Science.gov

Sample records for adsorption reactive probing

  1. Reactive spreading: Adsorption, ridging and compound formation

    SciTech Connect

    Saiz, E.; Cannon, R.M.; Tomsia, A.P.

    2000-09-11

    Reactive spreading, in which a chemically active element is added to promote wetting of noble metals on nonmetallic materials, is evaluated. Theories for the energetics and kinetics of the necessary steps involved in spreading are outlined and compared to the steps in compound formation that typically accompany reactive wetting. These include: fluid flow, active metal adsorption, including nonequilibrium effects, and triple line ridging. All of these can be faster than compound nucleation under certain conditions. Analysis and assessment of recently reported experiments on metal/ceramic systems lead to a focus on those conditions under which spreading proceeds ahead of the actual formation of a new phase at the interface. This scenario may be more typical than believed, and perhaps the most effective situation leading to enhanced spreading. A rationale for the pervasive variability and hysteresis observed during high temperature wetting also emerges.

  2. PROBING REACTIVITY OF DISSOLVED ORGANIC MATTER FOR DISINFECTION BY-PRODUCT FORMATION USING XAD-8 RESIN ADSORPTION AND ULTRAFILTRATION FRACTIONATION. (R828045)

    EPA Science Inventory

    The disinfection by-product (DBP) reactivity (yield and speciation upon reaction with chlorine) of dissolved organic matter (DOM) isolated from two surface waters was investigated. The source waters, each having significantly different specific ultraviolet absorbance (SUVA

  3. Adsorption of reactive dyes on to carbonate substituted nanohydroxyapatite

    NASA Astrophysics Data System (ADS)

    Vasugi, G.; Kumar, G. Suresh; Girija, E. K.

    2014-04-01

    Carbonate substituted nanohydroxyapatite (CHA) was synthesized and utilized for the removal of reactive red and reactive blue dye from aqueous solution, as it mimics the composition of conventional adsorbent animal bone charcoal. Also ionic substitution seems to alter the surface nature of the apatite structure. Physicochemical nature of adsorbent was characterized by XRD, FT-IR and SEM analysis. Adsorption as a function of contact time, adsorbent dosage and pH were studied by batch mode adsorption technique. Kinetic studies were performed to correlate the experimental kinetic data with theoretical models in order to understand the adsorption mechanism and the reaction rate.

  4. Kinetics of a reactive dye adsorption onto dolomitic sorbents.

    PubMed

    Walker, G M; Hansen, L; Hanna, J-A; Allen, S J

    2003-05-01

    A novel wastewater treatment technique has been investigated, for reactive dye removal, in batch kinetic systems. These experimental studies have indicated that charred dolomite has the potential to act as an adsorbent for the removal of Brilliant Red reactive dye from aqueous solution. The effect of initial dye concentration, adsorbent mass:liquid volume ratio, and agitation speed on dye removal have been determined with the experimental data mathematically described using empirical external mass transfer and intra-particle diffusion models. The experimental data show conformity with an adsorption process, with the removal rate heavily dependent on both external mass transfer and intra-particle diffusion.

  5. Recent advances in thiol and sulfide reactive probes.

    PubMed

    Wang, Ke; Peng, Hanjing; Wang, Binghe

    2014-06-01

    Because of the biological relevance of thiols and sulfides such as cysteine, homocysteine, glutathione and hydrogen sulfide, their detection has attracted a great deal of research interest. Fluorescent probes are emerging as a new strategy for thiol and hydrogen sulfide analysis due to their high sensitivity, low cost, and ability to detect and image thiols in biological samples. In this short review, we have summarized recent advances in the development of thiol and hydrogen sulfide reactive fluorescent probes. These probes are compared and contrasted with regard to their designing strategies, mechanisms, photophysical properties, and/or reaction kinetics. Biological applications of these probes are also discussed.

  6. On the mechanism of reactive adsorption of dibenzothiophene on organic waste derived carbons

    NASA Astrophysics Data System (ADS)

    Ania, C. O.; Parra, J. B.; Arenillas, A.; Rubiera, F.; Bandosz, T. J.; Pis, J. J.

    2007-04-01

    The mechanism of reactive adsorption of dibenzothiophene (DBT) on a series of modified carbons derived from the recycled PET was investigated. The influence of the oxygen functionalities of the adsorbent on the DBT adsorption capacity was explored. The results revealed that adsorption of DBT on activated carbons is governed by two types of contributions: physisorption on the microporous network of the carbons and chemisorption. Introduction of surface acidic groups enhanced the performance of the carbons as a result of their specific interactions with DBT. The nature of the acidic groups is a decisive factor in the selectivity of the reactive adsorption process.

  7. Organic Structure/Reactivity Relationships for Probing the Reactivity of Mineral/Water Interfaces

    NASA Astrophysics Data System (ADS)

    Stone, Alan

    2005-03-01

    Physical organic chemists have long used systematic variations in the functional groups and molecular structure of organic reactants to explore reaction mechanisms. To extend this approach towards investigating ligand-assisted dissolution of iron(III) and chromium(III) (hydr)oxides, it is useful to employ the following reaction scheme: M(surf) + L(aq) = ML(surf) = ML(aq). Capillary electrophoresis enables us to simultaneously monitor L(aq) and ML(aq), which in turn enables us to distinguish the adsorption step from subsequent metal atom detachment. The placement of amine Lewis Base groups is crucial. With iminodiacetate, an amine group is part of the linkage between two carboxylate groups. As a consequence, adsorption is low but overall dissolution rates are high. With aspartate, the amine group is not part of the linkage - it resides on a side arm of the molecule. As a result, adsorption is high but overall dissolution rates are low. Structure-reactivity relationships can also be used to investigate reductive dissolution reactions. Here, we are interested in how the placement of carbonyl groups relative to one another affects reactivity towards manganese(III,IV) (hydr)oxides. Extents of adsorption are low and electron transfer rates high, making it difficult to distinguish the two reaction steps. Structural changes that increase electronic delocalization (i.e. involving both carbonyl groups) give a substantial boost to overall reaction rates. For all types of surface reactions, structure/reactivity relationships provide the basis for making predictions. Knowing the functional groups and molecular structure of extracellular biochemicals (e.g. a siderophore) or synthetic organic contaminants (e.g. a herbicide) becomes the first step in evaluating reaction mechanisms, reaction timescales, and ultimate fate.

  8. Catalytic Role Of Palladium And Relative Reactivity Of Substituted Chlorines During Adsorption And Treatment Of PCBs On Reactive Activated Carbon

    EPA Science Inventory

    The adsorption-mediated dechlorination of polychlorinated biphenyls (PCBs) is a unique feature of reactive activated cabon (RAC). Here, we address the RAC system, containing a tunable amount of Fe as a primary electron donor coupled with Pd as an electrochemical catalyst to pote...

  9. A fiber optic, ultraviolet light-emitting diode-based, two wavelength fluorometer for monitoring reactive adsorption

    NASA Astrophysics Data System (ADS)

    Granz, Christopher D.; Schindler, Bryan J.; Peterson, Gregory W.; Whitten, James E.

    2016-03-01

    Construction and use of an ultraviolet light-emitting diode-based fluorometer for measuring photoluminescence (PL) from powder samples with a fiber optic probe is described. Fluorescence at two wavelengths is detected by miniature photomultiplier tubes, each equipped with a different band pass filter, whose outputs are analyzed by a microprocessor. Photoluminescent metal oxides and hydroxides, and other semiconducting nanoparticles, often undergo changes in their emission spectra upon exposure to reactive gases, and the ratio of the PL intensities at two wavelengths is diagnostic of adsorption. Use of this instrument for reactive gas sensing and gas filtration applications is illustrated by measuring changes in the PL ratio for zirconium hydroxide and zinc oxide particles upon exposure to air containing low concentrations of sulfur dioxide.

  10. Probing the mechanism of water adsorption in carbon micropores with multitemperature isotherms and water preadsorption experiments.

    PubMed

    Rutherford, S W

    2006-11-21

    The phenomenon of water adsorption in carbon micropores is examined through the study of water adsorption equilibrium in molecular sieving carbon. Adsorption and desorption isotherms are obtained over a wide range of concentrations from less than 0.1% to beyond 80% of the vapor pressure. Evidence is provided in support of a proposed bimodal water adsorption mechanism that involves the interaction of water molecules with functional groups at low relative pressures and the adsorption of water molecules between graphene layers at higher pressures. Decomposition of the equilibrium isotherm data through application of the extended cooperative multimolecular sorption theory, together with favorable quantitative comparison, provides support for the proposed adsorption mechanism. Additional support is obtained from a multitemperature study of water equilibrium. Temperatures of 20, 50, and 60 degrees C were probed in this investigation in order to provide isosteric heat of adsorption data for water interaction with the carbon molecular sieve. At low loading, the derived isosteric heat of adsorption is estimated to be 69 kJ/mol. This value is indicative of the adsorption of water to functional groups. At higher loading, the isosteric heat of adsorption decreases with increasing loading and approaches the heat of condensation, indicative of adsorption between graphene layers. Further support for the proposed adsorption mechanism is derived from carbon dioxide adsorption experiments on carbon molecular sieve that is preadsorbed with various amounts of water. Significant exclusion of carbon dioxide occurs, and a quantitative analysis that is based on the proposed bimodal water adsorption mechanism is employed in this investigation.

  11. Nanoengineered Carbon-Based Materials For Reactive Adsorption of Toxic Industrial Compounds

    DTIC Science & Technology

    2015-01-13

    Mendoza, T.J. Bandosz. Reactive adsorption of ammonia on Cu-based MOF /graphene composites , Langmuir, (7 2010): . doi: Kavindra Singh, Nikolina A...graphite oxide composites on the adsorption of ammonia , Journal of Colloid and Interface Science, (03 2014): 0. doi: 10.1016/j.jcis.2013.11.010... ammonia on graphene/nanoporous carbon composites, Carbon, (4 2013): 0. doi: 10.1016/j.carbon.2012.12.024 Oluwaniyi Mabayoje, Mykola Seredych, Teresa

  12. Screening of active metals for reactive adsorption desulfurization adsorbent using density functional theory

    NASA Astrophysics Data System (ADS)

    Wang, Lei; Zhao, Liang; Xu, Chunming; Wang, Yuxian; Gao, Jinsen

    2017-03-01

    To explore characteristics of active metals for reactive adsorption desulfurization (RADS) technology, the adsorption of thiophene on M (100) (M = Cr, Mo, Co, Ni, Cu, Au, and Ag) surfaces was systematically studied by density functional theory with vdW correction (DFT + D3). We found that, in all case, the most stable molecular adsorption site was the hollow site and adsorptive capabilities of thiophene followed the order: Cr > Mo > Co ≈ Ni > Cu > Au ≈ Ag. By analyzing the nature of binding between thiophene and corresponding metals and the electronic structure of metals, the excessive activities of Cr and Mo were found to have a negative regeneration, the passive activities of Au and Ag were found to have an inactive adsorption for RADS adsorbent alone, while Ni and Co have appropriate characteristics as the active metals for RADS, followed by Cu.

  13. Adsorption of probe molecules in pillared interlayered clays: Experiment and computer simulation

    SciTech Connect

    Gallardo, A. Guil, J. M.; Lomba, E.; Almarza, N. G.; Khatib, S. J.; Cabrillo, C.; Sanz, A.; Pires, J.

    2014-06-14

    In this paper we investigate the adsorption of various probe molecules in order to characterize the porous structure of a series of pillared interlayered clays (PILC). To that aim, volumetric and microcalorimetric adsorption experiments were performed on various Zr PILC samples using nitrogen, toluene, and mesitylene as probe molecules. For one of the samples, neutron scattering experiments were also performed using toluene as adsorbate. Various structural models are proposed and tested by means of a comprehensive computer simulation study, using both geometric and percolation analysis in combination with Grand Canonical Monte Carlo simulations in order to model the volumetric and microcalorimetric isotherms. On the basis of this analysis, we propose a series of structural models that aim at accounting for the adsorption experimental behavior, and make possible a microscopic interpretation of the role played by the different interactions and steric effects in the adsorption processes in these rather complex disordered microporous systems.

  14. Goethite surface reactivity: a macroscopic investigation unifying proton, chromate, carbonate, and lead(II) adsorption.

    PubMed

    Villalobos, Mario; Pérez-Gallegos, Ayax

    2008-10-15

    The goethite surface structure has been extensively studied, but no convincing quantitative description of its highly variable surface reactivity as inversely related to its specific surface area (SSA) has been found. The present study adds experimental evidence and provides a unified macroscopic explanation to this anomalous behavior from differences in average adsorption capacities, and not in average adsorption affinities. We investigated the chromate anion and lead(II) cation adsorption behavior onto three different goethites with SSA varying from 50 to 94 m(2)/g, and analyzed an extensive set of published anion adsorption and proton charging data for variable SSA goethites. Maximum chromate adsorption was found to occupy on average from 3.1 to 9.7 sites/nm(2), inversely related to SSA. Congruency of oxyanion and Pb(II) adsorption behavior based on fractional site occupancy using these values, and a site density analysis suggest that: (i) ion binding occurs to singly and doubly coordinated sites, (ii) proton binding occurs to singly and triply coordinated sites (ranging from 6.2 to 8 total sites/nm(2), in most cases), and (iii) a predominance of (210) and/or (010) faces explains the high reactivity of low SSA goethites. The results imply that the macroscopic goethite adsorption behavior may be predicted without a need to investigate extensive structural details of each specific goethite of interest.

  15. Photoluminescence Probing of Complex H2O Adsorption on InGaN/GaN Nanowires.

    PubMed

    Maier, Konrad; Helwig, Andreas; Müller, Gerhard; Hille, Pascal; Teubert, Jörg; Eickhoff, Martin

    2017-02-08

    We demonstrate that the complex adsorption behavior of H2O on InGaN/GaN nanowire arrays is directly revealed by their ambient-dependent photoluminescence properties. Under low-humidity, ambient-temperature, and low-excitation-light conditions, H2O adsorbates cause a quenching of the photoluminescence. In contrast, for high humidity levels, elevated temperature, and high excitation intensity, H2O adsorbates act as efficient photoluminescence enhancers. We show that this behavior, which can only be detected due to the low operation temperature of the InGaN/GaN nanowires, can be explained on the basis of single H2O adsorbates forming surface recombination centers and multiple H2O adsorbates forming surface passivation layers. Reversible creation of such passivation layers is induced by the photoelectrochemical splitting of adsorbed water molecules and by the interaction of reactive H3O(+) and OH(-) ions with photoactivated InGaN surfaces. Due to electronic coupling of adsorbing molecules with photoactivated surfaces, InGaN/GaN nanowires act as sensitive nanooptical probes for the analysis of photoelectrochemical surface processes.

  16. Single and binary adsorption of reactive dyes from aqueous solutions onto clinoptilolite.

    PubMed

    Sismanoglu, Tuba; Kismir, Yasemin; Karakus, Selcan

    2010-12-15

    The adsorption of Reactive Blue 21 (RB21) and Reactive Red 195 (RR195) onto clinoptilolite type natural zeolite (ZEC) has been investigated at 298.15K. The uptake of single and binary reactive dyes from aqueous solutions has been determined by UV-vis spectroscopy. Two mono-component (RB21 and RR195) and binary component (RB21 with RR195, and RR195 with RB21), isotherms were determined. The mono-component Langmuir isotherm model was applied to experimental data and the isotherm constants were calculated for RB21 and RR195 dyes. The monolayer coverage capacities of clinoptilolite for RB21 and RR195 dyes in single solution system were found as 9.652 and 3.186 mg/g, respectively. Equilibrium adsorption for binary systems was analyzed by using the extended Langmuir models. The rate of kinetic processes of single and binary dye systems onto clinoptilolite was described by using two kinetics adsorption models. The pseudo-second-order model was the best choice among the kinetic models to describe the adsorption behaviour of single and binary dyes onto clinoptilolite.

  17. Adsorption of reactive dyes from aqueous solutions by fly ash: kinetic and equilibrium studies.

    PubMed

    Dizge, N; Aydiner, C; Demirbas, E; Kobya, M; Kara, S

    2008-02-11

    Adsorption kinetic and equilibrium studies of three reactive dyes namely, Remazol Brillant Blue (RB), Remazol Red 133 (RR) and Rifacion Yellow HED (RY) from aqueous solutions at various initial dye concentration (100-500 mg/l), pH (2-8), particle size (45-112.5 microm) and temperature (293-323 K) on fly ash (FA) were studied in a batch mode operation. The adsorbent was characterized with using several methods such as SEM, XRD and FTIR. Adsorption of RB reactive dye was found to be pH dependent but both RR and RY reactive dyes were not. The result showed that the amount adsorbed of the reactive dyes increased with increasing initial dye concentration and contact time. Batch kinetic data from experimental investigations on the removal of reactive dyes from aqueous solutions using FA have been well described by external mass transfer and intraparticle diffusion models. It was found that external mass transfer and intraparticle diffusion had rate limiting affects on the removal process. This was attributed to the relatively simple macropore structure of FA particles. The adsorption data fitted well with Langmuir and Freundlich isotherm models. The optimum conditions for removal of the reactive dyes were 100mg/l initial dye concentration, 0.6g/100ml adsorbent dose, temperature of 293 K, 45 microm particle size, pH 6 and agitation speed of 250 rpm, respectively. The values of Langmuir and Freundlich constants were found to increase with increasing temperature in the range 135-180 and 15-34 mg/g for RB, 47-86 and 1.9-3.7 mg/g for RR and 37-61 and 3.0-3.6 mg/g for RY reactive dyes, respectively. Different thermodynamic parameters viz., changes in standard free energy, enthalpy and entropy were evaluated and it was found that the reaction was spontaneous and endothermic in nature.

  18. Activation of waste MDF sawdust charcoal and its reactive dye adsorption characteristics.

    PubMed

    Gan, Q; Allen, S J; Matthews, R

    2004-01-01

    This paper reports an experimental investigation of converting waste medium density fibreboard (MDF) sawdust into chars and activated carbon using chemical activation and thermal carbonisation processes. The MDF sawdust generated during the production of architectural mouldings was characterised and found to have unique properties in terms of fine particle size and high particle density. It also has a high content of urea formaldehyde resin used as a binder in the manufacturing of MDF board. Direct thermal carbonisation and chemical activation of the sawdust by metal impregnation and acid (phosphoric acid) treatment prior to pyrolysis treatment were carried out. The surface morphology of the raw dust, its chars and activated carbon were examined using scanning electron microscopy (SEM). Adsorptive properties and total pore volume of the materials were also analysed using the BET nitrogen adsorption method. Liquid adsorption of a reactive dye (Levafix Brilliant red E-4BA) by the derived sawdust carbon was investigated in batch isothermal adsorption process and the results compared to adsorption on to a commercial activated carbon (Filtrasorb F400). The MDF sawdust carbon exhibited in general a very low adsorption capacity towards the reactive dye, and physical characterisation of the carbon revealed that the conventional chemical activation and thermal carbonisation process were ineffective in developing a microporous structure in the dust particles. The small size of the powdery dust, the high particle density, and the presence of the urea formaldehyde resin all contributed to the difficulty of developing a proper porous structure during the thermal and chemical activation process. Finally, activation of the dust material in a consolidated form (cylindrical pellet) only achieved very limited improvement in the dye adsorption capacity. This original study, reporting some unexpected outcomes, may serve as a stepping-stone for future investigations of recycle and

  19. Modification of bentonite with a cationic surfactant: An adsorption study of textile dye Reactive Blue 19.

    PubMed

    Ozcan, Adnan; Omeroğlu, Ciğdem; Erdoğan, Yunus; Ozcan, A Safa

    2007-02-09

    The utilization of modified bentonite with a cationic surfactant (dodecyltrimethylammonium (DTMA) bromide) as an adsorbent was successfully carried out to remove a synthetic textile dye (Reactive Blue 19 (RB19)) by adsorption, from aqueous solutions. Batch studies were carried out to address various experimental parameters such as pH, contact time and temperature. The surface modification of bentonite with a surfactant was examined using the FTIR spectroscopic technique and elemental analysis. Effective pH for the adsorption of RB19 onto DTMA-bentonite was around 1.5. The Langmuir isotherm model was found to be the best to represent the equilibrium with experimental data. The maximum adsorption capacity (q(max)) has been found to be 3.30x10(-4)molg(-1) or 206.58mgg(-1). The thermodynamic study indicated that the adsorption of RB19 onto DTMA-bentonite was favored with the negative Gibbs free energy values. The pseudo-second-order rate equation was able to provide the best description of adsorption kinetics and the intraparticle diffusion model was also applicable up to 40min for the adsorption of RB19 onto DTMA-bentonite.

