylenimine (BPEI-AgNPs and polyethylene glycol (PEG-AgNPs were shown to be stable with 2% NaCl (non-aggregation, whereas both citrate (Cit-AgNPs and tannic acid (Tan-AgNPs rapidly aggregated in 2% NaCl solution. The values of the 50% effective concentration (EC50 for BPEI-AgNPs in marine bacteria strains (1.57 to 5.19 mg/L were lower than those for the other surface-coated AgNPs (i.e., Cit-AgNPs, Tan-AgNPs, and PEG-AgNPs. It appears that the toxicity of AgNPs could be activated by the interaction of positively charged AgNPs with the negatively charged bacterial cell wall from the results of LumiMARA. LumiMARA for toxicity screening has advantageous compared to a single-species bioassay and is applicable for environmental samples as displaying ranges of assessment results.

  16. The Materials Chemistry of Atomic Oxygen with Applications to Anisotropic Etching of Submicron Structures in Microelectronics and the Surface Chemistry Engineering of Porous Solids

    Science.gov (United States)

    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.

  17. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

    Energy Technology Data Exchange (ETDEWEB)

    Sych, N.V.; Trofymenko, S.I.; Poddubnaya, O.I.; Tsyba, M.M. [Institute for Sorption and Endoecology Problems, National Academy of Sciences of Ukraine, 13 General Naumov St., 03164 Kyiv (Ukraine); Sapsay, V.I.; Klymchuk, D.O. [M.G. Kholodny Institute of Botany, National Academy of Sciences of Ukraine, 2 Tereshchenkivska St., 01601 Kyiv (Ukraine); Puziy, A.M., E-mail: alexander.puziy@ispe.kiev.ua [Institute for Sorption and Endoecology Problems, National Academy of Sciences of Ukraine, 13 General Naumov St., 03164 Kyiv (Ukraine)

    2012-11-15

    Highlights: Black-Right-Pointing-Pointer Phosphoric acid activation results in formation of carbons with acidic surface groups. Black-Right-Pointing-Pointer Maximum amount of surface groups is introduced at impregnation ratio 1.25. Black-Right-Pointing-Pointer Phosphoric acid activated carbons show high capacity to copper. Black-Right-Pointing-Pointer Phosphoric acid activated carbons are predominantly microporous. Black-Right-Pointing-Pointer Maximum surface area and pore volume achieved at impregnation ratio 1.0. - Abstract: Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 Degree-Sign 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 (S{sub BET} = 2081 m{sup 2}/g, V{sub tot} = 1.1 cm{sup 3}/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).

  18. Gold nanoparticles: role of size and surface chemistry on blood protein adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Benetti, F., E-mail: filippo.benetti@unitn.it; Fedel, M. [BIOtech Research Centre (Italy); Minati, L.; Speranza, G. [Fondazione Bruno Kessler (Italy); Migliaresi, C. [BIOtech Research Centre (Italy)

    2013-06-15

    Material interaction with blood proteins is a critical issue, since it could influence the biological processes taking place in the body following implantation/injection. This is particularly important in the case of nanoparticles, where innovative properties, such as size and high surface to volume ratio can lead to a behavioral change with respect to bulk macroscopic materials and could be responsible for a potential risk for human health. The aim of this work was to compare gold nanoparticles (AuNP) and planar surfaces to study the role of surface curvature moving from the macro- to the nano-size in the process of blood protein adsorption. In the course of the study, different protocols were tested to optimize the analysis of protein adsorption on gold nanoparticles. AuNP with different size (10, 60 and 200 nm diameter) and surface coatings (citrate and polyethylene glycol) were carefully characterized. The stabilizing action of blood proteins adsorbed on AuNP was studied measuring the variation of size and solubility of the nanoparticles following incubation with single protein solutions (human serum albumin and fibrinogen) and whole blood plasma. In addition, we developed a method to elute proteins from AuNP to study the propensity of gold materials to adsorb plasma proteins in function of dimensional characteristics and surface chemistry. We showed a different efficacy of the various eluting media tested, proving that even the most aggressive agent cannot provide a complete detachment of the protein corona. Enhanced protein adsorption was evidenced on AuNP if compared to gold laminae (bare and PEGylated) used as macroscopic control, probably due to the superior AuNP surface reactivity.

  19. Electrolyte effects on the surface chemistry and cellular response of anodized titanium

    Energy Technology Data Exchange (ETDEWEB)

    Ohtsu, Naofumi, E-mail: nohtsu@mail.kitami-it.ac.jp [Instrumental Analysis Center, Kitami Institute of Technology, 165 Koen-cho, Kitami, Hokkaido 090-8507 (Japan); Kozuka, Taro; Hirano, Mitsuhiro [Instrumental Analysis Center, Kitami Institute of Technology, 165 Koen-cho, Kitami, Hokkaido 090-8507 (Japan); Arai, Hirofumi [Department of Biotechnology and Environmental Chemistry, Kitami Institute of Technology, Kitami, Hokkaido 090-8507 (Japan)

    2015-09-15

    Highlights: • Ti samples were anodized using various electrolytes. • Anodization decreased carbon adsorption, improving hydrophilicity. • Improved hydrophilicity led to improved cellular attachment. • Only one electrolyte showed any heteroatom incorporation into the TiO{sub 2} layer. • Choice of electrolyte played no role on the effects of anodization. - Abstract: Anodic oxidation of titanium (Ti) material is used to enhance biocompatibility, yet the effects of various electrolytes on surface characteristics and cellular behavior have not been completely elucidated. To investigate this topic, oxide layers were produced on Ti substrates by anodizing them in aqueous electrolytes of (NH{sub 4}){sub 2}O·5B{sub 2}O{sub 3}, (NH{sub 4}){sub 2}SO{sub 4}, or (NH{sub 4}){sub 3}PO{sub 4}, after which their surface characteristics and cellular responses were examined. Overall, no surface differences between the electrolytes were visually observed. X-ray photoelectron spectroscopy (XPS) revealed that the anodized surfaces are composed of titanium dioxide (TiO{sub 2}), while incorporation from electrolyte was only observed for (NH{sub 4}){sub 3}PO{sub 4}. Surface adsorption of carbon contaminants during sterilization was suppressed by anodization, leading to lower water contact angles. The attachment of MC3T3-E1 osteoblast-like cells was also improved by anodization, as evidenced by visibly enlarged pseudopods. This improved attachment performance is likely due to TiO{sub 2} formation. Overall, electrolyte selection showed no effect on either surface chemistry or cellular response of Ti materials.

  20. Surface chemistry and cytotoxicity of reactively sputtered tantalum oxide films on NiTi plates

    Energy Technology Data Exchange (ETDEWEB)

    McNamara, K. [Materials and Surface Science Institute, University of Limerick, Limerick (Ireland); Department of Physics & Energy, University of Limerick, Limerick (Ireland); Kolaj-Robin, O.; Belochapkine, S.; Laffir, F. [Materials and Surface Science Institute, University of Limerick, Limerick (Ireland); Gandhi, A.A. [Materials and Surface Science Institute, University of Limerick, Limerick (Ireland); Department of Physics & Energy, University of Limerick, Limerick (Ireland); Tofail, S.A.M., E-mail: tofail.syed@ul.ie [Materials and Surface Science Institute, University of Limerick, Limerick (Ireland); Department of Physics & Energy, University of Limerick, Limerick (Ireland)

    2015-08-31

    NiTi, an equiatomic alloy containing nickel and titanium, exhibits unique properties such as shape memory effect and superelasticity. NiTi also forms a spontaneous protective titanium dioxide (TiO{sub 2}) layer that allows its use in biomedical applications. Despite the widely perceived biocompatibility there remain some concerns about the sustainability of the alloy's biocompatibility due to the defects in the TiO{sub 2} protective layer and the presence of high amount of sub-surface Ni, which can give allergic reactions. Many surface treatments have been investigated to try to improve both the corrosion resistance and biocompatibility of this layer. For such purposes, we have sputter deposited tantalum (Ta) oxide thin films onto the surface of the NiTi alloy. Despite being one of the promising metals for biomedical applications, Ta, and its various oxides and their interactions with cells have received relatively less attention. The oxidation chemistry, crystal structure, morphology and biocompatibility of these films have been investigated. In general, reactive sputtering especially in the presence of a low oxygen mixture yields a thicker film with better control of the film quality. The sputtering power influenced the surface oxidation states of Ta. Both microscopic and quantitative cytotoxicity measurements show that Ta films on NiTi are biocompatible with little to no variation in cytotoxic response when the surface oxidation state of Ta changes. - Highlights: • Reactive sputtering in low oxygen mixture yields thicker better quality films. • Sputtering power influenced surface oxidation states of Ta. • Cytotoxicity measurements show Ta films on NiTi are biocompatible. • Little to no variation in cytotoxic response when oxidation state changes.

  1. Phase transition of a symmetric diblock copolymer induced by nanorods with different surface chemistry

    Science.gov (United States)

    Guo, Yu-qi; Pan, Jun-xing; Sun, Min-na; Zhang, Jin-jun

    2017-01-01

    We investigate the phase transition of a symmetric diblock copolymer induced by nanorods with different surface chemistry. The results demonstrate that the system occurs the phase transition from a disordered structure to ordered parallel lamellae and then to the tilted layered structure as the number of rods increases. The dynamic evolution of the domain size and the order parameter of the microstructure are also examined. Furthermore, the influence of rod property, rod-phase interaction, rod-rod interaction, rod length, and polymerization degree on the behavior of the polymer system is also investigated systematically. Moreover, longer amphiphilic nanorods tend to make the polymer system form the hexagonal structure. It transforms into a perpendicular lamellar structure as the polymerization degree increases. Our simulations provide an efficient method for determining how to obtain the ordered structure on the nanometer scales and design the functional materials with optical, electronic, and magnetic properties.

  2. Sulfobetaine-Vinylimidazole Block Copolymers: A Robust Quantum Dot Surface Chemistry Expanding Bioimaging's Horizons.

    Science.gov (United States)

    Tasso, Mariana; Giovanelli, Emerson; Zala, Diana; Bouccara, Sophie; Fragola, Alexandra; Hanafi, Mohamed; Lenkei, Zsolt; Pons, Thomas; Lequeux, Nicolas

    2015-11-24

    Long-term inspection of biological phenomena requires probes of elevated intra- and extracellular stability and target biospecificity. The high fluorescence and photostability of quantum dot (QD) nanoparticles contributed to foster their promise as bioimaging tools that could overcome limitations associated with traditional fluorophores. However, QDs' potential as a bioimaging platform relies upon a precise control over the surface chemistry modifications of these nano-objects. Here, a zwitterion-vinylimidazole block copolymer ligand was synthesized, which regroups all anchoring groups in one compact terminal block, while the rest of the chain is endowed with antifouling and bioconjugation moieties. By further application of an oriented bioconjugation approach with whole IgG antibodies, QD nanobioconjugates were obtained that display outstanding intra- and extracellular stability as well as biorecognition capacity. Imaging the internalization and intracellular dynamics of a transmembrane cell receptor, the CB1 brain cannabinoid receptor, both in HEK293 cells and in neurons, illustrates the breadth of potential applications of these nanoprobes.

  3. Chemically active colloids near osmotic-responsive walls with surface-chemistry gradients

    CERN Document Server

    Popescu, M N; Dietrich, S

    2016-01-01

    Chemically active colloids move by creating gradients in the composition of the surrounding solution and by exploiting the differences in their interactions with the various molecular species in solution. If such particles move near boundaries, e.g., the walls of the container confining the suspension, gradients in the composition of the solution are also created along the wall. This give rise to chemi-osmosis (via the interactions of the wall with the molecular species forming the solution), which drives flows coupling back to the colloid and thus influences its motility. Employing an approximate "point-particle" analysis, we show analytically that -- owing to this kind of induced active response (chemi-osmosis) of the wall -- such chemically active colloids can align with, and follow, gradients in the surface chemistry of the wall. In this sense, these artificial "swimmers" exhibit a primitive form of thigmotaxis with the meaning of sensing the proximity of a (not necessarily discontinuous) physical change ...

  4. Testing grain-surface chemistry in massive hot-core regions

    CERN Document Server

    Bisschop, S E; van Dischoeck, E F; de Wachter, E B M

    2007-01-01

    A partial submillimeter line-survey was performed toward 7 high-mass YSOs aimed at detecting complex organic species. The aim is to establish the chemical origin of a set of complex organic molecules thought to be produced by grain surface chemistry in high mass young stellar objects (YSOs). Rotation temperatures and beam-averaged column densities are determined. To correct for beam dilution and determine abundances for hot gas, the radius and H2 column densities of gas at temperatures >100 K are computed using 850 micron dust continuum data and source luminosity. Based on their rotation diagrams, molecules can be classified as either cold (100 K). Furthermore, the abundances of the hot oxygen-bearing species are correlated, as are those of HNCO and NH2CHO. This is suggestive of chemical relationships within, but not between, those two groups of molecules.

  5. SnSe Nanocrystals: Synthesis, Structure, Optical Properties, and Surface Chemistry

    KAUST Repository

    Baumgardner, William J.

    2010-07-21

    The colloidal synthesis of SnSe nanoparticles is accomplished through the injection of bis[bis(trimethylsilyl)amino]tin(II) into hot trioctylphosphine: selenium in the presence of oleylamine. Through the manipulation of reaction temperature particles are grown with the average diameter reliably tuned to 4-10 nm. Quantum confinement is examined by establishing a relationship between particle size and band gap while the in depth growth dynamics are illuminated through UV-vis-NIR spectroscopy. Surface chemistry effects are explored, including the demonstration of useful ligand exchanges and the development of routes toward anisotropic particle growth. Finally, transient current-voltage properties of SnSe nanocrystal films in the dark and light are examined. © 2010 American Chemical Society.

  6. The influence of oxygen on the surface chemistry of 1,2-propanediol on Pd(111)

    Science.gov (United States)

    Williams, Rhea M.; Medlin, J. Will

    2014-01-01

    The surface chemistry of 1,2-propanediol (PDO) has been studied on oxygen precovered Pd(111) using temperature programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). Adsorbed 1,2-propanedioxy (-OCH(CH3)CH2O-) forms from the activation of the O-H bonds. When the concentration of O(a) is large compared to 1,2-propanedioxy, no H2 is produced and the dialkoxide reacts to form H2O, CO through decarbonylation, and CO2 through decarboxylation. Unreacted oxygen also desorbs as O2 at high temperature. Conversely, when the concentration of O(a) is small relative to 1,2-propanedioxy, the dialkoxide reacts to form decomposition products (H2, CO), oxidation products (H2O, glyoxal, methylglyoxal, formaldehyde) and deoxygenation products (ethylene, propylene). Co-adsorbed oxygen increases the overall coverage of PDO that can undergo decomposition, which in turn strongly influences decomposition activation barriers and products.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  8. Surface chemistry and properties of carbon overcoats for magnetic data storage

    Science.gov (United States)

    Yun, Yang

    The surface chemistry and properties of amorphous carbon films used in magnetic hard disk data storage media were studied in this thesis. This thesis includes two projects: vapor phase lubrication of hydrogenated amorphous carbon (a-CHx) films and thermal stability analysis of fluorinated amorphous carbon (a-CFx) films. The surface heterogeneity of a-CHx film was probed through the use of temperature programmed desorption of small fluorocarbon models of Fomblin Zdol lubricants. Surface oxidation by exposing a-CHx film to air or O2 strengthens the hydrogen bond between the hydroxyl endgroups of Fomblin Zdol lubricant molecules and the a-CHx film surfaces. Thus the interaction between Fomblin Zdol lubricant molecules and the a-CHx film surfaces can be tailored by controlled oxidation of a-CHx film surfaces prior to vapor phase lubrication. Methods for the preparation of high thermal stability a-CFx films were evaluated by our analysis of a-CFx film thermal stability. a-CFx films having high concentrations of CF3 and CF 2 have better thermal stability than those with high fractions of CF. Oxidation, however, jeopardizes the thermal stability of a-CFx films and thus should be avoided in application. The oxidation of a-CHx films and a-CFx films and its kinetics were studied by analysis of the fresh carbon film surfaces before and after controlled oxidized. The most surprising observation has been that the exposure of a-CHx films and a-CFx films to low pressures (<10-3 Torr) of O2 or air leads to a higher level of oxidation than exposure to high pressures (100--1000 Torr) of O2 or air. It may be that this decrease in apparent oxidation during the exposure to high pressures of O2 or air is due to complete oxidation of surface carbon to CO or CO2 which desorbs from the surface ("ablation"). In essence this changes the surface composition during the oxidation process.

  9. Quantum Chemistry in Nanoscale Environments: Insights on Surface-Enhanced Raman Scattering and Organic Photovoltaics

    Science.gov (United States)

    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

  10. Manipulating the Surface Chemistry of Quantum Dots for Sensitive Ratiometric Fluorescence Detection of Sulfur Dioxide.

    Science.gov (United States)

    Li, Huihui; Zhu, Houjuan; Sun, Mingtai; Yan, Yehan; Zhang, Kui; Huang, Dejian; Wang, Suhua

    2015-08-11

    Herein, we report a novel approach to the rapid visual detection of gaseous sulfur dioxide (SO2) by manipulating the surface chemistry of 3-aminopropyltriethoxysilane (APTS)-modified quantum dots (QDs) using fluorescent coumarin-3-carboxylic acid (CCA) for specific reaction with SO2. The CCA molecules are attached to the surface amino groups of the QDs through electrostatic attraction, thus the fluorescence of CCA is greatly suppressed because of the formation of an ion-pair complex between the ATPS-modified QDs and CCA. Such an interaction is vulnerable to SO2 because SO2 can readily react with surface amino groups to form strong charge-transfer complexes and subsequently release the strongly fluorescent CCA molecules. The mechanism has been carefully verified through a series of control experiments. Upon exposure to different amounts of SO2, the fluorescent color of the nanoparticle-based sensor displays continuously changes from red to blue. Most importantly, the approach owns high selectivity for SO2 and a tolerance of interference, which enables the sensor to detect SO2 in a practical application. Using this fluorescence-based sensing method, we have achieved a visual detection limit of 6 ppb for gaseous SO2.

  11. Neutron reflectivity study of substrate surface chemistry effects on supported phospholipid bilayer formation on (1120) sapphire.

    Energy Technology Data Exchange (ETDEWEB)

    Oleson, Timothy A. [University of Wisconsin, Madison; Sahai, Nita [University of Akron; Wesolowski, David J [ORNL; Dura, Joseph A [ORNL; Majkrzak, Charles F [ORNL; Giuffre, Anthony J. [University of Wisconsin, Madison

    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.

  12. The nucleation rate surfaces design over diagram of phase equilibria and their applications for computational chemistry

    Science.gov (United States)

    Anisimov, M. P.

    2016-12-01

    One can find in scientific literature a pretty fresh idea of the nucleation rate surfaces design over the diagrams of phase equilibria. That idea looks like profitable for the nucleation theory development and for various practical applications where predictions of theory have no high enough accuracy for today. The common thermodynamics has no real ability to predict parameters of the first order phase transition. Nucleation experiment can be provided in very local nucleation conditions even the nucleation takes place from the critical line (in two-component case) down to the absolute zero temperature limit and from zero nucleation rates at phase equilibria up to the spinodal conditions. Theory predictions have low reliability as a rule. The computational chemistry has chance to make solution of that problem easier when a set of the used axiomatic statements will adapt enough progressive assumptions [1]. Semiempirical design of the nucleation rate surfaces over diagrams of phase equilibria have a potential ability to provide a reasonable quality information on nucleation rate for each channel of nucleation. Consideration and using of the nucleation rate surface topologies to optimize synthesis of a given phase of the target material can be available when data base on nucleation rates over diagrams of phase equilibria will be created.

  13. On the photoactivity of S-doped nanoporous carbons:Importance of surface chemistry and porosity

    Institute of Scientific and Technical Information of China (English)

    Teresa J. Bandosz; Mykola Seredych

    2014-01-01

    This minireview summarizes our recent findings on the photoactivity of S-doped nanoporous car-bons. The materials were either synthesized from the sulfur-containing polymers or obtained by heat treatment of commercial carbon with hydrogen sulfide. Their surface was extensively charac-terized from the points of view of its surface chemistry, porosity, morphology, and electronic prop-erties. The carbons showed enhanced activity towards oxidation of arsine and removal of diben-zothiophenes from model diesel fuel. The latter were oxidized to various oxygen containing inter-mediates and the cleavage of C-C bonds in aromatic ring was detected when carbon with adsorbed species was exposed to UV or visible light. Irradiation resulted in generation of photocurrent in a broad range of wavelength. The presence of sulfur led to the reduction of oxygen and contributed to an increased capacitive performance. We link these effects to the presence of reduced sulfur in the small pores which enhances the dispersive interactions via inducing a positive charge to carbon atoms, to sulfur in oxygenated forms which contribute to Faradaic reactions and increase the polar interactions, and to the hydrophobicity of a surface in small pores where oxygen can be reduced by excited electrons from chromophoric-like sulfur containing groups.

  14. Surface chemistry of InP quantum dots: a comprehensive study.

    Science.gov (United States)

    Cros-Gagneux, Arnaud; Delpech, Fabien; Nayral, Céline; Cornejo, Alfonso; Coppel, Yannick; Chaudret, Bruno

    2010-12-29

    Advanced (1)H, (13)C, and (31)P solution and solid-state NMR studies combined with IR spectroscopy were used to probe, at the molecular scale, the composition and the surface chemistry of indium phosphide (InP) quantum dots (QDs) prepared via a non-coordinating solvent strategy. This nanomaterial can be described as a core-multishell object: an InP core, with a zinc blende bulk structure, is surrounded first by a partially oxidized surface shell, which is itself surrounded by an organic coating. This organic passivating layer is composed, in the first coordination sphere, of tightly bound palmitate ligands which display two different bonding modes. A second coordination sphere includes an unexpected dialkyl ketone and residual long-chain non-coordinating solvents (ODE and its isomers) which interact through weak intermolecular bonds with the alkyl chains of the carboxylate ligands. We show that this ketone is formed during the synthesis process via a decarboxylative coupling route and provides oxidative conditions which are responsible for the oxidation of the InP core surface. This phenomenon has a significant impact on the photoluminescence properties of the as-synthesized QDs and probably accounts for the failure of further growth of the InP core.

  15. Plasmonically amplified fluorescence bioassay with microarray format

    Science.gov (United States)

    Gogalic, S.; Hageneder, S.; Ctortecka, C.; Bauch, M.; Khan, I.; Preininger, Claudia; Sauer, U.; Dostalek, J.

    2015-05-01

    Plasmonic amplification of fluorescence signal in bioassays with microarray detection format is reported. A crossed relief diffraction grating was designed to couple an excitation laser beam to surface plasmons at the wavelength overlapping with the absorption and emission bands of fluorophore Dy647 that was used as a label. The surface of periodically corrugated sensor chip was coated with surface plasmon-supporting gold layer and a thin SU8 polymer film carrying epoxy groups. These groups were employed for the covalent immobilization of capture antibodies at arrays of spots. The plasmonic amplification of fluorescence signal on the developed microarray chip was tested by using interleukin 8 sandwich immunoassay. The readout was performed ex situ after drying the chip by using a commercial scanner with high numerical aperture collecting lens. Obtained results reveal the enhancement of fluorescence signal by a factor of 5 when compared to a regular glass chip.

  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.

    Science.gov (United States)

    Asadishad, Bahareh; Ghoshal, Subhasis; Tufenkji, Nathalie

    2013-06-04

    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.

  17. Dust evolution, a global view: III. Core/mantle grains, organic nano-globules, comets and surface chemistry

    Science.gov (United States)

    Jones, A. P.

    2016-12-01

    Within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS), this work explores the surface processes and chemistry relating to core/mantle interstellar and cometary grain structures and their influence on the nature of these fascinating particles. It appears that a realistic consideration of the nature and chemical reactivity of interstellar grain surfaces could self-consistently and within a coherent framework explain: the anomalous oxygen depletion, the nature of the CO dark gas, the formation of `polar ice' mantles, the red wing on the 3 μm water ice band, the basis for the O-rich chemistry observed in hot cores, the origin of organic nano-globules and the 3.2 μm `carbonyl' absorption band observed in comet reflectance spectra. It is proposed that the reaction of gas phase species with carbonaceous a-C(:H) grain surfaces in the interstellar medium, in particular the incorporation of atomic oxygen into grain surfaces in epoxide functional groups, is the key to explaining these observations. Thus, the chemistry of cosmic dust is much more intimately related with that of the interstellar gas than has previously been considered. The current models for interstellar gas and dust chemistry will therefore most likely need to be fundamentally modified to include these new grain surface processes.

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

    Science.gov (United States)

    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.

  19. Effect of the nature of the substrate on the surface chemistry of atomic layer deposition precursors

    Science.gov (United States)

    Yao, Yunxi; Coyle, Jason P.; Barry, Seán T.; Zaera, Francisco

    2017-02-01

    The thermal chemistry of Cu(I)-sec-butyl-2-iminopyrrolidinate, a promising copper amidinate complex for atomic layer deposition (ALD) applications, was explored comparatively on several surfaces by using a combination of surface-sensitive techniques, specifically temperature-programmed desorption and x-ray photoelectron spectroscopy (XPS). The substrates explored include single crystals of transition metals (Ni(110) and Cu(110)), thin oxide films (NiO/Ni(110) and SiO2/Ta), and oxygen-treated metals (O/Cu(110)). Decomposition of the pyrrolidinate ligand leads to the desorption of several gas-phase products, including CH3CN, HCN and butene from the metals and CO and CO2 from the oxygen-containing surfaces. In all cases dehydrogenation of the organic moieties is accompanied by hydrogen removal from the surface, in the form of H2 on metals and mainly as water from the metal oxides, but the threshold for this chemistry varies wildly, from 270 K on Ni(110) to 430 K on O/Cu(110), 470 K on Cu(110), 500 K on NiO/Ni(110), and 570 K on SiO2/Ta. Copper reduction is also observed in both the Cu 2p3/2 XPS and the Cu L3 VV Auger (AES) spectra, reaching completion by 300 K on Ni(110) but occurring only between 500 and 600 K on Cu(110). On NiO/Ni(110), both Cu(I) and Cu(0) coexist between 200 and 500 K, and on SiO2/Ta a change happens between 500 and 600 K but the reduction is limited, with the copper atoms retaining a significant ionic character. Additional experiments to test adsorption at higher temperatures led to the identification of temperature windows for the self-limiting precursor uptake required for ALD between approximately 300 and 450 K on both Ni(110) and NiO/Ni(110); the range on SiO2 had been previously determined to be wider, reaching an upper limit at about 500 K. Finally, deposition of copper metal films via ALD cycles with O2 as the co-reactant was successfully accomplished on the Ni(110) substrate.

  20. 77 FR 14837 - Bioassay at Uranium Mills

    Science.gov (United States)

    2012-03-13

    ... COMMISSION Bioassay at Uranium Mills AGENCY: Nuclear Regulatory Commission. ACTION: Draft regulatory guide... for public comment draft regulatory guide (DG), DG-8051, ``Bioassay at Uranium Mills.'' This guide describes a bioassay program acceptable to the NRC staff for uranium mills and applicable portions...

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

    Science.gov (United States)

    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

  2. Facile Fabrication of a Silver Nanoparticle Immersed, Surface-Enhanced Raman Scattering Imposed Paper Platform through Successive Ionic Layer Absorption and Reaction for On-Site Bioassays.

    Science.gov (United States)

    Kim, Wansun; Kim, Yeon-Hee; Park, Hun-Kuk; Choi, Samjin

    2015-12-23

    We introduce a novel, facile, rapid, low-cost, highly reproducible, and power-free synthesizable fabrication method of paper-based silver nanoparticle (AgNP) immersed surface-enhanced Raman scattering (SERS) platform, known as the successive ionic layer absorption and reaction (SILAR) method. The rough and porous properties of the paper led to direct synthesis of AgNPs on the surface as well as in the paper due to capillary effects, resulting in improved plasmon coupling with interparticles and interlayers. The proposed SERS platform showed an enhancement factor of 1.1 × 10(9), high reproducibility (relative standard deviation of 4.2%), and 10(-12) M rhodamine B highly sensitive detection limit by optimizing the SILAR conditions including the concentration of the reactive solution (20/20 mM/mM AgNO3/NaBH4) and the number of SILAR cycles (six). The applicability of the SERS platform was evaluated using two samples including human cervical fluid for clinical diagnosis of human papillomavirus (HPV) infection, associated with cervical cancer, and a malachite green (MG) solution for fungicide and parasiticide in aquaculture, associated with human carcinogenesis. The AgNP-immersed SERS-functionalized platform using the SILAR technique allowed for high chemical structure sensitivity without additional tagging or chemical modification, making it a good alternative for early clinical diagnosis of HPV infection and detection of MG-activated human carcinogenesis.

  3. Evolution of interfacial intercalation chemistry on epitaxial graphene/SiC by surface enhanced Raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ferralis, Nicola, E-mail: ferralis@mit.edu [Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Carraro, Carlo [Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA 94720 (United States)

    2014-11-30

    Highlights: • H-intercalated epitaxial graphene–SiC interface studied with surface enhanced Raman. • Evolution of graphene and H–Si interface with UV-ozone, annealing and O-exposure. • H–Si interface and quasi-freestanding graphene are retained after UV-ozone treatment. • Enhanced ozonolytic reactivity at the edges of H-intercalated defected graphene. • Novel SERS method for characterizing near-surface graphene–substrate interfaces. - Abstract: 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{sup −1} corresponding to the Si-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.

  4. Scanning near-field optical microscopy on rough surfaces: applications in chemistry, biology, and medicine

    Directory of Open Access Journals (Sweden)

    2006-01-01

    Full Text Available Shear-force apertureless scanning near-field optical microscopy (SNOM with very sharp uncoated tapered waveguides relies on the unexpected enhancement of reflection in the shear-force gap. It is the technique for obtaining chemical (materials contrast in the optical image of “real world” surfaces that are rough and very rough without topographical artifacts, and it is by far less complicated than other SNOM techniques that can only be used for very flat surfaces. The experimental use of the new photophysical effect is described. The applications of the new technique are manifold. Important mechanistic questions in solid-state chemistry (oxidation, diazotization, photodimerization, surface hydration, hydrolysis are answered with respect to simultaneous AFM (atomic force microscopy and detailed crystal packing. Prehistoric petrified bacteria and concomitant pyrite inclusions are also investigated with local RAMAN SNOM. Polymer beads and unstained biological objects (rabbit heart, shrimp eye allow for nanoscopic analysis of cell organelles. Similarly, human teeth and a cancerous tissue are analyzed. Bladder cancer tissue is clearly differentiated from healthy tissue without staining and this opens a new highly promising diagnostic tool for precancer diagnosis. Industrial applications are demonstrated at the corrosion behavior of dental alloys (withdrawal of a widely used alloy, harmless substitutes, improvement of paper glazing, behavior of blood bags upon storage, quality assessment of metal particle preparations for surface enhanced RAMAN spectroscopy, and determination of diffusion coefficient and light fastness in textile fiber dyeing. The latter applications include fluorescence SNOM. Local fluorescence SNOM is also used in the study of partly aggregating dye nanoparticles within resin/varnish preparations. Unexpected new insights are obtained in all of the various fields that cannot be obtained by other techniques.

  5. Surface chemistry and size influence the release of model therapeutic nanoparticles from poly(ethylene glycol) hydrogels

    Energy Technology Data Exchange (ETDEWEB)

    Hume, Stephanie L.; Jeerage, Kavita M., E-mail: jeerage@boulder.nist.gov [National Institute of Standards and Technology (NIST), Applied Chemicals and Materials Division, Material Measurement Laboratory (United States)

    2013-05-15

    Nanoparticles have emerged as promising therapeutic and diagnostic tools, due to their unique physicochemical properties. The specific core and surface chemistries, as well as nanoparticle size, play critical roles in particle transport and interaction with biological tissue. Localized delivery of therapeutics from hydrogels is well established, but these systems generally release molecules with hydrodynamic radii less than {approx}5 nm. Here, model nanoparticles with biologically relevant surface chemistries and diameters between 10 and 35 nm are analyzed for their release from well-characterized hydrogels. Functionalized gold nanoparticles or quantum dots were encapsulated in three-dimensional poly(ethylene glycol) hydrogels with varying mesh size. Nanoparticle size, surface chemistry, and hydrogel mesh size all influenced the release of particles from the hydrogel matrix. Size influenced nanoparticle release as expected, with larger particles releasing at a slower rate. However, citrate-stabilized gold nanoparticles were not released from hydrogels. Negatively charged carboxyl or positively charged amine-functionalized quantum dots were released from hydrogels at slower rates than neutrally charged PEGylated nanoparticles of similar size. Transmission electron microscopy images of gold nanoparticles embedded within hydrogel sections demonstrated uniform particle distribution and negligible aggregation, independent of surface chemistry. The nanoparticle-hydrogel interactions observed in this work will aid in the development of localized nanoparticle delivery systems.

  6. Surface chemistry and size influence the release of model therapeutic nanoparticles from poly(ethylene glycol) hydrogels

    Science.gov (United States)

    Hume, Stephanie L.; Jeerage, Kavita M.

    2013-05-01

    Nanoparticles have emerged as promising therapeutic and diagnostic tools, due to their unique physicochemical properties. The specific core and surface chemistries, as well as nanoparticle size, play critical roles in particle transport and interaction with biological tissue. Localized delivery of therapeutics from hydrogels is well established, but these systems generally release molecules with hydrodynamic radii less than 5 nm. Here, model nanoparticles with biologically relevant surface chemistries and diameters between 10 and 35 nm are analyzed for their release from well-characterized hydrogels. Functionalized gold nanoparticles or quantum dots were encapsulated in three-dimensional poly(ethylene glycol) hydrogels with varying mesh size. Nanoparticle size, surface chemistry, and hydrogel mesh size all influenced the release of particles from the hydrogel matrix. Size influenced nanoparticle release as expected, with larger particles releasing at a slower rate. However, citrate-stabilized gold nanoparticles were not released from hydrogels. Negatively charged carboxyl or positively charged amine-functionalized quantum dots were released from hydrogels at slower rates than neutrally charged PEGylated nanoparticles of similar size. Transmission electron microscopy images of gold nanoparticles embedded within hydrogel sections demonstrated uniform particle distribution and negligible aggregation, independent of surface chemistry. The nanoparticle-hydrogel interactions observed in this work will aid in the development of localized nanoparticle delivery systems.

  7. Surface-Enhanced Resonance Raman Scattering and Visible Extinction Spectroscopy of Copper Chlorophyllin: An Upper Level Chemistry Experiment

    Science.gov (United States)

    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…

  8. Bioassay for investigation of auxin transport in single cell layers

    Directory of Open Access Journals (Sweden)

    Alina B. Wodzicki

    2014-02-01

    Full Text Available Auxin was collected from the cambial region of Pinus sylvestris by applying agar strips to the cut surfaces of stem sections which comprised a single layer of 2 to 4-mm long, mainly intact fusiform cells. Sections of the agar strips were either bioassayed immediately to determine their auxin content or stored for several months at -80oC, extracted with 80% MeOH and redissolved in hot agar prior to bioassay. Auxin concentrations were determined by Went's oat coleoptile test, as described by Funke, which was modified considerably to give highly reproducible results. The modifications proved essential for good replication of results and are described in detail together with the use of the bioassay to determine changes in cambial cell polarity during ageing and senescence in P. sylvestris.

  9. Impact of small changes in particle surface chemistry for unentangled polymer nanocomposites.

    Science.gov (United States)

    Ranka, Moulik; Varkey, Nihal; Ramakrishnan, Subramanian; Zukoski, Charles F

    2015-02-28

    We report microstructural and rheological consequences of altering silica particle surface chemistry when the particles are suspended in unentangled polyethylene glycol with a molecular weight of 400. The particle surfaces are altered by reacting them with isobutyltrimethyoxysilane. Levels of silanization are chosen so that the particles remain dispersed in the polymer at all volume fractions studied. Our studies indicate that at the levels studied, silanization does not alter the hydrodynamic thickness of the absorbed polymer layer thickness. Rheological properties are not sensitive to levels of silanization up to particle volume fractions where the average particle separation h ∼ 6Rg (4.8 nm). At these volume fractions, composite microstructure undergoes changes associated with jamming of soft particles (decorrelations in the first peak of the particle structure factor and the onset of a non-diffusive mechanism that dominates particle density fluctuations at short times.) In the region of volume fractions where h/Rg silanization with a decrease in the zero-shear rate viscosity by four orders of magnitude observed for the highest levels of silanization studied in comparison to the bare particles.

  10. Cyclodextrin-modified zeolites: host-guest surface chemistry for the construction of multifunctional nanocontainers.

    Science.gov (United States)

    Szarpak-Jankowska, Anna; Burgess, Christine; De Cola, Luisa; Huskens, Jurriaan

    2013-10-25

    The functionalization of nanoporous zeolite L crystals with β-cyclodextrin (CD) has been demonstrated. The zeolite surface was first modified with amino groups by using two different aminoalkoxysilanes. Then, 1,4-phenylene diisothiocyanate was reacted with the amino monolayer and used to bind CD heptamine by using its remaining isothiocyanate groups. The use of the different aminoalkoxysilanes, 3-aminopropyl dimethylethoxysilane (APDMES) and 3-aminopropyl triethoxysilane (APTES), led to drastic differences in uptake and release properties. Thionine was found to be absorbed and released from amino- and CD-functionalized zeolites when APDMES was used, whereas functionalization by APTES led to complete blockage of the zeolite channels. Fluorescence microscopy showed that the CD groups covalently attached to the zeolite crystals could bind adamantyl-modified dyes in a specific and reversible manner. This strategy allowed the specific immobilization of His-tagged proteins by using combined host-guest and His-tag-Ni-nitrilotriacetic acid (NTA) coordination chemistry. Such multifunctional systems have the potential for encapsulation of drug molecules inside the zeolite pores and non-covalent attachment of other (for example, targeting) ligand molecules on its surface.