  20. Measuring reactive oxygen and nitrogen species with fluorescent probes: challenges and limitations

    PubMed Central

    Kalyanaraman, Balaraman; Darley-Usmar, Victor; Davies, Kelvin J.A.; Dennery, Phyllis A.; Forman, Henry Jay; Grisham, Matthew B.; Mann, Giovanni E.; Moore, Kevin; Roberts, L. Jackson; Ischiropoulos, Harry

    2013-01-01

    The purpose of this position paper is to present a critical analysis of the challenges and limitations of the most widely used fluorescent probes for detecting and measuring reactive oxygen and nitrogen species. Where feasible, we have made recommendations for the use of alternate probes and appropriate analytical techniques that measure the specific products formed from the reactions between fluorescent probes and reactive oxygen and nitrogen species. We have proposed guidelines that will help present and future researchers with regard to the optimal use of selected fluorescent probes and interpretation of results. PMID:22027063

  1. Kinetic studies of the liquid-phase adsorption of a reactive dye onto activated lignite

    SciTech Connect

    Petrolekas, P.D.; Maggenakis, G.

    2007-02-14

    The kinetics of batch adsorption of a commercial reactive dye onto activated lignite has been investigated at temperatures of 26, 40, and 55{sup o}C, using aqueous solutions with initial dye concentrations in the range of 15-60 mg/L. An empirical single parameter relationship of the adsorbent loading versus the square root of contact time was proposed, which was determined to provide a very good description of the batch adsorption transients up to equilibrium. The data were also examined by means of the Elovich equation. The effect of the temperature and the initial dye concentration on the adsorption kinetics was analyzed, and the results were discussed by considering that intraparticle diffusion is the dominant mechanism.

  2. Adsorption, Mobility and Organisation of Organic Molecules at Clay Surfaces Probed by Photophysics and Photochemistry

    DTIC Science & Technology

    1989-06-15

    unambiguous. The time-dependent fluorescence of the organo - clay systems, has also been studied. Several functions have been used to describe the...ADSORPTION, MOBILITY AND ORGANISATION OF ORGANIC MOLECULES AT CLAY SURFACES PROBED BY PHOTOPHYSICS AND Lfl PHOTOCHEMISTRY C~%I SIXTH INTERIM REPORT...CONTENTS A.-iluster formation of detergents on the clay surface. B. kdsorption of aromatic compounds on colloidal silica C.-ttudy of the fluorescence decay

  3. Labeling of target mRNAs using a photo-reactive microRNA probe.

    PubMed

    Nakamoto, Kosuke; Minami, Koichiro; Akao, Yukihiro; Ueno, Yoshihito

    2016-05-10

    To identify target mRNAs of an miRNA, we synthesized photo-reactive miRNA probes, which contained a photo-reactive nucleoside analog, 1-O-[4-(3-trifluoromethyl-3H-diazirine-3-yl)]benzyl-β-d-ribofuranose, in the middle of the strand. The photo-reactive miRNA-145 probe was found to specifically label the target mRNAs, FSCN1 and KLF4, by UV-A irradiation in human colon cancer DLD-1 cells.

  4. Sensitivity of activatable reactive oxygen species probes by fluorescence spectroelectrochemistry

    PubMed Central

    Wang, Steven T.; Zhegalova, Natalia G.; Gustafson, Tiffany P.; Zhou, Andy; Sher, Joel; Achilefu, Samuel; Berezinand, Oleg Y.

    2013-01-01

    We have developed a new analytical method of evaluating activatable fluorescent probes for ROS detection using integrated fluorescence spectroelectrochemistry. Tafel formalism was applied to describe the process of the probes’ oxidation under electrochemical conditions and identify a novel parameter defined as the threshold oxidation potential. This potential can serve as an approximation to the equilibrium potential and can be utilized for determining the sensitivity of a probe to oxidation. Based upon the measured values of threshold potentials, the order of sensitivity towards oxidation among several mostly used probes was determined to be following (from highest to lowest): 2,7-dichlorodihydrofluorescein > dihydroethidium > dihydrorhodamine 123 > dihydrorhodamine 6G. The presented approach opens up a new direction in synthesizing and screening novel ROS probes with a well-defined sensitivity for in vitro and in vivo applications. PMID:23736882

  5. Adsorption-desorption characteristics of phenol and reactive dyes from aqueous solution on mesoporous activated carbon prepared from waste tires.

    PubMed

    Tanthapanichakoon, W; Ariyadejwanich, P; Japthong, P; Nakagawa, K; Mukai, S R; Tamon, H

    2005-04-01

    Liquid-phase adsorption-desorption characteristics and ethanol regeneration efficiency of an activated carbon prepared from waste tires and a commercial activated carbon were investigated. Water vapor adsorption experiments reveal that both activated carbons showed hydrophobic surface characteristics. Adsorption experiments reveal that the prepared activated carbon possessed comparable phenol adsorption capacity as the commercial one but clearly larger adsorption capacity of two reactive dyes, Black 5 and Red 31. It was ascertained that the prepared activated carbon exhibited less irreversible adsorption of phenol and the two dyes than its commercial counterpart. Moreover, ethanol regeneration efficiency of the prepared AC saturated with either dye was higher than that of the commercial AC. Because of its superior liquid-phase adsorption-desorption characteristics as well as higher ethanol regeneration efficiency, the prepared activated carbon is more suitable for wastewater treatment, especially for adsorbing similarly bulky adsorbates.

  6. On the reactive adsorption of ammonia on activated carbons modified by impregnation with inorganic compounds.

    PubMed

    Bandosz, Teresa J; Petit, Camille

    2009-10-15

    Ammonia adsorption was studied under dynamic conditions, at room temperature, on activated carbons of different origins (coal-based, wood-based and coconut-shell-based carbons) before and after their impregnation with various inorganic compounds including metal chlorides, metal oxides and polycations. The role of humidity was evaluated by running tests in both dry and moist conditions. Adsorbents were analyzed before and after exposure to ammonia by thermal analyses, sorption of nitrogen, potentiometric titration, X-ray diffraction and FTIR spectroscopy. Results of breakthrough tests show significant differences in terms of adsorption capacity depending on the parent carbon, the impregnates and the experimental conditions. It is found that surface chemistry governs ammonia adsorption on the impregnated carbons. More precisely, it was demonstrated that a proper combination of the surface pH, the strength, type and amount of functional groups present on the adsorbents' surface is a key point in ammonia uptake. Water can have either positive or negative effects on the performance of adsorbents. It can enhance NH(3) adsorption capacity since it favors ammonia dissolution and thus enables reaction between ammonium ions and carboxylic groups from the carbons' surface. On the other hand, water can also reduce the performance from the strength of adsorption standpoint. It promotes dissolution of ammonia and that ammonia is first removed from the system when the adsorbent bed is purged with air. Ammonia, besides adsorption by van der Waals forces and dissolution in water, is also retained on the surface via reactive mechanisms such as acid-base reactions (Brønsted and Lewis) or complexation. Depending on the materials used and the experimental conditions, 6-47% ammonia adsorbed is strongly retained on the surface even when the bed is purged with air.

  7. Adsorption of textile reactive dyestuffs by treatment sludges of inorganic nature.

    PubMed

    Tünay, Olcay; Metin, Emine; Olmez-Hanci, Tuğba; Kabdaşli, Işik

    2012-01-01

    Colour removal from industrial effluents, particularly from the textile industry, has become an important requirement as the adverse effects ofdyestuffs, such as toxicity, on the environment have been proven. Adsorption is a commonly used treatment method for colour removal. Although activated carbon is very effective for this purpose, a number of natural materials and waste materials, such as waste sludges generated from treatment systems, have been tested to reduce the cost of the process. In this paper, sludges arising from the operation of an electrocoagulation process that used stainless steel or aluminium electrodes were investigated as adsorbents for decolorization of reactive dyestuffs. Electrocoagulation waste sludges produced with the use of stainless steel electrodes provided higher than 90% or complete decolorization of Crimson HEXL, Yellow HE4R and RB5 dyestuffs. The sludge produced with aluminium electrodes yielded colour adsorption between 95% and 100% at a 1 g/L dose and pH 8.5-9.1 for two of the dyestuffs; the removal of RB5 did not exceed 60% up to a 4.76 g/L dose. FeCl3 coagulation and adsorption using freshly precipitated coagulation sludge resulted in poor colour removals of 10% for all three dyestuffs. The superior colour adsorption performance of electrocoagulation waste sludges was attributed to modification of the surface properties of the sludges during the electrocoagulation operation. A batch-wise kinetic study indicated that the adsorption of RB5 on to electrocoagulation waste sludges was well fitted by the pseudo-second-order kinetic model, suggesting the intra-particle diffusion process as the rate-limiting step of the adsorption process.

  8. On the reactive adsorption of ammonia on activated carbons modified by impregnation with inorganic compounds

    SciTech Connect

    Bandosz, T.J.; Petit, C.

    2009-10-15

    Ammonia adsorption was studied under dynamic conditions, at room temperature, on activated carbons of different origins (coal-based, wood-based and coconut-shell-based carbons) before and after their impregnation with various inorganic compounds including metal chlorides, metal oxides and polycations. The role of humidity was evaluated by running tests in both dry and moist conditions. Adsorbents were analyzed before and after exposure to ammonia by thermal analyses, sorption of nitrogen, potentiometric titration, X-ray diffraction and FTIR spectroscopy. Results of breakthrough tests show significant differences in terms of adsorption capacity depending on the parent carbon, the impregnates and the experimental conditions. It is found that surface chemistry governs ammonia adsorption on the impregnated carbons. More precisely, it was demonstrated that a proper combination of the surface pH, the strength, type and amount of functional groups present on the adsorbents' surface is a key point in ammonia uptake. Water can have either positive or negative effects on the performance of adsorbents. It can enhance NH{sub 3} adsorption capacity since it favors ammonia dissolution and thus enables reaction between ammonium ions and carboxylic groups from the carbons' surface. On the other hand, water can also reduce the performance from the strength of adsorption standpoint. It promotes dissolution of ammonia and that ammonia is first removed from the system when the adsorbent bed is purged with air. Ammonia, besides adsorption by van der Waals forces and dissolution in water, is also retained on the surface via reactive mechanisms such as acid-base reactions (Bronsted and Lewis) or complexation. Depending on the materials used and the experimental conditions, 6-47% ammonia adsorbed is strongly retained on the surface even when the bed is purged with air.

  9. Equilibrium and kinetic modeling of adsorption of reactive dye on cross-linked chitosan beads.

    PubMed

    Chiou, Ming Shen; Li, Hsing Ya

    2002-07-22

    The adsorption of reactive dye (Reactive Red 189) from aqueous solutions on cross-linked chitosan beads was studied in a batch system. The equilibrium isotherms at different particle sizes (2.3-2.5, 2.5-2.7 and 3.5-3.8mm) and the kinetics of adsorption with respect to the initial dye concentration (4320, 5760 and 7286 g/m(3)), temperature (30, 40 and 50 degrees C), pH (1.0, 3.0, 6.0 and 9.0), and cross-linking ratio (cross-linking agent/chitosan weight ratio: 0.2, 0.5, 0.7 and 1.0) were investigated. Langmuir and Freundlich adsorption models were applied to describe the experimental isotherms and isotherm constants. Equilibrium data fitted very well to the Langmuir model in the entire saturation concentration range (0-1800 g/m(3)). The maximum monolayer adsorption capacities obtained from the Langmuir model are very large, which are 1936, 1686 and 1642 g/kg for small, mediumand large particle sizes, respectively, at pH 3.0, 30 degrees C, and the cross-linking ratio of 0.2. The pseudo first- and second-order kinetic models were used to describe the kinetic data, and the rate constants were evaluated. The experimental data fitted well to the second-order kinetic model, which indicates that the chemical sorption is the rate-limiting step, instead of mass transfer. The initial dye concentration and the solution pH both significantly affect the adsorption capacity, but the temperature and the cross-linking ratio are relatively minor factors. An increase in initial dye concentration results in the increase of adsorption capacity, which also increases with decreasing pH. The activation energy is 43.0 kJ/mol for the adsorption of the dye on the cross-linked chitosan beads at pH 3.0 and initial dye concentration 3768 g/m(3).

  10. Removal of reactive dyes from wastewater by adsorption on coir pith activated carbon.

    PubMed

    Santhy, K; Selvapathy, P

    2006-07-01

    The removal efficiency of activated carbon prepared from coir pith towards three highly used reactive dyes in textile industry was investigated. Batch experiments showed that the adsorption of dyes increased with an increase in contact time and carbon dose. Maximum de-colorisation of all the dyes was observed at acidic pH. Adsorption of dyes was found to follow the Freundlich model. Kinetic studies indicated that the adsorption followed first order and the values of the Lagergren rate constants of the dyes were in the range of 1.77 x 10(-2)-2.69 x 10(-2)min(-1). The column experiments using granular form of the carbon (obtained by agglomeration with polyvinyl acetate) showed that adsorption efficiency increased with an increase in bed depth and decrease of flow rate. The bed depth service time (BDST) analysis carried out for the dyes indicated a linear relationship between bed depth and service time. The exhausted carbon could be completely regenerated and put to repeated use by elution with 1.0M NaOH. The coir pith activated carbon was not only effective in removal of colour but also significantly reduced COD levels of the textile wastewater.

  11. Correlation of adsorption isotherms of hydrogen isotopes on mordenite adsorbents using reactive vacancy solution theory

    SciTech Connect

    Munakata, K.; Nakamura, A.; Kawamura, Y.

    2015-03-15

    The authors have applied the isotherm equations derived from the reactive vacancy solution theory (RVST) to correlation of experimental and highly non-ideal adsorption isotherms of hydrogen and deuterium on a mordenite adsorbent, and have examined the ability of the isotherm equations to match this correlation. Several isotherm equations such as Langmuir, Freundlich, Toth, Vacancy Solution Theory and so forth were also tested, but they did not work. For the Langmuir-Freundlich equation tests have indicated that its 'ability to correlate' of the adsorption isotherms is not satisfactory. For the multi-site Langmuir-Freundlich (MSLF) equation the correlation of the isotherms appears to be somewhat improved but remains unsatisfactory. The results show that the isotherm equations derived from RVST can better correlate the experimental isotherms.

  12. Scanning probe microscopy studies on the adsorption of selected molecular dyes on titania

    PubMed Central

    Zajac, Lukasz; Olszowski, Piotr; Jöhr, Res; Hinaut, Antoine; Glatzel, Thilo; Such, Bartosz; Meyer, Ernst; Szymonski, Marek

    2016-01-01

    Titanium dioxide, or titania, sensitized with organic dyes is a very attractive platform for photovoltaic applications. In this context, the knowledge of properties of the titania–sensitizer junction is essential for designing efficient devices. Consequently, studies on the adsorption of organic dyes on titania surfaces and on the influence of the adsorption geometry on the energy level alignment between the substrate and an organic adsorbate are necessary. The method of choice for investigating the local environment of a single dye molecule is high-resolution scanning probe microscopy. Microscopic results combined with the outcome of common spectroscopic methods provide a better understanding of the mechanism taking place at the titania–sensitizer interface. In the following paper, we review the recent scanning probe microscopic research of a certain group of molecular assemblies on rutile titania surfaces as it pertains to dye-sensitized solar cell applications. We focus on experiments on adsorption of three types of prototypical dye molecules, i.e., perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), phtalocyanines and porphyrins. Two interesting heteromolecular systems comprising molecules that are aligned with the given review are discussed as well. PMID:28144513

  13. Scanning probe microscopy studies on the adsorption of selected molecular dyes on titania.

    PubMed

    Prauzner-Bechcicki, Jakub S; Zajac, Lukasz; Olszowski, Piotr; Jöhr, Res; Hinaut, Antoine; Glatzel, Thilo; Such, Bartosz; Meyer, Ernst; Szymonski, Marek

    2016-01-01

    Titanium dioxide, or titania, sensitized with organic dyes is a very attractive platform for photovoltaic applications. In this context, the knowledge of properties of the titania-sensitizer junction is essential for designing efficient devices. Consequently, studies on the adsorption of organic dyes on titania surfaces and on the influence of the adsorption geometry on the energy level alignment between the substrate and an organic adsorbate are necessary. The method of choice for investigating the local environment of a single dye molecule is high-resolution scanning probe microscopy. Microscopic results combined with the outcome of common spectroscopic methods provide a better understanding of the mechanism taking place at the titania-sensitizer interface. In the following paper, we review the recent scanning probe microscopic research of a certain group of molecular assemblies on rutile titania surfaces as it pertains to dye-sensitized solar cell applications. We focus on experiments on adsorption of three types of prototypical dye molecules, i.e., perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), phtalocyanines and porphyrins. Two interesting heteromolecular systems comprising molecules that are aligned with the given review are discussed as well.

  14. Granular activated carbon adsorption and fluid-bed reactivation at Manchester, New Hampshire. Final report Mar 77-Apr 82

    SciTech Connect

    Kittredge, D.; Beaurivage, R.; Paris, D.

    1983-10-01

    Treatment performances of virgin and reactivated GAC were evaluated during three reactivation-exhaustion cycles by measuring total organic carbon (TOC), trihalomethanes (THM), and trihalomethane formation potential (THMFP). GAC adsorptive capacity was measured using traditional test parameters including iodine number, molasses decolorizing index, BET, and pore-size distribution. The GAC was reactivated on-site by a 500 lb/hr fluidized-bed unit. Results of this study demonstrated that onsite reactivation was a cost-effective method of restoring the adsorptive properties of spent GAC. During a 10-month period, more than 1.8 million lb of GAC was reactivated at a total cost of less than 22 cents/lb as compared with a delivered cost of 61.5 cents/lb for virgin GAC. The average total carbon loss resulting from transportation and reactivation was 11.5% by volume.

  15. A study of Reactive Red 198 adsorption on iron filings from aqueous solutions.

    PubMed

    Azhdarpoor, Abooalfazl; Nikmanesh, Roya; Khademi, Fahime

    2014-01-01

    In recent years, reactive dyes have been widely used in textile industries with particular efficiency. They dyes are often toxic, carcinogenic and mutagenic. Improper treatment and non-scientific disposal of dyed wastewater from these industries into water sources has created many environmental problems and concerns around the world. The purpose of the present study is to investigate the efficiency of iron filings in adsorption of Reactive Red 198 from aqueous solutions. This study was conducted using an experimental method at the laboratory scale. In this study, the effects of operating parameters such as pH (1-11), initial dye concentration (40-400 mg/L), contact time (5-120 min) and iron dose (0.1-1 g) with a mesh of<100 were studied. Dye concentration was determined using a spectrophotometer at a wavelength of 520 nm. The results indicated that maximum adsorption capacity of the dye in question was obtained at pH 3, contact time of 60 min and adsorbent dose of 1 g. At initial dye concentration of 100 and 200 mg/L, by increasing the dose of waste iron from 0.1 to 1 g, the removal percentage increased from approximately 76.89% to 97.28% and from 22.64% to 68.03%, respectively. At pH 3, contact time of 5 min and constant waste iron dose of 0.8 g, the dye removal efficiency was 85.34%. By increasing the contact time to 120 min, the removal efficiency increased to 99.2%. Welding iron waste as an inexpensive and available adsorbent has an optimum ability for adsorption of Reactive Red 198 from aqueous solutions.

  16. Phosphorous adsorption and precipitation in a permeable reactive wall: Applications for wastewater disposal systems

    SciTech Connect

    Baker, M.J.; Blowes, D.W. |; Placek, C.J. |

    1997-12-31

    A permeable reactive mixture has been developed using low cost, readily available materials that is capable of providing effective, long-term phosphorous treatment in areas impacted by on-land wastewater disposal. The reactive mixture creates a geochemical environment suitable for P-attenuation by both adsorption and precipitation reactions. Potential benefits include significant reductions in phosphorous loading to receiving groundwater and surface water systems, and the accumulation of P-mass in a finite and accessible volume of material. The mixture may be applied as a component within surface treatment systems or in subsurface applications such as horizontal or vertical permeable reactive walls. The mixture averaged > 90% treatment efficiency over 3.6 years of continuous-flow laboratory column experiments. The mixture was further evaluated at the pilot-scale to treat municipal wastewater, and the field-scale to treat a well-characterized septic system plume using an in situ funnel and gate system. Average PO{sub 4}-P concentrations in effluent exiting the reactive mixture range between 0 - 0.3 mg/L. Mineralogical analyses have isolated the phases responsible for phosphorous uptake, and discrete phosphate precipitates have been identified.

  17. Adsorption behavior of a textile dye of Reactive Blue 19 from aqueous solutions onto modified bentonite

    NASA Astrophysics Data System (ADS)

    Gök, Özer; Özcan, A. Safa; Özcan, Adnan

    2010-06-01

    The aim of this study is to evaluate adsorption kinetics, isotherms and thermodynamic parameters of Reactive Blue 19 (RB19) onto modified bentonite from aqueous solutions. The effects of pH, contact time, initial dye concentration and temperature were investigated in the experimentally. Natural bentonite was modified by using 1,6-diamino hexane (DAH) as a modifying agent. The characterization of modified bentonite (DAH-bentonite) was accomplished by using FTIR, TGA, BET and elemental analysis techniques. The optimum pH value for the adsorption experiments was found to be 1.5 and all the experiments were carried out at this pH value. The pseudo-second-order kinetic model agrees very well with the experimental results. Equilibrium data were also fitted well to the Langmuir isotherm model in the studied concentration range of RB19 at 20 °C. The results indicate that DAH-modified bentonite is a suitable adsorbent for the adsorption of textile dyes.

  18. Characterization of humic acid reactivity modifications due to adsorption onto α-Al2O3.

    PubMed

    Janot, Noémie; Reiller, Pascal E; Zheng, Xing; Croué, Jean-Philippe; Benedetti, Marc F

    2012-03-01

    Adsorption of purified Aldrich humic acid (PAHA) onto α-Al(2)O(3) is studied by batch experiments at different pH, ionic strength and coverage ratios R (mg of PAHA by m(2) of mineral surface). After equilibration, samples are centrifuged and the concentration of PAHA in the supernatants is measured. The amount of adsorbed PAHA per m(2) of mineral surface is decreasing with increasing pH. At constant pH value, the amount of adsorbed PAHA increases with initial PAHA concentration until a pH-dependent constant value is reached. UV/Visible specific parameters such as specific absorbance SUVA(254), ratio of absorbance values E(2)/E(3) and width of the electron-transfer absorbance band Δ(ET) are calculated for supernatant PAHA fractions of adsorption experiments at pH 6.8, to have an insight on the evolution of PAHA characteristics with varying coverage ratio. No modification is observed compared to original compound for R ≥ 20 mg(PAHA)/g(α)(-)(A)1₂(O)₃. Below this ratio, aromaticity decreases with initial PAHA concentration. Size-exclusion chromatography - organic carbon detection measurements on these supernatants also show a preferential adsorption of more aromatic and higher-sized fractions. Spectrophotometric titrations were done to estimate changes of reactivity of supernatants from adsorption experiments made at pH ≈6.8 and different PAHA concentrations. Evolutions of UV/Visible spectra with varying pH were treated to obtain titration curves that are interpreted within the NICA-Donnan framework. Protonation parameters of non-sorbed PAHA fractions are compared to those obtained for the PAHA before contact with the oxide. The amount of low proton-affinity type of sites and the value of their median affinity constant decrease after adsorption. From PAHA concentration in the supernatant and mass balance calculations, "titration curves" are experimentally proposed for the adsorbed fractions for the first time. These changes in reactivity to our opinion could

  19. Cross-linked chitosan thin film coated onto glass plate as an effective adsorbent for adsorption of reactive orange 16.

    PubMed

    Jawad, Ali H; Azharul Islam, Md; Hameed, B H

    2017-02-01

    Fabrication of an immobilized cross-linked chitosan-epichlorohydrine thin film (CLCETF) onto glass plate for adsorption of reactive orange 16 (RO16) dye was successfully studied using the direct casting technique. Adsorption experiments were performed as a function of contact time, initial dye concentration (25mg/L to 350mg/L), and pH (3-11). The adsorption isotherm followed the Langmuir model. The adsorption capacity of CLECTF for RO16 was 356.50mg/g at 27±2°C. The kinetics closely followed the pseudo-second-order model. Results supported the potential use of an immobilized CLECTF as effective adsorbent for the treatment of reactive dye without using filtration process.

  20. Two-step kinetic study on the adsorption and desorption of reactive dyes at cationic polymer/bentonite.

    PubMed

    Li, Qian; Yue, Qin-Yan; Su, Yuan; Gao, Bao-Yu; Li, Jing

    2009-06-15

    The adsorption kinetics of two reactive dyes, namely, Reactive Blue K-GL and Reactive Yellow K-4G onto the new cationic polymer/bentonite, i.e., polyepicholorohydrin-dimethylamine/bentonite (EPI-DMA/bentonite), were studied under different conditions. The result indicated that the adsorption processes were found to follow the two-step kinetic rate equation with two different adsorption rate constants (k(1) and k(2)) and also to follow the intraparticle diffusion model with two different diffusion rate constants (k(int,1) and k(int,2)). The corresponding values of energies of activation of adsorption, enthalpies of activation and entropies of activation for both the two adsorption kinetic steps have been calculated, suggesting that the adsorption processes were endothermic and physical. The desorption kinetics of two dyes from EPI-DMA/bentonite were studied in NaOH solution with different concentrations, which were also found to obey the two-step kinetic rate equation with two different desorption rate constants (k(d,1) and k(d,2)).

  1. Hyperbolic theory for pH-dependent adsorption in reactive transport in porous media

    NASA Astrophysics Data System (ADS)

    Prigiobbe, V.; Hesse, M. A.; Bryant, S. L.

    2012-12-01

    We use the hyperbolic theory of conservation laws to analyze the transport of strontium (Sr2+) through a porous medium with surface complexation. An hydrophilic iron-oxide surface was considered where Sr2+ and hydrogen (H+) compete for the same site leading to competitive adsorption described by an pH-dependent Langmuir isotherm. Despite the importance of pH-dependent adsorption in environmental applications, the basic structure of the displacement has received little attention. In reactive transport problems with pH-dependent adsorption, one of the conservation laws is for the total hydrogen (cHtot = cH+-cOH-) in the system, also called the acidity. The presence of this equation gives rise to additional nonlinearity in the problems that distinguishes them from other competitive sorption problems where hydrogen is not involved. We analyze a 1D reactive transport model with an incompressible fluid containing H+, Sr2+, sodium (Na+), and chlorine (Cl-) flowing through a reactive porous media made of goethite. Under the assumption of overall charge balance and of only advection for Na+ and Cl-, the mathematical problem reduces to a strictly hyperbolic 3x3 system of partial dierential equations (PDEs) for cHtot, Sr2+ (cSr2+), and effective anions (ca = cCl--cNa+) which are coupled by the adsorption isotherms for H+ and Sr2+ and have the non-linearity in the accumulation terms. One characteristic field is linearly degenerate while the other two are non-genuinely nonlinear due to inflection loci in both isotherms. We derived the complete set of analytical solutions to the Riemann problem (constant initial and injected states) and described the characteristic waves that may arise, concluding that only nine combinations of a contact discontinuity with rarefactions, shocks, shock-rarefactions are possible. The composite shock-rarefaction waves arise from the inflection loci in the isotherms and are absent in classic competitive Langmuir sorption. The inflection loci divide

  2. A simple and straightforward expression for curling probe electron density diagnosis in reactive plasmas

    NASA Astrophysics Data System (ADS)

    Arshadi, Ali; Brinkmann, Ralf Peter; Hotta, Masaya; Nakamura, Keiji

    2017-04-01

    Active plasma resonance spectroscopy (APRS) refers to the family of plasma diagnostic methods which utilize the ability of plasmas to resonate at frequencies close to the plasma frequency. APRS operates by exciting the plasma with a weak RF signal by means of a small electric probe. The response of the plasma is recorded by a network analyzer (NA). A mathematical model is applied to derive characteristics like the electron density and the electron temperature. The curling probe is a promising realization of APRS. The curling probe is well-qualified for the local measurement of the electron density in reactive plasmas. This spiral probe resonates in plasma at a larger density dependent frequency than the plasma frequency. This manuscript represents a simple and straightforward expression relating this resonance frequency to the electron density of the plasma. A good agreement is observed between the proposed expression and the results obtained from previous studies and numerical simulations.

  3. Ab Initio Study of Water Adsorption and Reactivity on the (211) Surface of Anatase TiO2

    NASA Astrophysics Data System (ADS)

    Xu, Jing; Xu, Li-Fang; Li, Zhen-Zhen; Wang, Jian-Tao; Lin, Zhe-Shuai; Liu, Kai; Cao, Yong-Ge; Selloni, Annabella

    2016-06-01

    The reactivity of the anatase TiO2 (211) surface is systematically studied by ab initio calculations of the surface energy and water-adsorption energy. We find that anatase (211) has a high surface energy of 0.97 J /m2 , close to that of the (001) surface, and the unsaturated fourfold-coordinated Ti4 atom is more reactive than the unsaturated fivefold-coordinated Ti5 atom. Accordingly, for water adsorption on the (211) surface, a dissociative form is favored on Ti4 sites, with a large adsorption energy Δ HH ,OH˜1.28 eV , while a nondissociative molecular form is favored on Ti5 sites, with a smaller adsorption energy Δ HH2O˜0.78 eV . Such distinct surface properties lead to a mixed dissociative and molecular adsorption configuration when the coverage is increased from 1 /3 to 1 monolayer. These results suggest that, similar to the (001) surface, the anatase (211) surface exhibits high reactivity and may be useful in catalytic and photocatalytic applications as well.

  4. A possible explanation of the anomalous emissive probe behavior in a reactive RF plasma

    NASA Astrophysics Data System (ADS)

    Kar, R.; Barve, S. A.; Chopade, S. S.; Das, A. K.; Patil, D. S.

    2012-10-01

    Emissive probe diagnostics in saturated floating potential mode was carried out in RF plasmas of argon (Ar)-methane (CH4) and Ar-CH4-hexa methyl disiloxane (HMDSO). These plasmas are used for the deposition of diamond-like carbon (DLC) and SiOx-containing DLC films, respectively. While performing the experiments it was found that the probe characteristics had two saturation regions instead of one. The same measurements when repeated in Ar and Ar-N2 plasmas showed a single saturation as expected. The first experiments when repeated again showed the same anomaly. The experimental findings question the validity of emissive probe diagnostics in reactive plasmas. A possible model of dust formation inside the reactive plasma is predicted and the first saturation is linked to dust. The second saturation is credited as the actual plasma potential. The concept of dust was invoked after being sure that no effects of RF and reference electrode contamination are responsible for this behavior. The results indicate that we should remain cautious when using emissive probes in reactive plasmas as they may occasionally lead to erroneous results.

  5. Understanding In-line Probing Experiments by Modeling Cleavage of Non-reactive RNA Nucleotides.

    PubMed

    Mlynsky, Vojtech; Bussi, Giovanni

    2017-02-15

    Ribonucleic acid (RNA) is involved in many regulatory and catalytic processes in the cell. The function of any RNA molecule is intimately related with its structure. In-line probing experiments provide valuable structural datasets for a variety of RNAs and are used to characterize conformational changes in riboswitches. However, the structural determinants that lead to differential reactivities in unpaired nucleotides have not been investigated yet. In this work we used a combination of theoretical approaches, i.e., classical molecular dynamics simulations, multiscale quantum mechanical/molecular mechanical calculations, and enhanced sampling techniques in order to compute and interpret the differential reactivity of individual residues in several RNA motifs including members of the most important GNRA and UNCG tetraloop families. Simulations on the multi ns timescale are required to converge the related free-energy landscapes. The results for uGAAAg and cUUCGg tetraloops and double helices are compared with available data from in-line probing experiments and show that the introduced technique is able to distinguish between nucleotides of the uGAAAg tetraloop based on their structural predispositions towards phosphodiester backbone cleavage. For the cUUCGg tetraloop, more advanced ab initio calculations would be required. This study is the first attempt to computationally classify chemical probing experiments and paves the way for an identification of tertiary structures based on the measured reactivity of non-reactive nucleotides.

  6. Synergic adsorption of Pb2 + and reactive dye — RB5 on two series of organomodified bentonites

    NASA Astrophysics Data System (ADS)

    Jović-Jovičić, N. P.; Milutinović-Nikolić, A. D.; Žunić, M. J.; Mojović, Z. D.; Banković, P. T.; Gržetić, I. A.; Jovanović, D. M.

    2013-07-01

    Two series of organobentonites (OBs) were synthesized from Na+-exchanged bentonite clay from Bogovina, Serbia. In the first series the starting material was modified using hexadecyltrimethylammonium (HDTMA+) ion in the amounts corresponding to 0.2, 0.5, 1.0 and 2.0 of the CEC value. The second series was obtained using quaternary alkyl ammonium cations (QAACs) with different alkyl chain lengths: hexadecyltrimethylammonium (HDTMA+), dodecyltrimethylammonium (DDTMA+) and tetramethylammonium (TMA+) ions. The synthesized OBs were characterized. The adsorption of anionic reactive dye Reactive Black 5 (RB5) and Pb2 + from single component solutions and their bi-component solution was investigated for both series of OBs. The adsorptive properties of the OBs were correlated to the amount and type of incorporated QAACs. The correlation was tested using different mathematical models and best fits were found. Experimental results showed that simultaneous adsorption of RB5 and Pb2 + exhibited synergic effect. The adsorption capacity for both RB5 and Pb2 + was higher in their bi-component solution than in single-component solutions. These results indicate the creation of new adsorption sites during the simultaneous adsorption.

  7. Probing protein adsorption on a nanoparticle surface using second harmonic light scattering.

    PubMed

    Das, A; Chakrabarti, A; Das, P K

    2016-09-21

    A new application of second harmonic light scattering to probe protein physisorption on a gold nanoparticle surface in aqueous buffer is reported. The free energies of adsorption, the number of protein molecules adsorbed on the surface and the binding affinity of a moderate size protein, alcohol dehydrogenase (ADH), and a small protein, insulin, have been determined using the change in the second harmonic scattered light signal as a function of binding. Four different size gold nanoparticles from 15 to 60 nm were used to determine the effect of size on the free energy change, the affinity constant and the number of protein molecules adsorbed on the surface. All were shown to increase with an increase in size. The binding can be reversed by centrifugation, and the protein molecules can be desorbed quantitatively. The application of this method for studying thermodynamic parameters of weakly interacting biomolecules with nanoparticles for nanoparticle based diagnostic and therapeutic formulations is important.

  8. Unique Reactivity of Transition Metal Atoms Embedded in Graphene to CO, NO, O₂ and O Adsorption: A First-Principles Investigation.

    PubMed

    Chu, Minmin; Liu, Xin; Sui, Yanhui; Luo, Jie; Meng, Changgong

    2015-10-27

    Taking the adsorption of CO, NO, O₂ and O as probes, we investigated the electronic structure of transition metal atoms (TM, TM = Fe, Co, Ni, Cu and Zn) embedded in graphene by first-principles-based calculations. We showed that these TM atoms can be effectively stabilized on monovacancy defects on graphene by forming plausible interactions with the C atoms associated with dangling bonds. These interactions not only give rise to high energy barriers for the diffusion and aggregation of the embedded TM atoms to withstand the interference of reaction environments, but also shift the energy levels of TM-d states and regulate the reactivity of the embedded TM atoms. The adsorption of CO, NO, O₂ and O correlates well with the weight averaged energy level of TM-d states, showing the crucial role of interfacial TM-C interactions on manipulating the reactivity of embedded TM atoms. These findings pave the way for the developments of effective monodispersed atomic TM composites with high stability and desired performance for gas sensing and catalytic applications.

  9. Probing titanate nanowire surface acidity through methylene blue adsorption in colloidal suspension and on thin films.

    PubMed

    Horváth, Endre; Szilágyi, István; Forró, László; Magrez, Arnaud

    2014-02-15

    The interaction of the cationic dye methylene blue (MB) with titanate nanowires (TiONWs) was investigated in different pH environments using visible spectroscopy and electrophoresis on thin films as well as in aqueous suspension. The surface charge of the TiONWs depends on the pH and ionic strength leading to positive charge under acidic and negative under alkaline conditions. The TiONWs have the same adsorption capacity on films and in suspensions at neutral pH while under alkaline conditions they are able to adsorb significantly more MB in suspension due to their higher surface area. Detailed adsorption studies in water revealed that dye cations form monomers, dimers and larger aggregates of H-type (face-to-face) on the TiONW films. The results indicate that below pH = 4.0 the TiONWs' external surface consists of Brøntsted acid sites capable of protonating MB. It was suggested that reversible indicator role of MB molecule dimers probes the TiONW surface acidity (Brøntsted sites).