  11. Interactive effect of hysteresis and surface chemistry on gated silicon nanowire gas sensors.

    Science.gov (United States)

    Paska, Yair; Haick, Hossam

    2012-05-01

    Gated silicon nanowire gas sensors have emerged as promising devices for chemical and biological sensing applications. Nevertheless, the performance of these devices is usually accompanied by a "hysteresis" phenomenon that limits their performance under real-world conditions. In this paper, we use a series of systematically changed trichlorosilane-based organic monolayers to study the interactive effect of hysteresis and surface chemistry on gated silicon nanowire gas sensors. The results show that the density of the exposed or unpassivated Si-OH groups (trap states) on the silicon nanowire surface play by far a crucial effect on the hysteresis characteristics of the gated silicon nanowire sensors, relative to the effect of hydrophobicity or molecular density of the organic monolayer. Based on these findings, we provide a tentative model-based understanding of (i) the relation between the adsorbed organic molecules, the hysteresis, and the related fundamental parameters of gated silicon nanowire characteristics and of (ii) the relation between the hysteresis drift and possible screening effect on gated silicon nanowire gas sensors upon exposure to different analytes at real-world conditions. The findings reported in this paper could be considered as a launching pad for extending the use of the gated silicon nanowire gas sensors for discriminations between polar and nonpolar analytes in complex, real-world gas mixtures.

  12. Tuning microstructure and surface chemistry of reduced graphene oxide by mild reduction

    Institute of Scientific and Technical Information of China (English)

    冷娴; 刘如铁; 邹俭鹏; 熊翔; 何捍卫

    2016-01-01

    Reduced graphene oxide (RGO) sheets with varied contents and types of oxygenated groups were synthesized by Hummers treatment of natural graphite powders followed by different nontoxic and mild reduction methods, which include thermal and chemical reduction with ethylene glycol, KOH and Fe powder. The changes in microstructure and surface chemistry of RGOs were extensively characterized by SEM, TEM, AFM, XRD, XPS and Raman spectrum. The results show that significant exfoliation occurs during oxidation and is retained in reduction processes, along with the formation of curled wavy morphology. Compared with larged spacing (0.852 nm) of graphene oxide (GO), the (002) plane distance decreases to 0.358−0.384 nm of RGOs, indicating efficient tuning of surface functionalities through mild reduction methods. TheID/IG ratio of RGOs is about 1.0−1.15, indicating that reconstructed sp2 domains have smaller sizes and larger quantity. The content of sp2 bonded C in GO (36.93%, molar fraction) increases to 45.48%−72.92% (molar fraction) in RGOs, along with a drastic decrease in hydroxyl and epoxy and minor changes in carbonyl and carboxyl. Thermal reduction or chemical reduction produces RGOs with residual functionalities, which may render different chemical activity and is desirable in various applications.

  13. Surface functionalization of two-dimensional metal chalcogenides by Lewis acid-base chemistry

    Science.gov (United States)

    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.

  14. Improving surface and defect center chemistry of fluorescent nanodiamonds for imaging purposes--a review.

    Science.gov (United States)

    Nagl, Andreas; Hemelaar, Simon Robert; Schirhagl, Romana

    2015-10-01

    Diamonds are widely used for jewelry owing to their superior optical properties accounting for their fascinating beauty. Beyond the sparkle, diamond is highly investigated in materials science for its remarkable properties. Recently, fluorescent defects in diamond, particularly the negatively charged nitrogen-vacancy (NV(-)) center, have gained much attention: The NV(-) center emits stable, nonbleaching fluorescence, and thus could be utilized in biolabeling, as a light source, or as a Förster resonance energy transfer donor. Even more remarkable are its spin properties: with the fluorescence intensity of the NV(-) center reacting to the presence of small magnetic fields, it can be utilized as a sensor for magnetic fields as small as the field of a single electron spin. However, a reproducible defect and surface and defect chemistry are crucial to all applications. In this article we review methods for using nanodiamonds for different imaging purposes. The article covers (1) dispersion of particles, (2) surface cleaning, (3) particle size selection and reduction, (4) defect properties, and (5) functionalization and attachment to nanostructures, e.g., scanning probe microscopy tips.

  15. Deuteration and evolution in the massive star formation process: the role of surface chemistry

    CERN Document Server

    Fontani, F; Palau, Aina; Caselli, P; A.,; Sanchez-Monge,; Tan, J C; Audard, M

    2014-01-01

    An ever growing number of observational and theoretical evidence suggests that the deuterated fraction (column density ratio between a species containing D and its hydrogenated counterpart, Dfrac) is an evolutionary indicator both in the low- and the high-mass star formation process. However, the role of surface chemistry in these studies has not been quantified from an observational point of view. In order to compare how the deuterated fractions of species formed only in the gas and partially or uniquely on grain surfaces evolve with time, we observed rotational transitions of CH3OH, 13CH3OH, CH2DOH, CH3OD at 3 and 1.3~mm, and of NH2D at 3~mm with the IRAM-30m telescope, and the inversion transitions (1,1) and (2,2) of NH3 with the GBT, towards most of the cores already observed by Fontani et al.~(2011, 2014) in N2H+, N2D+, HNC, DNC. NH2D is detected in all but two cores, regardless of the evolutionary stage. Dfrac(NH3) is on average above 0.1, and does not change significantly from the earliest to the most ...

  16. The Role of Grain Surface Reactions in the Chemistry of Star Forming Regions

    Science.gov (United States)

    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

  17. Surface chemistry and electronic structure of nonpolar and polar GaN films

    Energy Technology Data Exchange (ETDEWEB)

    Mishra, Monu; Krishna, T.C. Shibin; Aggarwal, Neha; Gupta, Govind, E-mail: govind@nplindia.org

    2015-08-01

    Highlights: • Surface chemistry and electronic structure of polar and nonpolar GaN is reported. • Influence of polarization on electron affinity of p & np GaN films is investigated. • Correlation between surface morphology and polarity has been deduced. - Abstract: Photoemission and microscopic analysis of nonpolar (a-GaN/r-Sapphire) and polar (c-GaN/c-Sapphire) epitaxial gallium nitride (GaN) films grown via RF-Molecular Beam Epitaxy is reported. The effect of polarization on surface properties like surface states, electronic structure, chemical bonding and morphology has been investigated and correlated. It was observed that polarization lead to shifts in core level (CL) as well as valence band (VB) spectra. Angle dependent X-ray Photoelectron Spectroscopic analysis revealed higher surface oxide in polar GaN film compared to nonpolar GaN film. On varying the take off angle (TOA) from 0° to 60°, the Ga−O/Ga−N ratio varied from 0.11–0.23 for nonpolar and 0.17–0.36 for polar GaN film. The nonpolar film exhibited N-face polarity while Ga-face polarity was perceived in polar GaN film due to the inherent polarization effect. Polarization charge compensated surface states were observed on the polar GaN film and resulted in downward band bending. Ultraviolet photoelectron spectroscopic measurements revealed electron affinity and ionization energy of 3.4 ± 0.1 eV and 6.8 ± 0.1 eV for nonpolar GaN film and 3.8 ± 0.1 eV and 7.2 ± 0.1 eV for polar GaN film respectively. Field Emission Scanning Electron Microscopy measurements divulged smooth morphology with pits on polar GaN film. The nonpolar film on the other hand showed pyramidal structures having facets all over the surface.

  18. Patterned porous silicon photonic crystals with modular surface chemistry for spatial control of neural stem cell differentiation

    Science.gov (United States)

    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

  19. Computer vision-based recognition of liquid surfaces and phase boundaries in transparent vessels, with emphasis on chemistry applications

    OpenAIRE

    Eppel, Sagi; Kachman, Tal

    2014-01-01

    The ability to recognize the liquid surface and the liquid level in transparent containers is perhaps the most commonly used evaluation method when dealing with fluids. Such recognition is essential in determining the liquid volume, fill level, phase boundaries and phase separation in various fluid systems. The recognition of liquid surfaces is particularly important in solution chemistry, where it is essential to many laboratory techniques (e.g., extraction, distillation, titration). A gener...

  20. Estimating the Analytical and Surface Enhancement Factors in Surface-Enhanced Raman Scattering (SERS): A Novel Physical Chemistry and Nanotechnology Laboratory Experiment

    Science.gov (United States)

    Pavel, Ioana E.; Alnajjar, Khadijeh S.; Monahan, Jennifer L.; Stahler, Adam; Hunter, Nora E.; Weaver, Kent M.; Baker, Joshua D.; Meyerhoefer, Allie J.; Dolson, David A.

    2012-01-01

    A novel laboratory experiment was successfully implemented for undergraduate and graduate students in physical chemistry and nanotechnology. The main goal of the experiment was to rigorously determine the surface-enhanced Raman scattering (SERS)-based sensing capabilities of colloidal silver nanoparticles (AgNPs). These were quantified by…

  1. The effect of C-OH functionality on the surface chemistry of biomass-derived molecules: ethanol chemistry on Rh(100).

    Science.gov (United States)

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

    2016-11-21

    The adsorption and decomposition of ethanol on Rh(100) was studied as a model reaction to understand the role of C-OH functionalities in the surface chemistry of biomass-derived molecules. A combination of experimental surface science and computational techniques was used: (i) temperature programmed reaction spectroscopy (TPRS), reflection absorption infrared spectroscopy (RAIRS), work function measurements (Kelvin Probe - KP), and density functional theory (DFT). Ethanol produces ethoxy (CH3CH2O) species via O-H bond breaking upon adsorption at 100 K. Ethoxy decomposition proceeds differently depending on the surface coverage. At low coverage, the decomposition of ethoxy species occurs viaβ-C-H cleavage, which leads to an oxometallacycle (OMC) intermediate. Decomposition of the OMC scissions (at 180-320 K) ultimately produces CO, H2 and surface carbon. At high coverage, along with the pathway observed in the low coverage case, a second pathway occurs around 140-200 K, which produces an acetaldehyde intermediate viaα-C-H cleavage. Further decomposition of acetaldehyde produces CH4, CO, H2 and surface carbon. However, even at high coverage this is a minor pathway, and methane selectivity is 10% at saturation coverage. The results suggests that biomass-derived oxygenates, which contain an alkyl group, react on the Rh(100) surface to produce synthesis gas (CO and H2), surface carbon and small hydrocarbons due to the high dehydrogenation and C-C bond scission activity of Rh(100).

  2. Surface chemistry of the atomic layer deposition of metals and group III oxides

    Science.gov (United States)

    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

  3. Variations in snow and firn chemistry along US ITASE traverses and the effect of surface glazing

    Directory of Open Access Journals (Sweden)

    D. A. Dixon

    2013-03-01

    Full Text Available This study provides a baseline from which changes in the chemistry of the atmosphere over Antarctica can be monitored under expected warming scenarios and continued intensification of industrial activities in the Southern Hemisphere. It 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 (ICP-SFMS. We also measure δ18O by isotope ratio mass spectrometry. Satellite remote sensing measurements of microwave backscatter and grain size are used to assist in the identification of glaze/dune areas across Antarctica and determine if these areas can possibly contain useful 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. The elements Cd, Pb, As and Bi are enriched across Antarctica relative to both ocean and upper crust elemental ratios. Local and global volcanic outgassing may account for the majority of the Bi measured in East and West Antarctica and for a significant fraction of the Cd and As. However, significant concentrations of Cd, Pb, and As remain across much of Antarctica.

  4. Preparation and application of a novel electrochemical sensing material based on surface chemistry of polyhydroquinone

    Energy Technology Data Exchange (ETDEWEB)

    Dang, Xueping [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules and College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062 (China); State Key Laboratory of Transducer Technology, Chinese Academy of Sciences, Beijing 10080 (China); Wang, Yingkai [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); Hu, Chengguo, E-mail: cghu@whu.edu.cn [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); State Key Laboratory of Transducer Technology, Chinese Academy of Sciences, Beijing 10080 (China); Huang, Jianlin; Chen, Huaixia; Wang, Shengfu [Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules and College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062 (China); Hu, Shengshui, E-mail: sshu@whu.edu.cn [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); State Key Laboratory of Transducer Technology, Chinese Academy of Sciences, Beijing 10080 (China)

    2014-07-01

    A new analogue of polydopamine (PDA), i.e., polyhydroquinone (PH{sub 2}Q), was polymerized and its surface chemistry was studied by different ways of characterization. PH{sub 2}Q was produced by the self-polymerization of H{sub 2}Q mediated by dissolved oxygen, and the self-polymerization process was strongly dependent on the type and the pH value of the buffer solutions. PH{sub 2}Q can not only achieve surface hydrophilization of different substrates like polyethylene terephthalate (PET) film, graphite strip, C{sub 12}SH/Au and wax slice, but also possess several unique properties like reversible adsorption, good solubility and low cost. These properties made PH{sub 2}Q an ideal polymeric modifier for the noncovalent functionalization of some nanomaterials. By simply grinding with PH{sub 2}Q, pristine multi-walled carbon nanotubes (MWNTs) can be readily dispersed in water with high solubility and good stability. The resulting MWNT–PH{sub 2}Q composite exhibited excellent electrochemical performance, which was employed for the simultaneous determination of dopamine (DA) and uric acid (UA). - Highlights: • Polyhydroquinone (PH{sub 2}Q) was produced by the self-polymerization of hydroquinone (H{sub 2}Q) mediated by dissolved oxygen. • PH{sub 2}Q can achieve surface hydrophilization of a variety of substrates. • PH{sub 2}Q is an ideal polymeric modifier for the functionalization of multi-walled carbon nanotubes (MWNTs). • The MWNT–PH{sub 2}Q composite can be employed for the simultaneous determination of dopamine (DA) and uric acid (UA)

  5. The coupling effect of gas-phase chemistry and surface reactions on oxygen permeation and fuel conversion in ITM reactors

    KAUST Repository

    Hong, Jongsup

    2015-08-01

    © 2015 Elsevier B.V. The effect of the coupling between heterogeneous catalytic reactions supported by an ion transport membrane (ITM) and gas-phase chemistry on fuel conversion and oxygen permeation in ITM reactors is examined. In ITM reactors, thermochemical reactions take place in the gas-phase and on the membrane surface, both of which interact with oxygen permeation. However, this coupling between gas-phase and surface chemistry has not been examined in detail. In this study, a parametric analysis using numerical simulations is conducted to investigate this coupling and its impact on fuel conversion and oxygen permeation rates. A thermochemical model that incorporates heterogeneous chemistry on the membrane surface and detailed chemical kinetics in the gas-phase is used. Results show that fuel conversion and oxygen permeation are strongly influenced by the simultaneous action of both chemistries. It is shown that the coupling somewhat suppresses the gas-phase kinetics and reduces fuel conversion, both attributed to extensive thermal energy transfer towards the membrane which conducts it to the air side and radiates to the reactor walls. The reaction pathway and products, in the form of syngas and C2 hydrocarbons, are also affected. In addition, the operating regimes of ITM reactors in which heterogeneous- or/and homogeneous-phase reactions predominantly contribute to fuel conversion and oxygen permeation are elucidated.

  6. Water chemistry of surface waters affected by the Fourmile Canyon wildfire, Colorado, 2010-2011

    Science.gov (United States)

    McCleskey, R. Blaine; Writer, Jeffrey H.; Murphy, Sheila F.

    2012-01-01

    In September 2010, the Fourmile Canyon fire burned about 23 percent of the Fourmile Creek watershed in Boulder County, Colo. Water-quality sampling of Fourmile Creek began within a month after the wildfire to assess its effects on surface-water chemistry. Water samples were collected from five sites along Fourmile Creek (above, within, and below the burned area) monthly during base flow, twice weekly during snowmelt runoff, and at higher frequencies during storm events. Stream discharge was also monitored. Water-quality samples were collected less frequently from an additional 6 sites on Fourmile Creek, from 11 tributaries or other inputs, and from 3 sites along Boulder Creek. The pH, electrical conductivity, temperature, specific ultraviolet absorbance, total suspended solids, and concentrations (dissolved and total) of major cations (calcium, magnesium, sodium, and potassium), anions (chloride, sulfate, alkalinity, fluoride, and bromide), nutrients (nitrate, ammonium, and phosphorus), trace metals (aluminum, arsenic, boron, barium, beryllium, cadmium, cobalt, chromium, copper, iron, mercury, lithium, manganese, molybdenum, nickel, lead, rubidium, antimony, selenium, strontium, vanadium, and zinc), and dissolved organic carbon are here reported for 436 samples collected during 2010 and 2011.

  7. Surface trimming of silicon photonics devices using controlled reactive ion etching chemistry

    Science.gov (United States)

    Chandran, S.; Das, B. K.

    2015-06-01

    Surface trimming of rib waveguides fabricated in 5-μm SOI substrate has been carried out successfully without any significant increase of propagation losses. A reactive ion etching chemistry has been optimized for trimming and an empirical model has been developed to obtain the resulting waveguide geometries. This technique has been used to demonstrate smaller footprint devices like multimode interference based power splitters and ring resonators after defining them photolithographically with relatively large cross-section rib waveguides. We have been also successful to fabricate 2D tapered spot-size converter useful for monolithic integration of waveguides with varying heights and widths. The taper length is again precisely controlled by photolithographic definition. Minimum insertion loss of such a spot-size converter integrated between waveguides with 3-μm height difference has been recorded to be ∼2 dB. It has been also shown that the overall fiber-to-chip coupling loss can be reduced by >3 dB by using such spot-size converters at the input/output side of the waveguides.

  8. Tuning optoelectronic properties of small semiconductor nanocrystals through surface ligand chemistry

    Science.gov (United States)

    Lawrence, Katie N.

    Semiconductor nanocrystals (SNCs) are a class of material with one dimension surface to volume ratio. Therefore, their electronic and photophysical properties are fundamentally dictated by their surface chemistry, and as such, even a minute variation of the surface ligation can have a colossal impact on these properties. Since the development of the hot injection-method by Bawendi et al., the synthetic methods of SNCs have evolved from high-temperature, highly toxic precursors to low-temperature, relatively benign precursors over the last 25 years. Unfortunately, optimization of their synthetic methods by appropriate surface ligation is still deficient. The deficiency lies in the incomplete or inappropriate surface passivation during the synthesis and/or post-synthetic modification procedure, which due to the high surface to volume ratio of ultrasmall SNCs, is a significant problem. Currently, direct synthetic methods produce SNCs that are either soluble in an aqueous media or soluble in organic solvents therefore limiting their applicability. In addition, use of insulating ligands hinder SNCs' transport properties and thus their potential application in solid state devices. Appropriate choice of surface ligation can provide 1) solubility, 2) stability, and 3) facilitate exciton delocalization. In this dissertation, the effects of appropriate surface ligation on strongly quantum confined ultrasmall SNCs was investigated. Due to their high surface to volume ratio, we are able to highly control their optical and electronic properties through surface ligand modification. Throughout this dissertation, we utilized a variety of ligands (e.g. oleylamine, cadmium benzoate, and PEGn-thiolate) in order to change the solubility of the SNC as well as investigate their optical and electronic properties. First delocalization of the excitonic wave function 1) into the ligand monolayer using metal carboxylates and 2) beyond the ligand monolayer to provide strong inter

  9. Surface chemistry analysis of lithium conditioned NSTX graphite tiles correlated to plasma performance

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, C.N., E-mail: chase.taylor@inl.gov [Purdue University, School of Nuclear Engineering, West Lafayette, IN 47906 (United States); Birck Nanotechnology Center, Discovery Park, West Lafayette, IN 47907 (United States); Luitjohan, K.E. [Purdue University, School of Nuclear Engineering, West Lafayette, IN 47906 (United States); Heim, B. [Purdue University, School of Nuclear Engineering, West Lafayette, IN 47906 (United States); Birck Nanotechnology Center, Discovery Park, West Lafayette, IN 47907 (United States); Kollar, L. [Purdue University, School of Nuclear Engineering, West Lafayette, IN 47906 (United States); Allain, J.P. [Purdue University, School of Nuclear Engineering, West Lafayette, IN 47906 (United States); Birck Nanotechnology Center, Discovery Park, West Lafayette, IN 47907 (United States); Skinner, C.H.; Kugel, H.W.; Kaita, R.; Roquemore, A.L. [Princeton Plasma Physics Laboratory, Princeton, NJ 08543 (United States); Maingi, R. [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States)

    2013-12-15

    Lithium wall conditioning in NSTX has resulted in reduced divertor recycling, improved energy confinement, and reduced frequency of edge-localized modes (ELMs), up to the point of complete ELM suppression. NSTX tiles were removed from the vessel following the 2008 campaign and subsequently analyzed using X-ray photoelectron spectroscopy as well as nuclear reaction ion beam analysis. In this paper we relate surface chemistry to deuterium retention/recycling, develop methods for cleaning of passivated NSTX tiles, and explore a method to effectively extract bound deuterium from lithiated graphite. Li–O–D and Li–C–D complexes characteristic of deuterium retention that form during NSTX operations are revealed by sputter cleaning and heating. Heating to ∼850 °C desorbed all deuterium complexes observed in the O 1s and C 1s photoelectron energy ranges. Tile locations within approximately ±2.5 cm of the lower vertical/horizontal divertor corner appear to have unused Li-O bonds that are not saturated with deuterium, whereas locations immediately outboard of this region indicate high deuterium recycling. X-ray photo electron spectra of a specific NSTX tile with wide ranging lithium coverage indicate that a minimum lithium dose, 100–500 nm equivalent thickness, is required for effective deuterium retention. This threshold is suspected to be highly sensitive to surface morphology. The present analysis may explain why plasma discharges in NSTX continue to benefit from lithium coating thickness beyond the divertor deuterium ion implantation depth, which is nominally <10 nm.

  10. Analysis of surface chemistry of boronized TZM samples in NSTX-U between plasma exposures

    Science.gov (United States)

    Schamis, Hanna; Bedoya, Felipe; Allain, Jean Paul; Kaita, Robert; Koel, Bruce

    2016-10-01

    In the National Spherical Torus Experiment Upgrade (NSTX-U) a new plasma facing component diagnostic, the Material Analysis and Particle Probe (MAPP), was installed. MAPP has the capability of conducting XPS studies on materials without exposing them to atmospheric conditions. MAPP was used to conduct XPS studies of TZM (99% Mo, 0.5% Ti, 0.08% Zr) samples. XPS gives information about the chemical composition of up to about 5 nm of the surface, and can be conducted on a day-to-day basis or at higher temporal resolutions e.g. close to in-between plasma shots. MAPP characterization gives insight on boron deposition and fuel retention by following the evolution of atomic concentrations and oxidation states. The data shows that the boron deposited layer was thicker than 5 nm. Additionally, the data shows evidence of sputtering of the boron layers following tens of plasma shots. The data also shows an increase in the oxygen concentration with plasma exposure. The next NSTX-U experimental campaign will feature TZM tiles in the lower divertor region, while the rest of the first wall will continue to be ATJ graphite. Our data provides the basis to analyze how the surface chemistry of the new set of tiles will be influenced by plasma operations, boron conditioning and carbon migration. Work supported by US DOE Contract No. DE-AC02-09CH11466, US DOE Contract No. DE-SC0010717, Award No. DE-SC0012890, and the DOE Science Undergraduate Laboratory Internship (SULI) Program.

  11. Chemistry of the sea-surface microlayer. 3. Studies on the nutrient chemistry of the northern Arabian Sea

    Digital Repository Service at National Institute of Oceanography (India)

    Singbal, S.Y.S.; Narvekar, P.V.; Nagarajan, R.

    with Chlorophyll values at 1 m depth. Relatively high enrichment factors, sea-surface microlayer (SML), in coastal waters could be attributed to the influence of freshwater carrying considerable quantities of nutrients into the sea either from land runoff or from...

  12. Soft X-ray absorption spectroscopy investigation of the surface chemistry and treatments of copper indium gallium diselenide (CIGS)

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, Craig; Nordlund, Dennis; Sokaras, Dimosthenis; Contreras, Miguel; Weng, Tsu-Chien; Mansfield, Lorelle; Hurst, Katherine E.; Dameron, Arrelaine; Ramanathan, Kannan; Prendergast, David; Christensen, Steven T.

    2017-02-01

    The surface and near surface structure of copper-indium-gallium-selenide (CIGS) absorber layers is integral to the producing a high-quality photovoltaic junction. By using X-ray absorption spectroscopy (XAS) and monitoring multiple elemental absorption edges with both theory and experiment, we are able to identify several features of the surface of CIGS as a function of composition and surface treatments. The XAS data shows trends in the near surface region of oxygen, copper, indium and gallium species as the copper content is varied in the films. The oxygen surface species are also monitored through a series of experiments that systematically investigates the effects of water and various solutions of: ammonium hydroxide, cadmium sulfate, and thiourea. These being components of cadmium sulfide chemical bath deposition (CBD). Characteristics of the CBD are correlated with a restorative effect that produces as normalized, uniform surface chemistry as measured by XAS. This surface chemistry is found in CIGS solar cells with excellent power conversion efficiency (<19%). The results provide new insight for CIGS processing strategies that seek to replace CBD and/or cadmium sulfide.

  13. Role of surface chemistry in adhesion between ZnO nanowires and carbon fibers in hybrid composites.

    Science.gov (United States)

    Ehlert, Gregory J; Galan, Ulises; Sodano, Henry A

    2013-02-01

    Low interface strength is a persistent problem in composite materials and cascades to limit a variety of bulk material properties such as lamina shear strength. Whiskerization has long been pursued as a method to reinforce the interphase and improve both the single fiber interface strength as well as the bulk properties. Recent developments have shown that ZnO nanowire whiskerization can effectively improve the properties of a bulk composite without requiring the high temperatures that previous deposition processes needed. Although the efficacy of a ZnO nanowire interphase has been established, the mechanism for adhesion of the interphase to the fiber has not been identified. Specifically, the addition of the ZnO nanowires to the surface of the fibers requires that the ZnO nanowires have strong chemical adhesion to the fiber surface. This work will create a variety of chemical environments on the surface of the fibers through new and common chemical functionalization procedures and quantify the surface chemistry through X-ray photoelectron spectroscopy. The effect of fiber surface chemistry on the adhesion of the ZnO is assessed through single fiber fragmentation testing. The interface strength is found to strongly correlate with the concentration of ketone groups on the surface of the fibers. Following the experimental observations, liftoff of a ZnO crystal from a graphene surface was simulated with a variety of surface functionalizations. The computational models confirm the preference for ketone groups in promoting adhesion between ZnO and graphite.

  14. Electrochemical functionalization of carbon surfaces by aromatic azide or alkyne molecules: a versatile platform for click chemistry.

    Science.gov (United States)

    Evrard, David; Lambert, François; Policar, Clotilde; Balland, Véronique; Limoges, Benoît

    2008-01-01

    The electrochemical reduction of phenylazide or phenylacetylene diazonium salts leads to the grafting of azido or ethynyl groups onto the surface of carbon electrodes. In the presence of copper(I) catalyst, these azide- or alkyne-modified surfaces react efficiently and rapidly with compounds bearing an acetylene or azide function, thus forming a covalent 1,2,3-triazole linkage by means of click chemistry. This was illustrated with the surface coupling of ferrocenes functionalized with an ethynyl or azido group and the biomolecule biotin terminated by an acetylene group.

  15. Transport of oxidized multi-walled carbon nanotubes through silica based porous media: influences of aquatic chemistry, surface chemistry, and natural organic matter.

    Science.gov (United States)

    Yang, Jin; Bitter, Julie L; Smith, Billy A; Fairbrother, D Howard; Ball, William P

    2013-12-17

    This paper provides results from studies of the transport of oxidized multi-walled carbon nanotubes (O-MWCNTs) of varying surface oxygen concentrations under a range of aquatic conditions and through uniform silica glass bead media. In the presence of Na(+), the required ionic strength (IS) for maximum particle attachment efficiency (i.e., the critical deposition concentration, or CDC) increased as the surface oxygen concentration of the O-MWCNTs or pH increased, following qualitative tenets of theories based on electrostatic interactions. In the presence of Ca(2+), CDC values were lower than those with Na(+) present, but were no longer sensitive to surface oxygen content, suggesting that Ca(2+) impacts the interactions between O-MWCNTs and glass beads by mechanisms other than electrostatic alone. The presence of Suwannee River natural organic matter (SRNOM) decreased the attachment efficiency of O-MWCNTs in the presence of either Na(+) or Ca(2+), but with more pronounced effects when Na(+) was present. Nevertheless, low concentrations of SRNOM (organic carbon) were sufficient to mobilize all O-MWCNTs studied at CaCl2 concentrations as high as 10 mM. Overall, this study reveals that NOM content, pH, and cation type show more importance than surface chemistry in affecting O-MWCNTs deposition during transport through silica-based porous media.

  16. Nanomaterial-Based Electrochemical Biosensors and Bioassays

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Guodong; Mao, Xun; Gurung, Anant; Baloda, Meenu; Lin, Yuehe; He, Yuqing

    2010-08-31

    This book chapter summarizes the recent advance in nanomaterials for electrochemical biosensors and bioassays. Biofunctionalization of nanomaterials for biosensors fabrication and their biomedical applications are discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yan-Juan [School of Chemical Engineering, Xiangtan University, Xiangtan 411105 (China); Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 36102 (China); Xing, Zhen-Jiao [Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 36102 (China); Duan, Zheng-Kang [School of Chemical Engineering, Xiangtan University, Xiangtan 411105 (China); Meng Li [Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 36102 (China); Wang, Yin, E-mail: yinwang@iue.ac.cn [Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 36102 (China)

    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 cm{sup 3} min{sup −1}. Under these conditions, AC with a BET surface area of 1210 m{sup 2} g{sup −1} and total pore volume of 0.542 cm{sup −3} g{sup −1}was 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{sup −1} for methylene blue (MB), which demonstrates its excellent potential for MB adsorption applications.

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

    Science.gov (United States)

    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.

  19. Dual-switchable surfaces between hydrophobic and superhydrophobic fabricated by the combination of click chemistry and RAFT

    Directory of Open Access Journals (Sweden)

    M. S. Han

    2014-07-01

    Full Text Available A dual-switchable surface between hydrophobic and superhydrophobic has been fabricated successfully by combining reversible addition-fragmentation chain transfer polymerization (RAFT polymeric technology and thiol-NCO click chemistry. Well-defined block copolymer, poly(7-(6-(acryloyloxy hexyloxy coumarin-b-poly(N-Isopropylacryl amide, was synthesized by RAFT, and then the block copolymer was grafted onto the surface of SiO2 modified by toluene disocynate (TDI via thiol-NCO click chemistry. The results of nuclear magnetic resonance (NMR and Fourier Transform Infrared (FTIR spectroscopies confirmed that the block copolymer (Number average molecular weight (Mn = 9400, polydispersity index (PDI = 1.22 has been synthesized successfully. The static contact angle (CA of the surface prepared by SiO2/P (7-6-AC-b-PNIPAAm switches from 98±2 to 137±2° by adjusting the temperature. Furthermore, the contact angle can also oscillate between 137±2 and 157±2° on the irradiation of UV light at 365 and 254 nm, respectively. The dual-switchable surfaces exhibit high stability between hydrophilicity and superhydrophobicity. Therefore, the method provides a new method to fabricate the dual-stimuli-responsive surface with tunable wettability, reversible switching, and also be easily extended to other dual-responsive surfaces. This ability to control the wettability by the adjustment of the temperature and UV light has applications in a broad range of fields.

  20. Efficient functionalization of oxide-free silicon(111) surfaces: thiol-yne versus thiol-ene click chemistry.

    Science.gov (United States)

    Bhairamadgi, Nagendra S; Gangarapu, Satesh; Caipa Campos, Mabel A; Paulusse, Jos M J; van Rijn, Cees J M; Zuilhof, Han

    2013-04-09

    Thiol-yne click (TYC) chemistry was utilized as a copper-free click reaction for the modification of alkyne-terminated monolayers on oxide-free Si(111) surfaces, and the results were compared with the analogous thiol-ene click (TEC) chemistry. A wide range of thiols such as 9-fluorenylmethoxy-carbonyl cysteine, thio-β-d-glucose tetraacetate, thioacetic acid, thioglycerol, thioglycolic acid, and 1H,1H,2H,2H-perfluorodecanethiol was immobilized using TYC under photochemical conditions, and all modified surfaces were characterized by static water contact angle measurements, X-ray photoelectron spectroscopy (including a simulation thereof by density functional calculations), and infrared absorption reflection spectroscopy. Surface-bound TYC proceeds with an efficiency of up to 1.5 thiols per alkyne group. This high surface coverage proceeds without oxidizing the Si surface. TYC yielded consistently higher surface coverages than TEC, due to double addition of thiols to alkyne-terminated monolayers. This also allows for the sequential and highly efficient attachment of two different thiols onto an alkyne-terminated monolayer.

  1. Bioconjugation of trypsin onto gold nanoparticles: Effect of surface chemistry on bioactivity

    Energy Technology Data Exchange (ETDEWEB)

    Hinterwirth, Helmut; Lindner, Wolfgang [Department of Analytical Chemistry, University of Vienna, Waehringerstrasse 38, 1090 Vienna (Austria); Laemmerhofer, Michael, E-mail: michael.laemmerhofer@uni-tuebingen.de [Department of Analytical Chemistry, University of Vienna, Waehringerstrasse 38, 1090 Vienna (Austria)

    2012-07-06

    Highlights: Black-Right-Pointing-Pointer Size and spacer affect bioactivity of nanoparticulate trypsin reactor. Black-Right-Pointing-Pointer Increase of GNP's size increases activity of bound trypsin. Black-Right-Pointing-Pointer Increase of spacer length increases amount and activity of immobilized enzyme by factor 6. Black-Right-Pointing-Pointer Decrease of digestion time up to less than 1 h when trypsin immobilized onto GNPs. Black-Right-Pointing-Pointer Reduced auto-digestion compared to trypsin in-solution. - Abstract: The systematic study of activity, long-time stability and auto-digestion of trypsin immobilized onto gold nanoparticles (GNPs) is described in this paper and compared to trypsin in-solution. Thereby, the influence of GNP's size and immobilization chemistry by various linkers differing in lipophilicity/hydrophilicity and spacer lengths was investigated with regard to the bioactivity of the conjugated enzyme. GNPs with different sizes were prepared by reduction and simultaneous stabilization with trisodium citrate and characterized by UV/vis spectra, dynamic light scattering (DLS), {zeta}-potential measurements and transmission electron microscopy (TEM). GNPs were derivatized by self-assembling of bifunctional thiol reagents on the nanoparticle (NP) surface via dative thiol-gold bond yielding a carboxylic acid functionalized surface. Trypsin was either attached directly via hydrophobic and ionic interactions onto the citrate stabilized GNPs or immobilized via EDC/NHS bioconjugation onto the carboxylic functionalized GNPs, respectively. The amount of bound trypsin was quantified by measuring the absorbance at 280 nm. The activity of bound enzyme and its Michaelis Menten kinetic parameter K{sub m} and v{sub max} were measured by the standard chromogenic substrate N{sub {alpha}}-Benzoyl-DL-arginine 4-nitroanilide hydrochloride (BApNA). Finally, digestion of a standard protein mixture with the trypsin-conjugated NPs followed by analysis with

  2. Nickel-free manganese bearing stainless steel in alkaline media-Electrochemistry and surface chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Elsener, B., E-mail: belsener@unica.i [Dipartimento di Chimica Inorganica ed Analitica, Universita di Cagliari, SS 554 bivio per Sestu, I-09042 Monserrato (Italy); ETH Zurich, Institute for Building Materials, ETH Hoenggerberg, CH-8093 Zurich (Switzerland); Addari, D. [Dipartimento di Chimica Inorganica ed Analitica, Universita di Cagliari, SS 554 bivio per Sestu, I-09042 Monserrato (Italy); Coray, S. [ETH Zurich, Institute for Building Materials, ETH Hoenggerberg, CH-8093 Zurich (Switzerland); Rossi, A., E-mail: rossi@unica.i [Dipartimento di Chimica Inorganica ed Analitica, Universita di Cagliari, SS 554 bivio per Sestu, I-09042 Monserrato (Italy)

    2011-04-30

    Research highlights: {yields} New nickel-free manganese bearing 18Cr18Mn2Mo stainless steel in alkaline media. {yields} XPS analysis shows Mo(VI) enrichment up to 6% in the passive film upon ageing. {yields} No pitting corrosion in alkaline media (pH 13) up to 4 M NaCl (14 wt%). {yields} Promising alternative stainless steel for reinforcement in concrete. - Abstract: The use of austenitic nickel-containing stainless steels as concrete reinforcement offers excellent corrosion protection for concrete structures in harsh chloride bearing environments but is often limited due to the very high costs of these materials. Manganese bearing nickel-free stainless steels can be a cost-effective alternative for corrosion resistant reinforcements. Little, however, is known about the electrochemistry and even less on surface chemistry of these materials in alkaline media simulating concrete pore solutions. In this work a combined electrochemical (ocp = open circuit potential) and XPS (X-ray photoelectron spectroscopy) surface analytical investigation on the austenitic manganese bearing DIN 1.4456 (X8CrMnMoN18-18-2) stainless steel immersed into 0.1 M NaOH and more complex alkaline concrete pore solutions was performed. The results show that the passive film composition changes with immersion time, being progressively enriched in chromium oxy-hydroxide becoming similar to the conventional nickel-containing stainless steels. The composition of the metal interface beneath the passive film is strongly depleted in manganese and enriched in iron; chromium has nearly the nominal composition. The results are discussed regarding the film growth mechanism (ageing) of the new nickel-free stainless steel in alkaline solutions compared to traditional austenitic steels. Combining the results from pitting potential measurements with the composition of the passive film and the underlying metal interface, it can be concluded that the resistance against localized corrosion of the new nickel

  3. Polydopamine meets solid-state nanopores: a bioinspired integrative surface chemistry approach to tailor the functional properties of nanofluidic diodes.

    Science.gov (United States)

    Pérez-Mitta, Gonzalo; Tuninetti, Jimena S; Knoll, Wolfgang; Trautmann, Christina; Toimil-Molares, María Eugenia; Azzaroni, Omar

    2015-05-13

    The ability to modulate the surface chemical characteristics of solid-state nanopores is of great interest as it provides the means to control the macroscopic response of nanofluidic devices. For instance, controlling surface charge and polarity of the pore walls is one of the most important applications of surface modification that is very relevant to attain accurate control over the transport of ions through the nanofluidic architecture. In this work, we describe a new integrative chemical approach to fabricate nanofluidic diodes based on the self-polymerization of dopamine (PDOPA) on asymmetric track-etched nanopores. Our results demonstrate that PDOPA coating is not only a simple and effective method to modify the inner surface of polymer nanopores fully compatible with the fabrication of nanofluidic devices but also a versatile platform for further integration of more complex molecules through different covalent chemistries and self-assembly processes. We adjusted the chemical modification strategy to obtain various configurations of the pore surface: (i) PDOPA layer was used as primer, precursor, or even responsive functional coating; (ii) PDOPA layer was used as a platform for anchoring chemical functions via the Michael addition reaction; and (iii) PDOPA was used as a reactive layer inducing the metallization of the pore walls through the in situ reduction of metallic precursors present in solution. We believe that the transversal concept of integrative surface chemistry offered by polydopamine in combination with the remarkable physical characteristics of asymmetric nanopores constitutes a new framework to design multifunctional nanofluidic devices employing soft chemistry-based nanofunctionalization techniques.