  10. Adsorption of 2-propanol on ice probed by ambient pressure X-ray photoelectron spectroscopy

    DOE PAGES

    Newberg, John T.; Bluhm, Hendrik

    2015-08-18

    The interaction of 2-propanol with ice was examined via ambient pressure X-ray photoelectron spectroscopy (APXPS), a surface sensitive technique that probes the adsorbed 2-propanol directly with submonolayer resolution. Isothermal uptake experiments were performed on vapor deposited ice at 227 K in the presence of the equilibrium water vapor pressure of 0.05 Torr and 2-propanol partial pressures ranging from 5 × 10-5 to 2 × 10-3 Torr. The C 1s APXPS spectra of adsorbed 2-propanol showed two characteristic peaks associated with the COH alcohol group and CMe methyl groups in a 1 : 2 ratio, respectively. Coverage increased with 2-propanol partialmore » pressure and followed first order Langmuir kinetics with a Langmuir constant of K = 6.3 × 103 Torr-1. The 1 : 2 ratio of COH : CMe remained constant with increasing coverage, indicating there is no chemical reaction upon adsorption. The observed Langmuir kinetics using APXPS is consistent with previous observations of other small chain alcohols via indirect adsorption methods using, e.g., Knudsen cell and coated wall flow tube reactors.« less

  11. Adsorption of 2-propanol on ice probed by ambient pressure X-ray photoelectron spectroscopy

    SciTech Connect

    Newberg, John T.; Bluhm, Hendrik

    2015-08-18

    The interaction of 2-propanol with ice was examined via ambient pressure X-ray photoelectron spectroscopy (APXPS), a surface sensitive technique that probes the adsorbed 2-propanol directly with submonolayer resolution. Isothermal uptake experiments were performed on vapor deposited ice at 227 K in the presence of the equilibrium water vapor pressure of 0.05 Torr and 2-propanol partial pressures ranging from 5 × 10-5 to 2 × 10-3 Torr. The C 1s APXPS spectra of adsorbed 2-propanol showed two characteristic peaks associated with the COH alcohol group and CMe methyl groups in a 1 : 2 ratio, respectively. Coverage increased with 2-propanol partial pressure and followed first order Langmuir kinetics with a Langmuir constant of K = 6.3 × 103 Torr-1. The 1 : 2 ratio of COH : CMe remained constant with increasing coverage, indicating there is no chemical reaction upon adsorption. The observed Langmuir kinetics using APXPS is consistent with previous observations of other small chain alcohols via indirect adsorption methods using, e.g., Knudsen cell and coated wall flow tube reactors.

  12. A reactivity-based probe of the intracellular labile ferrous iron pool

    PubMed Central

    Spangler, Benjamin; Morgan, Charles W.; Fontaine, Shaun D.; Vander Wal, Mark N.; Chang, Christopher J.; Wells, James A.; Renslo, Adam R.

    2016-01-01

    Improved methods for studying intracellular reactive iron(II) are of significant interest for studies of iron metabolism and disease relevant changes in iron homeostasis. Here we describe a highly-selective reactivity-based probe in which Fenton-type reaction with intracellular labile iron(II) leads to unmasking of the aminonucleoside puromycin. Puromycin leaves a permanent and dose-dependent mark on treated cells that can be detected with high sensitivity and precision using the high-content, plate-based immunofluorescence assay described. Using this new probe and screening approach, we detected alteration of cellular labile iron(II) in response extracellular iron conditioning, overexpression of iron storage and/or export proteins, and post-translational regulation of iron export. Finally, we utilized this new tool to demonstrate the presence of augmented labile iron(II) pools in cancer cells as compared to non-tumorigenic cells. PMID:27376690

  13. Recognition- and reactivity-based fluorescent probes for studying transition metal signaling in living systems.

    PubMed

    Aron, Allegra T; Ramos-Torres, Karla M; Cotruvo, Joseph A; Chang, Christopher J

    2015-08-18

    Metals are essential for life, playing critical roles in all aspects of the central dogma of biology (e.g., the transcription and translation of nucleic acids and synthesis of proteins). Redox-inactive alkali, alkaline earth, and transition metals such as sodium, potassium, calcium, and zinc are widely recognized as dynamic signals, whereas redox-active transition metals such as copper and iron are traditionally thought of as sequestered by protein ligands, including as static enzyme cofactors, in part because of their potential to trigger oxidative stress and damage via Fenton chemistry. Metals in biology can be broadly categorized into two pools: static and labile. In the former, proteins and other macromolecules tightly bind metals; in the latter, metals are bound relatively weakly to cellular ligands, including proteins and low molecular weight ligands. Fluorescent probes can be useful tools for studying the roles of transition metals in their labile forms. Probes for imaging transition metal dynamics in living systems must meet several stringent criteria. In addition to exhibiting desirable photophysical properties and biocompatibility, they must be selective and show a fluorescence turn-on response to the metal of interest. To meet this challenge, we have pursued two general strategies for metal detection, termed "recognition" and "reactivity". Our design of transition metal probes makes use of a recognition-based approach for copper and nickel and a reactivity-based approach for cobalt and iron. This Account summarizes progress in our laboratory on both the development and application of fluorescent probes to identify and study the signaling roles of transition metals in biology. In conjunction with complementary methods for direct metal detection and genetic and/or pharmacological manipulations, fluorescent probes for transition metals have helped reveal a number of principles underlying transition metal dynamics. In this Account, we give three recent

  14. Cross-linked chitosan/sepiolite composite for the adsorption of methylene blue and reactive orange 16.

    PubMed

    Marrakchi, F; Khanday, W A; Asif, M; Hameed, B H

    2016-12-01

    Cross-linked chitosan/sepiolite composite was prepared from sepiolite clay and chitosan, and was cross-linked using epichlorohydrin. Among the various weight ratio percentage of chitosan and sepiolite clay composites, CS50SP50 was selected as the best adsorbent for both methylene blue (MB) and reactive orange 16 (RO 16). At an optimum adsorbent dosage of 0.2g/100mL, the effects of initial dye concentration (25-400mg/L) and pH (3-11) on MB and RO 16 adsorption onto CS50SP50 composite were studied. Monolayer adsorption capacities of CS50SP50 composite for MB and RO 16 were 40.986mg/g and 190.965mg/g, respectively at 30°C. Freundlich, Langmuir and Temkin isotherms applied on the adsorption data for both the dyes reveal that data fitted best for Freundlich model. For both the dyes pseudo-second-order kinetics were found to describe the adsorption process better than pseudo-first-order kinetics. The adsorption capacity of CS50SP50 composite for both the dyes was found better compared to previous studies thus making it potentially low-cost adsorbent for removal of both cationic and reactive dyes.

  15. Adsorption of Reactive Red M-2BE dye from water solutions by multi-walled carbon nanotubes and activated carbon.

    PubMed

    Machado, Fernando M; Bergmann, Carlos P; Fernandes, Thais H M; Lima, Eder C; Royer, Betina; Calvete, Tatiana; Fagan, Solange B

    2011-09-15

    Multi-walled carbon nanotubes and powdered activated carbon were used as adsorbents for the successful removal of Reactive Red M-2BE textile dye from aqueous solutions. The adsorbents were characterised by infrared spectroscopy, N(2) adsorption/desorption isotherms and scanning electron microscopy. The effects of pH, shaking time and temperature on adsorption capacity were studied. In the acidic pH region (pH 2.0), the adsorption of the dye was favourable using both adsorbents. The contact time to obtain equilibrium at 298K was fixed at 1h for both adsorbents. The activation energy of the adsorption process was evaluated from 298 to 323K for both adsorbents. The Avrami fractional-order kinetic model provided the best fit to the experimental data compared with pseudo-first-order or pseudo-second-order kinetic adsorption models. For Reactive Red M-2BE dye, the equilibrium data were best fitted to the Liu isotherm model. Simulated dyehouse effluents were used to check the applicability of the proposed adsorbents for effluent treatment.

  16. Adsorption and reactivity of nitrogen atoms on silica surface under plasma exposure

    NASA Astrophysics Data System (ADS)

    Marinov, D.; Guaitella, O.; de los Arcos, T.; von Keudell, A.; Rousseau, A.

    2014-11-01

    The kinetics of adsorption, desorption and recombination of nitrogen atoms on a silica surface is investigated. Stable nitrogen atoms are grafted to the inner surface of a fused silica discharge tube by a discharge in N2 at 0.53 mbar. After the pre-treatment, the surface is analysed using x-ray photoelectron spectroscopy and an isotopic exchange technique. The latter consists of the exposure of the pre-treated surface with a discharge in the heavy nitrogen isotope 30N2. Nitrogen isotopologues 29N2 and 28N2 produced on the surface are detected using a mass spectrometer and provide information about the coverage and reactivity of adsorbed 14N atoms. It is found that during the pre-treatment, a silicon oxynitride (SiOxNy) layer is formed on the initially clean SiO2 surface. The coverage of N on the surface increases from 5  ×  1013 to 5  ×  1015 cm-2 for a pre-treatment duration in the range of 10-2 - 104 s. Atoms on the surface demonstrate a distribution of reactivity, which is attributed to a distribution of their binding energies and configurations on the surface. We demonstrate that stable chemisorbed Nads are not the main recombination sites for N atoms on the surface contrary to previous studies. We conclude that recombination takes place mainly on weakly bonding active sites with the binding energy smaller than 1 eV.

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

    EPA Science Inventory

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

  18. Immobilization of ɛ-polylysine onto the probe surface for molecular adsorption type endotoxin detection system

    NASA Astrophysics Data System (ADS)

    Ooe, Katsutoshi; Tsuji, Akihito; Nishishita, Naoki; Hirano, Yoshiaki

    2007-04-01

    adsorption reaction between ɛ-polylysine and endotoxin. ɛ-polylysine has the structure of straight chain molecule composed by 25-30 residues made by lysine, and it is used as an antimicrobial agent, moreover, cellulose beads with immobilized ɛ-polylysine is used as the barrier filter for endotoxin removal. Therefore, it is expected that the endotoxin be adsorbed to the immobilized ɛ-polylysine onto the probe. As the result of this reaction, the mass of the probe is increased, and endotoxin can be detected by using of Quartz Crystal Microbalance (QCM). In our previous research, we have already acquired the proteins immobilization technique onto Au and Si surface. In this report, the proposal of molecular adsorption type endotoxin detection system, and the immobilization of ɛ-polylysine onto the probe are described. We use X-ray Photoelectron Spectroscopy (XPS) to confirm the ɛ-polylysine immobilization, and the adsorptive activity of immobilized ɛ-polylysine is measured by XPS and AFM. The purpose of this study is to bring about the realization of "Real-time endotoxin detection system".

  19. A transmission infrared cell design for temperature-controlled adsorption and reactivity studies on heterogeneous catalysts

    NASA Astrophysics Data System (ADS)

    Cybulskis, Viktor J.; Harris, James W.; Zvinevich, Yury; Ribeiro, Fabio H.; Gounder, Rajamani

    2016-10-01

    A design is presented for a versatile transmission infrared cell that can interface with an external vacuum manifold to undergo in situ gas treatments and receive controlled doses of various adsorbates and probe molecules, allowing characterization of heterogeneous catalyst surfaces in order to identify and quantify active sites and adsorbed surface species. Critical design characteristics include customized temperature control for operation between cryogenic and elevated temperatures (100-1000 K) and modified Cajon fittings for operation over a wide pressure range (10-2-103 Torr) that eliminates the complications introduced when using sealants or flanges to secure cell windows. The customized, hand-tightened Cajon fittings simplify operation of the cell compared to previously reported designs, because they allow for rapid cell assembly and disassembly and, in turn, replacement of catalyst samples. In order to validate the performance of the cell, transmission infrared spectroscopic experiments are reported to characterize the Brønsted and Lewis acid sites present in H-beta and H-mordenite zeolites using cryogenic adsorption of CO (<150 K).

  20. Trends in the adsorption and reactivity of hydrogen on magnesium silicate nanoclusters.

    PubMed

    Oueslati, Ichraf; Kerkeni, Boutheïna; Bromley, Stefan T

    2015-04-14

    We study nanoclusters of Mg-rich olivine and pyroxene (having (MgO)6(SiO2)3 and (MgO)4(SiO2)4 compositions) with respect to their reactivity towards hydrogen atoms, using density functional calculations. Ultrasmall silicate particles are fundamental intermediates in cosmic dust grain formation and processing, and are thought to make up a significant mass fraction of the grain population. Due to their nanoscale dimensions and high surface area to bulk ratios, they are likely to also have a disproportionately large influence on surface chemistry in the interstellar medium. This work investigates the potential role of silicate nanoclusters in vital interstellar hydrogen-based chemistry by studying atomic H adsorption and H2 formation. Our extensive set of calculations confirm the generality of a Brønsted-Evans-Polanyi (BEP) relation between the H2 reaction barrier and the 2Hchem binding energy, suggesting it to be independent of silicate dust grain shape, size, crystallinity and composition. Our results also suggest that amorphous/porous grains with forsteritic composition would tend to dissociate H2, but relatively Mg-poor silicate grains (e.g. enstatite composition) and/or more crystalline/compact silicate grains would tend to catalyse H2 formation. The high structural thermostability of silicate nanoclusters with respect to the heat released during exothermic H2 formation reactions is also verified.

  1. COD and color removal of reactive orange 16 dye solution by electrochemical oxidation and adsorption method

    NASA Astrophysics Data System (ADS)

    Zakaria, Zuhailie; Ahmad, Wan Yaacob Wan; Yusop, Muhammad Rahimi; Othman, Mohamed Rozali

    2015-09-01

    Degradation of Reactive Orange 16 (RO16) dye was investigated using electrochemical oxidation and adsorption (batch method) using mixture of coconut trunk charcoal-graphite-tin-polyvinyl chloride(PVC). In batch studies for adsorbents pellet and powder form of the charcoal mixture were used. RO16 was chosen as the model dye because of its high resistance towards conventional treatment methods. NaCl and RO16 concentration, treatment duration, weight of electrode and adsorbent and volume of solution were kept constant for both methods. The effectiveness of the treatments were compared and evaluated by percentage of RO16 decolorization and chemical oxygen demand (COD) removal and results indicated that electrochemical oxidation method ables to decolorized RO16 dye up to 98.5% after 20 minutes electrolysis time while pellet and powder in batch method only removed 17.1 and 33.6% of RO16 color respectively. However, only 45.6% of COD can be removed using electrochemical oxidation method while pellet and powder in batch method removed 47.8 and 49.6% of COD respectively. The decolorization and COD removal of RO16 was determined using UV-Vis spectrophotometer (by the changes of absorption spectrum intensity of azo chromophore (-N=N-) at λ=388 and 492.50 nm and Hach spectrophotometer respectively. FTIR was used to determine functional groups present in the coconut trunk charcoal.

  2. Recognition- and Reactivity-Based Fluorescent Probes for Studying Transition Metal Signaling in Living Systems

    PubMed Central

    2015-01-01

    Conspectus Metals are essential for life, playing critical roles in all aspects of the central dogma of biology (e.g., the transcription and translation of nucleic acids and synthesis of proteins). Redox-inactive alkali, alkaline earth, and transition metals such as sodium, potassium, calcium, and zinc are widely recognized as dynamic signals, whereas redox-active transition metals such as copper and iron are traditionally thought of as sequestered by protein ligands, including as static enzyme cofactors, in part because of their potential to trigger oxidative stress and damage via Fenton chemistry. Metals in biology can be broadly categorized into two pools: static and labile. In the former, proteins and other macromolecules tightly bind metals; in the latter, metals are bound relatively weakly to cellular ligands, including proteins and low molecular weight ligands. Fluorescent probes can be useful tools for studying the roles of transition metals in their labile forms. Probes for imaging transition metal dynamics in living systems must meet several stringent criteria. In addition to exhibiting desirable photophysical properties and biocompatibility, they must be selective and show a fluorescence turn-on response to the metal of interest. To meet this challenge, we have pursued two general strategies for metal detection, termed “recognition” and “reactivity”. Our design of transition metal probes makes use of a recognition-based approach for copper and nickel and a reactivity-based approach for cobalt and iron. This Account summarizes progress in our laboratory on both the development and application of fluorescent probes to identify and study the signaling roles of transition metals in biology. In conjunction with complementary methods for direct metal detection and genetic and/or pharmacological manipulations, fluorescent probes for transition metals have helped reveal a number of principles underlying transition metal dynamics. In this Account, we give

  3. Low frequency sonochemical synthesis of nanoporous amorphous manganese dioxide (MnO{sub 2}) and adsorption of remazol reactive dye

    SciTech Connect

    Hasan, Siti Zubaidah; Yusop, Muhammad Rahimi; Othman, Mohamed Rozali

    2015-09-25

    Nanoporous amorphous-MnO{sub 2} was synthesized by sonochemical process (sonication) on the solid manganese (II) acetate tetrahydrate (Mn(CH{sub 3}COO){sub 2}.4H{sub 2}O) in 0.1 M KMnO{sub 4}. The product was characterized by X-ray diffraction (XRD), morphology of the material was scanned by Field Emission Scanning Electron Microscopy (FE-SEM) and absorptions of MnO{sub 2} bonding was characterized by Fourier Transform Infra-Red Spectrometer (FT-IR). Remazol reactive dye or Red 3BS, was used in the adsorption study using nanoporous amorphous-MnO{sub 2}. In batch experiment, 10 ppm of Remazol reactive dye was used and experiment was carried out at room temperature. Adsorption of Remazol dye on 0.2g synthesized nanoporous amorphous-MnO{sub 2} showed 99 – 100% decolorization.

  4. Probing the reactivity of different forms of azurin by flavin photoreduction.

    PubMed

    Alagaratnam, Sharmini; Meeuwenoord, Nico J; Navarro, José A; Hervás, Manuel; De la Rosa, Miguel A; Hoffmann, Maren; Einsle, Oliver; Ubbink, Marcellus; Canters, Gerard W

    2011-05-01

    The reactivity of a variant of the blue copper protein, azurin from Pseudomonas aeruginosa, was investigated with laser flash photolysis and compared with the reactivity of the wild-type (WT) protein. The variant was obtained by changing the Cu ligating His117 for a glycine. The mutation creates a gap in the ligand shell of the Cu that can be filled with external ligands or water molecules. The crystal structure of the H117G variant is reported. It shows that the immediate surrounding of the Cu site in the variant exhibits less rigidity than in the WT protein and that the loop containing the Cu ligands Cys112, His117 and Met121 in the WT protein has gained flexibility in the H117G variant. Flash photolysis experiments were performed with 5-deazariboflavin and 8α-imidazolyl-(N-propylyl)-amino riboflavin as electron donors to probe the reactivity of WT and H117G azurin, and of H117G azurin for which the gap in the Cu co-ordination shell was filled with imidazole. 8α-Imidazolyl-(N-propylyl)-amino riboflavin appears one to two orders less efficient as a photo-flash reductant than 5-deazariboflavin. The reactivity of the H117G variant in the absence of external ligands appears to be 2.5-fold lower than the WT reactivity (second-order rate constants of 51 ± 2 × 10(7) m(-1) ·s(-1) versus 21 ± 1 × 10(7) m(-1) ·s(-1) ), whereas the addition of imidazole restores reactivity to above the WT level (71 ± 4 × 10(7) m(-1) ·s(-1) ). The differences are discussed in terms of structural modifications and changes in reorganizational energy and electronic coupling. Database Structural data are available in the Protein Data Bank under the accession number 3N2J.

  5. Probing oxidative stress: Small molecule fluorescent sensors of metal ions, reactive oxygen species, and thiols

    PubMed Central

    Hyman, Lynne M.; Franz, Katherine J.

    2013-01-01

    Oxidative stress is a common feature shared by many diseases, including neurodegenerative diseases. Factors that contribute to cellular oxidative stress include elevated levels of reactive oxygen species, diminished availability of detoxifying thiols, and the misregulation of metal ions (both redox-active iron and copper as well as non-redox active calcium and zinc). Deciphering how each of these components interacts to contribute to oxidative stress presents an interesting challenge. Fluorescent sensors can be powerful tools for detecting specific analytes within a complicated cellular environment. Reviewed here are several classes of small molecule fluorescent sensors designed to detect several molecular participants of oxidative stress. We focus our review on describing the design, function and application of probes to detect metal cations, reactive oxygen species, and intracellular thiol-containing compounds. In addition, we highlight the intricacies and complications that are often faced in sensor design and implementation. PMID:23440254

  6. Enhancement in dibenzothiophene reactive adsorption from liquid fuel via incorporation of sulfur heteroatoms into the nanoporous carbon matrix.

    PubMed

    Seredych, Mykola; Khine, Monmon; Bandosz, Teresa J

    2011-01-17

    Adsorption of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (DMDBT) from simulated diesel fuel was investigated with polymer-derived carbon matrices. Sulfur was incorporated to the carbon surface via a high-temperature hydrogen sulfide reduction of oxygen-containing groups. The resultant carbons were characterized by nitrogen adsorption, thermal analysis, potentiometric titration, and elemental analysis. The selectivities for DBT and DMDBT adsorption were calculated with reference to naphthalene. The carbon matrices studied had comparable structures, hence, the effects of the sulfur functionalities were evident in an increase in dibenzothiophenes selectivity and the breakthrough capacity; this was especially visible at a breakthrough point where small pores are expected to be active in the adsorption process. Incorporation of sulfur atoms into the aromatic rings of the carbon matrix increases the ability of the surface to attract dibenzothiophenes via dispersive interactions (sulfur-sulfur bridges). Sulfur and sulfur-oxygen groups present in larger pores enhance the amount of adsorbed dibenzothiophenes via specific acid-base and polar interactions. They also contribute to the reactive adsorption of DBT and DMDBT (oxidized) and their chemisorption on the carbon surface.

  7. New detection targets for amyloid-reactive probes: spectroscopic recognition of bacterial spores

    NASA Astrophysics Data System (ADS)

    Jones, Guilford, II; Landsman, Pavel

    2005-05-01

    We report characteristic changes in fluorescence of amyloid-binding dyes Thioflavin T (TfT), pinacyanol (PIN) and related dyes, caused by their interaction with suspended Bacillus spore cultures (B. subtilis, B thuringiensis). The gain in TfT emission in the presence of spores allowed their immediate detection in aqueous suspensions, with a sensitivity limit of < 105 spores per ml. The spectroscopic signatures are consistent with a large number of binding sites for the two dyes on spore coats. The possible structural relationship of these dye binding loci with characteristic motifs (β-stacks) of amyloid deposits and other misfolded protein formations suggests new designs for probing biocontamination and also for clinical studies of non-microbial human pathogens (e.g., amyloid-related protein aggregates in prion-related transmissible encephalopathies or in Alzheimer's disease). Also reported is a special screening technique that was designed and used herein for calibration of new detection probes and assays for spore detection. It employed spectroscopic interactions between the candidate amyloid stains and poly(vinylpyrrolidone)-coated colloid silica (Percoll) nanoparticles that also display remarkable parallelism with the corresponding dye-amyloid and dye-spore reactivities. Percoll may thus find new applications as a convenient non-biological structural model mimicking the putative probe-targeted motifs in both classes of bioanalytes. These findings are important in the design of new probes and assays for important human pathogens (i.e. bacterial spores and amyloidogenic protein aggregates).

  8. UV absorption probing of the conformer-dependent reactivity of a Criegee intermediate CH3CHOO.

    PubMed

    Sheps, Leonid; Scully, Ashley M; Au, Kendrew

    2014-12-28

    We measure the UV absorption spectrum of a Criegee intermediate acetaldehyde oxide, CH3CHOO, using time-resolved broadband cavity-enhanced spectrometry. We separate the spectra of the two possible structural isomers, syn- and anti-CH3CHOO, based on their different reactivity towards H2O and SO2. Despite significant overlap, the spectra of the two conformers are sufficiently separated to allow direct conformer-specific probing of the reactions of CH3CHOO with other important tropospheric species.

  9. Using the Multipole Resonance Probe to Stabilize the Electron Density During a Reactive Sputter Process

    NASA Astrophysics Data System (ADS)

    Oberberg, Moritz; Styrnoll, Tim; Ries, Stefan; Bienholz, Stefan; Awakowicz, Peter

    2015-09-01

    Reactive sputter processes are used for the deposition of hard, wear-resistant and non-corrosive ceramic layers such as aluminum oxide (Al2O3) . A well known problem is target poisoning at high reactive gas flows, which results from the reaction of the reactive gas with the metal target. Consequently, the sputter rate decreases and secondary electron emission increases. Both parameters show a non-linear hysteresis behavior as a function of the reactive gas flow and this leads to process instabilities. This work presents a new control method of Al2O3 deposition in a multiple frequency CCP (MFCCP) based on plasma parameters. Until today, process controls use parameters such as spectral line intensities of sputtered metal as an indicator for the sputter rate. A coupling between plasma and substrate is not considered. The control system in this work uses a new plasma diagnostic method: The multipole resonance probe (MRP) measures plasma parameters such as electron density by analyzing a typical resonance frequency of the system response. This concept combines target processes and plasma effects and directly controls the sputter source instead of the resulting target parameters.

  10. Probing effects of polymer adsorption in colloidal particle suspensions by light scattering as relevant for the aquatic environment: An overview.

    PubMed

    Tiraferri, Alberto; Borkovec, Michal

    2015-12-01

    Modification of particle surfaces by adsorption of polymers is a process that governs particle behavior in aqueous environmental systems. The present article briefly reviews the current understanding of the adsorption mechanisms and the properties of the resulting layers, and it discusses two environmentally relevant cases of particle modification by polymers. In particular, the discussion focuses on the usefulness of methods based on light scattering to probe such adsorbed layers together with the resulting properties of the particle suspensions, and it highlights advantages and disadvantages of these techniques. Measurement of the electrophoretic mobility allows to follow the development of the adsorption layer and to characterize the charge of the modified particles. At saturation, the surface charge is governed by the charge of the adsorbed film. Dynamic light scattering provides information on the film thickness and on the behavior of the modified suspensions. The charge and the structure of the adsorbed layer influence the stability of the particles, as well as the applicability of the classical theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO). This fundamental knowledge is presented in the light of environmental systems and its significance for applied systems is underlined. In particular, the article discusses two examples of environmental processes involving adsorption of polymers, namely, the modification of particles by natural adsorption of humic substances and the tailoring of surface properties of iron-based particles used to remediate contaminated aquifers.

  11. Detection of reactive oxygen species in mainstream cigarette smoke by a fluorescent probe

    NASA Astrophysics Data System (ADS)

    Liu, Li; Xu, Shi-jie; Li, Song-zhan

    2009-07-01

    A mass of reactive oxygen species(ROS) are produced in the process of smoking. Superfluous ROS can induce the oxidative stress in organism, which will cause irreversible damage to cells. Fluorescent probe is taken as a marker of oxidative stress in biology and has been applied to ROS detection in the field of biology and chemistry for high sensitivity, high simplicity of data collection and high resolution. As one type of fluorescent probe, dihydrorhodamine 6G (dR6G) will be oxidized to the fluorescent rhodamine 6G, which could be used to detect ROS in mainstream cigarette smoke. We investigated the action mechanism of ROS on dR6G, built up the standard curve of R6G fluorescence intensity with its content, achieved the variation pattern of R6G fluorescence intensity with ROS content in mainstream cigarette smoke and detected the contents of ROS from the 4 types of cigarettes purchased in market. The result shows that the amount of ROS has close relationship with the types of tobacco and cigarette production technology. Compared with other detecting methods such as electronic spin resonance(ESR), chromatography and mass spectrometry, this detection method by the fluorescent probe has higher efficiency and sensitivity and will have wide applications in the ROS detection field.

  12. Interaction between Ni and HZSM-5 in aromatization-enhanced reactive adsorption desulfurization catalysts for FCC gasoline upgrading.

    PubMed

    Zhao, Jinchong; Zhang, Lulu; She, Nannan; Liu, Yunqi; Chai, Yongming; Liu, Chenguang

    A compound catalyst (RA) consisted of Ni, ZnO and HZSM-5 with functions of reactive adsorption desulfurization (RADS) and olefin aromatization for fluid catalytic cracking (FCC) gasoline upgrading was prepared. X-ray powder diffraction (XRD), temperature-programmed reduction and low-temperature N2 adsorption were used to characterize the properties of the catalysts. Performance evaluation by FCC gasoline was carried out, and the result showed that the catalyst RA performed well in desulfurization and aromatization. For comparison, RADS catalyst (represented by DS) consisted of Ni and ZnO and aromatization catalyst (represented by Ar) consisted of HZSM-5 were prepared, respectively. They were combined in different ways to help investigating interaction between Ni and HZSM-5. Performance evaluated by FCC gasoline showed that catalyst RA performed best in desulfurization with a slight octane number loss. Interaction between Ni and HZSM-5 is a significant factor which influences the performance of the catalyst.

  13. Probing the Role of the Hyper-Reactive Histidine Residue of Arginase

    SciTech Connect

    Colleluori,D.; Reczkowski, R.; Emig, F.; Cama, E.; Cox, J.; Scolnick, L.; Compher, K.; Jude, K.; Han, S.; et al, .

    2005-01-01

    Rat liver arginase (arginase I) is potently inactivated by diethyl pyrocarbonate, with a second-order rate constant of 113M(-1)s(-1) for the inactivation process at pH 7.0, 25 degrees C. Partial protection from inactivation is provided by the product of the reaction, l-ornithine, while nearly complete protection is afforded by the inhibitor pair, l-ornithine and borate. The role of H141 has been probed by mutagenesis, chemical modulation, and X-ray diffraction. The hyper-reactivity of H141 towards diethyl pyrocarbonate can be explained by its proximity to E277. A proton shuttling role for H141 is supported by its conformational mobility observed among the known arginase structures. H141 is proposed to serve as an acid/base catalyst, deprotonating the metal-bridging water molecule to generate the metal-bridging hydroxide nucleophile, and by protonating the amino group of the product to facilitate its departure.

  14. Intercomparison of the comparative reactivity method (CRM) and pump-probe technique for measuring total OH reactivity in an urban environment

    NASA Astrophysics Data System (ADS)

    Hansen, R. F.; Blocquet, M.; Schoemaecker, C.; Léonardis, T.; Locoge, N.; Fittschen, C.; Hanoune, B.; Stevens, P. S.; Sinha, V.; Dusanter, S.

    2015-10-01

    The investigation of hydroxyl radical (OH) chemistry during intensive field campaigns has led to the development of several techniques dedicated to ambient measurements of total OH reactivity, which is the inverse of the OH lifetime. Three techniques are currently used during field campaigns, including the total OH loss rate method, the pump-probe method, and the comparative reactivity method. However, no formal intercomparison of these techniques has been published so far, and there is a need to ensure that measurements of total OH reactivity are consistent among the different techniques. An intercomparison of two OH reactivity instruments, one based on the comparative reactivity method (CRM) and the other based on the pump-probe method, was performed in October 2012 in a NOx-rich environment, which is known to be challenging for the CRM technique. This study presents an extensive description of the two instruments, the CRM instrument from Mines Douai (MD-CRM) and the pump-probe instrument from the University of Lille (UL-FAGE), and highlights instrumental issues associated with the two techniques. It was found that the CRM instrument used in this study underestimates ambient OH reactivity by approximately 20 % due to the photolysis of volatile organic compounds (VOCs) inside the sampling reactor; this value is dependent on the position of the lamp within the reactor. However, this issue can easily be fixed, and the photolysis of VOCs was successfully reduced to a negligible level after this intercomparison campaign. The UL-FAGE instrument may also underestimate ambient OH reactivity due to the difficulty to accurately measure the instrumental zero. It was found that the measurements are likely biased by approximately 2 s-1, due to impurities in humid zero air. Two weeks of ambient sampling indicate that the measurements performed by the two OH reactivity instruments are in agreement, within the measurement uncertainties for each instrument, for NOx mixing ratios

  15. Intercomparison of the comparative reactivity method (CRM) and pump-probe technique for measuring total OH reactivity in an urban environment

    NASA Astrophysics Data System (ADS)

    Hansen, R. F.; Blocquet, M.; Schoemaecker, C.; Léonardis, T.; Locoge, N.; Fittschen, C.; Hanoune, B.; Stevens, P. S.; Sinha, V.; Dusanter, S.

    2015-06-01

    The investigation of hydroxyl radical (OH) chemistry during intensive field campaigns has led to the development of several techniques dedicated to ambient measurements of total OH reactivity, which is the inverse of the OH lifetime. Three techniques are currently used during field campaigns, including the total OH loss rate method, the pump-probe method, and the comparative reactivity method. However, no formal intercomparison of these techniques has been published so far, and there is a need to ensure that measurements of total OH reactivity are consistent among the different techniques. An intercomparison of two OH reactivity instruments, one based on the Comparative Reactivity Method (CRM) and the other based on the pump-probe method, was performed in October 2012 in a NOx-rich environment, which is known to be challenging for the CRM technique. This study presents an extensive description of the two instruments, the CRM instrument from Mines Douai (MD-CRM) and the pump-probe instrument from the University of Lille (UL-FAGE), and highlights instrumental issues associated with the two techniques. It was found that the CRM instrument used in this study underestimates ambient OH reactivity by approximately 20 % due to the photolysis of Volatile Organic Compounds (VOCs) inside the sampling reactor; this value is dependent on the position of the lamp within the reactor. However, this issue can easily be fixed, and the photolysis of VOCs was successfully reduced to a negligible level after this intercomparison campaign. The UL-FAGE instrument may also underestimate ambient OH reactivity due to the difficulty to accurately measure the instrumental zero. It was found that the measurements are likely biased by approximately 2 s-1, due to impurities in humid zero air. Two weeks of ambient sampling indicate that the measurements performed by the two OH reactivity instruments are in agreement, within the measurement uncertainties for each instrument, for NOx mixing ratios

  16. Enhanced reactive adsorption of hydrogen sulfide on the composites of graphene/graphite oxide with copper (hydr)oxychlorides.

    PubMed

    Mabayoje, Oluwaniyi; Seredych, Mykola; Bandosz, Teresa J

    2012-06-27

    Composites of copper (hydr)oxychlorides with graphite oxide or graphene were synthesized and used as adsorbents of hydrogen sulfide at dynamic conditions at ambient temperatures. The materials were extensively characterized before and after adsorption in order to link their performance to the surface features. X-ray diffraction, FTIR, thermal analysis, TEM, SEM/EDX, and adsorption of nitrogen were used. It was found that the composite with graphene has the most favorable surface features enhancing reactive adsorption of hydrogen sulfide. The presence of moisture in the H2S stream has a positive effect on the removal process owing to the dissociation process. H2S is retained on the surface via a direct replacement of OH groups and via acid-base reactions with the copper (hydr)oxide. Highly dispersed reduced copper species on the surface of the composite with graphene enhance activation of oxygen and cause formation of sulfites and sulfates. Higher conductivity of the graphene phase than that of graphite oxide helps in electron transfer in redox reactions.

  17. Metal inhibition on the reactivity of manganese dioxide toward organic contaminant oxidation in relation to metal adsorption and ionic potential.

    PubMed

    Jiang, Jing; Wang, Zhuopu; Chen, Yang; He, Anfei; Li, Jianliang; Sheng, G Daniel

    2017-03-01

    Coexisting metal ions may significantly inhibit the oxidative reactivity of manganese oxides toward organic contaminants in metal-organic multi-pollutant waters. While the metal inhibition on the oxidation of organic contaminants by manganese oxides has previously been reported, the extent of the inhibition in relation to metal properties has not been established. Six alkali, alkaline, and transition metals, as well as two testing metals were evaluated for their abilities to inhibit the reactivity of birnessite. Regardless of the pathways of phenol and diuron oxidation (polymerization vs. breakdown), the extent of metal inhibition depended mainly on the metal itself and its concentration. The observed metal inhibition efficiency followed the order of Mn(2+) > Co(2+) > Cu(2+) > Al(3+) > Mg(2+) > K(+), consistent with metal adsorption on birnessite. The first-order organic oxidation rate constant (kobs) was linearly negatively correlated with metal adsorption (qe) on birnessite. These observations demonstrated that the metal inhibition efficiency was determined by metal adsorption on birnessite. The slopes of the kobs-qe varied among metals and followed the order of K(+) > Ca(2+) > Mg(2+) > Mn(2+) > Cd(2+) > Co(2+) > Cu(2+) > Al(3+). These slopes defined intrinsic inhibitory abilities of metals. As metals were adsorbed hydrated on birnessite, the intrinsic inhibitory ability was significantly linearly correlated with ionic potentials of metals, leading to a single straight line. Metals with multiple d electrons in the outermost orbit with polarizing energy that promotes hydrolysis sat slightly below the line, and vice versa.

  18. Adsorption, Ordering, and Local Environments of Surfactant-Encapsulated Polyoxometalate Ions Probed at the Air–Water Interface

    DOE PAGES

    Doughty, Benjamin; Yin, Panchao; Ma, Ying-Zhong

    2016-07-23

    The continued development and application of surfactant-encapsulated polyoxometalates (SEPs) relies on understanding the ordering and organization of species at their interface and how these are impacted by the various local environments to which they are exposed. In this paper, we report on the equilibrium properties of two common SEPs adsorbed to the air–water interface and probed with surface-specific vibrational sum-frequency generation (SFG) spectroscopy. These results reveal clear shifts in vibrational band positions, the magnitude of which scales with the charge of the SEP core, which is indicative of a static field effect on the surfactant coating and the associated localmore » chemical environment. This static field also induces ordering in surrounding water molecules that is mediated by charge screening via the surface-bound surfactants. From these SFG measurements, we are able to show that Mo132-based SEPs are more polar than Mo72V30 SEPs. Disorder in the surfactant chain packing at the highly curved SEP surfaces is attributed to large conic volumes that can be sampled without interactions with neighboring chains. Measurements of adsorption isotherms yield free energies of adsorption to the air–water interface of -46.8 ± 0.4 and -44.8 ± 1.2 kJ/mol for the Mo132 and Mo72V30 SEPs, respectively, indicating a strong propensity for the fluid surface. Finally, the influence of intermolecular interactions on the surface adsorption energies is discussed.« less

  19. Probing gas adsorption in MOFs using an efficient ab initio widom insertion Monte Carlo method.

    PubMed

    Lee, Youhan; Poloni, Roberta; Kim, Jihan

    2016-12-15

    We propose a novel biased Widom insertion method that can efficiently compute the Henry coefficient, KH , of gas molecules inside porous materials exhibiting strong adsorption sites by employing purely DFT calculations. This is achieved by partitioning the simulation volume into strongly and weakly adsorbing regions and selectively biasing the Widom insertion moves into the former region. We show that only few thousands of single point energy calculations are necessary to achieve accurate statistics compared to many hundreds of thousands or millions of such calculations in conventional random insertions. The methodology is used to compute the Henry coefficient for CO2 , N2 , CH4 , and C2 H2 in M-MOF-74(M = Zn and Mg), yielding good agreement with published experimental data. Our results demonstrate that the DFT binding energy and the heat of adsorption are not accurate enough indicators to rank the guest adsorption properties at the Henry regime. © 2016 Wiley Periodicals, Inc.