  4. Characterization of surface chemistry and crystallization behavior of polypropylene composites reinforced with wood flour, cellulose, and lignin during accelerated weathering

    Energy Technology Data Exchange (ETDEWEB)

    Peng, Yao; Liu, Ru; Cao, Jinzhen, E-mail: caoj@bjfu.edu.cn

    2015-03-30

    Highlights: • AFM was firstly used to characterize the surface morphology and roughness of weathered wood–plastic composites. • Composites containing lignin showed less loss of flexural strength and modulus and less roughness on weathered surface compared with lignin-free composites. • ATR-FTIR and XPS analyses demonstrated in detail that significant chemistry changes occurred in wood flour, lignin, and cellulose. • The crystallinity of PP increased in all weathered samples due to chain scissions and recrystallization. • The stabilization and antioxidation effects of lignin were proved. - Abstract: In this study, six groups of polypropylene composites reinforced with wood flour (WF), cellulose, and lignin at different loading levels were exposed in a QUV accelerated weathering tester for a total duration of 960 h. The changes in surface morphology, chemistry, and thermal properties of weathered samples were characterized by atomic force microscope (AFM), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and differential scanning calorimetric (DSC), respectively. The flexural properties of all samples were tested after different durations of weathering. The results showed that: (1) the surface roughness of all samples increased after weathering; (2) composites containing lignin showed less loss of flexural strength and modulus and less roughness on weathered surface compared with lignin-free composites, indicating the functions of stabilization and antioxidation of lignin; (3) the crystallinity of PP increased in all weathered samples due to chain scissions and recrystallization; (4) ATR-FTIR and XPS analyses demonstrated in detail that significant changes occurred in surface chemistry, accompanied by the photodegradation and photo-oxidation of lignin and cellulose with prolonged weathering time.

  5. Influence of surface chemistry on the structural organization of monomolecular protein layers adsorbed to functionalized aqueous interfaces

    DEFF Research Database (Denmark)

    Lösche, M.; Piepenstock, M.; Diederich, A.;

    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...... 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...

  6. Experimental Investigations of Water Quality: The Bioassay.

    Science.gov (United States)

    Havel, John E.; And Others

    1997-01-01

    Describes a bioassay laboratory exercise designed to introduce students to both acute and chronic bioassay procedures. Reinforces ecological principles and provides opportunities for students to use knowledge learned in the classroom in a realistic and ecologically-relevant situation. Contains 11 references. (JRH)

  7. Nanoparticle-Based Biosensors and Bioassays

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Guodong; Wang, Jun; Lin, Yuehe; Wang, Joseph

    2007-10-11

    In this book chapter, we review the recent advances in nanoparticles based bioassay. The nanoparticles include quantum dots, silica nanoparticles and apoferritin nanoparticles. The new nanoparticles-based labels hold great promise for multiplex protein and DNA detection and for enhancing the sensitivity of other bioassays.

  8. Rapid bioassay for oil-contaminated soil

    Energy Technology Data Exchange (ETDEWEB)

    Ashworth, J. [ALS Environmental, Edmonton, AB (Canada); Oosterbroek, L. [HydroQual, Calgary, AB (Canada)

    2010-07-01

    This PowerPoint presentation described a study conducted to develop a rapid bioassay for soils contaminated with oil. The bioassay method was designed for a weight of evidence (WoE) approach and eco-contact guideline derivation protocol. Microtox bioassays were conducted on cyclodextrin extracts of soil quantified by solvent extraction and gas chromatography. The method was demonstrated using straight {beta}-cyclodextrin soil extracts and activated {beta}-cyclodextrin soil extracts. An analysis of the methods showed that the activation step weakens or breaks the cyclodextrin and polycyclic hydrocarbon (PHC) inclusion complex. The released PHC became toxic to the microtox organism. Results from the bioassays were then correlated with earthworm reproduction bioassay results. tabs., figs.

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

    Science.gov (United States)

    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

  10. Characterization of surface chemistry and crystallization behavior of polypropylene composites reinforced with wood flour, cellulose, and lignin during accelerated weathering

    Science.gov (United States)

    Peng, Yao; Liu, Ru; Cao, Jinzhen

    2015-03-01

    In this study, six groups of polypropylene composites reinforced with wood flour (WF), cellulose, and lignin at different loading levels were exposed in a QUV accelerated weathering tester for a total duration of 960 h. The changes in surface morphology, chemistry, and thermal properties of weathered samples were characterized by atomic force microscope (AFM), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and differential scanning calorimetric (DSC), respectively. The flexural properties of all samples were tested after different durations of weathering. The results showed that: (1) the surface roughness of all samples increased after weathering; (2) composites containing lignin showed less loss of flexural strength and modulus and less roughness on weathered surface compared with lignin-free composites, indicating the functions of stabilization and antioxidation of lignin; (3) the crystallinity of PP increased in all weathered samples due to chain scissions and recrystallization; (4) ATR-FTIR and XPS analyses demonstrated in detail that significant changes occurred in surface chemistry, accompanied by the photodegradation and photo-oxidation of lignin and cellulose with prolonged weathering time.

  11. Organic Chemistry in Two Dimensions: Surface-Functionalized Polymers and Self-Assembled Monolayer Films

    Science.gov (United States)

    1988-09-01

    adhesion. inhibition of corrosion , and control of friction, and they may prove important in the production of sensors and microelectronic devices. The...Materials Science 650 Harry Road K91B801 and Engineering San Jose, CA 95120 Cornell University Ithaca, Nem York 14853-1501 Or. William B. Moniz Chemistry Division Naval Research Laboratory Washington, D.C. 20375-5000

  12. Genotoxicity of copper oxide nanoparticles with different surface chemistry on rat bone marrow mesenchymal stem cells

    DEFF Research Database (Denmark)

    Zhang, Wenjing; Jiang, Pengfei; Chen, Wei

    2016-01-01

    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...... impact on the differentiation potential of the MSCs....

  13. Surface modification of poly(D,L-lactic acid) scaffolds for orthopedic applications: a biocompatible, nondestructive route via diazonium chemistry.

    Science.gov (United States)

    Mahjoubi, Hesameddin; Kinsella, Joseph M; Murshed, Monzur; Cerruti, Marta

    2014-07-09

    Scaffolds made with synthetic polymers such as polyesters are commonly used in bone tissue engineering. However, their hydrophobicity and the lack of specific functionalities make their surface not ideal for cell adhesion and growth. Surface modification of these materials is thus crucial to enhance the scaffold's integration in the body. Different surface modification techniques have been developed to improve scaffold biocompatibility. Here we show that diazonium chemistry can be used to modify the outer and inner surfaces of three-dimensional poly(D,L-lactic acid) (PDLLA) scaffolds with phosphonate groups, using a simple two-step method. By changing reaction time and impregnation procedure, we were able to tune the concentration of phosphonate groups present on the scaffolds, without degrading the PDLLA matrix. To test the effectiveness of this modification, we immersed the scaffolds in simulated body fluid, and characterized them with scanning electron microscopy, X-ray photoelectron spectroscopy, Raman, and infrared spectroscopy. Our results showed that a layer of hydroxyapatite particles was formed on all scaffolds after 2 and 4 weeks of immersion; however, the precipitation was faster and in larger amounts on the phosphonate-modified than on the bare PDLLA scaffolds. Both osteogenic MC3T3-E1 and chondrogenic ATDC5 cell lines showed increased cell viability/metabolic activity when grown on a phosphonated PDLLA surface in comparison to a control PDLLA surface. Also, more calcium-containing minerals were deposited by cultures grown on phosphonated PDLLA, thus showing the pro-mineralization properties of the proposed modification. This work introduces diazonium chemistry as a simple and biocompatible technique to modify scaffold surfaces, allowing to covalently and homogeneously bind a number of functional groups without degrading the scaffold's polymeric matrix.

  14. A Standardized Lepidopteran Bioassay to Investigate the Bioactivity of Insecticidal Proteins Produced in Transgenic Crops.

    Science.gov (United States)

    Graser, Gerson; Walters, Frederick S

    2016-01-01

    Insecticidal bioassays are the only reliable method to investigate the biological activity of an insecticidal protein and therefore provide an essential toolkit for the characterization and potency determination of these proteins. Here we present a standardized method for a lepidopteran larval bioassay, which is optimized to specifically estimate activity of insecticidal proteins produced in transgenic plants. The treatment can be either applied to the surface of the artificial diet, or blended into the diet.

  15. Cluster Chemistry

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    @@ Cansisting of eight scientists from the State Key Laboratory of Physical Chemistry of Solid Surfaces and Xiamen University, this creative research group is devoted to the research of cluster chemistry and creation of nanomaterials.After three-year hard work, the group scored a series of encouraging progresses in synthesis of clusters with special structures, including novel fullerenes, fullerene-like metal cluster compounds as well as other related nanomaterials, and their properties study.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  17. Surface modification of carbon nanotubes via combination of mussel inspired chemistry and chain transfer free radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Wan, Qing; Tian, Jianwen; Liu, Meiying; Zeng, Guangjian; Huang, Qiang [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Wang, Ke; Zhang, Qingsong [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China)

    2015-08-15

    Graphical abstract: A novel strategy combination of mussel inspired chemistry and chain transfer free radical polymerization has been developed for surface modification of carbon nanotubes with polymers for the first time. - Highlights: • Surface modification of CNTs via mussel inspired chemistry. • Preparation of aminated polymers through free radical polymerization. • Functionalized CNTs with aminated polymers via Michael addition reaction. • Highly dispersed CNTs in organic and aqueous solution. - Abstract: In this work, a novel strategy for surface modification of carbon nanotubes (CNTs) was developed via combination of mussel inspired chemistry and chain transfer free radical polymerization. First, pristine CNTs were functionalized with polydopamine (PDA), which is formed via self-polymerization of dopamine in alkaline conditions. These PDA functionalized CNTs can be further reacted with amino-terminated polymers (named as PDMC), which was synthesized through chain transfer free radical polymerization using cysteamine hydrochloride as chain transfer agent and methacryloxyethyltrimethyl ammonium chloride as the monomer. PDMC perfectly conjugated with CNT-PDA was ascertained by a series of characterization techniques including transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The dispersibility of obtained CNT nanocomposites (named as CNT-PDA-PDMC) was further examined. Results showed that the dispersibility of CNT-PDA-PDMC in aqueous and organic solutions was obviously enhanced. Apart from PDMC, many other amino-terminated polymers can also be used to functionalization of CNTs via similar strategy. Therefore, the method described in this work should be a general strategy for fabrication various polymer nanocomposites.

  18. Label-free nanopore proximity bioassay for platelet-derived growth factor detection.

    Science.gov (United States)

    Zhang, Ling; Zhang, Kaixiang; Liu, Guangchao; Liu, Mengjia; Liu, Yang; Li, Jinghong

    2015-06-02

    Rapid and sensitive detection of biomarkers with ultralow concentrations remains a great challenge in disease diagnostics. Herein, we present a label-free α-hemolysin (α-HL) nanopore proximity bioassay for protein biomarker detection by a binding-induced DNA strand displacement strategy. In this bioassay, an individual target protein, platelet-derived growth factor B-chain (PDGF-BB), was selectively recognized by two oligonucleotide affinity ligands in which an output DNA was released and translocated through α-HL nanopore with a spikelike short current block. The frequency of the current block events had a linear relationship with the concentration of PDGF-BB with a wide linear dynamic range of 5 orders of magnitude and a detection limit at 500 fM. The selectivity and anti-interference capability of this bioassay show great potential for biomarker detection in bioanalytical chemistry.

  19. Biomolecular interactions and tools for their recognition: focus on the quartz crystal microbalance and its diverse surface chemistries and applications.

    Science.gov (United States)

    Cheng, Cathy I; Chang, Yi-Pin; Chu, Yen-Ho

    2012-03-07

    Interactions between molecules are ubiquitous and occur in our bodies, the food we eat, the air we breathe, and myriad additional contexts. Although numerous tools are available for the recognition of biomolecular interactions, such tools are often limited in their sensitivity, expensive, and difficult to modify for various uses. In contrast, the quartz crystal microbalance (QCM) has sub-nanogram detection capabilities, is label-free, is inexpensive to create, and can be readily modified with a number of diverse surface chemistries to detect and characterize diverse interactions. To maximize the versatility of the QCM, scientists need to know available methods by which QCM surfaces can be modified. Therefore, in addition to summarizing the various tools currently used for biomolecular recognition, explicating the fundamental principles of the QCM as a tool for biomolecular recognition, and comparing the QCM with other acoustic sensors, we systematically review the numerous types of surface chemistries-including hydrophobic bonds, ionic bonds, hydrogen bonds, self-assembled monolayers, plasma-polymerized films, photochemistry, and sensing ionic liquids-used to functionalize QCMs for various purposes. We also review the QCM's diverse applications, which include the detection of gaseous species, detection of carbohydrates, detection of nucleic acids, detection of non-enzymatic proteins, characterization of enzymatic activity, detection of antigens and antibodies, detection of cells, and detection of drugs. Finally, we discuss the ultimate goals of and potential barriers to the development of future QCMs.

  20. Thermal modification of activated carbon surface chemistry improves its capacity as redox mediator for azo dye reduction

    OpenAIRE

    Pereira, Luciana; Pereira, Ricardo; Pereira, M. F. R.; Van der Zee, F. P.; Cervantes, F. J.; Alves, M.M.

    2010-01-01

    The surface chemistry of a commercial AC (AC0) was selectively modified, without changing significantly its textural properties, by chemical oxidation with HNO3 (ACHNO3 ) and O2 (ACO2 ), and thermal treatments under H2 (ACH2) or N2 (ACN2 ) flow. The effect of modified AC on anaerobic chemical dye reduction was assayed with sulphide at different pH values 5, 7 and 9. Four dyes were tested: Acid Orange 7, Reactive Red 2, Mordant Yellow 10 and Direct Blue 71. Batch experiments with l...

  1. Mass Spectrometric Analysis of the Cell Surface N-Glycoproteome by Combining Metabolic Labeling and Click Chemistry

    Science.gov (United States)

    Smeekens, Johanna M.; Chen, Weixuan; Wu, Ronghu

    2015-04-01

    Cell surface N-glycoproteins play extraordinarily important roles in cell-cell communication, cell-matrix interactions, and cellular response to environmental cues. Global analysis is exceptionally challenging because many N-glycoproteins are present at low abundances and effective separation is difficult to achieve. Here, we have developed a novel strategy integrating metabolic labeling, copper-free click chemistry, and mass spectrometry (MS)-based proteomics methods to analyze cell surface N-glycoproteins comprehensively and site-specifically. A sugar analog containing an azido group, N-azidoacetylgalactosamine, was fed to cells to label glycoproteins. Glycoproteins with the functional group on the cell surface were then bound to dibenzocyclooctyne-sulfo-biotin via copper-free click chemistry under physiological conditions. After protein extraction and digestion, glycopeptides with the biotin tag were enriched by NeutrAvidin conjugated beads. Enriched glycopeptides were deglycosylated with peptide- N-glycosidase F in heavy-oxygen water, and in the process of glycan removal, asparagine was converted to aspartic acid and tagged with 18O for MS analysis. With this strategy, 144 unique N-glycopeptides containing 152 N-glycosylation sites were identified in 110 proteins in HEK293T cells. As expected, 95% of identified glycoproteins were membrane proteins, which were highly enriched. Many sites were located on important receptors, transporters, and cluster of differentiation proteins. The experimental results demonstrated that the current method is very effective for the comprehensive and site-specific identification of the cell surface N-glycoproteome and can be extensively applied to other cell surface protein studies.

  2. Modulation of Protein Fouling and Interfacial Properties at Carbon Surfaces via Immobilization of Glycans Using Aryldiazonium Chemistry

    Science.gov (United States)

    Zen, Federico; Angione, M. Daniela; Behan, James A.; Cullen, Ronan J.; Duff, Thomas; Vasconcelos, Joana M.; Scanlan, Eoin M.; Colavita, Paula E.

    2016-01-01

    Carbon materials and nanomaterials are of great interest for biological applications such as implantable devices and nanoparticle vectors, however, to realize their potential it is critical to control formation and composition of the protein corona in biological media. In this work, protein adsorption studies were carried out at carbon surfaces functionalized with aryldiazonium layers bearing mono- and di-saccharide glycosides. Surface IR reflectance absorption spectroscopy and quartz crystal microbalance were used to study adsorption of albumin, lysozyme and fibrinogen. Protein adsorption was found to decrease by 30–90% with respect to bare carbon surfaces; notably, enhanced rejection was observed in the case of the tested di-saccharide vs. simple mono-saccharides for near-physiological protein concentration values. ζ-potential measurements revealed that aryldiazonium chemistry results in the immobilization of phenylglycosides without a change in surface charge density, which is known to be important for protein adsorption. Multisolvent contact angle measurements were used to calculate surface free energy and acid-base polar components of bare and modified surfaces based on the van Oss-Chaudhury-Good model: results indicate that protein resistance in these phenylglycoside layers correlates positively with wetting behavior and Lewis basicity. PMID:27108562

  3. Numerical study of the effects of surface topography and chemistry on the wetting transition using the string method

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yanan, E-mail: ynzhang@suda.edu.cn [School of Mathematical Sciences, Soochow University, Suzhou 215006 (China); Ren, Weiqing, E-mail: matrw@nus.edu.sg [Department of Mathematics, National University of Singapore, Singapore 119076 (Singapore); Institute of High Performance Computing, Singapore 138632 (Singapore)

    2014-12-28

    Droplets on a solid surface patterned with microstructures can exhibit the composite Cassie-Baxter (CB) state or the wetted Wenzel state. The stability of the CB state is determined by the energy barrier separating it from the wetted state. In this work, we study the CB to Wenzel transition using the string method [E et al., J. Chem. Phys. 126, 164103 (2007); W. Ren and E. Vanden-Eijnden, J. Chem. Phys. 138, 134105 (2013)]. We compute the transition states and energy barriers for a three-dimensional droplet on patterned surfaces. The liquid-vapor coexistence is modeled using the mean field theory. Numerical results are obtained for surfaces patterned with straight pillars and nails, respectively. It is found that on both type of surfaces, wetting occurs via infiltration of the liquid in a single groove. The reentrant geometry of nails creates large energy barrier for the wetting of the solid surface compared to straight pillars. We also study the effect of surface chemistry, pillar height, and inter-pillar spacing on the energy barrier and compare it with nails.

  4. Interfacial Atmospheric Chemistry: Quantum Chemical Calculations on the Mechanism of Protonation and Oligomerization of Isoprene on Aqueous Surfaces

    Science.gov (United States)

    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 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.

  5. Comparison of five in vitro bioassays to measure estrogenic activity in environmental waters.

    Science.gov (United States)

    Leusch, Frederic D L; de Jager, Christiaan; Levi, Yves; Lim, Richard; Puijker, Leo; Sacher, Frank; Tremblay, Louis A; Wilson, Vickie S; Chapman, Heather F

    2010-05-15

    Bioassays are well established in the pharmaceutical industry and single compound analysis, but there is still uncertainty about their usefulness in environmental monitoring. We compared the responses of five bioassays designed to measure estrogenic activity (the yeast estrogen screen, ER-CALUX, MELN, T47D-KBluc, and E-SCREEN assays) and chemical analysis on extracts from four different water sources (groundwater, raw sewage, treated sewage, and river water). All five bioassays displayed similar trends and there was good agreement with analytical chemistry results. The data from the ER-CALUX and E-SCREEN bioassays were robust and predictable, and well-correlated with predictions from chemical analysis. The T47D-KBluc appeared likewise promising, but with a more limited sample size it was less compelling. The YES assay was less sensitive than the other assays by an order of magnitude, which resulted in a larger number of nondetects. The MELN assay was less predictable, although the possibility that this was due to laboratory-specific difficulties cannot be discounted. With standardized bioassay data analysis and consistency of operating protocols, bioanalytical tools are a promising advance in the development of a tiered approach to environmental water quality monitoring.

  6. Episodic acidification of small streams in the northeastern united states: Fish mortality in field bioassays

    Science.gov (United States)

    Van Sickle, J.; Baker, J.P.; Simonin, H.A.; Baldigo, Barry P.; Kretser, W.A.; Sharpe, W.E.

    1996-01-01

    In situ bioassays were performed as part of the Episodic Response Project, to evaluate the effects of episodic stream acidification on mortality of brook trout (Salvelinus fontinalis) and forage fish species. We report the results of 122 bioassays in 13 streams of the three study regions: the Adirondack mountains of New York, the Catskill mountains of New York, and the Northern Appalachian Plateau of Pennsylvania. Bioassays during acidic episodes had significantly higher mortality than did bioassays conducted under nonacidic conditions, but there was little difference in mortality rates in bioassays experiencing acidic episodes and those experiencing acidic conditions throughout the test period. Multiple logistic regression models were used to relate bioassay mortality rates to summary statistics of time-varying stream chemistry (inorganic monomeric aluminum, calcium, pH, and dissolved organic carbon) estimated for the 20-d bioassay periods. The large suite of candidate regressors also included biological, regional, and seasonal factors, as well as several statistics summarizing various features of aluminum exposure duration and magnitude. Regressor variable selection and model assessment were complicated by multicol-linearity and overdispersion. For the target fish species, brook trout, bioassay mortality was most closely related to time-weighted median inorganic aluminum. Median Ca and minimum pH offered additional explanatory power, as did stream-specific aluminum responses. Due to high multicollinearity, the relative importance of different aluminum exposure duration and magnitude variables was difficult to assess, but these variables taken together added no significant explanatory power to models already containing median aluminum. Between 59 and 79% of the variation in brook trout mortality was explained by models employing between one and five regressors. Simpler models were developed for smaller sets of bioassays that tested slimy and mottled sculpin

  7. A Shrinkage Estimator for Combination of Bioassays

    Institute of Scientific and Technical Information of China (English)

    Jian Xiong; D.G. Chen; Zhen-hai Yang

    2007-01-01

    A shrinkage estimator and a maximum likelihood estimator are proposed in this paper for combination of bioassays. The shrinkage estimator is obtained in closed form which incorporates prior information just on the common log relative potency after the homogeneity test for combination of bioassays is accepted. It is a practical improvement over other estimators which require iterative procedure to obtain the estimator for the relative potency. A real data is also used to show the superiorities for the newly-proposed procedures.

  8. Thermal chemistry of hydrazine on clean and oxygen- and water-predosed Cu(110) single-crystal surfaces

    Science.gov (United States)

    Yao, Yunxi; Zaera, Francisco

    2016-08-01

    The chemistry of hydrazine on Cu(110) single-crystal surfaces was probed under ultrahigh vacuum (UHV) conditions by temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). Survey TPD experiments identified molecular nitrogen and ammonia as the main desorbing products from thermal activation of the adsorbate, but small amounts of diazene and NH2· radicals were also detected. At saturation coverage, N2 production leads NH3 desorption by approximately 10 K (with TPD peaks at 350 K versus 360 K, respectively), indicating a preference for dehydrogenation over N-N bond scission steps, and additional nitrogen was seen at even lower temperatures (320 K) in experiments starting with even higher doses of hydrazine. On the other hand, the formation of NH3 and NH2·, which desorb in a wide range of temperatures between approximately 300 K and 700 K, dominates in experiments with low N2H4 doses, presumably because a stronger interaction of the N-N bond with the metal in the flat adsorption geometry expected at such low coverages. Dosing at room temperature seems to also facilitate the dissociative adsorption, albeit via dehydrogenation steps that lead to the subsequent production of more significant amounts of diazene and of molecular hydrogen (in addition to N2, NH3, and NH2·). Preadsorption of oxygen on the Cu(110) surface helps stabilize the hydrazine, increasing its desorption temperature and helping with the low-temperature (320 K) production of N2. Coadsorption of hydrazine with water leads to facile proton exchange, as indicated by the production of NH2D in TPD experiments with N2H4 + D2O. This isotope scrambling must occur at cryogenic temperatures because all water desorbs from the surface below 200 K and no other changes in surface chemistry are observed after that. The implications of all this chemistry to practical applications that may use hydrazine in surface reactions with copper, including its use as a reducing agent in atomic layer

  9. Characterization and stability of gold nanoparticles depending on their surface chemistry: Contribution of capillary zone electrophoresis to a quality control.

    Science.gov (United States)

    Pallotta, Arnaud; Boudier, Ariane; Leroy, Pierre; Clarot, Igor

    2016-08-26

    Four kinds of gold nanoparticles (AuNP) quite similar in terms of gold core size (ca. 5nm) and shape (spherical) but differing by their surface chemistry (either negatively, or positively charged, or neutral) were synthesized. They were analyzed using both the classical physicochemical approach (spectrophotometry, dynamic light scattering coupled or not to electrophoresis and transmission electron microscopy) and capillary zone electrophoresis equipped with photodiode array detection. The results obtained by both methodologies (related to Surface Plasmon Band-maximal absorbance wavelength-, and zeta potential and electrophoretic mobilities) were well correlated. Moreover, taking advantage of the separation method, the sample heterogeneity was evaluated and an impurity profile was extracted. This allowed setting some specifications which were then applied on the one hand to a batch-to-batch survey to declare NP as conform or not after production and on the other hand to a stability study.

  10. Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst.

    Science.gov (United States)

    Merle, Nicolas; Le Quéméner, Frédéric; Bouhoute, Yassine; Szeto, Kai C; De Mallmann, Aimery; Barman, Samir; Samantaray, Manoja K; Delevoye, Laurent; Gauvin, Régis M; Taoufik, Mostafa; Basset, Jean-Marie

    2017-02-15

    The well-defined silica-supported molybdenum oxo alkyl species (≡SiO-)MoO(CH2(t)Bu)3 was selectively prepared by grafting of MoO(CH2(t)Bu)3Cl onto partially dehydroxylated silica (silica700) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO3/SiO2 olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

  11. Dielectric properties of nanosilica/low-density polyethylene composites: The surface chemistry of nanoparticles and deep traps induced by nanoparticles

    Directory of Open Access Journals (Sweden)

    S. Ju

    2014-09-01

    Full Text Available Four kinds of nanosilica particles with different surface modification were employed to fabricate low-density polyethylene (LDPE composites using melt mixing and hot molding methods. The surface chemistry of modified nanosilica was analyzed by X-ray photoelectron spectroscopy. All silica nanoparticles were found to suppress the space charge injection and accumulation, increase the volume resistivity, decrease the permittivity and dielectric loss factor at low frequencies, and decrease the dielectric breakdown strength of the LDPE polymers. The modified nanoparticles, in general, showed better dielectric properties than the unmodified ones. It was found that the carrier mobility, calculated from J–V curves using the Mott-Gurney equation, was much lower for the nanocomposites than for the neat LDPE.

  12. Influence of corrosive solutions on microhardness and chemistry of magnesium oxide /001/ surfaces

    Science.gov (United States)

    Ishigaki, H.; Miyoshi, K.; Buckley, D. H.

    1982-01-01

    X-ray photoelectron spectroscopy analyses and hardness experiments were conducted on cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved to specimen size along the /001/ surface, and indentations were made on the cleaved surface in corrosive solutions containing HCl, NaOH, or HNO3 and in water without exposing the specimen to any other environment. The results indicated that chloride (such as MgCl2) and sodium films are formed on the magnesium oxide surface as a result of interactions between an HCl-containing solution and a cleaved magnesium oxide surface. The chloride films soften the magnesium oxide surface. In this case microhardness is strongly influenced by the pH value of the solution. The lower the pH, the lower the microhardness. Sodium films, which are formed on the magnesium oxide surface exposed to an NaOH containing solution, do not soften the magnesium oxide surface.

  13. Supported organometallic complexes: Surface chemistry, spectroscopy, and catalysis. Progress report, March 15, 1988--July 14, 1989

    Energy Technology Data Exchange (ETDEWEB)

    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.

  14. Surface chemistry and moisture sorption properties of wood coated with multifunctional alkoxysilanes by sol-gel process

    DEFF Research Database (Denmark)

    Tshabalala, M.A.; Kingshott, P.; VanLandingham, M.R.

    2003-01-01

    Sol-gel surface deposition of a hydrophobic polysiloxane coating on wood was accomplished by using a mixture of a low molecular weight multifunctional alkoxysilane, methyltrimethoxysilane (MTMOS), and a high molecular weight multifunctional alkoxysilane, hexadecyltrimethoxysilane (HDTMOS). Invest......Sol-gel surface deposition of a hydrophobic polysiloxane coating on wood was accomplished by using a mixture of a low molecular weight multifunctional alkoxysilane, methyltrimethoxysilane (MTMOS), and a high molecular weight multifunctional alkoxysilane, hexadecyltrimethoxysilane (HDTMOS......). Investigation of the surface chemistry and morphology of the wood specimens by means of ATR-FTIR, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, SEM, and atomic force microscopy indicated that the sol-gel process results in deposition of polysiloxane networks that are bonded to the wood...... by polycondensation with surface hydroxyl groups. The surface hydroxyl groups involved in the bonds appear to be located predominantly on the cellulose component of the wood. The sol-gel deposit on the wood substrates lowered the rates of water and water vapor sorption. The low molecular weight MTMOS apparently...

  15. The surface chemistry resulting from low-pressure plasma treatment of polystyrene: The effect of residual vessel bound oxygen

    Science.gov (United States)

    Dhayal, Marshal; Alexander, Morgan R.; Bradley, James W.

    2006-09-01

    The surface chemistry of plasma treated polystyrene samples has been studied in a specially designed low-pressure argon discharge system incorporating in situ XPS analysis. By using an electrostatic grid biasing technique, the plasma source can also be used in a mode preventing ion interactions with the sample. The system, which utilizes a vacuum transfer chamber between plasma and XPS analysis has allowed us to differentiate between the level of oxygen incorporated at the polystyrene surface from residual gas during treatment and that from the exposure of the treated sample to the laboratory atmosphere. Using typical base pressures of about 5 × 10 -3 Pa (4 × 10 -5 Torr) the XPS results show that significant oxygen surface incorporation resulted from oxygen containing species in the plasma itself (i.e. water vapour with 2 × 10 -3 Pa partial pressure). The surface concentration of O was measured at 7.6 at.%. Subsequent atmospheric exposure of the treated samples resulted in only a small increase (of 0.6 at.%) in oxygen incorporation in the form of acid anhydride functionalities. XPS measurements of PS samples exposed to plasmas with no ion-surface component (i.e. exposure from VUV, UV and excited neutral species only) showed no appreciable change in oxygen incorporation compared to those with low-energy ion bombardment from the plasma (free radical sites in this discharge regime.

  16. Adsorption and enzymatic cleavage of osteopontin at interfaces with different surface chemistries

    DEFF Research Database (Denmark)

    Malmström, Jenny; Shipovskov, Stepan; Christensen, Brian;

    2009-01-01

    was able to bind and cleave the surface bound osteopontin at the hydrophobic surface. The altered levels of osteopontin binding, hydration of the layer, and susceptibility to thrombin cleavage suggest that osteopontin adopts different conformations and/or orientations at the different material surfaces....... with respect to post-translational modifications. Osteopontin adsorbed at all the surfaces formed thin (approximately 2-5 nm) hydrated layers with the highest amount of protein and the highest density layers observed at the hydrophobic surface. Less protein and a higher level of hydration was observed...

  17. Hot wire chemical vapor deposition chemistry in the gas phase and on the catalyst surface with organosilicon compounds.

    Science.gov (United States)

    Shi, Yujun

    2015-02-17

    shown that ring-opening reactions play a vital role in characterizing the reaction chemistry. On the other hand, exocyclic Si-H(CH3) bond cleavages are more important in the less-puckered disilacyclobutane molecules. Metal filaments are essential in HWCVD since they serve as catalysts to decompose precursor gases to reactive species, which initiate gas-phase reaction chemistry and thin film growth. We discuss the structural changes in metal filaments when exposed to various precursor gases. Depending on the nature of the radical intermediates formed from the hot-wire decomposition and subsequent gas-phase reactions, metal silicides and carbides can be formed. Overall, study of the gas-phase reaction chemistry in HWCVD provides important knowledge of the chemical species produced prior to their deposition on a substrate surface. This helps in identifying the major contributor to alloy formation on the filament itself and the film growth, and consequently, in determining the properties of the deposited films. An integrated knowledge of the gas-phase reaction chemistry, filament alloy formation, and thin film deposition is required for an efficient deposition of high-quality thin films and nanomaterials.

  18. Surface Wettability and Chemistry of Ozone Perfusion Processed Porous Collagen Scaffold

    Institute of Scientific and Technical Information of China (English)

    Chaozong Liu; Shirley Z. Shen; Zhiwu Han

    2011-01-01

    Crosslinking treatment of collagen has often been used to improve the biological stability and mechanical properties of 3D porous collagen scaffolds. However, accompanying these improvements, the collagen fibril surface becomes hydrophobic nature resulting in a reduced surface wettability. The wetting of the collagen fibril by culture medium is reduced and it is difficult for the medium to diffuse into the 3D structure of a porous collagen scaffold. This paper reports a "perfusion processing"strategy using ozone to improve the surface wettability of chemical crosslinked collagen scaffolds. Surface wettability, surface composition and biological stability were analyzed to evaluate the effectiveness of this surface processing strategy. It was observed that ozone perfusion processing improved surface wettability for both exterior and interior surfaces of the porous 3D collagen scaffold. The improvement in wettability is attributed to the incorporation of oxygen-containing functional groups onto the surface of the collagen fibrils, as confirmed by X-ray Photoelectron Spectroscopy (XPS) analysis. This leads to a significant improvement in water taking capability without compromising the bulk biological stability and mechanical properties, and confirms that ozone perfusion processing is an effective tool to modify the wettability both for interior and exterior surfaces throughout the scaffold.

  19. Specific uptake and genotoxicity induced by polystyrene nanobeads with distinct surface chemistry on human lung epithelial cells and macrophages.

    Science.gov (United States)

    Paget, Vincent; Dekali, Samir; Kortulewski, Thierry; Grall, Romain; Gamez, Christelle; Blazy, Kelly; Aguerre-Chariol, Olivier; Chevillard, Sylvie; Braun, Anne; Rat, Patrice; Lacroix, Ghislaine

    2015-01-01

    Nanoparticle surface chemistry is known to play a crucial role in interactions with cells and their related cytotoxic effects. As inhalation is a major route of exposure to nanoparticles, we studied specific uptake and damages of well-characterized fluorescent 50 nm polystyrene (PS) nanobeads harboring different functionalized surfaces (non-functionalized, carboxylated and aminated) on pulmonary epithelial cells and macrophages (Calu-3 and THP-1 cell lines respectively). Cytotoxicity of in mass dye-labeled functionalized PS nanobeads was assessed by xCELLigence system and alamarBlue viability assay. Nanobeads-cells interactions were studied by video-microscopy, flow cytometry and also confocal microscopy. Finally ROS generation was assessed by glutathione depletion dosages and genotoxicity was assessed by γ-H2Ax foci detection, which is considered as the most sensitive technique for studying DNA double strand breaks. The uptake kinetic was different for each cell line. All nanobeads were partly adsorbed and internalized, then released by Calu-3 cells, while THP-1 macrophages quickly incorporated all nanobeads which were located in the cytoplasm rather than in the nuclei. In parallel, the genotoxicity study reported that only aminated nanobeads significantly increased DNA damages in association with a strong depletion of reduced glutathione in both cell lines. We showed that for similar nanoparticle concentrations and sizes, aminated polystyrene nanobeads were more cytotoxic and genotoxic than unmodified and carboxylated ones on both cell lines. Interestingly, aminated polystyrene nanobeads induced similar cytotoxic and genotoxic effects on Calu-3 epithelial cells and THP-1 macrophages, for all levels of intracellular nanoparticles tested. Our results strongly support the primordial role of nanoparticles surface chemistry on cellular uptake and related biological effects. Moreover our data clearly show that nanoparticle internalization and observed adverse effects

  20. Specific Uptake and Genotoxicity Induced by Polystyrene Nanobeads with Distinct Surface Chemistry on Human Lung Epithelial Cells and Macrophages

    Science.gov (United States)

    Kortulewski, Thierry; Grall, Romain; Gamez, Christelle; Blazy, Kelly; Aguerre-Chariol, Olivier; Chevillard, Sylvie; Braun, Anne; Rat, Patrice; Lacroix, Ghislaine

    2015-01-01

    Nanoparticle surface chemistry is known to play a crucial role in interactions with cells and their related cytotoxic effects. As inhalation is a major route of exposure to nanoparticles, we studied specific uptake and damages of well-characterized fluorescent 50 nm polystyrene (PS) nanobeads harboring different functionalized surfaces (non-functionalized, carboxylated and aminated) on pulmonary epithelial cells and macrophages (Calu-3 and THP-1 cell lines respectively). Cytotoxicity of in mass dye-labeled functionalized PS nanobeads was assessed by xCELLigence system and alamarBlue viability assay. Nanobeads-cells interactions were studied by video-microscopy, flow cytometry and also confocal microscopy. Finally ROS generation was assessed by glutathione depletion dosages and genotoxicity was assessed by γ-H2Ax foci detection, which is considered as the most sensitive technique for studying DNA double strand breaks. The uptake kinetic was different for each cell line. All nanobeads were partly adsorbed and internalized, then released by Calu-3 cells, while THP-1 macrophages quickly incorporated all nanobeads which were located in the cytoplasm rather than in the nuclei. In parallel, the genotoxicity study reported that only aminated nanobeads significantly increased DNA damages in association with a strong depletion of reduced glutathione in both cell lines. We showed that for similar nanoparticle concentrations and sizes, aminated polystyrene nanobeads were more cytotoxic and genotoxic than unmodified and carboxylated ones on both cell lines. Interestingly, aminated polystyrene nanobeads induced similar cytotoxic and genotoxic effects on Calu-3 epithelial cells and THP-1 macrophages, for all levels of intracellular nanoparticles tested. Our results strongly support the primordial role of nanoparticles surface chemistry on cellular uptake and related biological effects. Moreover our data clearly show that nanoparticle internalization and observed adverse effects

  1. Untangling the Chemical Evolution of Titan's Atmosphere and Surface -- From Homogeneous to Heterogeneous Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    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. Novel antifouling surface with improved hemocompatibility by immobilization of polyzwitterions onto silicon via click chemistry

    Science.gov (United States)

    Zheng, Sunxiang; Yang, Qian; Mi, Baoxia

    2016-02-01

    A novel procedure is presented to develop an antifouling silicon surface with improved hemocompatibility by using a zwitterionic polymer, poly(sulfobetaine methacrylate) (polySBMA). Functionalization of the silicon surface with polySBMA involved the following three steps: (1) an alkyne terminated polySBMA was synthesized by RAFT polymerization; (2) a self-assembled monolayer with bromine end groups was constructed on the silicon surface, and then the bromine end groups were replaced by azide groups; and (3) the polySBMA was attached to the silicon surface by azide-alkyne cycloaddition click reaction. Membrane characterization confirmed a successful silicon surface modification with almost 100% coverage by polySBMA and an extremely hydrophilic surface after such modification. The polySBMA-modified silicon surface was found to have excellent anti-nonspecific adsorption properties for both bovine serum albumin (BSA) protein and model bacterial cells. Whole blood adsorption experiments showed that the polySBMA-modified silicon surface exhibited excellent hemocompatibility and effective anti-adhesion to blood cells. Silicon membranes with such antifouling and hemocompatible surfaces can be advantageously used to drastically extend the service life of implantable medical devices such as artificial kidney devices.