  20. Adsorption behavior and mechanism of reactive brilliant red X-3B in aqueous solution over three kinds of hydrotalcite-like LDHs

    NASA Astrophysics Data System (ADS)

    Zhang, Can; Yang, Shaogui; Chen, Hongzhe; He, Huan; Sun, Cheng

    2014-05-01

    Three kinds of layered double hydroxides (LDHs), including Ni/Al-LDH, Mg/Al-LDH and Co/Al-LDH, were adopted in this research to study the adsorption process of reactive brilliant red X-3B. Factors affecting adsorption such as contact time and temperature were investigated. The adsorption kinetic data fit well into the pseudo-second-order model, while the adsorption isotherm followed the Langmuir model. The thermodynamic tests indicated spontaneous and exothermic nature of X-3B adsorption. In order to examine the adsorption mechanism, pH effect was investigated and adsorbents and adsorption products of Ni/Al- and Mg/Al-LDHs were characterized further by several physicochemical techniques in view of their relative large capacity. The pH effect tests illustrated that electrostatic reaction and hydrogen bonding between dye molecules and LDH layers may be the major mechanisms involved in adsorption. The FT-IR analysis revealed that there was ion exchange during the adsorption process. The XPS, TG, and NMR experiments further proved that the hydrogen bonding between the adsorbent and adsorbate played the dominant role in this process and the -SO3 was the interaction site.

  1. Factors affecting the removal of ammonia from air on carbonaceous materials: Investigation of reactive adsorption mechanism

    NASA Astrophysics Data System (ADS)

    Petit, Camille

    Air pollution related to the release of industrial toxic gases, represents one of the main concerns of our modern world owing to its detrimental effect on the environment. To tackle this growing issue, efficient ways to reduce/control the release of pollutants are required. Adsorption of gases on porous materials appears as a potential solution. However, the physisorption of small molecules of gases such as ammonia is limited at ambient conditions. For their removal, adsorbents providing strong adsorption forces must be used/developed. In this study, new carbon-based materials are prepared and tested for ammonia adsorption at ambient conditions. Characterization of the adsorbents' texture and surface chemistry is performed before and after exposure to ammonia to identify the features responsible for high adsorption capacity and for controlling the mechanisms of retention. The characterization techniques include: nitrogen adsorption, thermal analysis, potentiometric titration, FT-IR spectroscopy, X-ray diffraction, Energy Dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and Electron Microscopy. The results obtained indicate that ammonia removal is governed by the adsorbent's surface chemistry. On the contrary, porosity (and thus physisorption) plays a secondary role in this process, unless strong dispersive forces are provided by the adsorbent. The surface chemistry features responsible for the enhanced ammonia adsorption include the presence of oxygen-(carboxyl, hydroxyl, epoxy) and sulfur- (sulfonic) containing groups. Metallic species improve the breakthrough capacity as well as they lead to the formation of Lewis acid-base interactions, hydrogen-bonding or complexation. In addition to the latter three mechanisms, ammonia is retained on the adsorbent surface via Bronsted acid-base interactions or via specific reactions with the adsorbent's functionalities leading to the incorporation of ammonia into the adsorbent's matrix. Another mechanism

  2. In Vivo Imaging of Retinal Oxidative Stress Using a Reactive Oxygen Species–Activated Fluorescent Probe

    PubMed Central

    Prunty, Megan C.; Aung, Moe H.; Hanif, Adam M.; Allen, Rachael S.; Chrenek, Micah A.; Boatright, Jeffrey H.; Thule, Peter M.; Kundu, Kousik; Murthy, Niren; Pardue, Machelle T.

    2015-01-01

    Purpose In vivo methods for detecting oxidative stress in the eye would improve screening and monitoring of the leading causes of blindness: diabetic retinopathy, glaucoma, and age-related macular degeneration. Methods To develop an in vivo biomarker for oxidative stress in the eye, we tested the efficacy of a reactive oxygen species (ROS)–activated, near-infrared hydrocyanine-800CW (H-800CW) fluorescent probe in light-induced retinal degeneration (LIRD) mouse models. After intravitreal delivery in LIRD rats, fluorescent microscopy was used to confirm that the oxidized H-800CW appeared in the same retinal layers as an established ROS marker (dichlorofluorescein). Results Dose–response curves of increasing concentrations of intravenously injected H-800CW demonstrated linear increases in both intensity and total area of fundus hyperfluorescence in LIRD mice, as detected by scanning laser ophthalmoscopy. Fundus hyperfluorescence also correlated with the duration of light damage and functional deficits in vision after LIRD. In LIRD rats with intravitreal injections of H-800CW, fluorescent labeling was localized to photoreceptor inner segments, similar to dichlorofluorescein. Conclusions Hydrocyanine-800CW detects retinal ROS in vivo and shows potential as a novel biomarker for ROS levels in ophthalmic diseases. PMID:26348635

  3. Chemical Reactivity Probes for Assessing Abiotic Natural Attenuation by Reducing Iron Minerals.

    PubMed

    Fan, Dimin; Bradley, Miranda J; Hinkle, Adrian W; Johnson, Richard L; Tratnyek, Paul G

    2016-02-16

    Increasing recognition that abiotic natural attenuation (NA) of chlorinated solvents can be important has created demand for improved methods to characterize the redox properties of the aquifer materials that are responsible for abiotic NA. This study explores one promising approach: using chemical reactivity probes (CRPs) to characterize the thermodynamic and kinetic aspects of contaminant reduction by reducing iron minerals. Assays of thermodynamic CRPs were developed to determine the reduction potentials (ECRP) of suspended minerals by spectrophotometric determination of equilibrium CRP speciation and calculations using the Nernst equation. ECRP varied as expected with mineral type, mineral loading, and Fe(II) concentration. Comparison of ECRP with reduction potentials measured potentiometrically using a Pt electrode (EPt) showed that ECRP was 100-150 mV more negative than EPt. When EPt was measured with small additions of CRPs, the systematic difference between EPt and ECRP was eliminated, suggesting that these CRPs are effective mediators of electron transfer between mineral and electrode surfaces. Model contaminants (4-chloronitrobenzene, 2-chloroacetophenone, and carbon tetrachloride) were used as kinetic CRPs. The reduction rate constants of kinetic CRPs correlated well with the ECRP for mineral suspensions. Using the rate constants compiled from literature for contaminants and relative mineral reduction potentials based on ECRP measurements, qualitatively consistent trends were obtained, suggesting that CRP-based assays may be useful for estimating abiotic NA rates of contaminants in groundwater.

  4. Probing Intramolecular versus Intermolecular CO2 Adsorption on Amine-Grafted SBA-15.

    PubMed

    Yoo, Chun-Jae; Lee, Li-Chen; Jones, Christopher W

    2015-12-15

    A mesoporous silica SBA-15 is modified with an array of amine-containing organosilanes including (i) propylamine, SiCH2CH2CH2NH2 (MONO), (ii) propylethylenediamine, SiCH2CH2CH2NHCH2CH2NH2 (DI), (iii) propyldiethylenetriamine, SiCH2CH2CH2NHCH2CH2NHCH2CH2NH2 (TRI), and (iv) propyltriethylenetetramine, SiCH2CH2CH2NHCH2CH2N(CH2CH2NH2)2 (TREN) and the low loading silane adsorbents (∼0.45 mmol silane/g) are evaluated for their CO2 adsorption properties, with a focus on gaining insight into the propensity for intramolecular vs intermolecular CO2 adsorption. Adsorption isotherms at low CO2 coverages are measured while simultaneously recording the heat evolved via a Tian-Calvet calorimeter. The results are compared on a silane molecule efficiency basis (mol CO2 adsorbed/mol silane) to assess the potential for intramolecular CO2 adsorption, employing two amine groups in a single silane molecule. As the number of amines in the silane molecule increases (MONO < DI < TREN ∼ TRI), the silane molecule efficiency is enhanced owing to the ability to intramolecularly capture CO2. Analysis of the CO2 uptake for samples with the surface silanols removed by capping demonstrates that cooperative uptake due to amine-CO2-silanol interactions is also possible over these adsorbents and is the primary mode of sorption for the MONO material at the studied low silane loading. As the propensity for intramolecular CO2 capture increases due to the presence of multiple amines in a single silane molecule (MONO < DI < TREN ∼ TRI), the measured heat of adsorption also increases. This study of various amine-containing silanes at low coverage is the first to provide significant, direct evidence for intramolecular CO2 capture in a single silane molecule. Furthermore, it provides evidence for the relative heats of adsorption for physisorption on a silanol laden surface (ca. 37 kJ/mol), a silanol-capped surface (ca. 25 kJ/mol), via amine-CO2-silanol interactions (ca. 46 kJ/mol), and via amine-CO2

  5. The effects of hazardous ions adsorption on the morphological and chemical properties of reactive cloth filter

    NASA Astrophysics Data System (ADS)

    Othman, Sameh H.; Sohsah, Moustfa A.; Ghoneim, Mohammad M.

    2009-11-01

    Reactive cloth filter is fabricated by grafting of acrylonitrile/methacrylic acid onto cotton cloth, using mutual irradiation technique and the subsequent amidoximation of the reactive intermediate nitrile groups. The incorporation of the amidoxime/carboxyl groups was confirmed by different techniques. The effect of the hazardous ions chelation from radioactive waste on the morphological and chemical structure was studied. The cloth filter possessed good morphological and chemical stability suitable for practical use. The fabricated cloth filter can be used for low-level radioactive waste treatments.

  6. Pore-scale dynamics of enzyme adsorption, swelling and reactive dissolution determine sugar yield in hemicellulose hydrolysis for biofuel production

    NASA Astrophysics Data System (ADS)

    Dutta, Sajal Kanti; Chakraborty, Saikat

    2016-12-01

    Hemicelluloses are the earth’s second most abundant structural polymers, found in lignocellulosic biomass. Efficient enzymatic depolymerization of xylans by cleaving their β-(1 → 4)-glycosidic bonds to produce soluble sugars is instrumental to the cost-effective production of liquid biofuels. Here we show that the multi-scale two-phase process of enzymatic hydrolysis of amorphous hemicelluloses is dominated by its smallest scale–the pores. In the crucial first five hours, two to fourfold swelling of the xylan particles allow the enzymes to enter the pores and undergo rapid non-equilibrium adsorption on the pore surface before they hydrolyze the solid polymers, albeit non-competitively inhibited by the products xylose and xylobiose. Rapid pore-scale reactive dissolution increases the solid carbohydrate’s porosity to 80–90%. This tightly coupled experimental and theoretical study quantifies the complex temporal dynamics of the transport and reaction processes coupled across scales and phases to show that this unique pore-scale phenomenon can be exploited to accelerate the depolymerization of hemicelluloses to monomeric sugars in the first 5–6 h. We find that an ‘optimal substrate loading’ of 5 mg/ml (above which substrate inhibition sets in) accelerates non-equilibrium enzyme adsorption and solid hemicellulose depolymerization at the pore-scale, which contributes three-quarters of the soluble sugars produced for bio-alcohol fermentation.

  7. Pore-scale dynamics of enzyme adsorption, swelling and reactive dissolution determine sugar yield in hemicellulose hydrolysis for biofuel production

    PubMed Central

    Dutta, Sajal Kanti; Chakraborty, Saikat

    2016-01-01

    Hemicelluloses are the earth’s second most abundant structural polymers, found in lignocellulosic biomass. Efficient enzymatic depolymerization of xylans by cleaving their β-(1 → 4)-glycosidic bonds to produce soluble sugars is instrumental to the cost-effective production of liquid biofuels. Here we show that the multi-scale two-phase process of enzymatic hydrolysis of amorphous hemicelluloses is dominated by its smallest scale–the pores. In the crucial first five hours, two to fourfold swelling of the xylan particles allow the enzymes to enter the pores and undergo rapid non-equilibrium adsorption on the pore surface before they hydrolyze the solid polymers, albeit non-competitively inhibited by the products xylose and xylobiose. Rapid pore-scale reactive dissolution increases the solid carbohydrate’s porosity to 80–90%. This tightly coupled experimental and theoretical study quantifies the complex temporal dynamics of the transport and reaction processes coupled across scales and phases to show that this unique pore-scale phenomenon can be exploited to accelerate the depolymerization of hemicelluloses to monomeric sugars in the first 5–6 h. We find that an ‘optimal substrate loading’ of 5 mg/ml (above which substrate inhibition sets in) accelerates non-equilibrium enzyme adsorption and solid hemicellulose depolymerization at the pore-scale, which contributes three-quarters of the soluble sugars produced for bio-alcohol fermentation. PMID:27905534

  8. Equilibrium and kinetic models on the adsorption of Reactive Black 5 from aqueous solution using Eichhornia crassipes/chitosan composite.

    PubMed

    El-Zawahry, Manal M; Abdelghaffar, Fatma; Abdelghaffar, Rehab A; Hassabo, Ahmed G

    2016-01-20

    New natural biopolymer composite was prepared using extracted cellulose from an environmentally problematic water hyacinth Eichhornia crassipes (EC). The extracted cellulose was functionalized by chitosan and TiO2 nanoparticles to form EC/Chitosan (EC/Cs) composite network. Surface characterization of EC/Cs natural biopolymer composite was examined by spectrum analysis FT-IR, specific surface area, micropore volume, pore width and SEM. Furthermore, the sorption experiments were carried out as a function of pH, various initial dye concentration and contact time. Experiment results showed that the EC/Cs composite have high ability to remove C.I. Reactive Black 5 from its dye-bath effluent. The equilibrium sorption evaluation of RB5 conformed and fitted well to Langmuir adsorption isotherm models and the maximum sorption capacity was 0.606 mg/g. The kinetic adsorption models followed pseudo-second order model and the dye intra-particle diffusion may suggesting a chemical reaction mechanism. Further, it was obvious from the investigation that this composite could be applied as a promising low cost adsorbent for anionic dye removal from aqueous solutions.

  9. Adsorption, Ordering, and Local Environments of Surfactant-Encapsulated Polyoxometalate Ions Probed at the Air–Water Interface

    SciTech Connect

    Doughty, Benjamin; Yin, Panchao; Ma, Ying-Zhong

    2016-07-23

    The continued development and application of surfactant-encapsulated polyoxometalates (SEPs) relies on understanding the ordering and organization of species at their interface and how these are impacted by the various local environments to which they are exposed. In this paper, we report on the equilibrium properties of two common SEPs adsorbed to the air–water interface and probed with surface-specific vibrational sum-frequency generation (SFG) spectroscopy. These results reveal clear shifts in vibrational band positions, the magnitude of which scales with the charge of the SEP core, which is indicative of a static field effect on the surfactant coating and the associated local chemical environment. This static field also induces ordering in surrounding water molecules that is mediated by charge screening via the surface-bound surfactants. From these SFG measurements, we are able to show that Mo132-based SEPs are more polar than Mo72V30 SEPs. Disorder in the surfactant chain packing at the highly curved SEP surfaces is attributed to large conic volumes that can be sampled without interactions with neighboring chains. Measurements of adsorption isotherms yield free energies of adsorption to the air–water interface of -46.8 ± 0.4 and -44.8 ± 1.2 kJ/mol for the Mo132 and Mo72V30 SEPs, respectively, indicating a strong propensity for the fluid surface. Finally, the influence of intermolecular interactions on the surface adsorption energies is discussed.

  10. Water adsorption on TiO2 surfaces probed by soft X-ray spectroscopies: bulk materials vs. isolated nanoparticles

    PubMed Central

    Benkoula, Safia; Sublemontier, Olivier; Patanen, Minna; Nicolas, Christophe; Sirotti, Fausto; Naitabdi, Ahmed; Gaie-Levrel, François; Antonsson, Egill; Aureau, Damien; Ouf, François-Xavier; Wada, Shin-Ichi; Etcheberry, Arnaud; Ueda, Kiyoshi; Miron, Catalin

    2015-01-01

    We describe an experimental method to probe the adsorption of water at the surface of isolated, substrate-free TiO2 nanoparticles (NPs) based on soft X-ray spectroscopy in the gas phase using synchrotron radiation. To understand the interfacial properties between water and TiO2 surface, a water shell was adsorbed at the surface of TiO2 NPs. We used two different ways to control the hydration level of the NPs: in the first scheme, initially solvated NPs were dried and in the second one, dry NPs generated thanks to a commercial aerosol generator were exposed to water vapor. XPS was used to identify the signature of the water layer shell on the surface of the free TiO2 NPs and made it possible to follow the evolution of their hydration state. The results obtained allow the establishment of a qualitative determination of isolated NPs’ surface states, as well as to unravel water adsorption mechanisms. This method appears to be a unique approach to investigate the interface between an isolated nano-object and a solvent over-layer, paving the way towards new investigation methods in heterogeneous catalysis on nanomaterials. PMID:26462615

  11. Intermolecular reactivity study to scale adsorption property of para- and meta-substituted nitrobenzene over 2:1 dioctahedral smectite

    NASA Astrophysics Data System (ADS)

    Chatterjee, Abhijit; Ebina, Takeo; Iwasaki, Takashi; Mizukami, Fujio

    2003-06-01

    Substituted nitrobenzene, a toxic series of molecules with its wide application in pesticides needs to be removed by a suitable sorbent, whose characteristic is to be determined using the reactivity index theory within the helm of the density-functional theory and as well inside the broad subject range of the hard-soft acid-base (HSAB) principle. We studied a series of meta- and para-substituted nitrobenzene molecules (NBMs) starting from -NH2, -OH, -OCH3, -CHO, -OCOCH3, -COCH3, -CF3, -CN, and -COOCH3 to monitor the effect of electrophilicity and nucleophilicity in their adsorption properties. From the values of the local softness and the charge on the hydrogen atom of the bridging/structural (occurring on the surface) hydroxyl attached to the octahedral/tetrahedral metal site present in smectite, it is concluded that the local acidities of the inorganic material systems are dependent on several characteristics which are of importance within the framework of HSAB principle. We used "group softness" for the interacting molecules, whose values were generated by adding the local softness values of constituent atoms of the respective group and found it can be a better descriptor for intermolecular interactions occurring in these NBMs. A semiquantitave scale is proposed from the group reactivity index present in NBM and the clay cluster.

  12. Controls on the surface chemical reactivity of volcanic ash investigated with probe gases

    NASA Astrophysics Data System (ADS)

    Maters, Elena C.; Delmelle, Pierre; Rossi, Michel J.; Ayris, Paul M.; Bernard, Alain

    2016-09-01

    Increasing recognition that volcanic ash emissions can have significant impacts on the natural and human environment calls for a better understanding of ash chemical reactivity as mediated by its surface characteristics. However, previous studies of ash surface properties have relied on techniques that lack the sensitivity required to adequately investigate them. Here we characterise at the molecular monolayer scale the surfaces of ash erupted from Eyjafjallajökull, Tungurahua, Pinatubo and Chaitén volcanoes. Interrogation of the ash with four probe gases, trimethylamine (TMA; N(CH3)3), trifluoroacetic acid (TFA; CF3COOH), hydroxylamine (HA; NH2OH) and ozone (O3), reveals the abundances of acid-base and redox sites on ash surfaces. Measurements on aluminosilicate glass powders, as compositional proxies for the primary constituent of volcanic ash, are also conducted. We attribute the greater proportion of acidic and oxidised sites on ash relative to glass surfaces, evidenced by comparison of TMA/TFA and HA/O3 uptake ratios, in part to ash interaction with volcanic gases and condensates (e.g., H2O, SO2, H2SO4, HCl, HF) during the eruption. The strong influence of ash surface processing in the eruption plume and/or cloud is further supported by particular abundances of oxidised and reduced sites on the ash samples resulting from specific characteristics of their eruptions of origin. Intense interaction with water vapour may result in a higher fraction of oxidised sites on ash produced by phreatomagmatic than by magmatic activity. This study constitutes the first quantification of ash chemical properties at the molecular monolayer scale, and is an important step towards better understanding the factors that govern the role of ash as a chemical agent within atmospheric, terrestrial, aquatic or biotic systems.