  3. A new P. putida instrumental toxicity bioassay.

    Science.gov (United States)

    Figueredo, Federico; Abrevaya, Ximena C; Cortón, Eduardo

    2015-05-01

    Here, we present a new toxicity bioassay (CO2-TOX), able to detect toxic or inhibitory compounds in water samples, based on the quantification of Pseudomonas putida KT2440 CO2 production. The metabolically produced CO2 was measured continuously and directly in the liquid assay media, with a potentiometric gas electrode. The optimization studies were performed using as a model toxicant 3,5-DCP (3,5-dichlorophenol); later, heavy metals (Pb(2+), Cu(2+), or Zn(2+)) and a metalloid (As(5+)) were assayed. The response to toxics was evident after 15 min of incubation and at relatively low concentrations (e.g., 1.1 mg/L of 3,5-DCP), showing that the CO2-TOX bioassay is fast and sensitive. The EC50 values obtained were 4.93, 0.12, 6.05, 32.17, and 37.81 mg/L for 3,5-DCP, Cu(2+), Zn(2+), As(5+), and Pb(2+), respectively, at neutral pH. Additionally, the effect of the pH of the sample and the use of lyophilized bacteria were also analyzed showing that the bioassay can be implemented in different conditions. Moreover, highly turbid samples and samples with very low oxygen levels were measured successfully with the new instrumental bioassay described here. Finally, simulated samples containing 3,5-DCP or a heavy metal mixture were tested using the proposed bioassay and a standard ISO bioassay, showing that our test is more sensible to the phenol but less sensible to the metal mixtures. Therefore, we propose CO2-TOX as a rapid, sensitive, low-cost, and robust instrumental bioassay that could perform as an industrial wastewater-process monitor among other applications.

  4. Trends in the chemistry of atmospheric deposition and surface waters in the Lake Maggiore catchment

    Directory of Open Access Journals (Sweden)

    M. Rogora

    2001-01-01

    Full Text Available The Lake Maggiore catchment is the area of Italy most affected by acid deposition. Trend analysis was performed on long-term (15-30 years series of chemical analyses of atmospheric deposition, four small rivers draining forested catchments and four high mountain lakes. An improvement in the quality of atmospheric deposition was detected, due to decreasing sulphate concentration and increasing pH. Similar trends were also found in high mountain lakes and in small rivers. Atmospheric deposition, however, is still providing a large and steady flux of nitrogen compounds (nitrate and ammonium which is causing increasing nitrogen saturation in forest ecosystems and increasing nitrate levels in rivers. Besides atmospheric deposition, an important factor controlling water acidification and recovery is the weathering of rocks and soils which may be influenced by climate warming. A further factor is the episodic deposition of Saharan calcareous dust which contributes significantly to base cation deposition. Keywords: trend, atmospheric deposition, nitrogen, stream water chemistry.

  5. Plasmonic Hot Electron Transport Driven Site-Specific Surface-Chemistry with Nanoscale Spatial Resolution

    CERN Document Server

    Cortés, Emiliano; Cambiasso, Javier; Jermyn, Adam S; Sundararaman, Ravishankar; Narang, Prineha; Schlücker, Sebastian; Maier, Stefan A

    2016-01-01

    Nanoscale localization of electromagnetic fields near metallic nanostructures underpins the fundamentals and applications of plasmonics. The unavoidable energy loss from plasmon decay, initially seen as a detriment, has now expanded the scope of plasmonic applications to exploit the generated hot carriers. However, quantitative understanding of the spatial localization of these hot carriers, akin to electromagnetic near-field maps, has been elusive. Here we spatially map hot-electron-driven reduction chemistry with 15 nanometre resolution as a function of time and electromagnetic field polarization for different plasmonic nanostructures. We combine experiments employing a six-electron photo-recycling process that modify the terminal group of a self-assembled monolayer on plasmonic silver nanoantennas, with theoretical predictions from first-principles calculations of non-equilibrium hot-carrier transport in these systems. The resulting localization of reactive regions, determined by hot carrier transport from...

  6. Surface chemistry of Au/TiO2: Thermally and photolytically activated reactions

    Science.gov (United States)

    Panayotov, Dimitar A.; Morris, John R.

    2016-03-01

    The fascinating particle size dependence to the physical, photophysical, and chemical properties of gold has motivated thousands of studies focused on exploring the ability of supported gold nanoparticles to catalyze chemical transformations. In particular, titanium dioxide-supported gold (Au/TiO2) nanoparticles may provide the right combination of electronic structure, structural dynamics, and stability to affect catalysis in important practical applications from environmental remediation to selective hydrogenation to carbon monoxide oxidation. Harnessing the full potential of Au/TiO2 will require a detailed atomic-scale understanding of the thermal and photolytic processes that accompany chemical conversion. This review describes some of the unique properties exhibited by particulate gold before delving into how those properties affect chemistry on titania supports. Particular attention is given first to thermally driven reactions on single crystal system. This review then addresses nanoparticulate samples in an effort begin to bridge the so-called materials gap. Building on the foundation provided by the large body of work in the field of thermal catalysis, the review describes new research into light-driven catalysis on Au/TiO2. Importantly, the reader should bear in mind throughout this review that thermal chemistry and thermal effects typically accompany photochemistry. Distinguishing between thermally-driven stages of a reaction and photo-induced steps remains a significant challenge, but one that experimentalists and theorists are beginning to decipher with new approaches. Finally, a summary of several state-of-the-art studies describes how they are illuminating new frontiers in the quest to exploit Au/TiO2 as an efficient catalyst and low-energy photocatalyst.

  7. Surface patterning with natural and synthetic polymers via an inverse electron demand Diels-Alder reaction employing microcontact chemistry.

    Science.gov (United States)

    Roling, Oliver; Mardyukov, Artur; Lamping, Sebastian; Vonhören, Benjamin; Rinnen, Stefan; Arlinghaus, Heinrich F; Studer, Armido; Ravoo, Bart Jan

    2014-10-21

    Bioorthogonal ligation methods are the focus of current research due to their versatile applications in biotechnology and materials science for post-functionalization and immobilization of biomolecules. Recently, inverse electron demand Diels-Alder (iEDDA) reactions employing 1,2,4,5-tetrazines as electron deficient dienes emerged as powerful tools in this field. We adapted iEDDA in microcontact chemistry (μCC) in order to create enhanced surface functions. μCC is a straightforward soft-lithography technique which enables fast and large area patterning with high pattern resolutions. In this work, tetrazine functionalized surfaces were reacted with carbohydrates conjugated with norbornene or cyclooctyne acting as strained electron rich dienophiles employing μCC. It was possible to create monofunctional as well as bifunctional substrates which were specifically addressable by proteins. Furthermore we structured glass supported alkene terminated self-assembled monolayers with a tetrazine conjugated atom transfer radical polymerization (ATRP) initiator enabling surface grafted polymerizations of poly(methylacrylate) brushes. The success of the surface initiated iEDDA via μCC as well as the functionalization with natural and synthetic polymers was verified via fluorescence and optical microscopy, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), atomic force microscopy (AFM) and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR).

  8. High-yielding and photolabile approaches to the covalent attachment of biomolecules to surfaces via hydrazone chemistry.

    Science.gov (United States)

    Lee, Ju Hun; Domaille, Dylan W; Noh, Hyunwoo; Oh, Taeseok; Choi, Chulmin; Jin, Sungho; Cha, Jennifer N

    2014-07-22

    The development of strategies to couple biomolecules covalently to surfaces is necessary for constructing sensing arrays for biological and biomedical applications. One attractive conjugation reaction is hydrazone formation--the reaction of a hydrazine with an aldehyde or ketone--as both hydrazines and aldehydes/ketones are largely bioorthogonal, which makes this particular reaction suitable for conjugating biomolecules to a variety of substrates. We show that the mild reaction conditions afforded by hydrazone conjugation enable the conjugation of DNA and proteins to the substrate surface in significantly higher yields than can be achieved with traditional bioconjugation techniques, such as maleimide chemistry. Next, we designed and synthesized a photocaged aryl ketone that can be conjugated to a surface and photochemically activated to provide a suitable partner for subsequent hydrazone formation between the surface-anchored ketone and DNA- or protein-hydrazines. Finally, we exploit the latent functionality of the photocaged ketone and pattern multiple biomolecules on the same substrate, effectively demonstrating a strategy for designing substrates with well-defined domains of different biomolecules. We expect that this approach can be extended to the production of multiplexed assays by using an appropriate mask with sequential photoexposure and biomolecule conjugation steps.

  9. Stability of carbon fiber surface chemistry under temperature and its influence on interfacial adhesion with polymer matrices

    Energy Technology Data Exchange (ETDEWEB)

    Vautard, Frederic [ORNL; Grappe, Hippolyte A [ORNL; Ozcan, Soydan [ORNL

    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.

  10. A Novel General Chemistry Laboratory: Creation of Biomimetic Superhydrophobic Surfaces through Replica Molding

    Science.gov (United States)

    Verbanic, Samuel; Brady, Owen; Sanda, Ahmed; Gustafson, Carolina; Donhauser, Zachary J.

    2014-01-01

    Biomimetic replicas of superhydrophobic lotus and taro leaf surfaces can be made using polydimethylsiloxane. These replicas faithfully reproduce the microstructures of the leaves' surface and can be analyzed using contact angle goniometry, self-cleaning experiments, and optical microscopy. These simple and adaptable experiments were used to…

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

    NARCIS (Netherlands)

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

    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

  12. Tuning the surface chemistry of lubricant-derived phosphate thermal films: The effect of boron

    Science.gov (United States)

    Spadaro, F.; Rossi, A.; Lainé, E.; Woodward, P.; Spencer, N. D.

    2017-02-01

    Understanding the interactions among the various additives in a lubricant is important because they can have a major influence on the performance of blends under tribological conditions. The present investigation is focused on the interactions occurring between ZnDTP and dispersant molecules in an oil formulation, and on their reactivity under purely thermal conditions in the presence of air-oxidized iron surfaces. Nuclear magnetic resonance spectroscopy (NMR) was performed on undiluted blends at different temperatures, while angle-resolved X-ray photoelectron spectroscopy (ARXPS) was exploited to investigate the surface reactivity on oxidized iron surfaces. The results indicate that the dispersant, generally added to blends for preventing the deposition of sludge, varnish and soot on the surface, might also inhibit the reaction of all other additives with the steel surface.

  13. Results of an in-situ mussel bioassay in the Puget Sound

    Energy Technology Data Exchange (ETDEWEB)

    Houkal, D.; Rummel, B.; Shephard, B. [URS Consultants, Inc., Seattle, WA (United States)

    1995-12-31

    As part of an ecological evaluation in the Puget Sound, Washington, an in situ bioassay using the blue mussel (Mytilus galloprovincialis) was conducted to determine the effect of sediment-borne chemicals on bioaccumulation and growth of shellfish. The assay included four sample stations from a contaminated embayment (Sinclair Inlet) and one station from a reference site (Holmes Harbor). At each station, 300 mussels were deployed 1 meter above the sediment surface and maintained for a period of 3 months. The length and total weight of each mussel was measured at the beginning of the exposure period and the length, total weight, tissue weight, and shell weight of each mussel was measured at the end of the exposure period. Composite tissue samples from 100 mussels were collected at the beginning and end of the exposure period and analyzed for semivolatile organic chemicals, chlorinated pesticides, polychlorinated biphenyls, inorganic chemicals, organotin, and lipids. Water quality measurements (including temperature, salinity, dissolved oxygen, and chlorophyll a) were made at each station every two weeks during the assay to characterize environmental factors influencing mussel bioaccumulation and growth. Weight growth was similar among stations in Sinclair Inlet, but was significantly greater in all Sinclair Inlet stations compared to the Holmes Harbor reference station. Length growth was statistically indistinguishable among stations in Sinclair Inlet. Only one Sinclair Inlet station had a significantly greater length growth compared to the Holmes Harbor reference station. The influence of water quality on mussel growth is presented. The correlation between sediment chemistry and bioaccumulation is discussed.

  14. The effect of ozone on nicotine desorption from model surfaces:evidence for heterogeneous chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Destaillats, Hugo; Singer, Brett C.; Lee, Sharon K.; Gundel, LaraA.

    2005-05-01

    Assessment of secondhand tobacco smoke exposure using nicotine as a tracer or biomarker is affected by sorption of the alkaloid to indoor surfaces and by its long-term re-emission into the gas phase. However, surface chemical interactions of nicotine have not been sufficiently characterized. Here, the reaction of ozone with nicotine sorbed to Teflon and cotton surfaces was investigated in an environmental chamber by monitoring nicotine desorption over a week following equilibration in dry or humid air (65-70 % RH). The Teflon and cotton surfaces had N{sub 2}-BET surface areas of 0.19 and 1.17 m{sup 2} g{sup -1}, and water mass uptakes (at 70 % RH) of 0 and 7.1 % respectively. Compared with dry air baseline levels in the absence of O{sub 3}, gas phase nicotine concentrations decrease, by 2 orders of magnitude for Teflon after 50 h at 20-45 ppb O{sub 3}, and by a factor of 10 for cotton after 100 h with 13-15 ppb O{sub 3}. The ratios of pseudo first-order rate constants for surface reaction (r) to long-term desorption (k) were r/k = 3.5 and 2.0 for Teflon and cotton surfaces, respectively. These results show that surface oxidation was competitive with desorption. Hence, oxidative losses could significantly reduce long-term re-emissions of nicotine from indoor surfaces. Formaldehyde, N-methylformamide, nicotinaldehyde and cotinine were identified as oxidation products, indicating that the pyrrolidinic N was the site of electrophilic attack by O{sub 3}. The presence of water vapor had no effect on the nicotine-O{sub 3} reaction on Teflon surfaces. By contrast, nicotine desorption from cotton in humid air was unaffected by the presence of ozone. These observations are consistent with complete inhibition of ozone-nicotine surface reactions in an aqueous surface film present in cotton but not in Teflon surfaces.

  15. Synthesis and processing of ELISA polymer substitute: The influence of surface chemistry and morphology on detection sensitivity

    Energy Technology Data Exchange (ETDEWEB)

    Hosseini, Samira; Ibrahim, Fatimah [Department of Biomedical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603 (Malaysia); Center for Innovation in Medical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603 (Malaysia); Djordjevic, Ivan, E-mail: ivan.djordjevic@um.edu.my [Department of Biomedical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603 (Malaysia); Center for Innovation in Medical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603 (Malaysia); Rothan, Hussin A.; Yusof, Rohana [Department of Molecular Medicine, Faculty of Medicine, University of Malaya, 50603 Kuala Lumpur (Malaysia); Marel, Cees van der [Philips Materials Analysis, High Tech Campus 11, 5656 AE Eindhoven (Netherlands); Koole, Leo H. [Department of Biomedical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603 (Malaysia); Center for Innovation in Medical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603 (Malaysia); Faculty of Health, Medicine and Life Sciences, Maastricht University (Netherlands)

    2014-10-30

    Highlights: • Polyacrylate coatings with controlled surface functionalities. • Impact of surface chemistry and morphology on dengue antibody immobilization. • Enhancement of detection signal as a result of bio-activation of polymer surface. - Abstract: Despite the known drawbacks of enzyme-linked immunosorbent assay (ELISA), one of the deficiencies that have relatively been ignored is the performance of ELISA substrate itself. Polystyrene (PS), as the cost effective material of choice for mass production of ELISA well-plates, has shown obvious lacks of suitable physical and chemical properties for protein attachment. The general concept of this work was to develop a potential substrate that can be suggested as a material of choice for production of a new generation of ELISA analytical kits. Spin-coated thin films of polymethyl methacrylate-co-methacrylic acid (PMMA-co-MAA) on silicon surfaces were designed and processed for detection of dengue virus. Coated surfaces of different molar ratios have been investigated as carboxyl-functionalized layers for obtaining platform for biomolecule immobilization with high level of protein activity. To improve the sensitivity of detection, we have used amine functional “spacers”, hexamethylenediamine (HMDA) and polyethyleneimine (PEI), which were covalently bonded to the surfaces of PMMA-co-MAA coatings. Results demonstrate that the variation of surface concentration of carboxyl groups of PMMA-co-MAA can be used to control the amine surface concentration after carbodiimide coupling with HMDA and PEI spacers. The presence of amine spacers increases hydrophilicity of the coatings and significantly impacts the polymer surface morphology. In particular, protein immobilization via amine-bearing spacers has been achieved in two effective steps: (1) carbodiimide bonding between amine spacer molecules and PMMA-co-MAA polymer coatings; and (2) covalent immobilization of antibody via glutaraldehyde reaction with amine groups

  16. The surface chemistry of NO(x) on mackinawite (FeS) surfaces : a DFT-D2 study

    NARCIS (Netherlands)

    Dzade, N.Y.; Roldan, A; de Leeuw, Nora H.

    2014-01-01

    We present density functional theory calculations with a correction for the long-range interactions (DFT-D2) of the bulk and surfaces of mackinawite (FeS), and subsequent adsorption and dissociation of NO(x) gases (nitrogen monoxide (NO) and nitrogen dioxide (NO2)). Our results show that these envir

  17. Corrosion resistance, chemistry, and mechanical aspects of Nitinol surfaces formed in hydrogen peroxide solutions

    Energy Technology Data Exchange (ETDEWEB)

    Shabalovskay, Svetlana A.; Anderegg, James W.; Undisz, Andreas; Rettenmayr, Markus; Rondelli, Gianni C.

    2012-06-12

    Ti oxides formed naturally on Nitinol surfaces are only a few nanometers thick. To increase their thickness, heat treatments are explored. The resulting surfaces exhibit poor resistance to pitting corrosion. As an alternative approach to accelerate surface oxidation and grow thicker oxides, the exposure of Nitinol to strong oxidizing H2O2 aqueous solutions (3 and 30%) for various periods of time was used. Using X-Ray Photoelectron Spectroscopy (XPS) and Auger spectroscopy, it was found that the surface layers with variable Ti (6–15 at %) and Ni (5–13 at %) contents and the thickness up to 100 nm without Ni-enriched interfaces could be formed. The response of the surface oxides to stress in superelastic regime of deformations depended on oxide thickness. In the corrosion studies performed in both strained and strain-free states using potentiodynamic and potentiostatic polarizations, the surfaces treated in H2O2 showed no pitting in corrosive solution that was assigned to higher chemical homogeneity of the surfaces free of secondary phases and inclusions that assist better biocompatibility of Nitinol medical devices. © 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 100B: 1490–1499, 2012

  18. The effect of heating rate on the surface chemistry of NiTi.

    Science.gov (United States)

    Undisz, Andreas; Hanke, Robert; Freiberg, Katharina E; Hoffmann, Volker; Rettenmayr, Markus

    2014-11-01

    The impact of the heating rate on the Ni content at the surface of the oxide layer of biomedical NiTi is explored. Heat treatment emulating common shape-setting procedures was performed by means of conventional and inductive heating for similar annealing time and temperature, applying various heating rates from ~0.25 K s(-1) to 250 K s(-1). A glow discharge optical emission spectroscopy method was established and employed to evaluate concentration profiles of Ni, Ti and O in the near-surface region at high resolution. The Ni content at the surface of the differently treated samples varies significantly, with maximum surface Ni concentrations of ~20 at.% at the lowest and ~1.5 at.% at the highest heating rate, i.e. the total amount of Ni contained in the surface region of the oxide layer decreases by >15 times. Consequently, the heating rate is a determinant for the biomedical characteristics of NiTi, especially since Ni available at the surface of the oxide layer may affect the hemocompatibility and be released promptly after surgical application of a respective implant. Furthermore, apparently contradictory results presented in the literature reporting surface Ni concentrations of ~3 at.% to >20 at.% after heat treatment are consistently explained considering the ascertained effect of the heating rate.

  19. Surface chemistry effects in finite element modeling of heat transfer in (micron)-fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Havstad, M

    2000-12-07

    Equations for modeling surface chemical kinetics by the interaction of gaseous and surface species are presented. The formulation is embedded in a finite element heat transfer code and an ordinary differential equation package is used to solve the surface system of chemical kinetic equations for each iteration within the heat transfer solver. The method is applied to a flow which includes methane and methanol in a microreactor on a chip. A simpler more conventional method, a plug flow reactor model, is then applied to a similar problem. Initial results for steam reforming of methanol are given.

  20. Measurement and control of in-plane surface chemistry during the oxidation of H-terminated (111) Si.

    Science.gov (United States)

    Gokce, Bilal; Adles, Eric J; Aspnes, David E; Gundogdu, Kenan

    2010-10-12

    In-plane directional control of surface chemistry during interface formation can lead to new opportunities regarding device structures and applications. Control of this type requires techniques that can probe and hence provide feedback on the chemical reactivity of bonds not only in specific directions but also in real time. Here, we demonstrate both control and measurement of the oxidation of H-terminated (111) Si. Control is achieved by externally applying uniaxial strain, and measurement by second-harmonic generation (SHG) together with the anisotropic-bond model of nonlinear optics. In this system anisotropy results because bonds in the strain direction oxidize faster than those perpendicular to it, leading in addition to transient structural changes that can also be detected at the bond level by SHG.

  1. Interactions between groundwater and surface water in a Virginia coastal plain watershed. 2. Acid-base chemistry

    Science.gov (United States)

    O'Brien, A. K.; Eshleman, K.N.; Pollard, J.S.

    1994-01-01

    At the Reedy Creek watershed sulphate concentrations were higher and alkalinity lower in the groundwater in the hillslope than in the stream. Sulphate concentrations and alkalinity observed in groundwater in the wetland were usually between those of the hillslope and stream. These data suggest that the wetland is a sink for sulphate and acidity; sulphate reduction may be an important mechanism for generating alkalinity in the wetland. The DOC concentrations were higher in the stream and wetland groundwater than in hillslope groundwater. No consistent spatial patterns in sulphate concentrations were observed in surface water chemistry under base flow conditions. Stream discharge was found to be positively correlated with base flow sulphate concentrations and inversely correlated with alkalinity. A sulphate mass balance indicated that approximately 30% of the estimated 24.9 kg SO42-/ha yr wet atmospheric input was exported from the watershed as sulphate in stream runoff in the water year 1990. -from Authors

  2. Surface chemistry and effects on bone regeneration of a novel biomimetic synthetic bone filler.

    Science.gov (United States)

    Morra, Marco; Giavaresi, Gianluca; Sartori, Maria; Ferrari, Andrea; Parrilli, Annapaola; Bollati, Daniele; Baena, Ruggero Rodriguez Y; Cassinelli, Clara; Fini, Milena

    2015-04-01

    The paper presents results of physico-chemical and biological investigations of a surface-engineered synthetic bone filler. Surface analysis confirms that the ceramic phosphate granules present a collagen nanolayer to the surrounding environment. Cell cultures tests show that, in agreement with literature reports, surface-immobilized collagen molecular cues can stimulate progression along the osteogenic pathway of undifferentiated human mesenchymal cells. Finally, in vivo test in a rabbit model of critical bone defects shows statistically significant increase of bone volume and mineral apposition rate between the biomimetic bone filler and collagen-free control. All together, obtained data confirm that biomolecular surface engineering can upgrade the properties of implant device, by promoting more specific and targeted implant-host cells interactions.

  3. Recent developments of surface complexation models applied to environmental aquatic chemistry

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Based on numerous latest references, the current developments in surface complexation, surface precipitation and the corresponding models (SCMs and SPMs), were reviewed. The contents involved comparison on surface charge composition and layer-structure of solid-solution interface for the classical 1-pK and 2- pK models, In addition, the fundamental concept and relations of the new models, i.e., multi-site complexation (MUSIC) and charge -distribution (CD) MUSIC models were described as well. To avoid misuse or abuse, it must be emphasized that the applicability nd limitation for each model should be considered carefully when selecting the concerned model(s). In addition, some new powerful techniques for surface characterization and analysis applied to model establishment and modification were also briefly introduced.

  4. Solid Oxide Fuel Cell Cathodes. Unraveling the Relationship Between Structure, Surface Chemistry and Oxygen Reduction

    Energy Technology Data Exchange (ETDEWEB)

    Gopalan, Srikanth [Boston Univ., MA (United States)

    2013-03-31

    In this work we have considered oxygen reduction reaction on LSM and LSCF cathode materials. In particular we have used various spectroscopic techniques to explore the surface composition, transition metal oxidation state, and the bonding environment of oxygen to understand the changes that occur to the surface during the oxygen reduction process. In a parallel study we have employed patterned cathodes of both LSM and LSCF cathodes to extract transport and kinetic parameters associated with the oxygen reduction process.

  5. A Potential Mechanism for Perchlorate Formation on Mars: Surface-Radiolysis-Initiated Atmospheric Chemistry

    Science.gov (United States)

    Wilson, Eric; Atreya, Sushil K.; Kaiser, Ralf-Ingo; Mahaffy, Paul

    2016-10-01

    Perchlorate (ClO4-) is prevalent on Earth, and with observations of perchlorate on lunar samples and chondrite meteorites, along with recent observations indicating the presence of perchlorate (ClO4-) in the Martian surface by the Phoenix lander and the Sample Analysis at Mars (SAM) on the Mars Science Laboratory (MSL) rover, it appears that the existence of perchlorate is widespread throughout the solar system. However, the abundance and isotopic composition of Martian perchlorate suggest that the perchlorate formation mechanism on Mars may involve a different path than perchlorate found elsewhere in the solar system. Motivated by this, we employ a one-dimensional chemical model to investigate the viability of perchlorate formation in the atmosphere of Mars, instigated by the radiolysis of the Martian surface by galactic cosmic rays. The surface-atmosphere interaction to produce Martian perchlorate involves the sublimation of chlorine oxides into the atmosphere, through surface radiolysis, and their subsequent synthesis to form perchloric acid (HClO4), followed by surface deposition and mineralization to form surface perchlorates. Considering the chlorine oxide, OClO, we find an OClO surface flux as low as 3.2x107 molecules cm-2 s-1, sublimated into the atmosphere from the surface could produce sufficient HClO4 to explain the perchlorate concentration on Mars, assuming an accumulation depth of 30 cm and integrated over the Amazonian period. Radiolysis provides an efficient pathway for the oxidation of chlorine, bypassing the efficient Cl/HCl recycling mechanism that characterizes HClO4 formation mechanisms proposed for the Earth but not Mars.

  6. Chemistry of Cu(acac){sub 2} on Ni(110) and Cu(110) surfaces: Implications for atomic layer deposition processes

    Energy Technology Data Exchange (ETDEWEB)

    Ma Qiang; Zaera, Francisco [Department of Chemistry, University of California, Riverside, California 92521 (United States)

    2013-01-15

    The thermal chemistry of copper(II)acetylacetonate, Cu(acac){sub 2}, on Ni(110) and Cu(110) single-crystal surfaces was probed under vacuum by using x-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD). Some data for acetylacetone (Hacac, CH{sub 3}COCH{sub 2}COCH{sub 3}) adsorbed on Ni(110) are also reported as reference. Chemical transformations were identified in several steps covering a temperature range from 150 K to at least 630 K. The desorption of Hacac and a 3-oxobutanal (CH{sub 3}COCH{sub 2}CHO) byproduct was observed first at 150 and 180 K on Ni(110) and at 160 and 185 K on Cu(110), respectively. Partial loss of the acetylacetonate (acac) ligands and a likely change in adsorption geometry are seen next, with the possible production of HCu(acac), which desorbs at 200 and 235 K from the nickel and copper surfaces, respectively. Molecular Cu(acac){sub 2} desorption is observed on both surfaces at approximately 300 K, probably from recombination of Cu(acac) and acac surface species. The remaining copper atoms on the surface lose their remaining acac ligands to the substrate and become reduced directly to metallic copper. At the same time, the organic ligands follow a series of subsequent surface reactions, probably involving several C-C bond-scissions, to produce other fragments, additional Hacac and HCu(acac) in the gas phase in the case of the copper surface, and acetone on nickel. A significant amount of acac must nevertheless survive on the surface to high temperatures, because Hacac peaks are seen in the TPD at about 515 and 590 K and the C 1s XPS split associated with acac is seen up to close to 500 K. In terms of atomic layer deposition processes, this suggests that cycles could be design to run at such temperatures as long as an effective hydrogenation agent is used as the second reactant to remove the surface acac as Hacac. Only a small fraction of carbon is left behind on Ni after heating to 800 K, whereas more carbon

  7. Atomic Scale Imaging of the Electronic Structure and Chemistry of Graphene and Its Precursors on Metal Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Flynn, George W [Columbia University

    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

  8. In vitro bioassays to evaluate complex chemical mixtures in recycled water.

    Science.gov (United States)

    Jia, Ai; Escher, Beate I; Leusch, Frederic D L; Tang, Janet Y M; Prochazka, Erik; Dong, Bingfeng; Snyder, Erin M; Snyder, Shane A

    2015-09-01

    With burgeoning population and diminishing availability of freshwater resources, the world continues to expand the use of alternative water resources for drinking, and the quality of these sources has been a great concern for the public as well as public health professionals. In vitro bioassays are increasingly being used to enable rapid, relatively inexpensive toxicity screening that can be used in conjunction with analytical chemistry data to evaluate water quality and the effectiveness of water treatment. In this study, a comprehensive bioassay battery consisting of 36 bioassays covering 18 biological endpoints was applied to screen the bioactivity of waters of varying qualities with parallel treatments. Samples include wastewater effluent, ultraviolet light (UV) and/or ozone advanced oxidation processed (AOP) recycled water, and infiltrated recycled groundwater. Based on assay sensitivity and detection frequency in the samples, several endpoints were highlighted in the battery, including assays for genotoxicity, mutagenicity, estrogenic activity, glucocorticoid activity, arylhydrocarbon receptor activity, oxidative stress response, and cytotoxicity. Attenuation of bioactivity was found to be dependent on the treatment process and bioassay endpoint. For instance, ozone technology significantly removed oxidative stress activity, while UV based technologies were most efficient for the attenuation of glucocorticoid activity. Chlorination partially attenuated genotoxicity and greatly decreased herbicidal activity, while groundwater infiltration efficiently attenuated most of the evaluated bioactivity with the exception of genotoxicity. In some cases, bioactivity (e.g., mutagenicity, genotoxicity, and arylhydrocarbon receptor) increased following water treatment, indicating that transformation products of water treatment may be a concern. Furthermore, several types of bioassays with the same endpoint were compared in this study, which could help guide the selection

  9. Use of North American and European air quality networks to evaluate global chemistry-climate modeling of surface ozone

    Directory of Open Access Journals (Sweden)

    J. L. Schnell

    2015-04-01

    Full Text Available We test the current generation of global chemistry-climate models in their ability to simulate observed, present-day surface ozone. Models are evaluated against hourly surface ozone from 4217 stations in North America and Europe that are averaged over 1° × 1° grid cells, allowing commensurate model-measurement comparison. Models are generally biased high during all hours of the day and in all regions. Most models simulate the shape of regional summertime diurnal and annual cycles well, correctly matching the timing of hourly (~ 15:00 and monthly (mid-June peak surface ozone abundance. The amplitude of these cycles is less successfully matched. The observed summertime diurnal range (~ 25 ppb is underestimated in all regions by about 7 ppb, and the observed seasonal range (~ 21 ppb is underestimated by about 5 ppb except in the most polluted regions where it is overestimated by about 5 ppb. The models generally match the pattern of the observed summertime ozone enhancement, but they overestimate its magnitude in most regions. Most models capture the observed distribution of extreme episode sizes, correctly showing that about 80% of individual extreme events occur in large-scale, multi-day episodes of more than 100 grid cells. The observed linear relationship showing increases in ozone by up to 6 ppb for larger-sized episodes is also matched.

  10. Surface chemistry and catalytic performance of amorphous NiB/Hβ catalyst for n-hexane isomerization

    Science.gov (United States)

    Chen, Jinshe; Cai, Tingting; Jing, Xiaohui; Zhu, Lijun; Zhou, Yulu; Xiang, Yuzhi; Xia, Daohong

    2016-12-01

    The amorphous NiB nanoparticles were synthesized and a novel type of NiB/Hβ catalyst was prepared for the isomerization of n-hexane. The optimum preparation conditions were investigated and the effect of preparation conditions on the surface chemistry information of catalysts was characterized by XRD, N2 sorption studies, XPS, TPD and other related means. It was demonstrated that the loading amounts of NiB have effect on textural properties and the acid properties of surface. The loading amounts of NiB were also related to the amount of strong Lewis acid sites and the ratios of weak acid to strong acid of samples. Meanwhile, calcination temperatures of samples were closely associated with the structure of active components that function as metal centers. When the loading amount of NiB was 5 wt.% and calcination temperature was 200 °C, the catalyst had proper surface acidity sites and metal active sites to provide suitable synergistic effects. The mechanism for n-hexane isomerization was also investigated and the existence of unique structure of Bsbnd Nisbnd H was proved, which could provide good hydrogenation-dehydrogenation functions.

  11. Catalytically Triggered Energy Release from Strained Organic Molecules: The Surface Chemistry of Quadricyclane and Norbornadiene on Pt(111).

    Science.gov (United States)

    Bauer, Udo; Mohr, Susanne; Döpper, Tibor; Bachmann, Philipp; Späth, Florian; Düll, Fabian; Schwarz, Matthias; Brummel, Olaf; Fromm, Lukas; Pinkert, Ute; Görling, Andreas; Hirsch, Andreas; Bachmann, Julien; Steinrück, Hans-Peter; Libuda, Jörg; Papp, Christian

    2017-01-31

    We have investigated the surface chemistry of the polycyclic valence-isomer pair norbornadiene (NBD) and quadricyclane (QC) on Pt(111). The NBD/QC system is considered to be a prototype for energy storage in strained organic compounds. By using a multimethod approach, including UV photoelectron, high-resolution X-ray photoelectron, and IR reflection-absorption spectroscopic analysis and DFT calculations, we could unambiguously identify and differentiate between the two molecules in the multilayer phase, which implies that the energy-loaded QC molecule is stable in this state. Upon adsorption in the (sub)monolayer regime, the different spectroscopies yielded identical spectra for NBD and QC at 125 and 160 K, when multilayer desorption takes place. This behavior is explained by a rapid cycloreversion of QC to NBD upon contact with the Pt surface. The NBD adsorbs in a η(2) :η(1) geometry with an agostic Pt-H interaction of the bridgehead CH2 subunit and the surface. Strong spectral changes are observed between 190 and 220 K because the hydrogen atom that forms the agostic bond is broke. This reaction yields a norbornadienyl intermediate species that is stable up to approximately 380 K. At higher temperatures, the molecule dehydrogenates and decomposes into smaller carbonaceous fragments.

  12. Surface chemistry and morphology of the solid electrolyte interphase on silicon nanowire lithium-ion battery anodes

    KAUST Repository

    Chan, Candace K.

    2009-04-01

    Silicon nanowires (SiNWs) have the potential to perform as anodes for lithium-ion batteries with a much higher energy density than graphite. However, there has been little work in understanding the surface chemistry of the solid electrolyte interphase (SEI) formed on silicon due to the reduction of the electrolyte. Given that a good, passivating SEI layer plays such a crucial role in graphite anodes, we have characterized the surface composition and morphology of the SEI formed on the SiNWs using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). We have found that the SEI is composed of reduction products similar to that found on graphite electrodes, with Li2CO3 as an important component. Combined with electrochemical impedance spectroscopy, the results were used to determine the optimal cycling parameters for good cycling. The role of the native SiO2 as well as the effect of the surface area of the SiNWs on reactivity with the electrolyte were also addressed. © 2009 Elsevier B.V. All rights reserved.

  13. Color and Surface Chemistry Changes of Pine Wood Flour after Extraction and Delignification

    Directory of Open Access Journals (Sweden)

    Yao Chen

    2014-04-01

    Full Text Available A detailed study was undertaken to examine the color and chemistry changes of pine wood flour when its extractives are removed and when it is delignified. The solvent systems employed were toluene/ethanol (TE, acetone/water (AW, and hot-water (HW, while sodium chlorite/acetic acid were used for delignification (i.e., lignin removal (LR. Samples were analyzed by attenuated total reflectance-Fourier transform infrared (ATR-FTIR spectroscopy, Fourier transform Raman (FT-Raman spectroscopy, and colorimetry. The study demonstrated that color parameters (i.e., CIE L*a*b* were only slightly affected by the removal of extractives, but changed noticeably when extractions were followed by delignification. TE extraction was more effective at removing the yellow colored substances, whereas AW mostly removed red colored substances that contained C=O groups. Inclusion of a HW extraction step after extraction with AW (AW-HW removed components that contained conjugated C=O structures. Inclusion of a delignification step after extraction with AW followed by HW extraction (AW-HW-LR was effective at removing yellow substances that contained non-conjugated C=O groups.