  13. Adsorption and coadsorption of CO and H 2 on Fe(111) probed by TEAS

    NASA Astrophysics Data System (ADS)

    Bernasek, Steven L.; Zappone, Marianne; Ping Jiang

    Thermal energy atom scattering (TEAS), as developed by Comsa and coworkers, has been widely used to study a variety of processes on smooth, close packed metal surfaces such as Pt(111). The He beam specular reflectivity of these surfaces is very high, and absorbates or defects usually have a relatively large scattering cross section. For TEAS to have a wider applicability, studies on more corrugated surfaces should be undertaken. We report here studies of CO and H 2 adsorption and coadsorption on the open Fe(111) surface. The He specular intensity drops rapidly and smoothly with CO exposure on the Fe(111) surface. In contrast to CO/Pt(111), the diffuse scattering of He from CO on Fe(111) is not a negligible fraction of the intensity. The surface exhibits a finite reflectivity even at high CO coverages. An effective scattering cross section of 56Å 2 was derived from a fit of the reflectivity data to a model taking this diffuse scattering into account. For H 2 exposure to the Fe(111) surface, the He specular reflectivity decreases less abruptly, with distinct slope changes as coverage increases. Angular and temperature dependent measurements suggest distinct adsorption sites for the dissociatively adsorbed hydrogen. When CO and H 2 are coadsorbed, the order of adsorption affects the final composition and coverage in the overlayer. If the surface is first saturated with CO, H 2 will not adsorb, as evidenced by constant TEAS signal. When H 2 is adsorbed first, even to saturation coverage, CO will adsorb, displacing H 2 from the surface. Evidence is obtained for CO and H 2 segregation on the surface at intermediate coverages.

  14. Surface adsorption and hopping cause probe-size-dependent microrheology of actin networks

    NASA Astrophysics Data System (ADS)

    He, Jun; Tang, Jay X.

    2011-04-01

    A network of filaments formed primarily by the abundant cytoskeletal protein actin gives animal cells their shape and elasticity. The rheological properties of reconstituted actin networks have been studied by tracking micron-sized probe beads embedded within the networks. We investigate how microrheology depends on surface properties of probe particles by varying the stickiness of their surface. For this purpose, we chose carboxylate polystyrene (PS) beads, silica beads, bovine serum albumin (BSA) -coated PS beads, and polyethylene glycol (PEG) -grafted PS beads, which show descending stickiness to actin filaments, characterized by confocal imaging and microrheology. Probe size dependence of microrheology is observed for all four types of beads. For the slippery PEG beads, particle-tracking microrheology detects weaker networks using smaller beads, which tend to diffuse through the network by hopping from one confinement “cage” to another. This trend is reversed for the other three types of beads, for which microrheology measures stiffer networks for smaller beads due to physisorption of nearby filaments to the bead surface. We explain the probe size dependence with two simple models. We also evaluate depletion effect near nonadsorption bead surface using quantitative image analysis and discuss the possible impact of depletion on microrheology. Analysis of these effects is necessary in order to accurately define the actin network rheology both in vitro and in vivo.

  15. Probing thyroglobulin in undiluted human serum based on pattern recognition and competitive adsorption of proteins

    NASA Astrophysics Data System (ADS)

    Wang, Ran; Huang, Shuai; Li, Jing; Chae, Junseok

    2014-10-01

    Thyroglobulin (Tg) is a sensitive indicator of persistent or recurrent differentiated thyroid cancer of follicular cell origin. Detection of Tg in human serum is challenging as bio-receptors, such as anti-Tg, used in immunoassay have relatively weak binding affinity. We engineer sensing surfaces using the competitive adsorption of proteins, termed the Vroman Effect. Coupled with Surface Plasmon Resonance, the "cross-responsive" interactions of Tg on the engineered surfaces produce uniquely distinguishable multiple signature patterns, which are discriminated using Linear Discriminant Analysis. Tg-spiked samples, down to 2 ng/ml Tg in undiluted human serum, are sensitively and selectively discriminated from the control (undiluted human serum).

  16. Adsorption of acridine on silver electrode: SERS spectra potential dependence as a probe of adsorbate state

    NASA Astrophysics Data System (ADS)

    Solovyeva, Elena V.; Myund, Liubov A.; Dem'yanchuk, Evgeniya M.; Makarov, Artiom A.; Denisova, Anna S.

    2013-02-01

    This work investigates acridine adsorption on the silver electrode surface. The dependence of the acridine SERS spectra on the electrode potential proved to be quite different for azaheterocycle molecules, while the pH effect as expected. The changes in the acridine SERS spectrum caused by the double electric layer (DEL) rearrangement can be explained by sorption/desorption rather than the adsorbate molecule reorientation. The presence of chloride anions close to the silver surface is important not only for the SERS-active properties but for the formation of the stabilised surface complexes of the protonated acridine as well.

  17. Probing environmentally significant surface radicals: Crystallographic and temperature dependent adsorption of phenol on ZnO

    NASA Astrophysics Data System (ADS)

    Thibodeaux, Chad A.; Poliakoff, E. D.; Kizilkaya, Orhan; Patterson, Matthew C.; DiTusa, Mark F.; Kurtz, Richard L.; Sprunger, P. T.

    2015-10-01

    Environmentally persistent free radicals (EPFRs) are toxic organic/metal oxide composite particles that have been discovered to form from substituted benzenes chemisorbed to metal oxides. Here, we perform photoelectron spectroscopy, electron energy loss spectroscopy, and low energy electron diffraction of phenol chemisorbed to ZnO(1 0 1 _ 0) and (0 0 0 1 _)-Zn to observe electronic structure changes and charge transfer as a function adsorption temperature. We show direct evidence of charge transfer from the ZnO surfaces to the phenol. This evidence can help gain a better understanding of EPFRs and be used to develop possible future remediation strategies.

  18. Probing environmentally significant surface radicals: Crystallographic and temperature dependent adsorption of phenol on ZnO

    PubMed Central

    Thibodeaux, Chad A.; Poliakoff, E.D.; Kizilkaya, Orhan; Patterson, Matthew C.; DiTusa, Mark F.; Kurtz, Richard L.

    2015-01-01

    Environmentally persistent free radicals (EPFRs) are toxic organic/metal oxide composite particles that have been discovered to form from substituted benzenes chemisorbed to metal oxides. Here, we perform photoelectron spectroscopy, electron energy loss spectroscopy, and low energy electron diffraction of phenol chemisorbed to ZnO(1 0 1̱ 0) and (0 0 0 1̱)-Zn to observe electronic structure changes and charge transfer as a function adsorption temperature. We show direct evidence of charge transfer from the ZnO surfaces to the phenol. This evidence can help gain a better understanding of EPFRs and be used to develop possible future remediation strategies. PMID:26388650

  19. Reactive Microcontact Printing of DNA Probes on (DMA-NAS-MAPS) Copolymer-Coated Substrates for Efficient Hybridization Platforms.

    PubMed

    Castagna, Rossella; Bertucci, Alessandro; Prasetyanto, Eko Adi; Monticelli, Marco; Conca, Dario Valter; Massetti, Matteo; Sharma, Parikshit Pratim; Damin, Francesco; Chiari, Marcella; De Cola, Luisa; Bertacco, Riccardo

    2016-04-05

    High-performing hybridization platforms fabricated by reactive microcontact printing of DNA probes are presented. Multishaped PDMS molds are used to covalently bind oligonucleotides over a functional copolymer (DMA-NAS-MAPS) surface. Printed structures with minimum width of about 1.5 μm, spaced by 10 μm, are demonstrated, with edge corrugation lower than 300 nm. The quantification of the immobilized surface probes via fluorescence imaging gives a remarkable concentration of 3.3 × 10(3) oligonucleotides/μm(2), almost totally active when used as probes in DNA-DNA hybridization assays. Indeed, fluorescence and atomic force microscopy show a 95% efficiency in target binding and uniform DNA hybridization over printed areas.

  20. Probing the contribution of different intermolecular forces to the adsorption of spheroproteins onto hydrophilic surfaces.

    PubMed

    Borges, João; Campiña, José M; Silva, A Fernando

    2013-12-27

    Protein adsorption is a delicate process, which results from the balance between the properties of proteins and their solid supports. Although the relevance of some of these parameters has been already unveiled, the precise involvement of electrostatics and other weaker intermolecular forces requires further comprehension. Aiming to contribute to this task, this work explores the attachment, rearrangement, and surface aggregation of a model spheroprotein, such as bovine β-lactoglobulin (β-LG), onto hydrophilic substrates prefunctionalized with different alkylthiol films. Thereby, a variety of electrostatic scenarios for the adsorption of β-LG could be recreated through the variation of the pH and the functional chemistry of the surfaces. The changes in surface mass density (plus associated water) and film flexibility were followed in situ with quartz crystal microbalance with dissipation monitoring. Film packing and aggregation were assessed by faradaic electrochemical measurements and ex situ atomic force microscopy and field effect scanning electron microscopy. In contrast to previous hypotheses arguing that electrostatic interactions between charged substrates and proteins would be the only driving force, a complex interplay between Coulombic and non-Coulombic intermolecular forces (which would depend upon the experimental conditions) has been suggested to explain the results.

  1. Adsorption and photocatalysis of nanocrystalline TiO2 particles for Reactive Red 195 removal: effect of humic acids, anions and scavengers.

    PubMed

    Chládková, B; Evgenidou, E; Kvítek, L; Panáček, A; Zbořil, R; Kovář, P; Lambropoulou, D

    2015-11-01

    In the present study, the coupling of adsorption capacity and photocatalytic efficiency of two different industrially produced titania catalysts was investigated and compared. The azo dye Reactive Red 195 was selected as a model compound. The tested catalysts, PK-10 and PK-180, exhibited different adsorption capacities due to their significant difference in their specific surface, but both have proven to be effective photocatalysts for photodegradation of the studied dye. PK-10 exhibited strong adsorption of the studied dye due to its high specific surface area, while the second studied catalyst, PK-180, demonstrated negligible adsorption of Reactive Red 195. The effect of the pH, the concentration of the catalyst and the initial concentration of the dye appear to affect the photocatalytic rate. The effect of the presence of humic acids and inorganic ions was also examined, while the contribution of various reactive species was indirectly evaluated through the addition of various scavengers. To evaluate the extent of mineralisation of the studied dye, total organic carbon (TOC) measurements during the experiment were also conducted. Besides total colour removal, evident reduction of TOC was also achieved using both catalysts.

  2. Communication: Reactions and adsorption at the surface of silver nanoparticles probed by second harmonic generation.

    PubMed

    Gan, Wei; Gonella, Grazia; Zhang, Min; Dai, Hai-Lung

    2011-01-28

    Even though nanoparticles have dimensions much smaller than the optical wavelength and shapes commonly with inversion symmetry, we show, for the first time, direct experimental evidence that second harmonic generation (SHG) can be detected from the surface layer of metallic nanoparticles, in this case 40 nm radius Ag particles. The SH intensity detected is shown to substantially decrease upon chemical bonding of thiol molecules to the Ag particle surface. The surface generated SH intensity can be used for probing properties and processes at the nanoparticle surface.

  3. Adsorption of biological molecules to a solid support for scanning probe microscopy.

    PubMed

    Müller, D J; Amrein, M; Engel, A

    1997-07-01

    Scanning probe microscopes are now established tools to study the surface structure of biological macromolecules under physiological conditions. Sample preparation methods for this microscopy all have the objective to attach the specimen firmly to a support. Here we analyse the commonly used method of adsorbing biological specimens to freshly cleaved mica. This is facilitated by adjusting the electrolyte concentration and the pH of the buffer solution. Native macromolecular systems absorbed to mica in this way can be reproducibly imaged at submolecular resolution.

  4. Efficient and rapid adsorption characteristics of templating modified guar gum and silica nanocomposite toward removal of toxic reactive blue and Congo red dyes.

    PubMed

    Pal, Sagar; Patra, Abhay Shankar; Ghorai, Soumitra; Sarkar, Amit Kumar; Mahato, Vivekananda; Sarkar, Supriyo; Singh, R P

    2015-09-01

    The present study highlights the potentiality of sol-gel synthesized guar gum-graft-poly (acrylamide)/silica (g-GG/SiO2) hybrid nanocomposite toward the rapid removal of toxic reactive blue 4 (RB) and Congo red (CR) dyes from aqueous solution. Various physicochemical characterizations support the feasibility of the functionalized guar gum matrix as efficient template for the formation of homogeneous nanoscale silica particles. The composite demonstrates rapid and superior adsorption efficiency of RB (Qmax: 579.01 mg g(-1) within 40 min) and CR (Qmax: 233.24 mg g(-1) within 30 min) dyes from aqueous environment. Here, the pH driven adsorption process depends strongly on the ionic strength of the salt solution. The adsorption kinetics data predicts that pseudo second-order (surface adsorption) and intraparticle diffusion take place simultaneously. The adsorption equilibrium is in good agreement with the Langmuir isotherm, while the thermodynamics study confirms spontaneous nature of the adsorption process. Desorption study predicts the excellent regenerative efficacy of nanocomposite.

  5. A DFT study of the acid-base properties of anatase TiO2 and tetragonal ZrO2 by adsorption of CO and CO2 probe molecules

    NASA Astrophysics Data System (ADS)

    Chen, Hsin-Yi Tiffany; Tosoni, Sergio; Pacchioni, Gianfranco

    2016-10-01

    We have performed a comparative study of the acid-base characteristics of the surfaces of anatase TiO2 and tetragonal ZrO2. To this end we performed DFT + U calculations on CO and CO2 probe molecules adsorbed both on terraces and steps of the two oxides. For titania, CO adsorption results in a moderate adsorption energy (about - 0.3 eV) and in a positive shift of the Csbnd O stretching frequency (about + 40 cm- 1), typical of Lewis acid sites, with no clear difference in the acidity between terraces or steps. For zirconia we found a similar CO binding energy as for titania, and a CO vibrational shift that depends on the location of the Zr cation: negligible on terraces, similar to TiO2 on steps. We conclude that the acidic properties are similar in the two oxide surfaces. Things are different for CO2 adsorption. On titania the interaction is weak and surface carbonates compete with physisorbed CO2, indicating a weak basic character. On the contrary, on zirconia three types of stable carbonates have been identified. Their vibrational frequencies are consistent with IR measurements reported in the literature. The most stable species forms on steps of the t-ZrO2 surface and consists of a CO32 - unit which lies flat on the surface with the O atoms pointing towards three Zr ions. The species forms spontaneously by extraction of a lattice oxygen by an incoming CO2 molecule. The different reactivity points towards a much more pronounced basic character of zirconia compared to titania, at least if measured by CO2 adsorption.

  6. Practical use of chemical probes for reactive oxygen species produced in biological systems by γ-irradiation

    NASA Astrophysics Data System (ADS)

    Lee, Min Hee; Moon, Yu Ran; Chung, Byung Yeoup; Kim, Jae-Sung; Lee, Kang-Soo; Cho, Jae-Young; Kim, Jin-Hong

    2009-05-01

    Application of chemical probes, for detection of reactive oxygen species (ROS), was tested during γ-irradiation. The ethanol/α-(4-pyridyl-1-oxide)- N- tert-butylnitrone (4-POBN) and 3,3'-diaminobenzidine (DAB) were structurally stable enough to detect rad OH and H 2O 2, increasingly generated by γ-irradiation up to 1000 Gy. Interestingly, the production rate of H 2O 2, but not rad OH, during γ-irradiation, was significantly different between in vitro systems of lettuce and spinach. These results suggest that 4-POBN and DAB could be utilized as a semi-quantitative probe to quantify rad OH and H 2O 2, produced by γ-irradiation up to 1000 Gy.

  7. Mesoporous magnetic activated carbon: Effect of preparation route on texture and surface properties and on effect for Reactive Black 5 adsorption.

    NASA Astrophysics Data System (ADS)

    Giannakoudakis, Dimitrios; Saroyan, Hayarpi; Lazaridis, Nikolaos; Deliyanni, Eleni

    2016-04-01

    Mesoporous magnetic activated carbon: Effect of preparation route on texture and surface properties and on effect for Reactive Black 5 adsorption. Dimitrios Giannakoudakis1, Hayarpi Saroyan2, Nikolaos Lazaridis2, Eleni Deliyanni2 1 City College of New York, Chemistry Department, 160 Convent Avenue, New York, United States 2 Laboratory of General and oInorganic Chemical Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24 Thessaloniki, Greece In this study, the effect of preparation route of a mesoporous magnetic activated carbon on Reactive Black 5 (RB5) adsorption was investigated. The synthesis of the magnetic activated carbon was achieved both with (i) impregnation method (Bmi), and (ii) co-precipitation with two precipitation agents: NaOH (Bm) and NH4OH (Bma). After synthesis, the full characterization with various techniques (SEM, FTIR, XRD, DTA, DTG, VSM) was achieved in order to testify the effect of the preparation route on its textural and surface properties. It was shown that after the precipitation method the prepared carbon presented a collapsed texture and small magnetic properties. Effects of initial solution pH, effect of temperature, adsorption isotherms and kinetics were investigated in order to conclude about the aforementioned effect of the preparation method on dye adsorption performance of the magnetic carbons. The adsorption evaluation of the magnetic activated carbon presented higher adsorption capacity of Bmi carbon (350 mg/g) and lower of Bm (150 mg/g). Equilibrium experiments are also performed studying the effect of contact time (pseudo-first and -second order equations) and temperature (isotherms at 25, 45 and 65 °C fitted to Langmuir and Freundlich model). A full thermodynamic evaluation was carried out, calculating the parameters of enthalpy, free energy and entropy (ΔHο, ΔGο and ΔSο). The characterization with various techniques revealed the possible interactions/forces of dye-composite system.

  8. Chemical characterization of diesel and hydrotreated vegetable oil (HVO) soot after reactive gas probing using diffuse reflectance FTIR spectroscopy (DRIFTS).

    PubMed

    Tapia, A; Salgado, M S; Martín, M P; Rodríguez-Fernández, J; Rossi, M J; Cabañas, B

    2017-01-23

    A chemical characterization of diesel and hydrotreated vegetable oil (HVO) soot has been developed using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) before and after the reaction with different probe gases. Samples were generated under combustion conditions corresponding to an urban operation mode of a diesel engine and were reacted with probe gas-phase molecules in a Knudsen flow reactor. Specifically, NH2OH, O3 and NO2 were used as reactants (probes) and selected according to their reactivities towards specific functional groups on the sample surface. Samples of previously ground soot were diluted with KBr and were introduced in a DRIFTS accessory. A comparison between unreacted and reacted soot samples was made in order to establish chemical changes on the soot surface upon reaction. It was concluded that the interface of diesel and HVO soot before reaction mainly consists polycyclic aromatic hydrocarbons, nitro and carbonyl compounds, as well as ether functionalities. The main difference between both soot samples was observed in the band of the C=O groups that in diesel soot was observed at 1719 cm(-1) but not in HVO soot. After reaction with probe gases, it was found that nitro compounds remain on the soot surface, that the degree of unsaturation decreases for reacted samples, and that new spectral bands such as hydroxyl groups are observed.