  14. Mussel-inspired chemistry for robust and surface-modifiable multilayer films.

    Science.gov (United States)

    Wu, Junjie; Zhang, Liang; Wang, Yongxin; Long, Yuhua; Gao, Huan; Zhang, Xiaoli; Zhao, Ning; Cai, Yuanli; Xu, Jian

    2011-11-15

    In this article, we report a bioinspired approach to preparing stable, functional multilayer films by the integration of mussel-inspired catechol oxidative chemistry into a layer-by-layer (LbL) assembly. A polyanion of poly(acrylic acid-g-dopamine) (PAA-dopamine) bearing catechol groups, a mussel adhesive protein-mimetic polymer, was synthesized as the building block for LbL assembly with poly(allylamine hydrochloride) (PAH). The oxidization of the incorporated catechol group under mild oxidative condition yields o-quinone, which exhibits high reactivity with amine and catechol, thus endowing the chemical covalence and retaining the assembled morphology of multilayer films. The cross-linked films showed excellent stability even in extremely acidic, basic, and highly concentrated aqueous salt solutions. The efficient chemical cross-linking allows for the production of intact free-standing films without using a sacrificial layer. Moreover, thiol-modified multilayer films with good stability were exploited by a combination of thiols-catechol addition and then oxidative cross-linking. The outstanding stability under harsh conditions and the facile functionalization of the PAA-dopamine/PAH multilayer films make them attractive for barriers, separation, and biomedical devices.

  15. Modelling the chemistry of Mn-doped MgO for bulk and (100) surfaces.

    Science.gov (United States)

    Logsdail, Andrew J; Downing, Christopher A; Keal, Thomas W; Sherwood, Paul; Sokol, Alexey A; Catlow, C Richard A

    2016-10-19

    We have investigated the energetic properties of Mn-doped MgO bulk and (100) surfaces using a QM/MM embedding computational method, calculating the formation energy for doped systems, as well as for surface defects, and the subsequent effect on chemical reactivity. Low-concentration Mn doping is endothermic for isovalent species in the bulk but exothermic for higher oxidation states under p-type conditions, and compensated by electrons going to the Fermi level rather than cation vacancies. The highest occupied dopant Mn 3d states are positioned in the MgO band gap, about 4.2 eV below the vacuum level. Surface Mn-doping is more favourable than subsurface doping, and marginally exothermic on a (100) surface at high O2 pressures. For both types of isovalent Mn-doped (100) surfaces, the formation energy for catalytically important oxygen defects is less than for pristine MgO, with F(0) and F(2+)-centres favoured in n- and p-type conditions, respectively. In addition, F(+)-centres are stabilised by favourable exchange coupling between the Mn 3d states and the vacancy-localised electrons, as verified through calculation of the vertical ionisation potential. The adsorption of CO2 on to the pristine and defective (100) surface is used as a probe of chemical reactivity, with isovalent subsurface Mn dopants mildly affecting reactivity, whereas isovalent surface-positioned Mn strongly alters the chemical interactions between the substrate and adsorbate. The differing chemical reactivity, when compared to pristine MgO, justifies further detailed investigations for more varied oxidation states and dopant species.

  16. Surface chemistry of alanine on Cu{111}: Adsorption geometry and temperature dependence

    Science.gov (United States)

    Baldanza, Silvia; Cornish, Alix; Nicklin, Richard E. J.; Zheleva, Zhasmina V.; Held, Georg

    2014-11-01

    Adsorption of L-alanine on the Cu{111} single crystal surface was investigated as a model system for interactions between small chiral modifier molecules and close-packed metal surfaces. Synchrotron-based X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy are used to determine the chemical state, bond coordination and out-of-plane orientation of the molecule on the surface. Alanine adsorbs in its anionic form at room temperature, whilst at low temperature the overlayer consists of anionic and zwitterionic molecules. NEXAFS spectra exhibit a strong angular dependence of the π* resonance associated with the carboxylate group, which allows determining the tilt angle of this group with respect to the surface plane (48° ± 2°) at room temperature. Low-energy electron diffraction (LEED) shows a p(2√{ 13} × 2√{ 13}) R 13 ° superstructure with only one domain, which breaks the mirror symmetry of the substrate and, thus, induces global chirality to the surface. Temperature-programmed XPS (TP-XPS) and temperature-programmed desorption (TPD) experiments indicate that the zwitterionic form converts into the anionic species (alaninate) at 293 K. The latter desorbs/decomposes between 435 K and 445 K.

  17. Recent advances in surface chemistry strategies for the fabrication of functional iron oxide based magnetic nanoparticles

    Science.gov (United States)

    Turcheniuk, Kostiantyn; Tarasevych, Arkadii V.; Kukhar, Valeriy P.; Boukherroub, Rabah; Szunerits, Sabine

    2013-10-01

    The synthesis of superparamagnetic nanostructures, especially iron-oxide based nanoparticles (IONPs), with appropriate surface functional groups has been intensively researched for many high-technological applications, including high density data storage, biosensing and biomedicine. In medicine, IONPs are nowadays widely used as contrast agents for magnetic resonance imaging (MRI), in hyperthermia therapy, but are also exploited for drug and gene delivery, detoxification of biological fluids or immunoassays, as they are relatively non-toxic. The use of magnetic particles in vivo requires IONPs to have high magnetization values, diameters below 100 nm with overall narrow size distribution and long time stability in biological fluids. Due to the high surface energies of IONPs agglomeration over time is often encountered. It is thus of prime importance to modify their surface to prevent aggregation and to limit non-specific adsorption of biomolecules onto their surface. Such chemical modifications result in IONPs being well-dispersed and biocompatible, and allow for targeted delivery and specific interactions. The chemical nature of IONPs thus determines not only the overall size of the colloid, but also plays a significant role for in vivo and in vitro applications. This review discusses the different concepts currently used for the surface functionalization and coating of iron oxide nanoparticles. The diverse strategies for the covalent linking of drugs, proteins, enzymes, antibodies, and nucleotides will be discussed and the chemically relevant steps will be explained in detail.

  18. Solid state chemistry of nitrogen oxides--part II: surface consumption of NO2.

    Science.gov (United States)

    Ioppolo, S; Fedoseev, G; Minissale, M; Congiu, E; Dulieu, F; Linnartz, H

    2014-05-14

    Nitrogen oxides are considered to be important astrochemical precursors of complex species and prebiotics. However, apart from the hydrogenation of solid NO that leads to the surface formation of hydroxylamine, little is known about the full solid state reaction network involving both nitrogen and oxygen. Our study is divided into two papers, hereby called Part I and Part II. In the accompanying paper, we investigate the surface reactions NO + O/O2/O3 and NO + N with a focus on the formation of NO2 ice. Here, we complement this study by measurements of the surface destruction of solid NO2, e.g., NO2 + H/O/N. Experiments are performed in two separate ultra-high vacuum setups and therefore under different experimental conditions to better constrain the experimental results. Surface reaction products are monitored by means of Fourier Transform Reflection Absorption Infrared Spectroscopy (FT-RAIRS) and Temperature Programmed Desorption (TPD) techniques using mass spectrometry. The surface destruction of solid NO2 leads to the formation of a series of nitrogen oxides such as NO, N2O, N2O3, and N2O4 as well as HNO, NH2OH, and H2O. When NO2 is mixed with an interstellar more relevant apolar (i.e., CO) ice, solid CO2 and HCOOH are also formed due to interactions between different reaction routes. The astrophysical implications of the full nitrogen and oxygen reaction network derived from Parts I and II are discussed.

  19. The interaction of climate and glacial landforms on subsurface and surface hydrology and chemistry across a heterogeneous boreal plain landscape

    Science.gov (United States)

    Hokanson, Kelly; Carrera-Hernández, Jaime; Devito, Kevin; Mendoza, Carl

    2016-04-01

    The Boreal Plains (BP) region of Canada is experiencing high levels of anthropogenic activity and may be susceptible to climate change to various degrees. The BP is characterized by heterogeneous glacial landforms, with large contrasts in storage and transmissivity, which when coupled with wet-dry climate cycles, results in complex groundwater-surface water interactions. Predicting the impacts of land use change, climate change, and the future performance of constructed and reclaimed landscapes is currently not possible due to our limited knowledge regarding the natural variability of water table fluctuations, geochemistry, and salinity across the various glacial landforms in the BP. We compare isotopes, EC, chemistry (DOC, Ca, Mg, SO4) and water table position between a drought (2003) and a wet (2013) year to examine the interactions between climate, landform, and geology on the variation in landscape connectivity and overall salinity distribution. Data were collected from surface waters to a depth of 40 m, along a 50 km transect encompassing pond-wetland-forestland sequences across the major glacial depositional types typical of the BP (coarse textured glaciofluvial outwash, fine textured stagnant ice moraine, and lacustrine clay plain). Within each landform, sites range from isolated local flow systems to large intermediate scale flow systems. High spatial variability of water table fluctuations and salinity illustrate the strong regional controls that climate and geology exerts over scales of groundwater flow between landforms and surface water bodies across the BP, reinforcing the need to link surface water and groundwater processes when developing conceptual models. Additionally, when coupled with a strong, physical hydrogeologic conceptual model, synoptic chemical and isotopic surveys can be used to confirm scales and directions of flow; however, without an understanding of the climatic and geologic influence of the region, such data cannot be used as a

  20. Analysis of Surface Chemistry and Detector Performance of Chemically Process CdZnTe crystals

    Energy Technology Data Exchange (ETDEWEB)

    HOSSAIN, A.; Yang, G.; Sutton, J.; Zergaw, T.; Babalola, O. S.; Bolotnikov, A. E.; Camarda. ZG. S.; Gul, R.; Roy, U. N., and James, R. B.

    2015-10-05

    The goal is to produce non-conductive smooth surfaces for fabricating low-noise and high-efficiency CdZnTe devices for gamma spectroscopy. Sample preparation and results are discussed. The researachers demonstrated various bulk defects (e.g., dislocations and sub-grain boundaries) and surface defects, and examined their effects on the performance of detectors. A comparison study was made between two chemical etchants to produce non-conductive smooth surfaces. A mixture of bromine and hydrogen peroxide proved more effective than conventional bromine etchant. Both energy resolution and detection efficiency of CZT planar detectors were noticeably increased after processing the detector crystals using improved chemical etchant and processing methods.

  1. Development of surface immobilized 3-azidocoumarin-based fluorogenic probe via strain promoted click chemistry.

    Science.gov (United States)

    Bharathi, M Vijaya; Chhabra, Mohit; Paira, Priyankar

    2015-12-15

    A new class of imaging probe, a fluorogenic version of 1, 3-dipolar cycloaddition of azides and alkynes has been developed. 3-azidocoumarin scaffolds were selectively immobilized on the DBCO modified bead surface via SPAAC and provide direct and strong fluorescence in fluorescence microscopy. This developed click-on beads could be applied to label various biomolecules, such as nucleic acids, proteins and other molecules. To this end, 5'(7-hydroxy 3-azido coumarin) labelled DNA primer also displayed strong fluorescence upon successful immobilization on the bead surface.

  2. Nano-clustered Pd catalysts formed on GaN surface for green chemistry

    Science.gov (United States)

    Hirayama, Motoi; Ueta, Yukiko; Konishi, Tomoya; Tsukamoto, Shiro

    2011-05-01

    We have succeeded in observing Pd nano-clusters, catalytic prime elements, on a GaN(0 0 0 1) surface by a scanning tunneling microscope for the first time. After the sample was reused, we found that nano-clusters (width: 11 nm, height: 2.2 nm) existed on the surface which still kept the catalytic activity, resulting that the neutral Pd atoms formed the nano-cluster. Moreover, the S-termination contributed to the formation of the dense and flat structure consisting of the Pd nano-clusters.

  3. Colloid and surface chemistry a laboratory guide for exploration of the nano world

    CERN Document Server

    Bucak, Seyda

    2013-01-01

    Scientific Research The research processEthics in Science Design of Experiments Fundamentals of Scientific Computing, Nihat Baysal Recording Data: Keeping a Good Notebook Presenting Data: Writing a Laboratory ReportReferencesCharacterization Techniques Surface Tension Measurements, Seyda BucakViscosity/Rheological Measurements, Patrick UnderhillElectrokinetic Techniques, Marek KosmulskiDiffraction (XRD), Deniz RendeScattering, Ulf OlssonMicroscopy, Cem Levent Altan and Nico A.J.M. SommerdijkColloids and Surfaces Experiment 1: SedimentationExperiment 2: Determination of Critical Micelle Concent

  4. Manganese phospate physical chemistry and surface properties; Fosfato de manganeso propiedades fisicoquimicas y de superficie

    Energy Technology Data Exchange (ETDEWEB)

    Najera R, N.; Romero G, E. T. [ININ, Carretera Mexico-Toluca s/n, Ocoyoacac 52750, Estado de Mexico (Mexico)], e-mail: elizabeth.romero@inin.gob.mx

    2008-07-01

    This paper presents the methodology for the manganese phosphate (III) synthesis (MnP0{sub 4}H{sub 2}0) from manganese chloride. The physicochemical characterization was carried out by: X-ray diffraction, scanning electron microscopy, infrared analysis and thermal gravimetric analysis. The surface characterization is obtained through the determination of surface area, point of zero charge and kinetics of moisture. As a phosphate compound of a metal with low oxidation state is a promising compound for removal pollutants from water and soil, can be used for the potential construction of containment barriers for radioactive wastes. (Author)

  5. Relation between surface topography and sea-salt snow chemistry from Princess Elizabeth Land, East Antarctica

    Directory of Open Access Journals (Sweden)

    K. Mahalinganathan

    2012-04-01

    Full Text Available Previous studies on Antarctic snow have established an unambiguous correlation between variability of sea-salt records and site specific features like elevation and proximity to the sea. On the other hand, variations of Cl/Na+ ratios in snow have been attributed to the reaction mechanisms involving atmospheric acids. In the present study, the annual records of Na+, Cl and SO42− were investigated using snow cores along a 180 km coast to inland transect in Princess Elizabeth Land, East Antarctica. Exceptionally high Na+ concentrations and large variations in Cl/Na+ ratios were observed up to 50 km (∼1100 m elevation of the transect. The steepest slope in the entire transect (49.3 m km−1 was between 20 and 30 km and the sea-salt records in snow from this area revealed extensive modifications, with Cl/Na+ ratios as low as 0.2. Statistical analysis showed a strong association between the slope and variations in Cl/Na+ ratios along the transect (r = −0.676, 99% confidence level. While distance from the coast accounted for some variability, the altitude by itself has no significant control over the sea-salt ion variability. However, the steep slopes influence the deposition of sea-salt aerosols in snow. The wind redistribution of snow due to the steep slopes on the coastal escarpment increases the concentration of Na+, resulting in a low Cl/Na+ ratios. We propose that the slope variations in the coastal regions of Antarctica could significantly influence the sea-salt chemistry of snow.

  6. Phosphate availability in the soil-root system: integration of oxide surface chemistry, transport and uptake.

    NARCIS (Netherlands)

    Geelhoed, J.S.

    1998-01-01

    A study is presented on the adsorption of phosphate on goethite, the interaction of phosphate with other adsorbing ions at the goethite surface, and the resulting availability of phosphate to plants. The plant-availability of sorbed phosphate was determined from phosphorus uptake of plants growing o

  7. Chemistry of the sea surface microlayer. 1. Fabrication and testing of the sampler

    Digital Repository Service at National Institute of Oceanography (India)

    Singbal, S.Y.S.; Narvekar, P.V.

    A screen sampler fabricated to study the sea surface microlayer (SML) has been described. The screen sampler was tested in the Mandovi estuary and adjacent waters. Physico-chemical parameters of the subsurface waters from a depth of 25 cm was also...

  8. Mineral Surface Chemistry and Nanoparticle-aggregation Control Membrane Self-Assembly

    Science.gov (United States)

    Sahai, Nita; Kaddour, Hussein; Dalai, Punam; Wang, Ziqiu; Bass, Garrett; Gao, Min

    2017-01-01

    The self-assembly of lipid bilayer membranes to enclose functional biomolecules, thus defining a “protocell,” was a seminal moment in the emergence of life on Earth and likely occurred at the micro-environment of the mineral-water interface. Mineral-lipid interactions are also relevant in biomedical, industrial and technological processes. Yet, no structure-activity relationships (SARs) have been identified to predict lipid self-assembly at mineral surfaces. Here we examined the influence of minerals on the self-assembly and survival of vesicles composed of single chain amphiphiles as model protocell membranes. The apparent critical vesicle concentration (CVC) increased in the presence of positively-charged nanoparticulate minerals at high loadings (mg/mL) suggesting unfavorable membrane self-assembly in such situations. Above the CVC, initial vesicle formation rates were faster in the presence of minerals. Rates were correlated with the mineral’s isoelectric point (IEP) and reactive surface area. The IEP depends on the crystal structure, chemical composition and surface hydration. Thus, membrane self-assembly showed rational dependence on fundamental mineral properties. Once formed, membrane permeability (integrity) was unaffected by minerals. Suggesting that, protocells could have survived on rock surfaces. These SARs may help predict the formation and survival of protocell membranes on early Earth and other rocky planets, and amphiphile-mineral interactions in diverse other phenomena. PMID:28266537

  9. Controlling embedment and surface chemistry of nanoclusters in metal-organic frameworks.

    Science.gov (United States)

    Coupry, D E; Butson, J; Petkov, P S; Saunders, M; O'Donnell, K; Kim, H; Buckley, C; Addicoat, M; Heine, T; Szilágyi, P Á

    2016-04-14

    A combined theoretical and experimental approach demonstrates that nanocluster embedment into the pores of metal-organic frameworks (MOF) may be influenced by the chemical functionalisation of the MOF. Furthermore, this results in the surface functionalisation of the embedded nanoclusters, highlighting the potential of MOF scaffolds for the design and synthesis of novel functional materials.

  10. Surface Chemistry and Structural Effects in the Stress Corrosion of Glass and Ceramic Materials.

    Science.gov (United States)

    1986-03-31

    elimination of ’weakened’ siloxane linkages, the creation of a ’ microplastic ’ surface layer, and consequently a more uniform distribution of applied stress...examined the impact toughness of plate glass treated at elevated temperatures with sulfur dioxide and also difluorodichloromethane. They, too, observed an

  11. On Surface-Initiated Atom Transfer Radical Polymerization Using Diazonium Chemistry To Introduce the Initiator Layer

    DEFF Research Database (Denmark)

    Chernyy, Sergey; Lillethorup, Mie; Ceccato, Marcel;

    2011-01-01

    of bromine shows a gradual transition from mushroom to brush-type conformation of the surface anchored chains in both polar and nonpolar reaction medium. Interestingly, it is revealed that very thick polymer brushes, on the order of 1 μm, can be obtained at high bromine content of the initiator layer...

  12. Role of surface chemistry in modified ACF (activated carbon fiber)-catalyzed peroxymonosulfate oxidation

    Science.gov (United States)

    Yang, Shiying; Li, Lei; Xiao, Tuo; Zheng, Di; Zhang, Yitao

    2016-10-01

    A commercial activated carbon fiber (ACF-0) was modified by three different methods: nitration treatment (ACF-N), heat treatment (ACF-H) and heat treatment after nitration (ACF-NH), and the effects of textural and chemical properties on the ability of the metal-free ACF-catalyzed peroxymonosulfate (PMS) oxidation of Reactive Black 5 (RB5), an azo dye being difficultly adsorbed onto ACF, in aqueous solution were investigated in this work. Surface density of functional groups, surface area changes, surface morphology and the chemical state inside ACF samples were characterized by Boehm titration, N2 adsorption, scanning electron microscopy in couple with energy dispersive spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy (XPS), respectively. XPS spectra deconvolution was applied to figure out the importance of surface nitrogen-containing function groups. We found that π-π, pyridine and amine have promoting effect on the catalytic oxidation while the -NO2 has inhibitory effect on the ACF/PMS systems for RB5 destroy. Sustainability and renewability of the typical ACF-NH for catalytic oxidation of RB5 were also discussed in detail. Information about our conclusions are useful to control and improve the performance of ACF-catalyzed PMS oxidation for organic pollutants in wastewater treatment.

  13. Photochemistry on TiO2: Mechanisms Behind the Surface Chemistry

    Science.gov (United States)

    2009-01-21

    ation in air causes water droplets to wet the TiO2 film surface, resulting in a lowering of the contact angle over time. The anatase TiO2 film was...have shown that under these conditions, the contact angle decreases slowly during interrupted irradiation periods, as shown in Fig. 9. Both anatase

  14. Cell surface physico chemistry alters biofilm development of Pseudomonas aeruginosa lipopolysaccharide mutants

    NARCIS (Netherlands)

    Flemming, CA; Palmer, RJ; Arrage, AA; Van der Mei, HC; White, DC

    1999-01-01

    The hydrophobic and electrostatic characteristics of bacterial cell surfaces were compared with attachment proclivity and biomass accumulation over time between wildtype Pseudomonas aeruginosa serotype O6 (possesses A and B band LPS), and three LPS-deficient mutants, vi;. A28 (A(+)B(-)), R5 (A(+)B(-

  15. Specific surface modification of the acetylene-linked glycolipid vesicle by click chemistry.

    Science.gov (United States)

    Ito, Hidehiro; Kamachi, Toshiaki; Yashima, Eiji

    2012-06-07

    A novel glycolipid with a terminal acetylene was synthesized and used to prepare unilamellar vesicles. Using these vesicles, a convenient method was developed for the specific modification of the vesicle surface using the photoresponsive copper complex [Cu(OH(2))(cage)] as the catalyst for a click reaction.

  16. Surface Chemistry of Aromatic Reactants on Pt- and Mo-Modified Pt Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, Allison M.; Mark, Lesli; Rasmussen, Mathew J.; Hensley, Jesse E.; Medlin, J. Will

    2016-11-01

    Supported catalysts containing an oxophilic metal such as Mo and a noble metal such as Pt have shown promising activity and selectivity for deoxygenation of biomass-derived compounds. Here, we report that PtMo catalysts also promote hydrogenolysis of the model compound benzyl alcohol, while decarbonylation is most prevalent over unmodified Pt. A combination of single crystal surface science studies, density functional theory (DFT) calculations, and vapor phase upgrading experiments using supported catalysts was carried out to better understand the mechanism by which Mo promotes deoxygenation. Molybdenum was deposited in submonolayer quantities on a Pt(111) surface and reduced at high temperature. Temperature-programmed desorption (TPD) experiments using benzyl alcohol as a reactant showed greatly enhanced yields of the deoxygenation product toluene at moderate Mo coverages. To understand how the interaction of the aromatic group with the surface influenced this reactivity, we investigated the adsorption of toluene as a probe molecule. We found that the addition of Mo to Pt(111) resulted in a significant decrease in toluene decomposition. DFT calculations indicated that this decrease was consistent with decreased aromatic adsorption strengths that accompany incorporation of Mo into the Pt subsurface. The weaker aromatic-surface interaction on Pt/Mo surfaces led to a tilted adsorption geometry for benzyl alcohol, which presumably promotes hydrogenolysis to produce toluene instead of decarbonylation to produce benzene and CO. Alumina-supported Pt and PtMo catalysts were also tested for benzyl alcohol deoxygenation. PtMo catalysts had a higher rate of toluene production and lower rates of benzene and benzaldehyde production. Additionally, when benzaldehyde was used as the reactant to measure decarbonylation activity the mass-normalized rate of benzene production was 2.5 times higher on Pt than PtMo. Overall, the results of TPD, DFT, and supported catalyst experiments

  17. Detailed DSMC surface chemistry modeling of the oxidation of carbon-based ablators

    Science.gov (United States)

    Borner, Arnaud; Swaminathan-Gopalan, Krishnan; Stephani, Kelly A.; Mansour, Nagi N.

    2016-11-01

    This work employs a recently developed gas-surface interaction model (referred to herein as PSMM) constructed from molecular beam experimental data for use with the direct simulation Monte Carlo (DSMC) method. While recent models have been proposed to produce macroscopic rates consistent with the experimental measurements for use in CFD solvers, this work aims to reproduce the microscopic details (including angular distributions and time-of-flight distributions) obtained from the experimental data for modeling gas-surface interactions in DSMC. The different mechanisms considered for the PSMM model include adsorption, desorption, surface participating and direct impact mechanisms. The microscopic data of probabilities and characteristic frequencies for each type of reaction are obtained from the macroscopic parameters of reaction rate constants and sticking coefficients. Numerical simulations closely resembling a recent set of molecular beam experiments were performed using this model within DSMC, and the performance of the Zhluktov-Abe and Alba models is also assessed. The molecular beam experiments in-volved the bombardment of a relatively smooth vitreous carbon surface using a hyperthermal O/O2 beam to understand the product formation and the detailed reaction mechanisms and scattering at the surface. A comparison of the numerical flux distributions from the Zhluktov-Abe and Alba models with experimental flux distributions of the scattered products at different temperatures showed significant discrepancies. The PSMM model was found to reproduce the scattered product mole fractions as a function of temperature, as well as the reactively scattered CO time-of-flight data. Future work will aim to improve the DSMC predicted time-of-flight data for inelastically and elastically scattered O atoms based on the experimental data.

  18. Single-molecule chemistry of metal phthalocyanine on noble metal surfaces.

    Science.gov (United States)

    Li, Zhenyu; Li, Bin; Yang, Jinlong; Hou, Jian Guo

    2010-07-20

    To develop new functional materials and nanoscale electronics, researchers would like to accurately describe and precisely control the quantum state of a single molecule on a surface. Scanning tunneling microscopy (STM), combined with first-principles simulations, provides a powerful technique for acquiring this level of understanding. Traditionally, metal phthalocyanine (MPc) molecules, composed of a metal atom surrounded by a ligand ring, have been used as dyes and pigments. Recently, MPc molecules have shown great promise as components of light-emitting diodes, field-effect transistors, photovoltaic cells, and single-molecule devices. In this Account, we describe recent research on the characterization and control of adsorption and electronic states of a single MPc molecule on noble metal surfaces. In general, the electronic and magnetic properties of a MPc molecule largely depend on the type of metal ion within the phthalocyanine ligand and the type of surface on which the molecule is adsorbed. However, with the STM technique, we can use on-site molecular "surgery" to manipulate the structure and the properties of the molecule. For example, STM can induce a dehydrogenation reaction of the MPc, which allows us to control the Kondo effect, which describes the spin polarization of the molecule and its interaction with the complex environment. A specially designed STM tip can allow researchers to detect certain molecule-surface hybrid states that are not accessible by other techniques. By matching the local orbital symmetry of the STM tip and the molecule, we can generate the negative differential resistance effect in the formed molecular junction. This orbital symmetry based mechanism is extremely robust and does not critically depend on the geometry of the STM tip. In summary, this simple model system, a MPc molecule absorbed on a noble metal surface, demonstrates the power of STM for quantum characterization and manipulation of single molecules, highlighting the

  19. The H4IIE cell bioassay as an indicator of dioxin-like chemicals in wildlife and the environment.

    Science.gov (United States)

    Whyte, J J; Schmitt, C J; Tillitt, D E

    2004-01-01

    The H4IIE cell bioassay has proven utility as a screening tool for planar halogenated hydrocarbons (PHHs) and structurally similar chemicals accumulated in organisms from the wild. This bioassay has additional applications in hazard assessment of PHH exposed populations. In this review, the toxicological principles, current protocols, performance criteria, and field applications for the assay are described. The H4IIE cell bioassay has several advantages over the analytical measurement of PHHs in environmental samples, but conclusions from studies can be strengthened when both bioassay and analytical chemistry data are presented together. Often, the bioassay results concur with biological effects in organisms and support direct measures of PHHs. For biomonitoring purposes and prioritization of PHH-contaminated environments, the H4IIE bioassay may be faster and less expensive than analytical measurements. The H4IIE cell bioassay can be used in combination with other biomarkers such as in vivo measurements of CYP1A1 induction to help pinpoint the sources and identities of dioxin-like chemicals. The number of studies that measure H4IIE-derived TCDD-EQs continues to increase, resulting in subtle improvements over time. Further experiments are required to determine if TCDD-EQs derived from mammalian cells are adequate predictors of toxicity to non-mammalian species. The H4IIE cell bioassay has been used in over 300 published studies, and its combination of speed, simplicity, and ability to integrate the effects of complex contaminant mixtures makes it a valuable addition to hazard assessment and biomonitoring studies.

  20. Aqueous and Surface Chemistries of Photocatalytic Fe-Doped CeO2 Nanoparticles

    Directory of Open Access Journals (Sweden)

    Duangdao Channei

    2017-01-01

    Full Text Available The present work describes the effects of water on Fe-doped nanoparticulate CeO2, produced by flame spray pyrolysis, which is a critical environmental issue because CeO2 is not stable in typical atmospheric conditions. It is hygroscopic and absorbs ~29 wt % water in the bulk when exposed to water vapor but, more importantly, it forms a hydrated and passivating surface layer when immersed in liquid water. In the latter case, CeO2 initially undergoes direct and/or reductive dissolution, followed by the establishment of a passivating layer calculated to consist of ~69 mol % solid CeO2·2H2O and ~30 mol % gelled Ce(OH4. Under static flow conditions, a saturated boundary layer also forms but, under turbulent flow conditions, this is removed. While the passivating hydrated surface layer, which is coherent probably owing to the continuous Ce(OH4 gel, would be expected to eliminate the photoactivity, this does not occur. This apparent anomaly is explained by the calculation of (a the thermodynamic stability diagrams for Ce and Fe; (b the speciation diagrams for the Ce4+-H2O, Ce3+-H2O, Fe3+-H2O, and Fe2+-H2O systems; and (c the Pourbaix diagrams for the Ce-H2O and Fe-H2O systems. Furthermore, consideration of the probable effects of the localized chemical and redox equilibria owing to the establishment of a very low pH (<0 at the liquid-solid interface also is important to the interpretation of the phenomena. These factors highlight the critical importance of the establishment of the passivating surface layer and its role in photocatalysis. A model for the mechanism of photocatalysis by the CeO2 component of the hydrated phase CeO2·2H2O is proposed, explaining the observation of the retention of photocatalysis following the apparent alteration of the surface of CeO2 upon hydration. The model involves the generation of charge carriers at the outer surface of the hydrated surface layer, followed by the formation of radicals, which decompose organic

  1. Use of North American and European Air Quality Networks to Evaluate Global Chemistry-Climate Modeling of Surface Ozone

    Science.gov (United States)

    Schnell, J. L.; Prather, M. J.; Josse, B.; Naik, V.; Horowitz, L. W.; Cameron-Smith, P.; Bergmann, D.; Zeng, G.; Plummer, D. A.; Sudo, K.; Nagashima, T.; Shindell, D. T.; Faluvegi, G.; Strode, S. A.

    2015-01-01

    We test the current generation of global chemistry-climate models in their ability to simulate observed, present-day surface ozone. Models are evaluated against hourly surface ozone from 4217 stations in North America and Europe that are averaged over 1 degree by 1 degree grid cells, allowing commensurate model-measurement comparison. Models are generally biased high during all hours of the day and in all regions. Most models simulate the shape of regional summertime diurnal and annual cycles well, correctly matching the timing of hourly (approximately 15:00 local time (LT)) and monthly (mid-June) peak surface ozone abundance. The amplitude of these cycles is less successfully matched. The observed summertime diurnal range (25 ppb) is underestimated in all regions by about 7 parts per billion, and the observed seasonal range (approximately 21 parts per billion) is underestimated by about 5 parts per billion except in the most polluted regions, where it is overestimated by about 5 parts per billion. The models generally match the pattern of the observed summertime ozone enhancement, but they overestimate its magnitude in most regions. Most models capture the observed distribution of extreme episode sizes, correctly showing that about 80 percent of individual extreme events occur in large-scale, multi-day episodes of more than 100 grid cells. The models also match the observed linear relationship between episode size and a measure of episode intensity, which shows increases in ozone abundance by up to 6 parts per billion for larger-sized episodes. We conclude that the skill of the models evaluated here provides confidence in their projections of future surface ozone.

  2. Characterizing interactions between surface water and groundwater in the Jialu River basin using major ion chemistry and stable isotopes

    Directory of Open Access Journals (Sweden)

    L. Yang

    2012-11-01

    Full Text Available The Jialu River, a secondary tributary of the Huaihe River, has been severely contaminated from major contaminant sources, such as a number of untreated or lightly treated sewage waste in some cities. Groundwater along the river is not an isolated component of the hydrologic system, but is instead connected with the surface water. This study aims to investigate temporal and spatial variations in water chemistry affected by humans and to characterize the relationships between surface water (e.g. reservoirs, lakes and rivers and groundwater near the river in the shallow Quaternary aquifer. Concentration of Cl in north Zhengzhou City increased prominently due to the discharge of a large amount of domestic water. Nitrate and potassium show maximum concentrations in groundwater in Fugou County. These high levels can be attributed to the use of a large quantity of fertilizer over this region. Most surface water appeared to be continuously recharged from the surrounding groundwater (regional wells based on comparison surface water with groundwater levels, stable-isotopes and major ion signatures. However, the groundwater of a transitional well (location SY3 seemed to be recharged by river water via bank infiltration in September 2010. Fractional contributions of river water to the groundwater were calculated based on isotopic and chemical data using a mass-balance approach. Results show that the groundwater was approximately composed of 60–70% river water. These findings should be useful for a better understanding of hydrogeological processes at the river-aquifer interface and ultimately benefit water management in the future.

  3. Adsorption of a Textile Dye on Commercial Activated Carbon: A Simple Experiment to Explore the Role of Surface Chemistry and Ionic Strength

    Science.gov (United States)

    Martins, Angela; Nunes, Nelson

    2015-01-01

    In this study, an adsorption experiment is proposed using commercial activated carbon as adsorbent and a textile azo dye, Mordant Blue-9, as adsorbate. The surface chemistry of the activated carbon is changed through a simple oxidation treatment and the ionic strength of the dye solution is also modified, simulating distinct conditions of water…

  4. Surface Chemistry Manipulation of Gold Nanorods Displays High Cellular Uptake In Vitro While Preserving Optical Properties for Bio-Imaging and Photo-Thermal Applications

    Science.gov (United States)

    2016-03-28

    two photon luminescence microscopy image intensity and photo-thermal cellular ablation compared to bare MTAB GNRs. These results demonstrate how TA...ROS assay ...........................................................................................................................5 3.8 RT- PCR ...luminescence microscopy image intensity and photo- thermal cellular ablation compared to bare MTAB GNRs. These results demonstrate how TA surface chemistry

  5. The design of a bipodal bis(pentafluorophenoxy)aluminate supported on silica as an activator for ethylene polymerization using surface organometallic chemistry.

    Science.gov (United States)

    Sauter, Dominique W; Popoff, Nicolas; Bashir, Muhammad Ahsan; Szeto, Kai C; Gauvin, Régis M; Delevoye, Laurent; Taoufik, Mostafa; Boisson, Christophe

    2016-04-04

    A new class of well-defined activating supports for olefin polymerization was obtained via the surface organometallic chemistry approach. High activities in slurry polymerization of ethylene along with industrial-grade physical properties of the resulting polyethylene were obtained when these activators were combined with metallocene complexes in the presence of triisobutylaluminium.

  6. Using Raman Spectroscopy and Surface-Enhanced Raman Scattering to Identify Colorants in Art: An Experiment for an Upper-Division Chemistry Laboratory

    Science.gov (United States)

    Mayhew, Hannah E.; Frano, Kristen A.; Svoboda, Shelley A.; Wustholz, Kristin L.

    2015-01-01

    Surface-enhanced Raman scattering (SERS) studies of art represent an attractive way to introduce undergraduate students to concepts in nanoscience, vibrational spectroscopy, and instrumental analysis. Here, we present an undergraduate analytical or physical chemistry laboratory wherein a combination of normal Raman and SERS spectroscopy is used to…

  7. Surface chemistry of nanoscale Fe3O4 dispersed in magnetic fluids

    Institute of Scientific and Technical Information of China (English)

    XIA; JianHan

    2007-01-01

    The interaction between stabilizers and nanoparticles is one of the important factors to prepare stable magnetic fluids. The magnetic nano-size Fe3O4 core with single domain and the average grain size around 8-12 nm were prepared by chemical precipitation method. The O/Fe molar ratio of the particle surface was measured by X-ray photoelectron spectroscopy (XPS). The heat effects of stabilizers adsorption on nanoparticles were measured by solution calorimetry. The excess amount of oxygen was possibly the result of the hydroxygen formed on the surface of the nanoparticles. The heat effects showed that compounds containing carboxyl groups can be adsorbed chemically on magnetite by forming chemical bonds. The other stabilizers involving NH-groups, such as polyethylene-imine, can be adsorbed physically. The exothermic value is about half of the former case.

  8. Surface chemistry-mediated penetration and gold nanorod thermotherapy in multicellular tumor spheroids

    Science.gov (United States)

    Jin, Shubin; Ma, Xiaowei; Ma, Huili; Zheng, Kaiyuan; Liu, Juan; Hou, Shuai; Meng, Jie; Wang, Paul C.; Wu, Xiaochun; Liang, Xing-Jie

    2012-12-01

    We investigated the penetration and thermotherapy efficiency of different surface coated gold nanorods (Au NRs) in multicellular tumor spheroids. The current data show that negatively charged Au NRs, other than positively charged Au NRs, can penetrate deep into the tumor spheroids and achieve a significant thermal therapeutic benefit.We investigated the penetration and thermotherapy efficiency of different surface coated gold nanorods (Au NRs) in multicellular tumor spheroids. The current data show that negatively charged Au NRs, other than positively charged Au NRs, can penetrate deep into the tumor spheroids and achieve a significant thermal therapeutic benefit. Electronic supplementary information (ESI) available: Materials and methods section. See DOI: 10.1039/c2nr31877f

  9. Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate

    Science.gov (United States)

    Waychunas, G. A.; Rea, B. A.; Fuller, C. C.; Davis, J. A.

    1993-05-01

    EXAFS spectra were collected on both the As and Fe K-edges from samples of two-line ferrihydrite with adsorbed (ADS) and coprecipitated (CPT) arsenate prepared over a range of conditions and arsenate surface coverages. Spectra also were collected for arsenate adsorbed on the surfaces of three FeOOH crystalline polymorphs, α (goethite), β (akaganeite), and γ (lepidocrocite), and as a free ion in aqueous: solution. Analyses of the As EXAFS show clear evidence for inner sphere bidentate (bridging) arsenate complexes on the ferrihydrite surface and on the surfaces of the crystalline FeOOH polymorphs. The bridging arsenate is attached to adjacent apices of edge-sharing Fe oxyhydroxyl octahedra. The arsenic-iron distance at the interface ( 3.28 ±0.01 Å) is close to that expected for this geometry on the FeOOH polymorph surfaces, but is slightly shorter on the ferrihydrite surfaces ( 3.25 ± 0.02 Å). Mono-dentate arsenate linkages ( 3.60 ± 0.03 Å) also occur on the ferrihydrite, but are not generally observed on the crystalline FeOOH polymorphs. The proportion of monodentate bonds appears largest for adsorption samples with the smallest As/Fe molar ratio. In all cases the arsenate tetrahedral complex is relatively undistorted with As-O bonds of 1.66 ± 0.01 Å. Precipitation of arsenate or scorodite-like phases was not observed for any samples, all of which were prepared at a pH value of 8. The Fe EXAFS results confirm that the Fe-Fe correlations in the ferrihydrite are progressively disrupted in the CPT samples as the As/Fe ratio is increased. Coherent crystallite size is probably no more than 10 Å in diameter and no Fe oxyhydroxyl octahedra corner-sharing linkages (as would be present in FeOOH polymorphs) are observed at the largest As/Fe ratios. Comparison of the number and type of Fe-Fe neighbors with the topological constraints imposed by the arsenate saturation limit in the CPT samples (about 0.7 As/Fe) indicates ferrihydrite units consisting mainly of Fe

  10. Control of Colloid Surface Chemistry through Matrix Confinement: Facile Preparation of Stable Antibody Functionalized Silver Nanoparticles

    Science.gov (United States)

    Skewis, Lynell R.; Reinhard, Björn M.

    2010-01-01

    Here we describe a simple yet efficient gel matrix assisted preparation method which improves synthetic control over the interface between inorganic nanomaterials and biopolymers and yields stable biofunctionalized silver nanoparticles. Covalent functionalization of the noble metal surface is aided by the confinement of polyethylene glycol acetate functionalized silver nanoparticles in thin slabs of a 1% agarose gel. The gel confined nanoparticles can be transferred between reaction and washing media simply by immersing the gel slab in the solution of interest. The agarose matrix retains nanoparticles but is swiftly penetrated by the antibodies of interest. The antibodies are covalently anchored to the nanoparticles using conventional crosslinking strategies, and the resulting antibody functionalized nanoparticles are recovered from the gel through electroelution. We demonstrate the efficacy of this nanoparticle functionalization approach by labeling specific receptors on cellular surfaces with functionalized silver nanoparticles that are stable under physiological conditions. PMID:20161660

  11. Coupling between bulk- and surface chemistry in suspensions of charged colloids

    Science.gov (United States)

    Heinen, M.; Palberg, T.; Löwen, H.

    2014-03-01

    The ionic composition and pair correlations in fluid phases of realistically salt-free charged colloidal sphere suspensions are calculated in the primitive model. We obtain the number densities of all ionic species in suspension, including low-molecular weight microions, and colloidal macroions with acidic surface groups, from a self-consistent solution of a coupled physicochemical set of nonlinear algebraic equations and non-mean-field liquid integral equations. Here, we study suspensions of colloidal spheres with sulfonate or silanol surface groups, suspended in demineralized water that is saturated with carbon dioxide under standard atmosphere. The only input required for our theoretical scheme are the acidic dissociation constants pKa, and effective sphere diameters of all involved ions. Our method allows for an ab initio calculation of colloidal bare and effective charges, at high numerical efficiency.

  12. Defect-free Perpendicular Diblock Copolymer Films: The Synergistic Effect of Surface Topography and Chemistry

    CERN Document Server

    Man, Xingkun; Tang, Jiuzhou; Yan, Dadong; Andelman, David

    2016-01-01

    We propose a direct self-assembly mechanism towards obtaining defect-free perpendicular lamellar phases of diblock copolymer (BCP) thin films. In our numerical study, a thin BCP film having a flat top surface is casted on a uni-directional corrugated solid substrate. The substrate is treated chemically and has a weak preference toward one of the two BCP components. Employing self-consistent field theory (SCFT), we find that there is an enhanced synergy between two substrate characteristics: its topography (geometrical roughness) combined with a weak surface preference. This synergy produces the desired perpendicular lamellar phase with perfect inplane ordering. Defect-free BCP lamellar phases are reproducible for several random initial states, and are obtained for a range of substrate roughness and chemical characteristics, even for a uni-directional multi-mode substrate roughness. Our theoretical study suggests possible experiments that will explore the interplay between uni-directional substrate corrugation...

  13. Role of surface chemistry in modified ACF (activated carbon fiber)-catalyzed peroxymonosulfate oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Shiying, E-mail: ysy@ouc.edu.cn [Key Laboratory of Marine Environment and Ecology, Ministry of Education, Qingdao 266100 (China); College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100 (China); Shandong Provincial Key Laboratory of Marine Environment and Geological Engineering (MEGE), Qingdao 266100 (China); Li, Lei [College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100 (China); Xiao, Tuo [College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100 (China); China City Environment Protection Engineering Limited Company, Wuhan 430071 (China); Zheng, Di; Zhang, Yitao [College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100 (China)

    2016-10-15

    Highlights: • ACF can efficiently activate peroxymonosulfate to degrade organic pollutants. • Basic functional groups may mainly increase the adsorption capacity of ACF. • C1, N1, N2 have promoting effect on the ACF catalyzed PMS oxidation. • Modification by heat after nitric acid is also a way of ACF regeneration. - Abstract: A commercial activated carbon fiber (ACF-0) was modified by three different methods: nitration treatment (ACF-N), heat treatment (ACF-H) and heat treatment after nitration (ACF-NH), and the effects of textural and chemical properties on the ability of the metal-free ACF-catalyzed peroxymonosulfate (PMS) oxidation of Reactive Black 5 (RB5), an azo dye being difficultly adsorbed onto ACF, in aqueous solution were investigated in this work. Surface density of functional groups, surface area changes, surface morphology and the chemical state inside ACF samples were characterized by Boehm titration, N{sub 2} adsorption, scanning electron microscopy in couple with energy dispersive spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy (XPS), respectively. XPS spectra deconvolution was applied to figure out the importance of surface nitrogen-containing function groups. We found that π-π, pyridine and amine have promoting effect on the catalytic oxidation while the −NO{sub 2} has inhibitory effect on the ACF/PMS systems for RB5 destroy. Sustainability and renewability of the typical ACF-NH for catalytic oxidation of RB5 were also discussed in detail. Information about our conclusions are useful to control and improve the performance of ACF-catalyzed PMS oxidation for organic pollutants in wastewater treatment.

  14. Chemistry of the interaction between azole type corrosion inhibitor molecules and metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Kovacevic, Natasa [Department of Physical and Organic Chemistry, Jozef Stefan Institute, Jamova 39, SI-1000 Ljubljana (Slovenia); Kokalj, Anton, E-mail: tone.kokalj@ijs.si [Department of Physical and Organic Chemistry, Jozef Stefan Institute, Jamova 39, SI-1000 Ljubljana (Slovenia)

    2012-11-15

    By means of density functional theory calculations, it has been shown how typical organic corrosion inhibitors-molecules that have the ability to remarkably slow down the corrosion of metals and alloys-interact with bare surfaces of various types of metals. As representative model systems, benzimidazole and benzotriazole inhibitors on iron, copper, and aluminum surfaces are considered. It is found that bonding depends sensitively on the type of metal. On transition metals with open d-band the inhibitor molecules can chemisorb strongly either parallel to the surface with a pronounced {pi}-d hybridization or perpendicularly with unsaturated N atom(s) through {sigma}-molecular orbitals, whereas on transition metals with fully occupied d-band and on sp-metals the molecules weakly chemisorb only with the latter mode. In addition to neutral inhibitor molecules also inhibitors in deprotonated (anionic) and protonated (cationic) forms are considered, because many corrosion inhibitors possess acidic hydrogens as well as basic heteroatoms. It is shown that the chemisorptive bonding is far the strongest for deprotonated inhibitors and, moreover, that even protonated inhibitors may chemisorb, although such bonding is characteristic of more reactive metals. However adsorbed protonated inhibitors are likely to deprotonate on all considered metals, whereas further deprotonation from neutral to deprotonated form is more likely on more reactive metals. Highlights: Black-Right-Pointing-Pointer Bonding of azole corrosion inhibitors onto metal surfaces characterized by DFT calculations. Black-Right-Pointing-Pointer Adsorption bonding depends sensitively on the type of metal. Black-Right-Pointing-Pointer Azoles bond with either {pi}-system or {sigma}-orbitals to transition metals with open d-band. Black-Right-Pointing-Pointer Azoles bond with {sigma}-orbitals to transition metals with fully occupied d-band and to sp-metals. Black-Right-Pointing-Pointer Among various molecular forms

  15. The influence of projectile ion induced chemistry on surface pattern formation

    Science.gov (United States)

    Karmakar, Prasanta; Satpati, Biswarup

    2016-07-01

    We report the critical role of projectile induced chemical inhomogeneity on surface nanostructure formation. Experimental inconsistency is common for low energy ion beam induced nanostructure formation in the presence of uncontrolled and complex contamination. To explore the precise role of contamination on such structure formation during low energy ion bombardment, a simple and clean experimental study is performed by selecting mono-element semiconductors as the target and chemically inert or reactive ion beams as the projectile as well as the source of controlled contamination. It is shown by Atomic Force Microscopy, Cross-sectional Transmission Electron Microscopy, and Electron Energy Loss Spectroscopy measurements that bombardment of nitrogen-like reactive ions on Silicon and Germanium surfaces forms a chemical compound at impact zones. Continuous bombardment of the same ions generates surface instability due to unequal sputtering and non-uniform re-arrangement of the elemental atom and compound. This instability leads to ripple formation during ion bombardment. For Argon-like chemically inert ion bombardment, the chemical inhomogeneity induced boost is absent; as a result, no ripples are observed in the same ion energy and fluence.

  16. Surface chemistry allows for abiotic precipitation of dolomite at low temperature.

    Science.gov (United States)

    Roberts, Jennifer A; Kenward, Paul A; Fowle, David A; Goldstein, Robert H; González, Luis A; Moore, David S

    2013-09-03

    Although the mineral dolomite is abundant in ancient low-temperature sedimentary systems, it is scarce in modern systems below 50 °C. Chemical mechanism(s) enhancing its formation remain an enigma because abiotic dolomite has been challenging to synthesize at low temperature in laboratory settings. Microbial enhancement of dolomite precipitation at low temperature has been reported; however, it is still unclear exactly how microorganisms influence reaction kinetics. Here we document the abiotic synthesis of low-temperature dolomite in laboratory experiments and constrain possible mechanisms for dolomite formation. Ancient and modern seawater solution compositions, with identical pH and pCO2, were used to precipitate an ordered, stoichiometric dolomite phase at 30 °C in as few as 20 d. Mg-rich phases nucleate exclusively on carboxylated polystyrene spheres along with calcite, whereas aragonite forms in solution via homogeneous nucleation. We infer that Mg ions are complexed and dewatered by surface-bound carboxyl groups, thus decreasing the energy required for carbonation. These results indicate that natural surfaces, including organic matter and microbial biomass, possessing a high density of carboxyl groups may be a mechanism by which ordered dolomite nuclei form. Although environments rich in organic matter may be of interest, our data suggest that sharp biogeochemical interfaces that promote microbial death, as well as those with high salinity may, in part, control carboxyl-group density on organic carbon surfaces, consistent with origin of dolomites from microbial biofilms, as well as hypersaline and mixing zone environments.

  17. Formation of alkenes and oxygenated VOCs from light mediated surface chemistry of nonanoic acid at the air-seawater interface

    Science.gov (United States)

    Gonzalez, L.; Volkamer, R.; Ciuraru, R.; Bernard, F.; George, C.

    2013-12-01

    Organic carbon is relevant in the atmosphere because it affects oxidative capacity that determines the removal rate of climate active gases and modifies aerosols. The significant presence of organic compounds at the surface of the ocean is a source for primary and secondary aerosol formation that potentially can modify cloud cover. Field observations of glyoxal over the remote marine boundary layer, and the tropical free troposphere remain unexplained by atmospheric models, and indicate missing sources of marine organic carbon species from heterogeneous processes mediated by light. We have studied the light induced surface chemistry of synthetic aqueous -mixtures containing NaCl, NaBr, NaI, photosensitizers (humic acids) and an organic surfactant (nonanoic acid) in a photochemical Quartz flowreactor. The air from the flowreactor was transferred to a dark reactor where the products from photosensitized reactions at the air/sea interface were further exposed to ozone. The products were sampled in the presence/absence of light and ozone by Proton Transfer Reaction Time of Flight Mass Spectrometry (PTR-ToF-MS) and Light-Emitting-Diode Cavity-Enhanced Differential Optical Absorption Spectroscopy (LED-CE-DOAS). In the presence of light nonenal formation is observed. Addition of ozone leads to the formation of glyoxal, among other products. Further experiments were conducted in an atmospheric simulation chamber. We discuss first results and atmospheric implications.

  18. Comparison of surface water chemistry and weathering effects of two lake basins in the Changtang Nature Reserve, China.

    Science.gov (United States)

    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.

  19. Surface chemistry and spectroscopy of UG8 asphaltene Langmuir film, part 2.

    Science.gov (United States)

    Orbulescu, Jhony; Mullins, Oliver C; Leblanc, Roger M

    2010-10-05

    While there has been much focus on asphaltenes in toluene, there has been much less focus on asphaltenes in other solvents. It is important to quantify characteristics of asphaltenes in solvents besides toluene in order to better assess their molecular architecture as well as their fundamental aggregation characteristics. The present work focuses on the investigation of UG8 asphaltene Langmuir films at the air-water interface using chloroform as spreading solvent. The results are compared to the results recently obtained using toluene as spreading solvent. Surface pressure-area isotherms and UV-vis spectroscopy indicate that asphaltenes form smaller nanoaggregates in chloroform than in toluene in similar concentration ranges. Still these nanoaggreates share common features with those in toluene. From the surface pressure-area and compression-decompression isotherms, Brewster angle microscopy, and p-polarized infrared reflection-absorption spectroscopy, it was concluded that small size aggregates are spread on the water surface and the compression of the film leads to formation of large aggregates. The films (Langmuir-Schaefer and Langmuir-Blodgett) studied by atomic force microscopy reveal the existence of nanoaggregates spread on the water surface that coexist with large aggregates formed during compression. In addition to these findings, the spreading solvent, chloroform, allows the determination of asphaltene absorption bands using in situ UV-vis spectroscopy at the air-water interface after 15 min waiting time period. The absorbance data carried out after waiting a time period of 1 h shows similar features with the ones carried out after only 15 min; therefore, there is no need to wait 1 h as in the case when toluene is used as spreading solvent. A comparison of the data obtained from chloroform and toluene shows that smaller aggregate sizes are obtained from chloroform as suggested from the surface pressure-area isotherm, in situ UV-vis spectroscopy, and

  20. Luminescent Lanthanide Reporters for High-Sensitivity Novel Bioassays.

    Energy Technology Data Exchange (ETDEWEB)

    Anstey, Mitchell R.; Fruetel, Julia A.; Foster, Michael E.; Hayden, Carl C.; Buckley, Heather L.; Arnold, John

    2013-09-01

    Biological imaging and assay technologies rely on fluorescent organic dyes as reporters for a number of interesting targets and processes. However, limitations of organic dyes such as small Stokes shifts, spectral overlap of emission signals with native biological fluorescence background, and photobleaching have all inhibited the development of highly sensitive assays. To overcome the limitations of organic dyes for bioassays, we propose to develop lanthanide-based luminescent dyes and demonstrate them for molecular reporting applications. This relatively new family of dyes was selected for their attractive spectral and chemical properties. Luminescence is imparted by the lanthanide atom and allows for relatively simple chemical structures that can be tailored to the application. The photophysical properties offer unique features such as narrow and non-overlapping emission bands, long luminescent lifetimes, and long wavelength emission, which enable significant sensitivity improvements over organic dyes through spectral and temporal gating of the luminescent signal.Growth in this field has been hindered due to the necessary advanced synthetic chemistry techniques and access to experts in biological assay development. Our strategy for the development of a new lanthanide-based fluorescent reporter system is based on chelation of the lanthanide metal center using absorbing chromophores. Our first strategy involves "Click" chemistry to develop 3-fold symmetric chelators and the other involves use of a new class of tetrapyrrole ligands called corroles. This two-pronged approach is geared towards the optimization of chromophores to enhance light output.

  1. A Surface Chemistry Approach to Enhancing Colloidal Quantum Dot Solids for Photovoltaics

    Science.gov (United States)

    Carey, Graham Hamilton

    Colloidal quantum dot (CQD) photovoltaic devices have improved rapidly over the past decade of research. By taking advantage of the quantum confinement effect, solar cells constructed using films of infrared-bandgap nanoparticles are able to capture previously untapped ranges of the solar energy spectrum. Additionally, films are fabricated using simple, cheap, reproducible solution processing techniques, enabling the creation of low-cost, flexible photovoltaic devices. A key factor limiting the creation of high efficiency CQD solar cells is the short charge carrier diffusion length in films. Driven by a combination of limited carrier mobility, poor nanoparticle surface passivation, and the presence of unexamined electrically active impurities throughout the film, the poor diffusion length limits the active layer thickness in CQD solar cells, leading to lower-than-desired light absorption, and curtailing the photocurrent generated by such devices. This thesis seeks to address poor diffusion length by addressing each of the limiting factors in turn. Electrical transport in quantum dot solids is examined in the context of improved quantum dot packing; methods are developed to improve packing by using actively densifying components, or by dramatically lowering the volume change required between quantum dots in solution and in solid state. Quantum dot surface passivation is improved by introducing a crucial secondary, small halide ligand source, and by surveying the impact of the processing environment on the final quality of the quantum dot surface. A heretofore unidentified impurity present in quantum dot solids is identified, characterized, and chemically eliminated. Finally, lessons learned through these experiments are combined into a single, novel materials system, leading to quantum dot devices with a significantly improved diffusion length (enhanced from 70 to 230 nm). This enabled thick, high current density (30 mA cm -2, compared to typical values in the 20

  2. Surface chemistry and spectroscopy of UG8 asphaltene Langmuir film, part 1.

    Science.gov (United States)

    Orbulescu, Jhony; Mullins, Oliver C; Leblanc, Roger M

    2010-10-05

    This research focuses on a systematic investigation of UG8 asphaltene Langmuir films at the air-water interface using toluene as the spreading solvent. From the surface pressure-area isotherms, it was concluded that small-sized aggregates are spread on the water surface and the compression of the film leads to formation of large aggregates. Our methods provide a stringent test and confirmation for the formation of corresponding asphaltene nanoaggregates that have recently been proposed for bulk solutions. These results were confirmed by compression-decompression isotherms, Brewster angle microscopy, and p-polarized infrared reflection-absorption spectroscopy. The transfer of a single layer using both the Langmuir-Schaefer and Langmuir-Blodgett deposition techniques shows different aggregate shapes depending on the technique used as imaged using atomic force microscopy. The films reveal the existence of nanoaggregates spread on the water surface that coexist with large aggregates formed during compression. For the nanoaggregate, the thickness of the Langmuir-Schaefer and Langmuir-Blodgett films determined by AFM is consistent with small aggregation numbers of nanoaggregates determined by Langmuir film compression. In addition to these findings, the spreading solvent, toluene, was found to be trapped within the aggregates as confirmed by in situ UV-vis spectroscopy at the air-water interface. This result was possible only after waiting a time period of 1 h to allow the complete evaporation of the spreading solvent. This is the only study that reveals the presence of the in situ toluene within the UG8 aggregates directly at the air-water interface.

  3. Tungsten Incorporation into Gallium Oxide: Crystal Structure, Surface and Interface Chemistry, Thermal Stability and Interdiffusion

    Energy Technology Data Exchange (ETDEWEB)

    Rubio, E. J.; Mates, T. E.; Manandhar, S.; Nandasiri, M.; Shutthanandan, V.; Ramana, C. V.

    2016-12-01

    Tungsten (W) incorporated gallium oxide (Ga2O3) (GWO) thin films were deposited by radio-frequency magnetron co-sputtering of W-metal and Ga2O3-ceramic targets. Films were produced by varying sputtering power applied to the W-target in order to achieve variable W-content (0-12 at%) into Ga2O3 while substrate temperature was kept constant at 500 °C. Chemical composition, chemical valence states, microstructure and crystal structure of as-deposited and annealed GWO films were evaluated as a function of W-content. The structural and chemical analyses indicate that the samples deposited without any W-incorporation are stoichiometric, nanocrystalline Ga2O3 films, which crystallize in β-phase monoclinic structure. While GWO films also crystallize in monoclinic β-Ga2O3 phase, W-incorporation induces surface amorphization as revealed by structural studies. The chemical valence state of Ga ions probed by X-ray photoelectron spectroscopic (XPS) analyses is characterized by the highest oxidation state i.e., Ga3+. No changes in Ga chemical state are noted for variable W-incorporation in the range of 0-12 at%. Rutherford backscattering spectrometry (RBS) analyses indicate the uniform distribution of W-content in the GWO films. However, XPS analyses indicate the formation of mixed valence states for W ions, which may be responsible for surface amorphization in GWO films. GWO films were stable up to 900 oC, at which point thermally induced secondary phase (W-oxide) formation was observed. A transition to mesoporous structure coupled with W interdiffusion occurs due to thermal annealing as derived from the chemical analyses at the GWO films’ surface as well as depth-profiling towards the GWO-Si interface. A model has been formulated to account for the mechanism of W-incorporation, thermal stability and interdiffusion via pore formation in GWO films.

  4. A Finite-Rate Gas-Surface Interaction Model Informed by Fundamental Computational Chemistry Simulations

    Science.gov (United States)

    2013-03-31

    oxygen interactions with a specific crystalline polymorph of SiO2 (called β- cristobalite ). Computer images of this crystal lattice are shown in Fig...2. The choice of β- cristobalite is motivated by experimental studies from Balat-Pichelin et al. [15,22,23] where silicon-carbide (SiC) surfaces were...conclusion that the measured loss rates correspond to β- cristobalite was based on the fact that for polymorph diagrams of SiO2, β- cristobalite is most stable

  5. Photo-Induced Click Chemistry for DNA Surface Structuring by Direct Laser Writing.

    Science.gov (United States)

    Kerbs, Antonina; Mueller, Patrick; Kaupp, Michael; Ahmed, Ishtiaq; Quick, Alexander S; Abt, Doris; Wegener, Martin; Niemeyer, Christof M; Barner-Kowollik, Christopher; Fruk, Ljiljana

    2017-02-15

    Oligonucleotides containing photo-caged dienes were prepared and shown to react quantitatively in a light-induced Diels-Alder cycloaddition with functional maleimides in aqueous solution within minutes. Due to its high yield and fast rate, the reaction was exploited for DNA surface patterning with sub-micrometer resolution employing direct laser writing (DLW). Functional DNA arrays were written by direct laser writing (DLW) in variable patterns, which were further encoded with fluorophores and proteins through DNA directed immobilization. This mild and efficient light-driven platform technology holds promise for the fabrication of complex bioarrays with sub-micron resolution.

  6. The effect of nanoparticle size, shape, and surface chemistry on biological systems.

    Science.gov (United States)

    Albanese, Alexandre; Tang, Peter S; Chan, Warren C W

    2012-01-01

    An understanding of the interactions between nanoparticles and biological systems is of significant interest. Studies aimed at correlating the properties of nanomaterials such as size, shape, chemical functionality, surface charge, and composition with biomolecular signaling, biological kinetics, transportation, and toxicity in both cell culture and animal experiments are under way. These fundamental studies will provide a foundation for engineering the next generation of nanoscale devices. Here, we provide rationales for these studies, review the current progress in studies of the interactions of nanomaterials with biological systems, and provide a perspective on the long-term implications of these findings.

  7. Theoretical investigations of metallic surfaces for water chemistry; Theoretische Untersuchungen metallischer Oberflaechen fuer die Wasserstoffchemie

    Energy Technology Data Exchange (ETDEWEB)

    Schnur, Sebastian

    2010-11-19

    Properties of the metal-water interface have been addressed by periodic density functional theory calculations, in particular with respect to the electronic and geometric structures of water bilayers on several transition metal surfaces. The structure and the vibrational spectra of water bilayers at room temperatures have been studied performing ab initio molecular dynamics simulations. In order to model varying electrode potentials, an explicite counter electrode has been implemented in a periodic density functional theory code, and first preliminary results using this implementation will be presented. (orig.)

  8. Benchmarking organic micropollutants in wastewater, recycled water and drinking water with in vitro bioassays.

    Science.gov (United States)

    Escher, Beate I; Allinson, Mayumi; Altenburger, Rolf; Bain, Peter A; Balaguer, Patrick; Busch, Wibke; Crago, Jordan; Denslow, Nancy D; Dopp, Elke; Hilscherova, Klara; Humpage, Andrew R; Kumar, Anu; Grimaldi, Marina; Jayasinghe, B Sumith; Jarosova, Barbora; Jia, Ai; Makarov, Sergei; Maruya, Keith A; Medvedev, Alex; Mehinto, Alvine C; Mendez, Jamie E; Poulsen, Anita; Prochazka, Erik; Richard, Jessica; Schifferli, Andrea; Schlenk, Daniel; Scholz, Stefan; Shiraishi, Fujio; Snyder, Shane; Su, Guanyong; Tang, Janet Y M; van der Burg, Bart; van der Linden, Sander C; Werner, Inge; Westerheide, Sandy D; Wong, Chris K C; Yang, Min; Yeung, Bonnie H Y; Zhang, Xiaowei; Leusch, Frederic D L

    2014-01-01

    Thousands of organic micropollutants and their transformation products occur in water. Although often present at low concentrations, individual compounds contribute to mixture effects. Cell-based bioassays that target health-relevant biological endpoints may therefore complement chemical analysis for water quality assessment. The objective of this study was to evaluate cell-based bioassays for their suitability to benchmark water quality and to assess efficacy of water treatment processes. The selected bioassays cover relevant steps in the toxicity pathways including induction of xenobiotic metabolism, specific and reactive modes of toxic action, activation of adaptive stress response pathways and system responses. Twenty laboratories applied 103 unique in vitro bioassays to a common set of 10 water samples collected in Australia, including wastewater treatment plant effluent, two types of recycled water (reverse osmosis and ozonation/activated carbon filtration), stormwater, surface water, and drinking water. Sixty-five bioassays (63%) showed positive results in at least one sample, typically in wastewater treatment plant effluent, and only five (5%) were positive in the control (ultrapure water). Each water type had a characteristic bioanalytical profile with particular groups of toxicity pathways either consistently responsive or not responsive across test systems. The most responsive health-relevant endpoints were related to xenobiotic metabolism (pregnane X and aryl hydrocarbon receptors), hormone-mediated modes of action (mainly related to the estrogen, glucocorticoid, and antiandrogen activities), reactive modes of action (genotoxicity) and adaptive stress response pathway (oxidative stress response). This study has demonstrated that selected cell-based bioassays are suitable to benchmark water quality and it is recommended to use a purpose-tailored panel of bioassays for routine monitoring.

  9. Fine-tuning of substrate architecture and surface chemistry promotes muscle tissue development.

    Science.gov (United States)

    Guex, A G; Kocher, F M; Fortunato, G; Körner, E; Hegemann, D; Carrel, T P; Tevaearai, H T; Giraud, M N

    2012-04-01

    Tissue engineering has been increasingly brought to the scientific spotlight in response to the tremendous demand for regeneration, restoration or substitution of skeletal or cardiac muscle after traumatic injury, tumour ablation or myocardial infarction. In vitro generation of a highly organized and contractile muscle tissue, however, crucially depends on an appropriate design of the cell culture substrate. The present work evaluated the impact of substrate properties, in particular morphology, chemical surface composition and mechanical properties, on muscle cell fate. To this end, aligned and randomly oriented micron (3.3±0.8 μm) or nano (237±98 nm) scaled fibrous poly(ε-caprolactone) non-wovens were processed by electrospinning. A nanometer-thick oxygen functional hydrocarbon coating was deposited by a radio frequency plasma process. C2C12 muscle cells were grown on pure and as-functionalized substrates and analysed for viability, proliferation, spatial orientation, differentiation and contractility. Cell orientation has been shown to depend strongly on substrate architecture, being most pronounced on micron-scaled parallel-oriented fibres. Oxygen functional hydrocarbons, representing stable, non-immunogenic surface groups, were identified as strong triggers for myotube differentiation. Accordingly, the highest myotube density (28±15% of total substrate area), sarcomeric striation and contractility were found on plasma-coated substrates. The current study highlights the manifold material characteristics to be addressed during the substrate design process and provides insight into processes to improve bio-interfaces.

  10. Quantum dot surface chemistry and functionalization for cell targeting and imaging.

    Science.gov (United States)

    Bilan, Regina; Fleury, Fabrice; Nabiev, Igor; Sukhanova, Alyona

    2015-04-15

    Quantum dots (QDs) are highly fluorescent nanoscale crystals with size-dependent emission spectra. Due to their excellent photophysical properties, QDs are a promising alternative to organic fluorescent dyes and fluorescent proteins for cell targeting, imaging, and drug delivery. For biomedical applications, QDs should be chemically modified to be stable in aqueous solutions and tagged with the recognition molecules or drugs. Here, we review surface modification approaches to, and strategies for, conjugation of bioactive molecules with QDs. There are a variety of methods of QD surface modification and QD incorporation into larger delivery systems that yield fluorescent nanocarriers from 10 nm to several micrometers. Conjugates of QDs with peptides, proteins, antibodies, oligonucleotides, and small molecules have been used for fluorescent targeting, tracking, and imaging both in vitro and in vivo. Due to an extremely high stability to photobleaching, QDs were used for long-term visualization. QD applications pave the way for new generations of ultrasensitive detection, diagnostic systems, as well as drug delivery approaches, combining accurate targeting, delivery, and imaging in a single assay.

  11. Interpretation of friction and wear in DLC film: role of surface chemistry and test environment

    Science.gov (United States)

    Polaki, S. R.; Kumar, N.; Madapu, K.; Ganesan, K.; Krishna, N. G.; Srivastava, S. K.; Abhaya, S.; Kamruddin, M.; Dash, S.; Tyagi, A. K.

    2016-11-01

    In spite of the large amount of tribological work carried out to explain the friction and wear mechanism in diamond-like carbon (DLC) films, some of the core issues relating to the evolution of reactive species across sliding interfaces and their role on the friction and wear mechanism remain unclear. The phase composition, film density and hydrogen content present in a DLC film can be tailored by substrate biasing during film deposition to achieve a nearly vanishing friction coefficient. Furthermore, nitrogen doping in DLC films significantly improves wear resistance, and sliding occurs in a nearly wearless regime. Undoped and nitrogen-doped DLC films exhibit a nearly frictionless value with ultra-low wear behavior when tests are performed in argon, nitrogen and methane atmospheres. The antifriction and antiwear properties of the DLC films were improved with the reduction of adsorbed oxygen impurities on the film surface. This behavior was understood by correlating the oxygen impurities present at the surface/subsurface region of the DLC film while using x-ray photoelectron spectroscopy and depth-resolved Auger electron spectroscopy.

  12. Effect of surface chemistry on the behaviour of solid particles in multiphase flow

    Energy Technology Data Exchange (ETDEWEB)

    Gulbrandsen, Egil; Pedersen, Anette

    2006-03-15

    The surface chemical properties of solids particles strongly influence their behaviour in multiphase flow, e.g. their tendency to be transported by the oil or water phase, their tendency to stick to the oil-water interfaces, or their tendency to aggregate. The behaviour of the solid particles may influence various processes such as emulsion breakdown, oil-water separation, or sedimentation of solids in a pipeline, and thereby issues as erosion, and corrosion under deposits. These issues were addressed in the present laboratory study. The reported results focus on behaviour of sand in a simple oil-water system in presence of a model corrosion inhibitor compound, cetyltrimethylammonium bromide. A refined oil was used in the tests. The system was studied by various methods like zeta-potential measurements, assessment of wetting properties and tendency of aggregation and sedimentation in oil-water system. It was found that surface-active corrosion inhibitor could strongly influence the wetting of the sand. By addition of the corrosion inhibitor, the sand changed from water wet to oil wet. This change induced a tendency to aggregation of the sand grains. The aggregation led to sticky deposits of sand. This may have an impact on under deposit corrosion phenomena. (Author)

  13. Degradable polyester scaffolds with controlled surface chemistry combining minimal protein adsorption with specific bioactivation

    Science.gov (United States)

    Grafahrend, Dirk; Heffels, Karl-Heinz; Beer, Meike V.; Gasteier, Peter; Möller, Martin; Boehm, Gabriele; Dalton, Paul D.; Groll, Jürgen

    2011-01-01

    Advanced biomaterials and scaffolds for tissue engineering place high demands on materials and exceed the passive biocompatibility requirements previously considered acceptable for biomedical implants. Together with degradability, the activation of specific cell-material interactions and a three-dimensional environment that mimics the extracellular matrix are core challenges and prerequisites for the organization of living cells to functional tissue. Moreover, although bioactive signalling combined with minimization of non-specific protein adsorption is an advanced modification technique for flat surfaces, it is usually not accomplished for three-dimensional fibrous scaffolds used in tissue engineering. Here, we present a one-step preparation of fully synthetic, bioactive and degradable extracellular matrix-mimetic scaffolds by electrospinning, using poly(D,L-lactide-co-glycolide) as the matrix polymer. Addition of a functional, amphiphilic macromolecule based on star-shaped poly(ethylene oxide) transforms current biomedically used degradable polyesters into hydrophilic fibres, which causes the suppression of non-specific protein adsorption on the fibres’ surface. The subsequent covalent attachment of cell-adhesion-mediating peptides to the hydrophilic fibres promotes specific bioactivation and enables adhesion of cells through exclusive recognition of the immobilized binding motifs. This approach permits synthetic materials to directly control cell behaviour, for example, resembling the binding of cells to fibronectin immobilized on collagen fibres in the extracellular matrix of connective tissue.

  14. Effect of particle structure and surface chemistry on PMMA adsorption to silica nanoparticles.

    Science.gov (United States)

    Madathingal, Rajesh Raman; Wunder, Stephanie L

    2010-04-06

    The interphase layer of polymers adsorbed to silica surfaces can be affected by the surface silanol density as well as the relative size of the polymer compared with the size of the adsorbing substrate. Here, the nonequilibrium adsorption of PMMA onto individual colloidal Stober silica (SiO(2)) particles, where R(particle) (100 nm) > R(PMMA) (approximately 6.5 nm) was compared with the adsorption onto fumed silica, where R(particle) (7 nm) approximately R(PMMA) (6.5 nm) bonded to the silanols, and was independent of particle morphology. For methylated silica, (CH(3))(3)SiO(2), the adsorption isotherms were identical for colloidal and fumed silica, but T(g) was depressed for the former, and comparable to the bulk value for the latter. The increased T(g) of PMMA adsorbed onto fumed (CH(3))(3)SiO(2) was attributed to the larger loops formed by the bridging PMMA chains between the silica aggregates.

  15. Multilayer modeling of porous grain surface chemistry I. The GRAINOBLE model

    CERN Document Server

    Taquet, Vianney; Kahane, Claudine

    2011-01-01

    Mantles of iced water, mixed with CO, H2CO, and CH3OH are formed during the so called prestellar core phase. In addition, radicals are also thought to be formed on the grain surfaces, and to react to form complex organic molecules later on, during the warm-up phase of the protostellar evolution. The aim of this work is to study the formation of the grain mantles during the prestellar core phase and the abundance of H2CO, CH3OH, and radicals trapped in them. We have developed a macrosopic statistic multilayer model that follows the formation of grain mantles with time and that includes two effects that may increase the number of radicals trapped in the mantles: i) at each time of the mantle formation, only the surface layer is chemically active rather than the entire bulk, and ii) the porous structure of grains allows to trap reactive particles. The model considers a network of H, O and CO forming neutral species such as water, CO, formaldehyde, and methanol, plus several radicals. We run a large grid of model...

  16. Non-lithographic SERS substrates: tailoring surface chemistry for Au nanoparticle cluster assembly.

    Science.gov (United States)

    Adams, Sarah M; Campione, Salvatore; Caldwell, Joshua D; Bezares, Francisco J; Culbertson, James C; Capolino, Filippo; Ragan, Regina

    2012-07-23

    Near-field plasmonic coupling and local field enhancement in metal nanoarchitectures, such as arrangements of nanoparticle clusters, have application in many technologies from medical diagnostics, solar cells, to sensors. Although nanoparticle-based cluster assemblies have exhibited signal enhancements in surface-enhanced Raman scattering (SERS) sensors, it is challenging to achieve high reproducibility in SERS response using low-cost fabrication methods. Here an innovative method is developed for fabricating self-organized clusters of metal nanoparticles on diblock copolymer thin films as SERS-active structures. Monodisperse, colloidal gold nanoparticles are attached via a crosslinking reaction on self-organized chemically functionalized poly(methyl methacrylate) domains on polystyrene-block-poly(methyl methacrylate) templates. Thereby nanoparticle clusters with sub-10-nanometer interparticle spacing are achieved. Varying the molar concentration of functional chemical groups and crosslinking agent during the assembly process is found to affect the agglomeration of Au nanoparticles into clusters. Samples with a high surface coverage of nanoparticle cluster assemblies yield relative enhancement factors on the order of 10⁹ while simultaneously producing uniform signal enhancements in point-to-point measurements across each sample. High enhancement factors are associated with the narrow gap between nanoparticles assembled in clusters in full-wave electromagnetic simulations. Reusability for small-molecule detection is also demonstrated. Thus it is shown that the combination of high signal enhancement and reproducibility is achievable using a completely non-lithographic fabrication process, thereby producing SERS substrates having high performance at low cost.

  17. Aqueous bromine etching of InP: a specific surface chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Causier, A.; Bouttemy, M.; Gerard, I.; Aureau, D.; Vigneron, J.; Etcheberry, A. [Institut Lavoisier de Versailles, Versailles-Saint-Quentin University, UMR CNRS 8180, 45 Av. des Etats-Unis, 78035 Versailles (France)

    2012-06-15

    The n -InP behaviour in HBr (0.1-1.0 M)/Br{sub 2} (1.25 x 10{sup -2}M) aqueous solutions is studied by AAS, XPS and SEM-FEG. Indium AAS-titrations of the HBr/Br{sub 2} solutions demonstrate that InP undergoes an etching mechanism whatever the HBr/Br{sub 2} formulation. The etching process is always linear with time but its rate depends on the HBr concentration. XPS analyses permit to link the apparent slow-down of the dissolution process when decreasing the HBr molarity from 1.0 M to 0.1 M to the presence of a mixed (In,P){sub ox} oxide layer on the surface. Therefore, the dissolution process of InP in HBr/Br{sub 2} solution appears to be ruled by the surface chemical state (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  18. Revisiting 30 years of Biofunctionalization and Surface Chemistry of Inorganic Nanoparticles for Nanomedicine

    Directory of Open Access Journals (Sweden)

    João eConde

    2014-07-01

    Full Text Available In the last 30 years we have assisted to a massive advance of nanomaterials in material science. Nanomaterials and structures, in addition to their small size, have properties that differ from those of larger bulk materials, making them ideal for a host of novel applications. The spread of nanotechnology in the last years has been due to the improvement of synthesis and characterization methods on the nanoscale, a field rich in new physical phenomena and synthetic opportunities. In fact, the development of functional nanoparticles has progressed exponentially over the past two decades. This work aims to extensively review 30 years of different strategies of surface modification and functionalization of noble metal (gold nanoparticles, magnetic nanocrystals and semiconductor nanoparticles, such as quantum dots. The aim of this review is not only to provide in-depth insights into the different biofunctionalization and characterization methods, but also to give an overview of possibilities and limitations of the available nanoparticles.

  19. Silicon and germanium nanoparticles with tailored surface chemistry as novel inorganic fiber brightening agents.

    Science.gov (United States)

    Deb-Choudhury, Santanu; Prabakar, Sujay; Krsinic, Gail; Dyer, Jolon M; Tilley, Richard D

    2013-07-31

    Low-molecular-weight organic molecules, such as coumarins and stilbenes, are used commercially as fluorescent whitening agents (FWAs) to mask photoyellowing and to brighten colors in fabrics. FWAs achieve this by radiating extra blue light, thus changing the hue and also adding to the brightness. However, organic FWAs can rapidly photodegrade in the presence of ultraviolet (UV) radiation, exacerbating the yellowing process through a reaction involving singlet oxygen species. Inorganic nanoparticles, on the other hand, can provide a similar brightening effect with the added advantage of photostability. We report a targeted approach in designing new inorganic silicon- and germanium-based nanoparticles, functionalized with hydrophilic (amine) surface terminations as novel inorganic FWAs. When applied on wool, by incorporation in a sol-gel Si matrix, the inorganic FWAs improved brightness properties, demonstrated enhanced photostability toward UV radiation, especially the germanium nanoparticles, and also generated considerably lower levels of reactive oxygen species compared to a commercial stilbene-based organic FWA, Uvitex NFW.

  20. Tailoring the Surface Chemistry of Zeolite Templated Carbon by Electrochemical Methods

    Directory of Open Access Journals (Sweden)

    R. Berenguer

    2013-01-01

    Full Text Available One option to optimize carbon materials forsupercapacitor applications is the generation ofsurface functional groups that contribute to thepseudocapacitance without losing the designedphysical properties. This requires suitablefunctionalization techniques able to selectivelyintroduce a given amount of electroactive oxygengroups. In this work, the influence of the chemical andelectrochemical oxidation methods, on the chemicaland physical properties of a zeolite templated carbon(ZTC, as a model carbon material, have beenstudied and compared. Although both oxidationmethods generally produce a loss of the originalZTC physical properties with increasing amount ofoxidation, the electrochemical method shows muchbetter controllability and, unlike chemical treatments,enables the generation of a large number of oxygengroups (O = 11000- 3300 μmol/g, with a higherproportion of active functionalities, while retaining ahigh surface area (ranging between 1900-3500 m2/g,a high microporosity and an ordered 3-D structure.

  1. Analysis of post wet chemistry heat treatment effects on Nb SRF surface resistance

    CERN Document Server

    Dhakal, Pashupati; Kneisel, Peter; Myneni, Ganapati Rao

    2013-01-01

    Most of the current research in superconducting radio frequency (SRF) cavities is focused on ways to reduce the construction and operating cost of SRF based accelerators as well as on the development of new or improved cavity processing techniques. The increase in quality factors is the result of the reduction of the surface resistance of the materials. A recent test on a 1.5 GHz single cell cavity made from ingot niobium of medium purity and heat treated at 1400 C in a ultra-high vacuum induction furnace resulted in a residual resistance of about 1nanoohm and a quality factor at 2.0 K increasing with field up to 5x10^10 at a peak magnetic field of 90 mT. In this contribution, we present some results on the investigation of the origin of the extended Q0-increase, obtained by multiple HF rinses, oxypolishing and heat treatment of all Nb cavities.

  2. Revisiting 30 years of Biofunctionalization and Surface Chemistry of Inorganic Nanoparticles for Nanomedicine

    Science.gov (United States)

    Conde, João; Dias, Jorge; Grazú, Valeria; Moros, Maria; Baptista, Pedro; De La Fuente, Jesús

    2014-07-01

    In the last 30 years we have assisted to a massive advance of nanomaterials in material science. Nanomaterials and structures, in addition to their small size, have properties that differ from those of larger bulk materials, making them ideal for a host of novel applications. The spread of nanotechnology in the last years has been due to the improvement of synthesis and characterization methods on the nanoscale, a field rich in new physical phenomena and synthetic opportunities. In fact, the development of functional nanoparticles has progressed exponentially over the past two decades. This work aims to extensively review 30 years of different strategies of surface modification and functionalization of noble metal (gold) nanoparticles, magnetic nanocrystals and semiconductor nanoparticles, such as quantum dots. The aim of this review is not only to provide in-depth insights into the different biofunctionalization and characterization methods, but also to give an overview of possibilities and limitations of the available nanoparticles.

  3. An Assessment of Cell Culture Plate Surface Chemistry for in Vitro Studies of Tissue Engineering Scaffolds

    Directory of Open Access Journals (Sweden)

    Alexander Röder

    2015-11-01

    Full Text Available The use of biopolymers as a three dimensional (3D support structure for cell growth is a leading tissue engineering approach in regenerative medicine. Achieving consistent cell seeding and uniform cell distribution throughout 3D scaffold culture in vitro is an ongoing challenge. Traditionally, 3D scaffolds are cultured within tissue culture plates to enable reproducible cell seeding and ease of culture media change. In this study, we compared two different well-plates with different surface properties to assess whether seeding efficiencies and cell growth on 3D scaffolds were affected. Cell attachment and growth of murine calvarial osteoblast (MC3T3-E1 cells within a melt-electrospun poly-ε-caprolactone scaffold were assessed when cultured in either “low-adhesive” non-treated or corona discharged-treated well-plates. Increased cell adhesion was observed on the scaffold placed in the surface treated culture plates compared to the scaffold in the non-treated plates 24 h after seeding, although it was not significant. However, higher cell metabolic activity was observed on the bases of all well-plates than on the scaffold, except for day 21, well metabolic activity was higher in the scaffold contained in non-treated plate than the base. These results indicate that there is no advantage in using non-treated plates to improve initial cell seeding in 3D polymeric tissue engineering scaffolds, however non-treated plates may provide an improved metabolic environment for long-term studies.

  4. Surface Chemistry and Interface Evolution during the Atomic Layer Deposition of High-k Metal Oxides on InAs(100) and GaAs(100) Surfaces

    Science.gov (United States)

    Henegar, Alex J.

    Device scaling has been key for creating faster and more powerful electronic devices. Integral circuit components like the metal-oxide semiconductor field-effect transistor (MOSFET) now rely on material deposition techniques, like atomic layer deposition (ALD), that possess atomic-scale thickness precision. At the heart of the archetypal MOSFET is a SiO2/Si interface which can be formed to near perfection. However when the thickness of the SiO 2 layer is shrunk down to a few nanometers several complications arise like unacceptably high leakage current and power consumption. Replacing Si with III-V semiconductors and SiO2 with high-k dielectric materials is appealing but comes with its own set of challenges. While SiO2 is practically defect-free, the native oxides of III-Vs are poor dielectrics. In this dissertation, the surface chemistry and interface evolution during the ALD of high-k metal oxides on Si(100), GaAs(100) and InAs(100) was studied. In particular, the surface chemistry and crystallization of TiO2 films grown on Si(100) was investigated using transmission Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Large, stable, and highly reactive anatase TiO2 grains were found to form during a post-deposition heat treatment after the ALD at 100 °C. The remainder of this work was focused on the evolution of the interfacial oxides during the deposition of TiO2 and Al2O3 on InAs(100) and GaAs(100) and during the deposition of Ta2O 5 on InAs(100). In summary the ALD precursor type, deposited film, and substrate had an influence in the evolution of the native oxides. Alkyl amine precursors fared better at removing the native oxides but the deposited films (TiO2 and Ta2O5) were susceptible to significant native oxide diffusion. The alkyl precursor used for the growth of Al 2O3 was relatively ineffective at removing the oxides but was

  5. The Impact of Surface Chemistry on Bio-derived Carbon Performance as Supercapacitor Electrodes

    KAUST Repository

    Alshareef, Niman H.

    2016-12-23

    In this study, we demonstrate that highly functionalized and porous carbons can be derived from palm-leaf waste using the template-free facile synthesis process. The derived carbons have high content of nitrogen dopant, high surface area, and various defects. Moreover, these carbons exhibit a high electrical conductivity (107 S m−1). Thanks to the high content of edge N (64.3%) and highly microporous nature (82% of microspores), these biomass-derived carbons show promising performance when used as supercapacitor electrodes. To be specific, these carbonaceous materials show a specific capacitance as high as 197 and 135 F g−1 at 2 and 20 A g−1 in three-electrode configuration, respectively. Furthermore, the symmetrical cells using palm-leaf-derived carbon show an energy density of 8.4 Wh Kg−1 at a power density of 0.64 kW Kg−1, with high cycling life stability (∼8% loss after 10,000 continuous charge–discharge cycles at 20 A g−1). Interestingly, as the power density increases from 4.4 kW kg−1 to 36.8 kW kg−1, the energy density drops slowly from 8.4 Wh kg−1 to 3.4 Wh kg−1. Getting such extremely high power density without significant loss of energy density indicates that these palm-leaf-derived carbons have excellent electrode performance as supercapacitor electrodes.

  6. The Impact of Surface Chemistry on Bio-derived Carbon Performance as Supercapacitor Electrodes

    Science.gov (United States)

    Alshareef, Niman H.; Whitehair, Daniel; Xia, Chuan

    2016-12-01

    In this study, we demonstrate that highly functionalized and porous carbons can be derived from palm-leaf waste using the template-free facile synthesis process. The derived carbons have high content of nitrogen dopant, high surface area, and various defects. Moreover, these carbons exhibit a high electrical conductivity (107 S m-1). Thanks to the high content of edge N (64.3%) and highly microporous nature (82% of microspores), these biomass-derived carbons show promising performance when used as supercapacitor electrodes. To be specific, these carbonaceous materials show a specific capacitance as high as 197 and 135 F g-1 at 2 and 20 A g-1 in three-electrode configuration, respectively. Furthermore, the symmetrical cells using palm-leaf-derived carbon show an energy density of 8.4 Wh Kg-1 at a power density of 0.64 kW Kg-1, with high cycling life stability (˜8% loss after 10,000 continuous charge-discharge cycles at 20 A g-1). Interestingly, as the power density increases from 4.4 kW kg-1 to 36.8 kW kg-1, the energy density drops slowly from 8.4 Wh kg-1 to 3.4 Wh kg-1. Getting such extremely high power density without significant loss of energy density indicates that these palm-leaf-derived carbons have excellent electrode performance as supercapacitor electrodes.

  7. Multivariate statistical analysis of surface water chemistry: A case study of Gharasoo River, Iran

    Directory of Open Access Journals (Sweden)

    MH Sayadi

    2014-09-01

    Full Text Available Regional water quality is a hot spot in the environmental sciences for inconsistency of pollutants. In this paper, the surface water quality of the Gharasoo River in western Iran is assessed incorporating multivariate statistical techniques. Parameters like EC, TDS, pH, HCO3-, Cl-, SO4 2-, Ca2+, Mg2+ and Na+ were analyzed. Principal component and factor analysis is showed the parameters generated 3 significant factors, which explained 73.06% of the variance in data sets. Factor 1 may be derived from agricultural activities and subsequent release of EC, TDS, SO4 2- and Na+ to the water. Factor 2 could be influenced by domestic pollution and explained the deliverance of HCO3-, Cl- and Mg2+ into the water. Factor 3 contains hydro-geochemical variable Ca2+ and pH, originating from mineralization of the geological components of bed sediments and soils of watershed area. Likewise, the clustering analysis generated 3 groups of the stations as the groups had similar characteristic features. Pearson correlation analysis showed significant correlations between HCO3- and Mg2+ (0.775, Ca2+ (0.552 as well as TDS and Na+ (0.726. With reference to multivariate statistical analyses it can be concluded that the agricultural, domestic and hydro-geochemical sources are releasing the pollutants into the Gharasoo River water.

  8. Interfacial chemistry of organic conversion film on AZ61 magnesium alloy surface

    Science.gov (United States)

    Yang, Xu; Pan, Fusheng; Zhang, Dingfei

    2008-12-01

    The anodic electrochemical behavior of AZ61 magnesium alloy in sodium hydroxide medium in the absence and presence of p-nitro-benzene-azo-resorcinol (PNBAR) was studied using electrochemical techniques. In the presence of PNBAR, organic conversion film formed on the surface of magnesium alloy. The nature of chemical mechanisms, bonds, and structures at the interface of PNBAR/magnesium alloy was investigated by using energy dispersive spectrometer (EDS) analysis and Fourier transform infrared spectroscopy. An in situ electrochemical deposition was evidenced to produce a corrosion protective barrier by the formation of organic conversion film of magnesium-PNBAR complex and to enhance film adhesion by the covalent bonds of Mg sbnd O sbnd N linkage. The linear sweep voltammetry experiments and the score tests were used to investigate the adhesion and evaluate the potential of corrosion resistance of organic conversion film. The results indicated the corrosion resistance of magnesium alloy was improved, the organic conversion film showed excellent adhesion not only to the substrate but also to the outer paint coatings.

  9. Surface chemistry of lipid raft and amyloid Aβ (1-40) Langmuir monolayer.

    Science.gov (United States)

    Thakur, Garima; Pao, Christine; Micic, Miodrag; Johnson, Sheba; Leblanc, Roger M

    2011-10-15

    Lipid rafts being rich in cholesterol and sphingolipids are considered to provide ordered lipid environment in the neuronal membranes, where it is hypothesized that the cleavage of amyloid precursor protein (APP) to Aβ (1-40) and Aβ (1-42) takes place. It is highly likely that the interaction of lipid raft components like cholesterol, sphingomylein or GM1 leads to nucleation of Aβ and results in aggregation or accumulation of amyloid plaques. One has investigated surface pressure-area isotherms of the lipid raft and Aβ (1-40) Langmuir monolayer. The compression-decompression cycles and the stability of the lipid raft Langmuir monolayer are crucial parameters for the investigation of interaction of Aβ (1-40) with the lipid raft Langmuir monolayer. It was revealed that GM1 provides instability to the lipid raft Langmuir monolayer. Adsorption of Aβ (1-40) onto the lipid raft Langmuir monolayer containing neutral (POPC) or negatively charged phospholipid (DPPG) was examined. The adsorption isotherms revealed that the concentration of cholesterol was important for adsorption of Aβ (1-40) onto the lipid raft Langmuir monolayer containing POPC whereas for the lipid raft Langmuir monolayer containing DPPG:cholesterol or GM1 did not play any role. In situ UV-vis absorption spectroscopy supported the interpretation of results for the adsorption isotherms.

  10. The Impact of Surface Chemistry on Bio-derived Carbon Performance as Supercapacitor Electrodes

    Science.gov (United States)

    Alshareef, Niman H.; Whitehair, Daniel; Xia, Chuan

    2017-03-01

    In this study, we demonstrate that highly functionalized and porous carbons can be derived from palm-leaf waste using the template-free facile synthesis process. The derived carbons have high content of nitrogen dopant, high surface area, and various defects. Moreover, these carbons exhibit a high electrical conductivity (107 S m-1). Thanks to the high content of edge N (64.3%) and highly microporous nature (82% of microspores), these biomass-derived carbons show promising performance when used as supercapacitor electrodes. To be specific, these carbonaceous materials show a specific capacitance as high as 197 and 135 F g-1 at 2 and 20 A g-1 in three-electrode configuration, respectively. Furthermore, the symmetrical cells using palm-leaf-derived carbon show an energy density of 8.4 Wh Kg-1 at a power density of 0.64 kW Kg-1, with high cycling life stability (˜8% loss after 10,000 continuous charge-discharge cycles at 20 A g-1). Interestingly, as the power density increases from 4.4 kW kg-1 to 36.8 kW kg-1, the energy density drops slowly from 8.4 Wh kg-1 to 3.4 Wh kg-1. Getting such extremely high power density without significant loss of energy density indicates that these palm-leaf-derived carbons have excellent electrode performance as supercapacitor electrodes.

  11. Anticorrelation between Surface and Subsurface Point Defects and the Impact on the Redox Chemistry of TiO2(110)

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Yeohoon; Du, Yingge; Garcia, Juan C.; Zhu, Zihua; Wang, Zhitao; Petrik, Nikolay G.; Kimmel, Gregory A.; Dohnalek, Zdenek; Henderson, Michael A.; Rousseau, Roger J.; Deskins, N. Aaron; Lyubinetsky, Igor

    2015-02-02

    Using combination of STM, DFT and SIMS, we explored the interplay and relative impact of surface vs. subsurface defects on the surface chemistry of rutile TiO2. STM results show that surface O vacancies (VO’s) are virtually absent in the vicinity of positively-charged subsurface point-defects. This observation is consistent with DFT calculations of impact of subsurface defect proximity on VO formation energy. To monitor the influence of such lateral anticorrelation on surface redox chemistry, a test reaction of the dissociative adsorption of O2 is employed, which is observed to be suppressed around them. DFT results attribute this to a perceived absence of the intrinsic (Ti) (and likely extrinsic) interstitials in the nearest subsurface layer beneath “inhibited” areas. We also postulate that the entire nearest subsurface region could be voided of any charged point-defects, whereas prevalent VO’s are largely responsible for mediation of the redox chemistry at reduced TiO2(110) surface.

  12. Green chemistry focus on optimization of silver nanoparticles using response surface methodology (RSM) and mosquitocidal activity: Anopheles stephensi (Diptera: Culicidae).

    Science.gov (United States)

    Ondari Nyakundi, Erick; Padmanabhan, M Nalini

    2015-01-01

    There is an exigent necessity for development of environmental friendly bio-control agent(s) for elimination of mosquito due to increased resistance resurgence against synthetic control agents. Mosquito control strategy will lay a strong foundation to malaria exclusion or it can be curbed to certain level especially in the developing nations. In this study, silver nanoparticles were synthesized by green chemistry approach using Tridax procumbens leaf extract as a reducing agent. The reaction medium involved in the synthesis process was optimized by statistical experimental design using response surface methodology to obtain better yield, uniform size, shape and stability. Further, these synthesized nanoparticles were confirmed through UV-Visible, FT-IR spectroscopy, PSA and SEM Subsequently, the bioefficacy of these particles were investigated on Anopheles stephensi for larvicidal and pupicidal activity. Interestingly, time period of 90 min, temperature of 76±2 °C, pH 7.2±2, 2 mM silver nitrate (AgNO3), 3mM PEG and 2mM PVP showed excellent parameters for bioprocess design for large scale production of stabilized nanoparticles. A concentration of 5 ppm of PVP stabilized nanoparticles exhibited 100% mortality. Thus, the obtained results clearly suggest that silver nanoparticles stabilized by PEG and PVP may have important function as stabilizers, dispersants as well as larvicides for mosquito control.

  13. Surface modification of carbon nanotubes via combination of mussel inspired chemistry and chain transfer free radical polymerization

    Science.gov (United States)

    Wan, Qing; Tian, Jianwen; Liu, Meiying; Zeng, Guangjian; Huang, Qiang; Wang, Ke; Zhang, Qingsong; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2015-08-01

    In this work, a novel strategy for surface modification of carbon nanotubes (CNTs) was developed via combination of mussel inspired chemistry and chain transfer free radical polymerization. First, pristine CNTs were functionalized with polydopamine (PDA), which is formed via self-polymerization of dopamine in alkaline conditions. These PDA functionalized CNTs can be further reacted with amino-terminated polymers (named as PDMC), which was synthesized through chain transfer free radical polymerization using cysteamine hydrochloride as chain transfer agent and methacryloxyethyltrimethyl ammonium chloride as the monomer. PDMC perfectly conjugated with CNT-PDA was ascertained by a series of characterization techniques including transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The dispersibility of obtained CNT nanocomposites (named as CNT-PDA-PDMC) was further examined. Results showed that the dispersibility of CNT-PDA-PDMC in aqueous and organic solutions was obviously enhanced. Apart from PDMC, many other amino-terminated polymers can also be used to functionalization of CNTs via similar strategy. Therefore, the method described in this work should be a general strategy for fabrication various polymer nanocomposites.

  14. Carbon nanotubes' surface chemistry determines their potency as vaccine nanocarriers in vitro and in vivo

    Science.gov (United States)

    Hassan, Hatem A.F.M.; Smyth, Lesley; Rubio, Noelia; Ratnasothy, Kulachelvy; Wang, Julie T.-W.; Bansal, Sukhvinder S.; Summers, Huw D.; Diebold, Sandra S.; Lombardi, Giovanna; Al-Jamal, Khuloud T.

    2016-01-01

    Carbon nanotubes (CNTs) have shown marked capabilities in enhancing antigen delivery to antigen presenting cells. However, proper understanding of how altering the physical properties of CNTs may influence antigen uptake by antigen presenting cells, such as dendritic cells (DCs), has not been established yet. We hypothesized that altering the physical properties of multi-walled CNTs (MWNTs)-antigen conjugates, e.g. length and surface charge, can affect the internalization of MWNT-antigen by DCs, hence the induced immune response potency. For this purpose, pristine MWNTs (p-MWNTs) were exposed to various chemical reactions to modify their physical properties then conjugated to ovalbumin (OVA), a model antigen. The yielded MWNTs-OVA conjugates were long MWNT-OVA (~ 386 nm), bearing net positive charge (5.8 mV), or short MWNTs-OVA (~ 122 nm) of increasing negative charges (− 23.4, − 35.8 or − 39 mV). Compared to the short MWNTs-OVA bearing high negative charges, short MWNT-OVA with the lowest negative charge demonstrated better cellular uptake and OVA-specific immune response both in vitro and in vivo. However, long positively-charged MWNT-OVA showed limited cellular uptake and OVA specific immune response in contrast to short MWNT-OVA displaying the least negative charge. We suggest that reduction in charge negativity of MWNT-antigen conjugate enhances cellular uptake and thus the elicited immune response intensity. Nevertheless, length of MWNT-antigen conjugate might also affect the cellular uptake and immune response potency; highlighting the importance of physical properties as a consideration in designing a MWNT-based vaccine delivery system. PMID:26802552

  15. Surface chemistry and flotation behavior of monazite, apatite, ilmenite, quartz, rutile, and zircon using octanohydroxamic acid collector

    Science.gov (United States)

    Nduwa Mushidi, Josue

    Global increase in rare earth demand and consumption has led to further understanding their beneficiation and recovery. Monazite is the second most important rare earth mineral that can be further exploited. In this study, the surface chemistry of monazite in terms of zeta potential, adsorption density, and flotation response by microflotation using octanohydroxamic acid is determined. Apatite, ilmenite, quartz, rutile, and zircon are minerals that frequently occur with monazite among other minerals. Hence they were chosen as gangue minerals in this study. The Iso Electric Point (IEP) of monazite, apatite, ilmenite, quartz, rutile, and zircon are 5.3, 8.7, 3.8, 3.4, 6.3, and 5.1 respectively. The thermodynamic parameters of adsorption were also evaluated. Ilmenite, rutile and zircon have high driving forces for adsorption with DeltaGads. = 20.48, 22.10, and 22.4 kJ/mol respectively. The free energy of adsorption is 14.87 kJ/mol for monazite. Adsorption density testing shows that octanohydroxamic acid adsorbs on negatively charged surfaces of monazite and its gangue minerals which indicates chemisorption. This observation was further confirmed by microflotation experiments. Increasing the temperature to 80°C raises the adsorption and flotability of monazite and gangue minerals. This does not allow for effective separation. Sodium silicate appeared to be most effective to depress associated gangue minerals. Finally, the fundamentals learned were applied to the flotation of monazite ore from Mt. Weld. However, these results showed no selectivity due to the presence of goethite as fine particles and due to a low degree of liberation of monazite in the ore sample.

  16. A Unified Monte Carlo Treatment of Gas-Grain Chemistry for Large Reaction Networks. II. A Multiphase Gas-Surface-Layered Bulk Model

    CERN Document Server

    Vasyunin, A I

    2012-01-01

    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 ...

  17. Understanding of catalysis on early transition metal oxide-based catalysts through exploration of surface structure and chemistry during catalysis using in-situ approaches

    Energy Technology Data Exchange (ETDEWEB)

    Tao, Franklin [Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry

    2015-09-14

    Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co3O4 or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with different binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few

  18. Study of surface chemistry and microstructure of TiO2 nanostructures on Pt(111)/Si wafer and FTO glass substrates: a comparative approach

    Science.gov (United States)

    Roy Moulik, Samik; Ghatak, Ankita; Ghosh, Barnali

    2016-09-01

    We report, the kinetically controlled growth of the (002)-oriented TiO2 nanorods on fluorine-doped tin oxide (FTO) coated glass substrate via a cost effective hydrothermal synthesis route of binary oxides. In addition to this, the nanoflowered like growth of TiO2 nanorods using cubic structure Pt(111)/SiO2/Si substrate has also been demonstrated. Tuning of shape, crystallographic structure issues has been discussed by controlling the surface chemistry of the substrate on which the nanostructures were grown. The crystallographic structural aspects of the grown nanorods was confirmed both on ensemble and single nanowire level using spatially resolved tools and techniques. Growth mechanism for different shape, size and crystallographic structure depending on the surface chemistry of the substrate has been proposed. Understanding of growth of oriented TiO2 nanorods and interaction mechanism is quite promising and encouraging for designing optoelectronic and photocatalytic devices to enhanced electron transport and lower exciton recombination rates.

  19. A New Approach for Detection Improvement of the Creutzfeldt-Jakob Disorder through a Specific Surface Chemistry Applied onto Titration Well

    Directory of Open Access Journals (Sweden)

    Dominique Debarnot

    2012-10-01

    Full Text Available This work illustrates the enhancement of the sensitivity of the ELISA titration for recombinant human and native prion proteins, while reducing other non-specific adsorptions that could increase the background signal and lead to a low sensitivity and false positives. It is achieved thanks to the association of plasma chemistry and coating with different amphiphilic molecules bearing either ionic charges and/or long hydrocarbon chains. The treated support by 3-butenylamine hydrochloride improves the signal detection of recombinant protein, while surface modification with the 3,7-dimethylocta-2,6-dien-1-diamine (geranylamine enhances the sensitivity of the native protein. Beside the surface chemistry effect, these different results are associated with protein conformation.

  20. A versatile electrowetting-based digital microfluidic platform for quantitative homogeneous and heterogeneous bio-assays

    Science.gov (United States)

    Vergauwe, Nicolas; Witters, Daan; Ceyssens, Frederik; Vermeir, Steven; Verbruggen, Bert; Puers, Robert; Lammertyn, Jeroen

    2011-05-01

    Electrowetting-on-dielectric (EWOD) lab-on-a-chip systems have already proven their potential within a broad range of bio-assays. Nevertheless, research on the analytical performance of those systems is limited, yet crucial for a further breakthrough in the diagnostic field. Therefore, this paper presents the intrinsic possibilities of an EWOD lab-on-a-chip as a versatile platform for homogeneous and heterogeneous bio-assays with high analytical performance. Both droplet dispensing and splitting cause variations in droplet size, thereby directly influencing the assay's performance. The extent to which they influence the performance is assessed by a theoretical sensitivity analysis, which allows the definition of a basic framework for the reduction of droplet size variability. Taking advantage of the optimized droplet manipulations, both homogeneous and heterogeneous bio-assays are implemented in the EWOD lab-on-a-chip to demonstrate the analytical capabilities and versatility of the device. A fully on-chip enzymatic assay is realized with high analytical performance. It demonstrates the promising capabilities of an EWOD lab-on-a-chip in food-related and medical applications, such as nutritional and blood analyses. Further, a magnetic bio-assay for IgE detection using superparamagnetic nanoparticles is presented whereby the nanoparticles are used as solid carriers during the bio-assay. Crucial elements are the precise manipulation of the superparamagnetic nanoparticles with respect to dispensing and separation. Although the principle of using nano-carriers is demonstrated for protein detection, it can be easily extended to a broader range of bio-related applications like DNA sensing. In heterogeneous bio-assays the chip surface is actively involved during the execution of the bio-assay. Through immobilization of specific biological compounds like DNA, proteins and cells a reactive chip surface is realized, which enhances the bio-assay performance. To demonstrate

  1. Results of ground-water, surface-water, and water-chemistry monitoring, Black Mesa area, northeastern Arizona, 1994

    Science.gov (United States)

    Littin, G.R.; Monroe, S.A.

    1995-01-01

    The Black Mesa monitoring program is designed to document long-term effects of ground-water pumping from the N aquifer by industrial and municipal users. The N aquifer is the major source of water in the 5,400-square-mile Black Mesa area, and the ground water occurs under confined and unconfined conditions. Monitoring activities include continuous and periodic measurements of (1) ground-water pumpage from the confined and unconfined areas of the aquifer, (2) ground-water levels in the confined and unconfined areas of the aquifer, (3) surface-water discharge, and (4) chemistry of the ground water and surface water. In 1994, ground-water withdrawals for industrial and municipal use totaled about 7,000 acre-feet, which is an 8-percent increase from the previous year. Pumpage from the confined part of the aquifer increased by about 9 percent to 5,400 acre-feet, and pumpage from the unconfined part of the aquifer increased by about 2 percent to 1,600 acre-feet. Water-level declines in the confined area during 1994 were recorded in 10 of 16 wells, and the median change was a decline of about 2.3 feet as opposed to a decline of 3.3 feet for the previous year. The median change in water levels in the unconfined area was a rise of 0.1 foot in 1994 as opposed to a decline of 0.5 foot in 1993. Measured low-flow discharge along Moenkopi Wash decreased from 3.0 cubic feet per second in 1993 to 2.9 cubic feet per second in 1994. Eleven low-flow measurements were made along Laguna Creek between Tsegi, Arizona, and Chinle Wash to determine the amount of discharge that would occur as seepage from the N aquifer under optimal base-flow conditions. Discharge was 5.6 cubic feet per second near Tsegi and 1.5 cubic feet per second above the confluence with Chinle Wash. Maximum discharge was 5.9 cubic feet per second about 4 miles upstream from Dennehotso. Discharge was measured at three springs. The changes in discharge at Burro and Whisky Springs were small and within the uncertainty of

  2. Understanding the Effect of Surface Chemistry on Charge Generation and Transport in Poly (3-hexylthiophene)/CdSe Hybrid Solar Cells

    DEFF Research Database (Denmark)

    Lek, Jun Yan; Xi, Lifei; Kardynal, Beata

    2011-01-01

    For hybrid solar cells, interfacial chemistry is one of the most critical factors for good device performance. We have demonstrated that the size of the surface ligands and the dispersion of nanoparticles in the solvent and in the polymer are important criteria in obtaining optimized device...... potential as ligand replacement for poly(3-hexylthiophene)/CdSe hybrid solar cells. With the right ligand combination, we have shown that the power conversion efficiency improved by a factor of 6 after ligand exchange....

  3. Effects of Architecture and Surface Chemistry of Three-Dimensionally Ordered Macroporous Carbon Solid Contacts on Performance of Ion-Selective Electrodes

    OpenAIRE

    2010-01-01

    The effects of the architecture and surface chemistry of three-dimensionally ordered macroporous (3DOM) carbon solid contacts on the properties of ion-selective electrodes (ISEs) were examined. Infiltration of the plasticized PVC membrane into the pores of the carbon created a large interfacial area between the sensing membrane and the solid contact, as shown by cryo-SEM and elemental analysis. This large interfacial area, along with the high capacitance of the 3DOM carbon solid contacts (as ...

  4. New molecular species of potential interest to atmospheric chemistry: isomers on the [H, S2, Br] potential energy surface.

    Science.gov (United States)

    de Oliveira-Filho, Antonio Gustavo S; Aoto, Yuri Alexandre; Ornellas, Fernando R

    2009-02-19

    This work reports a state-of-the-art theoretical characterization of four new sulfur-bromine species and five transition states on the [H, S(2), Br] potential energy surface. Our highest level theoretical approach employed the method coupled cluster singles and doubles with perturbative contributions of connected triples, CCSD(T), along with the series of correlation-consistent basis sets and with extrapolation to the complete basis set (CBS) limit in the optimization of the geometrical parameters and to quantify the energetic quantities. The structural and vibrational frequencies here reported are unique and represent the most accurate investigation to date of these species. The global minimum corresponds to a skewed structure HSSBr with a disulfide bond; this is followed by a pyramidal-like structure, SSHBr, 18.85 kcal/mol above the minimum. Much higher in energy, we found another skewed structure, HSBrS (50.29 kcal/mol), with one S-Br dative-type bond, and another pyramidal-like one, HBrSS (109.80 kcal/mol), with two S-Br dative-type bonds. The interconversion of HSSBr into SSHBr can occur via a transfer of either the hydrogen or the bromine atom but involves a very high barrier of about 43 kcal/mol. These molecules are potentially a new route of coupling the sulfur and bromine chemistry in the atmosphere, and conditions of high concentration of H(2)S like in volcanic eruptions might contribute to their formation. We note that HSSBr can act as a reservoir molecule for the reaction between the radicals HSS and Br. Also, an assessment of the methods DFT/B3LYP/CBS and MP2/CBS relative to CCSD(T)/CBS provides insights on the expected performance of these methods on the characterization of polysulfides and also of more complex systems containing disulfide bridges.

  5. Chemistry and isotopic composition of precipitation and surface waters in Khumbu valley (Nepal Himalaya): N dynamics of high elevation basins.

    Science.gov (United States)

    Balestrini, Raffaella; Polesello, Stefano; Sacchi, Elisa

    2014-07-01

    We monitored the chemical and isotopic compositions of wet depositions, at the Pyramid International Laboratory (5050 ma.s.l.), and surrounding surface waters, in the Khumbu basin, to understand precipitation chemistry and to obtain insights regarding ecosystem responses to atmospheric inputs. The major cations in the precipitation were NH4(+) and Ca(2+), whereas the main anion was HCO3(-), which constituted approximately 69% of the anions, followed by NO3(-), SO4(2-) and Cl(-). Data analysis suggested that Na(+), Cl(-) and K(+) were derived from the long-range transport of marine aerosols. Ca(2+), Mg(2+) and HCO3(-) were related to rock and soil dust contributions and the NO3(-) and SO4(2-) concentrations were derived from anthropogenic sources. Furthermore, NH4(+) was derived from gaseous NH3 scavenging. The isotopic composition of weekly precipitation ranged from -1.9 to -23.2‰ in δ(18)O, and from -0.8 to -174‰ in δ(2)H, with depleted values characterizing the central part of the monsoon period. The chemical composition of the stream water was dominated by calcite and/or gypsum dissolution. However, the isotopic composition of the stream water did not fully reflect the composition of the monsoon precipitation, which suggested that other water sources contributed to the stream flow. Precipitation contents for all ions were the lowest ones among those measured in high elevation sites around the world. During the monsoon periods the depositions were not substantially influenced by anthropogenic inputs, while in pre- and post-monsoon seasons the Himalayas could not represent an effective barrier for airborne pollution. In the late monsoon phase, the increase of ionic contents in precipitation could also be due to a change in the moisture source. The calculated atmospheric N load (0.30 kg ha(-1) y(-1)) was considerably lower than the levels that were measured in other high-altitude environments. Nevertheless, the NO3(-) concentrations in the surface waters

  6. Laboratory Bioassays with Three Different Substrates to Test the Efficacy of Insecticides against Various Stages of Drosophila suzukii (Diptera: Drosophilidae)

    Science.gov (United States)

    Pavlova, Aneliya Koleva; Dahlmann, Melanie; Hauck, Mirjam

    2017-01-01

    Rapid worldwide spread and polyphagous nature of the spotted wing Drosophila Drosophila suzukii Matsumura (Diptera: Drosophilidae) calls for efficient and selective control strategies to prevent severe economic losses in various fruit crops. The use of insecticides is one option for management of this invasive pest insect. Efficacy of insecticides is usually assessed first in laboratory bioassays, which are compounded by the cryptic nature of D. suzukii larvae and the fact that fruits used in bioassays often start to rot and dissolve before larvae have reached the adult stage. Here, we report on laboratory bioassays using three different types of substrates allowing a thorough screening of insecticides for their potential effects against D. suzukii eggs, larvae and adults. Suitability of our bioassays was validated in an assessment of the efficacy of four bioinsecticides and one synthetic insecticide against various developmental stages of D. suzukii. Water-apple juice agar used as a bioassay substrate allowed egg counting and observation of larval development due to its transparency, while apple-nutrition medium allowed complete metamorphosis. Use of grape berries in bioassays made it possible to assess effects of an insecticide present on a fruit’s surface on oviposition and larval hatch from eggs. Insecticides tested in these three different bioassays with acetamiprid, spinosad or natural pyrethrins as active ingredients achieved a significant D. suzukii control if they were applied before egg deposition. Number of adult flies was significantly reduced if the bioassay medium was treated with an azadirachtin A containing insecticide both before or after egg deposition. PMID:28042104

  7. In-situ bioassays using caged bivalves

    Energy Technology Data Exchange (ETDEWEB)

    Salazar, M.H.; Salazar, S.M.

    1995-12-31

    It is important to make the distinction between chemical measurements to assess bioaccumulation potential versus biological measurements to assess potential bioeffects because bioaccumulation is not a bioeffect. Caging provides a unique opportunity to make synoptic measurements of each and facilitates making these measurements over space and time. Measuring bioaccumulation in resident and transplanted bivalves has probably been the most frequently used form of an in-situ bioassay because bivalves concentrate chemicals in their tissues. They are also easy to collect, cage, and measure. The authors have refined bivalve bioassay methods by minimizing the size range of test animals, making repetitive measurements of the same individuals, and standardizing test protocols for a variety of applications. They are now attempting to standardize criteria for accepting and interpreting data in the same way that laboratory bioassays have been standardized. Growth measurements can serve two purposes in this assessment strategy: (1) An integrated biological response endpoint that is easily quantifiable and with significance to the population, and (2) A means of calibrating bioaccumulation by assessing the relative health and physiological state of tissues that have accumulated the chemicals. In general, the authors have found the highest bioconcentration factors associated with the highest growth rates, the highest concentrations ({micro}g/g) of chemicals in juvenile mussels, and the highest chemical content ({micro}g/animal) in adult mussels. Without accounting for possible dilution of chemical concentrations by tissue growth or magnification through degrowth, contaminant concentrations can be misleading. Examples are provided for the Sudbury River in Massachusetts (Elliptio complanata), San Diego Bay (Mytilus galloprovincialis), and the Harbor Island Superfund Site in Puget Sound (Mytilus trossulus).

  8. A Multichannel Bioluminescence Determination Platform for Bioassays.

    Science.gov (United States)

    Kim, Sung-Bae; Naganawa, Ryuichi

    2016-01-01

    The present protocol introduces a multichannel bioluminescence determination platform allowing a high sample throughput determination of weak bioluminescence with reduced standard deviations. The platform is designed to carry a multichannel conveyer, an optical filter, and a mirror cap. The platform enables us to near-simultaneously determine ligands in multiple samples without the replacement of the sample tubes. Furthermore, the optical filters beneath the multichannel conveyer are designed to easily discriminate colors during assays. This optical system provides excellent time- and labor-efficiency to users during bioassays.

  9. Aspartame bioassay findings portend human cancer hazards.

    Science.gov (United States)

    Huff, James; LaDou, Joseph

    2007-01-01

    The U.S. Food and Drug Administration (FDA) should reevaluate its position on aspartame as being safe under all conditions. Animal bioassay results predict human cancer risks, and a recent animal study confirms that there is a potential aspartame risk to humans. Aspartame is produced and packaged in China for domestic use and global distribution. Japan, France, and the United States are also major producers. No study of long-term adverse occupational health effects on aspartame workers have been conducted. The FDA should consider sponsoring a prospective epidemiologic study of aspartame workers.

  10. Coupling aerosol surface and bulk chemistry with a kinetic double layer model (K2-SUB: oxidation of oleic acid by ozone

    Directory of Open Access Journals (Sweden)

    C. Pfrang

    2010-05-01

    Full Text Available We present a kinetic double layer model coupling aerosol surface and bulk chemistry (K2-SUB based on the PRA framework of gas-particle interactions (Pöschl-Rudich-Ammann, 2007. K2-SUB is applied to a popular model system of atmospheric heterogeneous chemistry: the interaction of ozone with oleic acid. We show that our modelling approach allows de-convoluting surface and bulk processes, which has been a controversial topic and remains an important challenge for the understanding and description of atmospheric aerosol transformation. In particular, we demonstrate how a detailed treatment of adsorption and reaction at the surface can be coupled to a description of bulk reaction and transport that is consistent with traditional resistor model formulations.

    From literature data we have derived a consistent set of kinetic parameters that characterise mass transport and chemical reaction of ozone at the surface and in the bulk of oleic acid droplets. Due to the wide range of rate coefficients reported from different experimental studies, the exact proportions between surface and bulk reaction rates remain uncertain. Nevertheless, the model results suggest an important role of chemical reaction in the bulk and an approximate upper limit of ~10−11 cm2 s−1 for the surface reaction rate coefficient. Sensitivity studies show that the surface accommodation coefficient of the gas-phase reactant has a strong non-linear influence on both surface and bulk chemical reactions. We suggest that K2-SUB may be used to design, interpret and analyse future experiments for better discrimination between surface and bulk processes in the oleic acid-ozone system as well as in other heterogeneous reaction systems of atmospheric relevance.

  11. Surface chemistry of the preferred (111) and (220) crystal oriented microcrystalline Si films by radio-frequency plasma-enhanced chemical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Ohba, Daisuke; Koshino, Hideto; Tang, Zeguo; Shirai, Hajime [Graduate School of Science and Engineering, Saitama University, Sakura (Japan)

    2011-10-15

    The surface chemistry of the preferentially (111) and (220) crystal orientated chlorinated hydrogenated microcrystalline silicon ({mu}c-Si:H:Cl) films was studied using a rf PE-CVD of a dichlorosilane (SiH{sub 2}Cl{sub 2}) and H{sub 2} mixture. The growing surface for the preferentially (220) crystal oriented {mu}c-Si:H:Cl films included much voids and dangling bonds, whereas the growing surface with the preferential (111) crystal orientation was chemically stable relatively. These findings suggest that the sticking process of deposition precursors and/or the reconstruction of Si clusters within the sub-surface determine the preferential crystal orientation. (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  12. Surface tailoring for selective endothelialization and platelet inhibition via a combination of SI-ATRP and click chemistry using Cys-Ala-Gly-peptide.

    Science.gov (United States)

    Khan, Musammir; Yang, Jing; Shi, Changcan; Lv, Juan; Feng, Yakai; Zhang, Wencheng

    2015-07-01

    Surface tailoring is an attractive approach to enhancing selective endothelialization, which is a prerequisite for current vascular prosthesis applications. Here, we modified polycarbonate urethane (PCU) surface with both poly(ethylene glycol) and Cys-Ala-Gly-peptide (CAG) for the purpose of creating a hydrophilic surface with targeting adhesion of endothelial cells (ECs). In the first step, PCU-film surface was grafted with poly(ethylene glycol) methacrylate (PEGMA) to covalently tether hydrophilic polymer brushes via surface initiated atom transfer radical polymerization (SI-ATRP), followed by grafting of an active monomer pentafluorophenyl methacrylate (PFMA) by a second ATRP. The postpolymerization modification of the terminal reactive groups with allyl amine molecules created pendant allyl groups, which were subsequently functionalized with cysteine terminated CAG-peptide via photo-initiated thiol-ene click chemistry. The functionalized surfaces were characterized by water contact angle and XPS analysis. The growth and proliferation of human ECs or human umbilical arterial smooth muscle cells on the functionalized surfaces were investigated for 1, 3 and 7 day/s. The results indicated that these peptide functionalized surfaces exhibited enhanced EC adhesion, growth and proliferation. Furthermore, they suppressed platelet adhesion in contact with platelet-rich plasma for 2h. Therefore, these surfaces with EC targeting ligand could be an effective anti-thrombogenic platform for vascular tissue engineering application.

  13. A statistical treatment of bioassay pour fractions

    Science.gov (United States)

    Barengoltz, Jack; Hughes, David

    A bioassay is a method for estimating the number of bacterial spores on a spacecraft surface for the purpose of demonstrating compliance with planetary protection (PP) requirements (Ref. 1). The details of the process may be seen in the appropriate PP document (e.g., for NASA, Ref. 2). In general, the surface is mechanically sampled with a damp sterile swab or wipe. The completion of the process is colony formation in a growth medium in a plate (Petri dish); the colonies are counted. Consider a set of samples from randomly selected, known areas of one spacecraft surface, for simplicity. One may calculate the mean and standard deviation of the bioburden density, which is the ratio of counts to area sampled. The standard deviation represents an estimate of the variation from place to place of the true bioburden density commingled with the precision of the individual sample counts. The accuracy of individual sample results depends on the equipment used, the collection method, and the culturing method. One aspect that greatly influences the result is the pour fraction, which is the quantity of fluid added to the plates divided by the total fluid used in extracting spores from the sampling equipment. In an analysis of a single sample’s counts due to the pour fraction, one seeks to answer the question: What is the probability that if a certain number of spores are counted with a known pour fraction, that there are an additional number of spores in the part of the rinse not poured. This is given for specific values by the binomial distribution density, where detection (of culturable spores) is success and the probability of success is the pour fraction. A special summation over the binomial distribution, equivalent to adding for all possible values of the true total number of spores, is performed. This distribution when normalized will almost yield the desired quantity. It is the probability that the additional number of spores does not exceed a certain value. Of course

  14. Ground-Water, Surface-Water, and Water-Chemistry Data, Black Mesa Area, Northeastern Arizona - 2006-07

    Science.gov (United States)

    Truini, Margot; Macy, J.P.

    2008-01-01

    The N aquifer is the major source of water in the 5,400 square-mile Black Mesa area in northeastern Arizona. Availability of water is an important issue in northeastern Arizona because of continued water requirements for industrial and municipal use and the needs of a growing population. Precipitation in the Black Mesa area is typically about 6 to 14 inches per year. The water-monitoring program in the Black Mesa area began in 1971 and is designed to provide information about the long-term effects of ground-water withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected for the monitoring program in the Black Mesa area from January 2006 to September 2007. The monitoring program includes measurements of (1) ground-water withdrawals, (2) ground-water levels, (3) spring discharge, (4) surface-water discharge, and (5) ground-water chemistry. Periodic testing of ground-water withdrawal meters is completed every 4 to 5 years. The Navajo Tribal Utility Authority (NTUA) yearly totals for the ground-water metered withdrawal data were unavailable in 2006 due to an up-grade within the NTUA computer network. Because NTUA data is often combined with Bureau of Indian Affairs data for the total withdrawals in a well system, withdrawals will not be published in this year's annual report. From 2006 to 2007, annually measured water levels in the Black Mesa area declined in 3 of 11 wells measured in the unconfined areas of the N aquifer, and the median change was 0.0 feet. Measurements indicated that water levels declined in 8 of 17 wells measured in the confined area of the aquifer. The median change for the confined area of the aquifer was 0.2 feet. From the prestress period (prior to 1965) to 2007, the median water-level change for 30 wells was -11.1 feet. Median water-level changes were 2.9 feet for 11 wells measured in the unconfined areas and -40.2 feet for 19 wells measured in the confined area. Spring flow was measured

  15. The atmospheric chemistry general circultation model ECHAM5/MESSy1: Consistent simulation of ozone from the surface to the mesosphere

    NARCIS (Netherlands)

    Jöckel, P.; Tost, H.; Pozzer, A.; Brülh, Ch.; Buchholz, J.; Ganzeveld, L.N.; Hoor, P.; Kerkweg, A.; Lawrence, M.G.; Sander, R.; Steil, B.; Stiller, G.; Tanarhte, M.; Taraborrelli, D.; Aardenne, van J.A.; Lelieveld, J.

    2006-01-01

    The new Modular Earth Submodel System (MESSy) describes atmospheric chemistry and meteorological processes in a modular framework, following strict coding standards. It has been coupled to the ECHAM5 general circulation model, which has been slightly modified for this purpose. A 90-layer model setup

  16. Comprehensive integration of homogeneous bioassays via centrifugo-pneumatic cascading.

    Science.gov (United States)

    Godino, Neus; Gorkin, Robert; Linares, Ana V; Burger, Robert; Ducrée, Jens

    2013-02-21

    This work for the first time presents the full integration and automation concept for a range of bioassays leveraged by cascading a centrifugo-pneumatic valving scheme to sequentially move several liquids through shared channel segments for multi-step sample preparation into the detection zone. This novel centrifugo-pneumatic liquid handling significantly simplifies system manufacture by obviating the need for complex surface functionalization procedures or hybrid material integration, as it is common in conventional valving methods such as capillary burst valves or sacrificial valves. Based on the centrifugo-pneumatic valving scheme, this work presents a toolkit of operational elements implementing liquid loading/transfer, metering, mixing and sedimentation in a microstructured polymer disc. As a proof of concept for the broad class of homogeneous bioassays, the full integration and automation of a colorimetric nitrate/nitrite test for the detection of clinically relevant nitric oxide (NO) in whole blood is implemented. First, 40 μL of plasma is extracted from a 100 μL sample of human blood, incubated for one hour with the enzymatic mixture (60 μL), and finally reacted with 100 μL of colorimetric (Greiss) reagents. Following just a single loading phase at the beginning of the process, all of these steps are automated through the centrifugo-pneumatic cascade with a high level of flow control and synchronization. Our system shows good correlation with controls up to 50 μM of nitrate, which adequately covers the healthy human range (4 to 45.3 μM).

  17. Final Technical Report. Reactivity of Iron-Bearing Minerals and CO2 Sequestration and Surface Chemistry of Pyrite. An Interdisciplinary Approach

    Energy Technology Data Exchange (ETDEWEB)

    Strongin, Daniel [Temple Univ., Philadelphia, PA (United States)

    2014-12-31

    Over the course of the scientific program, two areas of research were pursued: reactions of iron oxides with supercritical CO2 and sulfide and surface reactivity of pyrite. The latter area of interest was to understand the chemistry that results when supercritical CO2 (scCO2 ) with H2 S and/or SO2 in deep saline formations (DFS) contacts iron bearing minerals. Understanding the complexities the sulfur co-injectants introduce is a critical step in developing CO2 sequestration as a climate-mitigating strategy. The research strategy was to understand macroscopic observations of this chemistry with an atomic/molecular level view using surface analytical techniques. Research showed that the exposure of iron (oxyhdr)oxides (which included ferrihydrite, goethite, and hematite) to scCO2 in the presence of sulfide led to reactions that formed siderite (FeCO3). The results have important implications for the sequestration of CO2 via carbonation reactions in the Earth’s subsurface. An earlier area of focus in the project was to understand pyrite oxidation in microscopic detail. This understanding was used to understand macroscopic observations of pyrite reactivity. Results obtained from this research led to a better understanding how pyrite reacts in a range of chemical environments. Geochemical and modern surface science techniques were used to understand the chemistry of pyrite in important environmental conditions. The program relied on a strong integration the results of these techniques to provide a fundamental understanding to the macroscopic chemistry exhibited by pyrite in the environment. Major achievements during these studies included developing an understanding of the surface sites on pyrite that controlled its reactivity under oxidizing conditions. In particular sulfur anion vacancies and/or ferric sites were sites of reactivity. Studies also showed that the

  18. Combustion chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Brown, N.J. [Lawrence Berkeley Laboratory, CA (United States)

    1993-12-01

    This research is concerned with the development and use of sensitivity analysis tools to probe the response of dependent variables to model input variables. Sensitivity analysis is important at all levels of combustion modeling. This group`s research continues to be focused on elucidating the interrelationship between features in the underlying potential energy surface (obtained from ab initio quantum chemistry calculations) and their responses in the quantum dynamics, e.g., reactive transition probabilities, cross sections, and thermal rate coefficients. The goals of this research are: (i) to provide feedback information to quantum chemists in their potential surface refinement efforts, and (ii) to gain a better understanding of how various regions in the potential influence the dynamics. These investigations are carried out with the methodology of quantum functional sensitivity analysis (QFSA).

  19. Immobilization of poly(acrylamide) brushes onto poly(caprolactone) surface by combining ATRP and “click” chemistry: Synthesis, characterization and evaluation of protein adhesion

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Yuhao; Bian, Xinxiu; He, Liu; Cai, Mengtan; Xie, Xiaoxiong [College of Polymer Science and Engineering, Sichuan University, Chengdu 610065 (China); Luo, Xianglin, E-mail: luoxl@scu.edu.cn [College of Polymer Science and Engineering, Sichuan University, Chengdu 610065 (China); State Key Laboratory of Polymer Material and Engineering, Sichuan University, Chengdu 610065 (China)

    2015-02-28

    Highlights: • Poly(caprolacone) (PCL) film surface was chemically modified by a novel method through combining ATRP and “click” chemistry. • Poly(acrylamide) (PAAm) of tailored chain length were synthesized and “clicked” onto PCL surface. • The modified PCL surface showed reduced BSA and Fg adsorption, and the protein resist ability in terms of chain length through its impact on grafting reaction and modified surface was investigated. - Abstract: Developments of poly(caprolactone) in blood-contacting applications are often restricted due to its intrinsic hydrophobicity. One common way to improve its hemocompatibility is to attach hydrophilic polymers. Here we developed a non-destructive method to graft hydrophilic poly(acrylamide) (PAAm) onto poly(caprolactone) (PCL) surface. In this strategy, azido-ended PCL with low molecular weights was synthesized and blended with PCL to create a surface with “clickable” property. Alkyne-ended poly(acrylamide)s with controlled chain lengths were then synthesized by atom transfer radical polymerization (ATRP), and finally were immobilized onto PCL surface by “click” reaction. The occurrence of immobilization was verified qualitatively by water contact angle measurement and quantitatively by X-ray photoelectron spectroscopy (XPS). The PAAm grafted surface exhibited fouling resistant properties, as demonstrated by reduced bovine serum albumin (BSA) and fibrinogen (Fg) adhesion.

  20. Bioassay for Toxic and Hazardous Materials. Training Manual.

    Science.gov (United States)

    Office of Water Program Operations (EPA), Cincinnati, OH. National Training and Operational Technology Center.

    This course is intended for personnel who have an operational or administrative responsibility for the design and use of bioassay and biomonitoring, and who have no experience in conducting static bioassays. The training consists of classroom discussions, laboratory exercises and demonstrations, and demonstration and observation activities. (CO)

  1. Are bioassays useful tools to assess redox processes and biodegradation?

    DEFF Research Database (Denmark)

    Albrechtsen, Hans-Jørgen; Pedersen, Philip Grinder; Ludvigsen, L.

    2002-01-01

    sensitive hydrochemical or geochemical parameters, levels of hydrogen, and redox potential. However, all these approaches have to be evaluated against TEAP-bioassays as the most direct measure. We assessed successfully ongoing microbial-mediated redox processes by TEAP-bioassays in degradation studies...

  2. Simultaneous bioassays in a microfluidic channel on plugs of different magnetic particles.

    Science.gov (United States)

    Bronzeau, Sandrine; Pamme, Nicole

    2008-02-18

    Magnetic particles coated with specific biomolecules are often used as solid supports for bioassays but conventional test tube based techniques are time consuming and labour intensive. An alternative is to work on magnetic particle plugs immobilised inside microfluidic channels. Most research so far has focussed on immobilising one type of particle to perform one type of assay. Here we demonstrate how several assays can be performed simultaneously by flushing a sample solution over several plugs of magnetic particles with different surface coatings. Within a microchannel, three plugs of magnetic particles were immobilised with external magnets. The particles featured surface coatings of glycine, streptavidin and protein A, respectively. Reagents were then flushed through the three plugs. Molecular binding occurred between matching antigens and antibodies in continuous flow and was detected by fluorescence. This first demonstration opens the door to a quicker and easier technique for simultaneous bioassays using magnetic particles.

  3. Química organometálica de superfície aplicada à preparação de catalisadores heterogêneos bem definidos Surface organometallic chemistry applied to the preparation of well defined heterogeneous catalysts

    Directory of Open Access Journals (Sweden)

    Silvana I. Wolke

    2002-11-01

    Full Text Available The study of the reactions of organometallic complexes with the surfaces of inorganic oxides, zeolites and metals constitutes the basis of Surface Organometallic Chemistry (SOMC. The basic rules of organometallic chemistry are often valid when applied to surfaces and well-defined surface organometallic complexes can be obtained. These complexes can be used as heterogeneous catalysts or, by controlled reactions, can be transformed in other species useful for a given catalytic reaction. In some cases, these catalysts exhibit higher activity and/or selectivity than their analogous molecular complexes.

  4. Cell-based bioassays in microfluidic systems

    Science.gov (United States)

    Itle, Laura J.; Zguris, Jeanna C.; Pishko, Michael V.

    2004-12-01

    The development of cell-based bioassays for high throughput drug screening or the sensing of biotoxins is contingent on the development of whole cell sensors for specific changes in intracellular conditions and the integration of those systems into sample delivery devices. Here we show the feasibility of using a 5-(and-6)-carboxy SNARF-1, acetoxymethyl ester, acetate, a fluorescent dye capable of responding to changes in intracellular pH, as a detection method for the bacterial endotoxin, lipopolysaccharide. We used photolithography to entrap cells with this dye within poly(ethylene) glyocol diacrylate hydrogels in microfluidic channels. After 18 hours of exposure to lipopolysaccharide, we were able to see visible changes in the fluorescent pattern. This work shows the feasibility of using whole cell based biosensors within microfluidic networks to detect cellular changes in response to exogenous agents.

  5. Modelling larval movement data from individual bioassays.

    Science.gov (United States)

    McLellan, Chris R; Worton, Bruce J; Deasy, William; Birch, A Nicholas E

    2015-05-01

    We consider modelling the movements of larvae using individual bioassays in which data are collected at a high-frequency rate of five observations per second. The aim is to characterize the behaviour of the larvae when exposed to attractant and repellent compounds. Mixtures of diffusion processes, as well as Hidden Markov models, are proposed as models of larval movement. These models account for directed and localized movements, and successfully distinguish between the behaviour of larvae exposed to attractant and repellent compounds. A simulation study illustrates the advantage of using a Hidden Markov model rather than a simpler mixture model. Practical aspects of model estimation and inference are considered on extensive data collected in a study of novel approaches for the management of cabbage root fly.

  6. Final Technical Report for DOE Grant, number DE-FG02-05ER15701; Probing Surface Chemistry Under Catalytic Conditions: Olefin Hydrogenation,Cyclization and Functionalization.

    Energy Technology Data Exchange (ETDEWEB)

    Neurock, Matthew

    2011-05-26

    The specific goal of this work was to understanding the catalytic reactions pathways for the synthesis of vinyl acetate over Pd, Au and PdAu alloys. A combination of both experimental methods (X-ray and Auger spectroscopies, low-energy ion scattering (LEIS), low-energy electron diffraction (LEED) and theory (Density Functional Theory (DFT) calculations and Monte Carlo methods under various different reactions) were used to track the surface chemistry and the influence of alloying. The surface intermediates involved in the various reactions were characterized using reflection-absorption infrared spectroscopy and LEED to identify the nature of the surface species and temperature-programmed desorption (TPD) to follow the decomposition pathways and measure heats of adsorption. These results along with those from density functional theoretical calculations were used determine the kinetics for elementary steps. The results from this work showed that the reaction proceeds via the Samanos mechanism over Pd surfaces whereby the ethylene directly couples with acetate to form an acetoxyethyl intermediate that subsequently undergoes a beta-hydride elimination to form the vinyl acetate monomer. The presence of Au was found to modify the adsorption energies and surface coverages of important surface intermediates including acetate, ethylidyne and ethylene which ultimately influences the critical C-H activation and coupling steps. By controlling the surface alloy composition or structure one can begin to control the steps that control the rate and even the mechanism.

  7. Surface functionalization of a poly(butylene terephthalate) (PBT) melt-blown filtration membrane by wet chemistry and photo-grafting.

    Science.gov (United States)

    Salvagnini, Claudio; Roback, Alexandre; Momtaz, Maryam; Pourcelle, Vincent; Marchand-Brynaert, Jacqueline

    2007-01-01

    The surface functionalization of PBT melt-blown membrane, making up a whole filter of blood components, was achieved via two methods. Hydroxyl chain-end activation by tosylation (method A), followed by coupling of F- and (3)H-tagged molecules (probes), led to 1% of surface derivatization (XPS) and 290 pmol/cm(2) of lysine fixation (LSC). Deposition of O-succinimidyl 4-(p-azido-phenyl)butanoate ("molecular clip") and 2 h irradiation at 254 nm led to the implanting of activated ester functions, randomly on the polymer surface (method B). Further coupling of F- and (3)H-probes by wet chemistry gave highly functionalized surface (4% by XPS and 1000 pmol/cm(2) by LSC). However, control experiments showed that about 80% of the surface derivatization resulted from the UV treatment alone. Thus, the effect of UV irradiation on PBT membrane was systematically studied and analyzed by XPS, contact angle measurements, GPC and surface reactivity assays. The optimized conditions of "molecular clip" photo-grafting (negligible polymer photo-oxidation/photo-degradation) led to the covalent fixation of 45 pmol/cm(2) of (3)H-probe. Throughout our study, the behaviour of PBT melt-blown membrane was compared to PBT film and PET track-etched membrane similarly treated. Lastly, the method B was applied to couple GRGDS peptide on the PBT membrane; this material showed improved properties of leukocyte depletion in buffy coat filtration experiments.

  8. Decoupling the effects of surface chemistry and humidity on solid-state hydrolysis of aspirin in the presence of dicalcium phosphate dihydrate.

    Science.gov (United States)

    Cassidy, Andrew M; Gardner, Catherine E; Auffret, Tony; Aldous, Barry; Jones, William

    2012-04-01

    Atomic force microscopy (AFM) cantilevers were functionalized with particles of dicalcium phosphate dihydrate (DCP), and AFM, in force-displacement mode, was used to bring these probes into contact with aspirin (100) and (001) surfaces in order to investigate the effect of aspirin surface chemistry on the interaction between the two materials as a function of relative humidity (RH). The force of adhesion measurements showed a strong dependence on RH for the interactions between DCP and the aspirin (100) surface, with stronger interactions occurring at higher humudities. Relatively much weaker interactions were measured between DCP and the aspirin (001) surface under all RH conditions. Topographic imaging showed that contact between DCP and the aspirin (100) surface at high RH led to localised development of etch pits and, in some cases, growth normal to the surface. The methodology allows for the creation of a localised solid-solid interface between pharmaceutically relevant materials, providing a means of studying solid-state excipient-active ingredient decomposition reactions.

  9. Groundwater, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona—2012–2013

    Science.gov (United States)

    Macy, Jamie P.; Truini, Margot

    2016-03-02

    The Navajo (N) aquifer is an extensive aquifer and the primary source of groundwater in the 5,400-square-mile Black Mesa area in northeastern Arizona. Availability of water is an important issue in northeastern Arizona because of continued water requirements for industrial and municipal use by a growing population and because of low precipitation in the arid climate of the Black Mesa area. Precipitation in the area typically is between 6 and 14 inches per year.The U.S. Geological Survey water-monitoring program in the Black Mesa area began in 1971 and provides information about the long-term effects of groundwater withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected as part of the monitoring program in the Black Mesa area from January 2012 to September 2013. The monitoring program includes measurements of (1) groundwater withdrawals, (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry.In calendar year 2012, total groundwater withdrawals were 4,010 acre-ft, industrial withdrawals were 1,370 acre-ft, and municipal withdrawals were 2,640 acre-ft. Total withdrawals during 2012 were about 45 percent less than total withdrawals in 2005 because of Peabody Western Coal Company’s discontinued use of water to transport coal in a coal slurry pipeline. From 2011 to 2012 total withdrawals decreased by 10 percent; industrial withdrawals decreased by approximately 1 percent, and total municipal withdrawals decreased by 15 percent.From 2012 to 2013, annually measured water levels in the Black Mesa area declined in 6 of 16 wells that were available for comparison in the unconfined areas of the N aquifer, and the median change was 0.8 feet. Water levels declined in 5 of 16 wells measured in the confined area of the aquifer. The median change for the confined area of the aquifer was 0.3 feet. From the prestress period (prior to 1965) to 2013, the median water

  10. Groundwater, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona: 2011-2012

    Science.gov (United States)

    Macy, Jamie P.; Unema, Joel A.

    2014-01-01

    The Navajo (N) aquifer is an extensive aquifer and the primary source of groundwater in the 5,400-square-mile Black Mesa area in northeastern Arizona. Availability of water is an important issue in northeastern Arizona because of continued water requirements for industrial and municipal use by a growing population and because of low precipitation in the arid climate of the Black Mesa area. Precipitation in the area typically is between 6 and 14 inches per year. The U.S. Geological Survey water-monitoring program in the Black Mesa area began in 1971 and provides information about the long-term effects of groundwater withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected as part of the monitoring program in the Black Mesa area from January 2011 to September 2012. The monitoring program includes measurements of (1) groundwater withdrawals, (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In 2011, total groundwater withdrawals were 4,480 acre-ft, industrial withdrawals were 1,390 acre-ft, and municipal withdrawals were 3,090 acre-ft. Total withdrawals during 2011 were about 39 percent less than total withdrawals in 2005 because of Peabody Western Coal Company’s discontinued use of water to transport coal in a slurry. From 2010 to 2011 total withdrawals increased by 11 percent; industrial withdrawals increased by approximately 19 percent, and total municipal withdrawals increased by 8 percent. From 2011 to 2012, annually measured water levels in the Black Mesa area declined in 8 of 15 wells that were available for comparison in the unconfined areas of the N aquifer, and the median change was -0.1 feet. Water levels declined in 9 of 18 wells measured in the confined area of the aquifer. The median change for the confined area of the aquifer was 0.0 feet. From the prestress period (prior to 1965) to 2012, the median water-level change for 34 wells in both

  11. Plasmonically amplified bioassay - Total internal reflection fluorescence vs. epifluorescence geometry.

    Science.gov (United States)

    Hageneder, Simone; Bauch, Martin; Dostalek, Jakub

    2016-08-15

    This paper investigates plasmonic amplification in two commonly used optical configurations for fluorescence readout of bioassays - epifluorescence (EPF) and total internal reflection fluorescence (TIRF). The plasmonic amplification in the EPF configuration was implemented by using crossed gold diffraction grating and Kretschmann geometry of attenuated total reflection method (ATR) was employed in the TIRF configuration. Identical assay, surface architecture for analyte capture, and optics for the excitation, collection and detection of emitted fluorescence light intensity were used in both TIRF and EPF configurations. Simulations predict that the crossed gold diffraction grating (EPF) can amplify the fluorescence signal by a factor of 10(2) by the combination of surface plasmon-enhanced excitation and directional surface plasmon-coupled emission in the red part of spectrum. This factor is about order of magnitude higher than that predicted for the Kretschmann geometry (TIRF) which only took advantage of the surface plasmon-enhanced excitation. When applied for the readout of sandwich interleukin 6 (IL-6) immunoassay, the plasmonically amplified EPF geometry designed for Alexa Fluor 647 labels offered 4-times higher fluorescence signal intensity compared to TIRF. Interestingly, both geometries allowed reaching the same detection limit of 0.4pM despite of the difference in the fluorescence signal enhancement. This is attributed to inherently lower background of fluorescence signal for TIRF geometry compared to that for EPF which compensates for the weaker fluorescence signal enhancement. The analysis of the inflammation biomarker IL-6 in serum at medically relevant concentrations and the utilization of plasmonic amplification for the fluorescence measurement of kinetics of surface affinity reactions are demonstrated for both EPF and TIRF readout.

  12. In-situ Evaluation of Soil Organic Molecules: Functional Group Chemistry Aggregate Structures, Metal & Surface Complexation Using Soft X-Ray

    Energy Technology Data Exchange (ETDEWEB)

    Myneni, Satish, C

    2008-11-30

    Organic molecules are common in all Earth surface environments, and their composition and chemistry play an important role in a variety of biogeochemical reactions, such as mineral weathering, nutrient cycling and the solubility and transport of contaminants. However, most of what we know about the chemistry of these molecules comes from spectroscopy and microscopy studies of organic molecules extracted from different natural systems using either inorganic or organic solvents. Although all these methods gave us clues about the composition of these molecules, their composition and structure change with the extraction and the type of ex-situ analysis, their true behavior is less well understood. The goal of this project is to develop synchrotron instrumentation for studying natural organics, and to apply these recently developed synchrotron X-ray spectroscopy and microscopy techniques for understanding the: (1) functional group composition of naturally occurring organic molecules; (2) macromolecular structures of organic molecules; and (3) the nature of interactions of organic molecules with mineral surfaces in different environmental conditions.

  13. Study of the Effect of Grafting Method on Surface Polarity of Tempo-Oxidized Nanocellulose Using Polycaprolactone as the Modifying Compound: Esterification versus Click-Chemistry

    Directory of Open Access Journals (Sweden)

    Abdelhaq Benkaddour

    2013-12-01

    Full Text Available Esterification and click-chemistry were evaluated as surface modification treatments for TEMPO-oxidized nanocelluloses (TONC using Polycaprolactone-diol (PCL as modifying compound in order to improve the dispersion of nanofibers in organic media. These two grafting strategies were analyzed and compared. The first consists of grafting directly the PCL onto TONC, and was carried out by esterification between hydroxyl groups of PCL and carboxyl groups of TONC. The second strategy known as click-chemistry is based on the 1,3-dipolar cycloaddition reaction between azides and alkyne terminated moieties to form the triazole ring between PCL and TONC. The grafted samples were characterized by transmission electron microscopy (TEM, Fourier transform infrared spectroscopy (FTIR, X-ray photoelectron spectroscopy (XPS, and Thermogravimetry analysis (TGA. Further, the effects of the two treatments on the surface hydrophobization of TONC were investigated by contact angle measurements. The results show that both methods confirm the success of such a modification and the click reaction was significantly more effective than esterification.

  14. Oxygen-Induced Restructuring of Rutile TiO(2)(110): Formation Mechanism, Atomic Models, and Influence on Surface Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Li, Min; Hebenstreit, Wilhelm; Diebold, Ulrike; Henderson, Michael A.; Jennison, Dwight R.

    1999-07-07

    The rutile TiO{sub 2} (110) (1x1) surface is considered the prototypical ''well-defined'' system in the surface science of metal oxides. Its popularity results partly from two experimental advantages: bulk-reduced single crystals do not exhibit charging, and stoichiometric surfaces--as judged by electron spectroscopes--can be prepared reproducibly by sputtering and annealing in oxygen. We present results that show that this commonly-applied preparation procedure may result in a surface structure that is by far more complex than generally anticipated. Flat, (1x1) terminated surfaces are obtained by sputtering and annealing in ultrahigh vacuum. When re-annealed in oxygen at moderate temperatures (470 K to 660 K), irregular networks of partially-connected, pseudohexagonal rosettes (6.5 x 6 {angstrom} wide), one-unit cell wide strands, and small ({approximately} tens of {angstrom}) (1x1) islands appear. This new surface phase is formed through reaction of oxygen gas with interstitial Ti from the reduced bulk. Because it consists of an incomplete, kinetically-limited (1x1) layer, this phenomenon has been termed restructuring. We report a combined experimental and theoretical study that systematically explores this restructuring process. The influence of several parameters (annealing time, temperature, pressure, sample history, gas) on the surface morphology is investigated using STM. The surface coverage of the added phase as well as the kinetics of the restructuring process are quantified by LEIS and SSIMS measurements in combination with annealing in {sup 18}O-enriched gas. Atomic models of the essential structural elements are presented and are shown to be stable with first-principles density functional calculations. The effect of oxygen-induced restructuring on surface chemistry and its importance for TiO{sub 2} and other bulk-reduced oxide materials is briefly discussed.

  15. Controlling Foam Morphology of Poly(methyl methacrylate via Surface Chemistry and Concentration of Silica Nanoparticles and Supercritical Carbon Dioxide Process Parameters

    Directory of Open Access Journals (Sweden)

    Deniz Rende

    2013-01-01

    Full Text Available Polymer nanocomposite foams have received considerable attention because of their potential use in advanced applications such as bone scaffolds, food packaging, and transportation materials due to their low density and enhanced mechanical, thermal, and electrical properties compared to traditional polymer foams. In this study, silica nanofillers were used as nucleating agents and supercritical carbon dioxide as the foaming agent. The use of nanofillers provides an interface upon which CO2 nucleates and leads to remarkably low average cell sizes while improving cell density (number of cells per unit volume. In this study, the effect of concentration, the extent of surface modification of silica nanofillers with CO2-philic chemical groups, and supercritical carbon dioxide process conditions on the foam morphology of poly(methyl methacrylate, PMMA, were systematically investigated to shed light on the relative importance of material and process parameters. The silica nanoparticles were chemically modified with tridecafluoro-1,1,2,2-tetrahydrooctyl triethoxysilane leading to three different surface chemistries. The silica concentration was varied from 0.85 to 3.2% (by weight. The supercritical CO2 foaming was performed at four different temperatures (40, 65, 75, and 85°C and between 8.97 and 17.93 MPa. By altering the surface chemistry of the silica nanofiller and manipulating the process conditions, the average cell diameter was decreased from 9.62±5.22 to 1.06±0.32 μm, whereas, the cell density was increased from 7.5±0.5×108 to 4.8±0.3×1011 cells/cm3. Our findings indicate that surface modification of silica nanoparticles with CO2-philic surfactants has the strongest effect on foam morphology.

  16. Colour Chemistry

    Science.gov (United States)

    Griffiths, J.; Rattee, I. D.

    1973-01-01

    Discusses the course offerings in pure color chemistry at two universities and the three main aspects of study: dyestuff chemistry, color measurement, and color application. Indicates that there exists a constant challenge to ingenuity in the subject discipline. (CC)

  17. Chemistry Dashboard

    Science.gov (United States)

    The Chemistry Dashboard is part of a suite of dashboards developed by EPA to help evaluate the safety of chemicals. The Chemistry Dashboard provides access to a variety of information on over 700,000 chemicals currently in use.

  18. Chemistry Notes

    Science.gov (United States)

    School Science Review, 1976

    1976-01-01

    Described are eight chemistry experiments and demonstrations applicable to introductory chemistry courses. Activities include: measure of lattice enthalpy, Le Chatelier's principle, decarboxylation of soap, use of pocket calculators in pH measurement, and making nylon. (SL)

  19. Biophysical chemistry.

    Science.gov (United States)

    Häussinger, Daniel; Pfohl, Thomas

    2010-01-01

    Biophysical chemistry at the Department of Chemistry, University of Basel, covers the NMR analysis of protein-protein interaction using paramagnetic tags and sophisticated microscopy techniques investigating the dynamics of biological matter.

  20. Heterocyclic chemistry

    OpenAIRE

    Hemming, Karl

    2011-01-01

    Recent progress in the synthesis of heterocyclic compounds is presented\\ud 2010 offered highlights in pericyclic chemistry, particularly 1,3-dipolar cycloaddition chemistry, asymmetric synthesis, gold catalysis, organocatalysis, hydroamination, C–H activation and multicomponent reactions.