  9. Chemical Probes for Molecular Imaging and Detection of Hydrogen Sulfide and Reactive Sulfur Species in Biological Systems

    PubMed Central

    2014-01-01

    Hydrogen sulfide (H2S), a gaseous species produced by both bacteria and higher eukaryotic organisms, including mammalian vertebrates, has attracted attention in recent years for its contributions to human health and disease. H2S has been proposed as a cytoprotectant and gasotransmitter in many tissue types, including mediating vascular tone in blood vessels as well as neuromodulation in the brain. The molecular mechanisms dictating how H2S affects cellular signaling and other physiological events remain insufficiently understood. Furthermore, the involvement of H2S in metal-binding interactions and formation of related RSS such as sulfane sulfur may contribute to other distinct signaling pathways. Owing to its widespread biological roles and unique chemical properties, H2S is an appealing target for chemical biology approaches to elucidate its production, trafficking, and downstream function. In this context, reaction-based fluorescent probes offer a versatile set of screening tools to visualize H2S pools in living systems. Three main strategies used in molecular probe development for H2S detection include azide and nitro group reduction, nucleophilic attack, and CuS precipitation. Each of these approaches exploit the strong nucleophilicity and reducing potency of H2S to achieve selectivity over other biothiols. In addition, a variety of methods have been developed for the detection of other reactive sulfur species (RSS), including sulfite and bisulfite, as well as sulfane sulfur species and related modifications such as S-nitrosothiols. Access to this growing chemical toolbox of new molecular probes for H2S and related RSS sets the stage for applying these developing technologies to probe reactive sulfur biology in living systems. PMID:25474627

  10. Probing molecular adsorption and mechanics at the atomic scale: The Nanocar family of molecules

    NASA Astrophysics Data System (ADS)

    Osgood, Andrew J.

    Molecular machines, typically thought to be only the fanciful imaginings of speculative fiction, have taken great strides in recent years towards real-world viability and usefulness. Under variable temperature scanning tunneling microscopy, (STM) one family of these nascent devices is characterized with atomic resolution, and probed and manipulated with sub-angstrom precision, adding to the growing body of knowledge of how molecular devices behave and react at nanometer scales. Evidence of temperature-dependent rolling of wheel-like fullerene constituents on the Nanocar is discussed in light of newly developed image analysis techniques. Additionally, charge-transfer mediated behavior at step edges, both static and dynamic, is investigated on a Au(111) surface for a more complete understanding of translation and surface diffusion. Molecular flexibility is thought to aid in this three-dimensional atomic-step-crossing diffusion, and is explored and discussed across many species in the Nanocar family of molecules. In all, many similar molecules have been characterized and explored via STM with an eye towards their dynamic capabilities and surface behaviors, in the hopes that future, more complex versions can build on the nascent knowledge base beginning to be established here.

  11. Probing reactivity of PQQ-dependent carbohydrate dehydrogenases using artificial electron acceptor.

    PubMed

    Tetianec, Lidija; Bratkovskaja, Irina; Kulys, Juozas; Casaite, Vida; Meskys, Rolandas

    2011-02-01

    The kinetic parameters of carbohydrate oxidation catalyzed by Acinetobacter calcoaceticus pyrroloquinoline quinone (PQQ)-dependent glucose dehydrogenase (GDH) and Escherichia coli PQQ-dependent aldose sugar dehydrogenase (ASDH) were determined using various electron acceptors. The radical cations of organic compounds and 2,6-dichlorophenolindophenol are the most reactive with both enzymes in presence of glucose. The reactivity of dioxygen with ASDH is low; the bimolecular constant k (ox) = 660 M(-1) s(-1), while GDH reactivity with dioxygen is even less. The radical cation of 3-(10H-phenoxazin-10-yl)propionic acid was used as electron acceptor for reduced enzyme in the study of dehydrogenases carbohydrates specificity. Mono- and disaccharide reactivity with GDH is higher than the reactivity of oligosaccharides. For ASDH, the reactivity increased with the carbohydrate monomer number increase. The specificity of quinoproteins was compared with specificity of flavoprotein Microdochium nivale carbohydrate oxidase due to potential enzymes application for lactose oxidation.

  12. ZnS:Cu nanoparticles loaded on activated carbon as novel adsorbent for kinetic, thermodynamic and isotherm studies of Reactive Orange 12 and Direct yellow 12 adsorption.

    PubMed

    Ghaedi, Mehrorang; Ansari, Amin; Sahraei, Reza

    2013-10-01

    The objective of this work is the study of adsorption of Reactive Orange 12 (RO-12) and Direct yellow 12 (DY 12) by zinc sulfide:copper (ZnS-Cu-NP-AC) nanoparticles loaded on activated carbon. This new material with high efficiency in a routine manner was synthesized in our laboratory and its surface properties viz surface area, pore volume and functional groups was characterized with different techniques such FT-IR, SEM, and BET analysis. Generally, in batch adsorption procedure variables including amount of adsorbent, initial dyes concentration, contact time, temperature on dyes removal percentage has great effect on removal percentage that their influence was optimized. The kinetic of proposed adsorption processes efficiently followed, pseudo-second-order, and intra-particle diffusion kinetic models. The equilibrium data the removal strongly follow Langmuir monolayer adsorption with high adsorption capacity in short time. This novel adsorbent by small amount (0.08 g) really is applicable for removal of high amount of both dyes (RO 12 and DY 12) in short time (<20 min). Based on the calculated thermodynamic parameters such as enthalpy (ΔH), entropy (ΔS), activation energy (Ea), sticking probability (S*) and Gibb's free energy changes (ΔG), it is noticeable that the sorption of both dyes onto ZnS:Cu-AC was spontaneous and endothermic process. At optimum values all variables the effect of contact time on adsorption was investigated and the dependency of adsorption data to different kinetic model such as pseudo-first-order, pseudo-second-order, Elovich and intra-particle diffusion was assessed and it was found that the removal processes follow pseudo second order kinetics and interparticle diffusion mechanism.

  13. Non-hydrolyzable Diubiquitin Probes Reveal Linkage-Specific Reactivity of Deubiquitylating Enzymes Mediated by S2 Pockets

    PubMed Central

    Flierman, Dennis; van der Heden van Noort, Gerbrand J.; Ekkebus, Reggy; Geurink, Paul P.; Mevissen, Tycho E.T.; Hospenthal, Manuela K.; Komander, David; Ovaa, Huib

    2016-01-01

    Summary Ubiquitin chains are important post-translational modifications that control a large number of cellular processes. Chains can be formed via different linkages, which determines the type of signal they convey. Deubiquitylating enzymes (DUBs) regulate ubiquitylation status by trimming or removing chains from attached proteins. DUBs can contain several ubiquitin-binding pockets, which confer specificity toward differently linked chains. Most tools for monitoring DUB specificity target binding pockets on opposing sides of the active site; however, some DUBs contain additional pockets. Therefore, reagents targeting additional pockets are essential to fully understand linkage specificity. We report the development of active site-directed probes and fluorogenic substrates, based on non-hydrolyzable diubiquitin, that are equipped with a C-terminal warhead or a fluorogenic activity reporter moiety. We demonstrate that various DUBs in lysates display differential reactivity toward differently linked diubiquitin probes, as exemplified by the proteasome-associated DUB USP14. In addition, OTUD2 and OTUD3 show remarkable linkage-specific reactivity with our diubiquitin-based reagents. PMID:27066941

  14. 15N solid-state NMR provides a sensitive probe of oxidized flavin reactive sites.

    PubMed

    Koder, Ronald L; Walsh, Joseph D; Pometun, Maxim S; Dutton, P Leslie; Wittebort, Richard J; Miller, Anne-Frances

    2006-11-29

    Flavins are central to the reactivity of a wide variety of enzymes and electron transport proteins. There is great interest in understanding the basis for the different reactivities displayed by flavins in different protein contexts. We propose solid-state nuclear magnetic resonance (SS-NMR) as a tool for directly observing reactive positions of the flavin ring and thereby obtaining information on their frontier orbitals. We now report the SS-NMR signals of the redox-active nitrogens N1 and N5, as well as that of N3. The chemical shift tensor of N5 is over 720 ppm wide, in accordance with the predictions of theory and our calculations. The signal of N3 can be distinguished on the basis of coupling to 1H absent for N1 and N5, as well as the shift tensor span of only 170 ppm, consistent with N3's lower aromaticity and lack of a nonbonding lone pair. The isotropic shifts and spans of N5 and N1 reflect two opposite extremes of the chemical shift range for "pyridine-type" N's, consistent with their electrophilic and nucleophilic chemical reactivities, respectively. Upon flavin reduction, N5's chemical shift tensor contracts dramatically to a span of less than 110 ppm, and the isotropic chemical shift changes by approximately 300 ppm. Both are consistent with loss of N5's nonbonding lone pair and decreased aromaticity, and illustrate the responsiveness of the 15N chemical shift principal values to electronic structure. Thus. 15N chemical shift principal values promise to be valuable tools for understanding electronic differences that underlie variations in flavin reactivity, as well as the reactivities of other heterocyclic cofactors.

  15. Adaptive Neuro-Fuzzy Inference system analysis on adsorption studies of Reactive Red 198 from aqueous solution by SBA-15/CTAB composite

    NASA Astrophysics Data System (ADS)

    Aghajani, Khadijeh; Tayebi, Habib-Allah

    2017-01-01

    In this study, the Mesoporous material SBA-15 were synthesized and then, the surface was modified by the surfactant Cetyltrimethylammoniumbromide (CTAB). Finally, the obtained adsorbent was used in order to remove Reactive Red 198 (RR 198) from aqueous solution. Transmission electron microscope (TEM), Fourier transform infra-red spectroscopy (FTIR), Thermogravimetric analysis (TGA), X-ray diffraction (XRD), and BET were utilized for the purpose of examining the structural characteristics of obtained adsorbent. Parameters affecting the removal of RR 198 such as pH, the amount of adsorbent, and contact time were investigated at various temperatures and were also optimized. The obtained optimized condition is as follows: pH = 2, time = 60 min and adsorbent dose = 1 g/l. Moreover, a predictive model based on ANFIS for predicting the adsorption amount according to the input variables is presented. The presented model can be used for predicting the adsorption rate based on the input variables include temperature, pH, time, dosage, concentration. The error between actual and approximated output confirm the high accuracy of the proposed model in the prediction process. This fact results in cost reduction because prediction can be done without resorting to costly experimental efforts. SBA-15, CTAB, Reactive Red 198, adsorption study, Adaptive Neuro-Fuzzy Inference systems (ANFIS).

  16. Physicochemical modeling of reactive violet 5 dye adsorption on home-made cocoa shell and commercial activated carbons using the statistical physics theory

    NASA Astrophysics Data System (ADS)

    Sellaoui, Lotfi; Lima, Éder Cláudio; Dotto, Guilherme Luiz; Dias, Silvio L. P.; Ben Lamine, Abdelmottaleb

    Two equilibrium models based on statistical physics, i.e., monolayer model with single energy and multilayer model with saturation, were developed and employed to access the steric and energetic aspects in the adsorption of reactive violet 5 dye (RV-5) on cocoa shell activated carbon (AC) and commercial activated carbon (CAC), at different temperatures (from 298 to 323 K). The results showed that the multilayer model with saturation was able to represent the adsorption system. This model assumes that the adsorption occurs by a formation of certain number of layers. The n values ranged from 1.10 to 2.98, indicating that the adsorbate molecules interacted in an inclined position on the adsorbent surface and aggregate in solution. The study of the total number of the formed layers (1 + L2) showed that the steric hindrance is the dominant factor. The description of the adsorbate-adsorbent interactions by calculation of the adsorption energy indicated that the process occurred by physisorption in nature, since the values were lower than 40 kJ mol-1.

  17. Understanding the site selectivity in small-sized neutral and charged Al(n) (4 ≤ N ≤ 7) clusters using density functional theory based reactivity descriptors: a validation study on water molecule adsorption.

    PubMed

    Das, Susanta; Pal, Sourav; Krishnamurty, Sailaja

    2013-09-12

    Aluminum clusters are now technologically important due to their high catalytic activity. Our present study on the small-sized aluminum clusters applies density functional theory (DFT)-based reactivity descriptors to identify potential sites for adsorption and eventual chemical reaction. Depending on symmetry, susceptibility of various type of reactive sites within a cluster toward an impending electrophilic and/or nucleophilic attack is predicted using the reactivity descriptors. In addition, the study devises general rules as to how the size, shape, and charge of the cluster influences the number of available sites for an electrophilic and/or nucleophilic attack. The predictions by reactivity descriptors are validated by performing an explicit adsorption of water molecule on Al clusters with four atoms. The adsorption studies demonstrate that the most stable water-cluster complex is obtained when the molecule is adsorbed through an oxygen atom on the site with the highest relative electrophilicity.

  18. Adsorption study of anionic reactive dye from aqueous solution to Mg-Fe-CO3 layered double hydroxide (LDH)

    NASA Astrophysics Data System (ADS)

    Ahmed, I. M.; Gasser, M. S.

    2012-10-01

    Mg-Fe-Cl Layered double hydroxides (LDHs) have been prepared using a method involving separate nucleation and aging steps with Mg/Fe = 3. The interlayer anions readily replaced by carbonate are characterized by X-ray diffraction (XRD) and FTIR. The effects of different parameters, such as pH, contact time, concentration of dye and temperature on the capacity and adsorption mechanism of Mg-Fe-CO3-LDH in removing an anionic dye (congo red, CR) from aqueous solution were separately investigated. The results show that Mg-Fe-CO3-LDH is particularly efficient in removing CR and the dye removal increases with decreasing pH. The adsorption of CR on Mg-Fe-CO3-LDH reached equilibrium after 15 min where 100 mg/L CR was removed. The equilibrium isotherm indicates that the adsorption of CR onto Mg-Fe-CO3-LDH fits to Langmuir and Freundlich equation as well. The adsorption data obtained from the Langmuir model gave good values of the determination coefficient and the saturated adsorption capacity of Mg-Fe-CO3-LDH for CR was found to be 104.6 mg/g. The regeneration study indicates that the prepared LDH could be used for several cycles. The thermodynamic parameters have been calculated, and the adsorption process was found to be spontaneous, endothermic in nature and follows a pseudo-second-order kinetic model.

  19. Using iron-loaded sepiolite obtained by adsorption as a catalyst in the electro-Fenton oxidation of Reactive Black 5.

    PubMed

    Iglesias, O; Fernández de Dios, M A; Pazos, M; Sanromán, M A

    2013-09-01

    This study explores the possibility of using iron-loaded sepiolite, obtained by recovering iron from polluted water, as a catalyst in the electro-Fenton oxidation of organic pollutants in textile effluents. The removal of iron ions from aqueous solution by adsorption on sepiolite was studied in batch tests at iron concentrations between 100 and 1,000 ppm. Electro-Fenton experiments were carried out in an electrochemical cell with a working volume of 0.15 L, an air flow of 1 L/min, and 3 g of iron-loaded sepiolite. An electric field was applied using a boron-doped diamond anode and a graphite sheet cathode connected to a direct current power supply with a constant potential drop. Reactive Black 5 (100 mg/L) was selected as the model dye. The adsorption isotherms proved the ability of the used adsorbent. The removal of the iron ion by adsorption on sepiolite was in the range of 80-100 % for the studied concentration range. The Langmuir and Freundlich isotherms were found to be applicable in terms of the relatively high regression values. Iron-loaded sepiolite could be used as an effective heterogeneous catalyst for the degradation of organic dyes in the electro-Fenton process. Successive batch processes were performed at optimal working conditions (5 V and pH 2). The results indicate the suitability of the proposed combined process, adsorption to iron remediation followed by the application of the obtained iron-loaded sepiolite to the electro-Fenton technique, to oxidize polluted effluents.

  20. Zinc (hydr)oxide/graphite oxide/AuNPs composites: role of surface features in H₂S reactive adsorption.

    PubMed

    Giannakoudakis, Dimitrios A; Bandosz, Teresa J

    2014-12-15

    Zinc hydroxide/graphite oxide/AuNPs composites with various levels of complexity were synthesized using an in situ precipitation method. Then they were used as H2S adsorbents in visible light. The materials' surfaces were characterized before and after H2S adsorption by various physical and chemical methods (XRD, FTIR, thermal analysis, potentiometric titration, adsorption of nitrogen and SEM/EDX). Significant differences in surface features and synergistic effects were found depending on the materials' composition. Addition of graphite oxide and the deposition of gold nanoparticles resulted in a marked increase in the adsorption capacity in comparison with that on the zinc hydroxide and zinc hydroxide/AuNP. Addition of AuNPs to zinc hydroxide led to a crystalline ZnO/AuNP composite while the zinc hydroxide/graphite oxide/AuNP composite was amorphous. The ZnOH/GO/AuNPs composite exhibited the greatest H2S adsorption capacity due to the increased number of OH terminal groups and the conductive properties of GO that facilitated the electron transfer and consequently the formation of superoxide ions promoting oxidation of hydrogen sulfide. AuNPs present in the composite increased the conductivity, helped with electron transfer to oxygen, and prevented the fast recombination of the electrons and holes.

  1. Adsorption And Simultaneous Dechlorination Of PCBs On GAC/Fe/Pd: Mechanistic Aspects And Reactive Capping Barrier Concept

    EPA Science Inventory

    There are many concerns and challenges in current remediation strategies for sediments contaminated with polychlorinated biphenyls (PCBs). Our efforts have been geared toward the development of granular activated carbon (GAC) impregnated with reactive iron/palladium (Fe/Pd) bime...

  2. Adsorption equilibrium and transport kinetics for a range of probe gases in Takeda 3A carbon molecular sieve.

    PubMed

    Rutherford, S W; Coons, J E

    2005-04-15

    Measurements of adsorption equilibria and transport kinetics for argon, oxygen and nitrogen at 20, 50, and 80 degrees C on commercially derived Takeda carbon molecular sieve (CMS) employed for air separation have been undertaken in an effort to elucidate fundamental mechanisms of transport. Results indicate that micropore diffusion which is modeled by a Fickian diffusion process, governs the transport of oxygen molecules and the pore mouth barrier controls argon and nitrogen transport which is characterized by a linear driving force (LDF) model. For the three temperatures studied, the pressure dependence of the diffusivity and the LDF rate constant appear to be well characterized by a formulation based on the chemical potential as the driving force for transport. Isosteric heat of adsorption at zero loading and activation energy measurements are compared with predictions made from a previously proposed molecular model for characterizing CMS.

  3. Theoretical Investigation of Hydrogen Adsorption and Dissociation on Iron and Iron Carbide Surfaces Using the ReaxFF Reactive Force Field Method

    SciTech Connect

    Zou, Chenyu; van Duin, Adri C.T.; Sorescu, Dan C.

    2012-06-01

    We have developed a ReaxFF reactive force field to describe hydrogen adsorption and dissociation on iron and iron carbide surfaces relevant for simulation of Fischer–Tropsch (FT) synthesis on iron catalysts. This force field enables large system (>>1000 atoms) simulations of hydrogen related reactions with iron. The ReaxFF force field parameters are trained against a substantial amount of structural and energetic data including the equations of state and heats of formation of iron and iron carbide related materials, as well as hydrogen interaction with iron surfaces and different phases of bulk iron. We have validated the accuracy and applicability of ReaxFF force field by carrying out molecular dynamics simulations of hydrogen adsorption, dissociation and recombination on iron and iron carbide surfaces. The barriers and reaction energies for molecular dissociation on these two types of surfaces have been compared and the effect of subsurface carbon on hydrogen interaction with iron surface is evaluated. We found that existence of carbon atoms at subsurface iron sites tends to increase the hydrogen dissociation energy barrier on the surface, and also makes the corresponding hydrogen dissociative state relatively more stable compared to that on bare iron. These properties of iron carbide will affect the dissociation rate of H{sub 2} and will retain more surface hydride species, thus influencing the dynamics of the FT synthesis process.

  4. Chemical reactive features of novel amino acids intercalated layered double hydroxides in As(III) and As(V) adsorption.

    PubMed

    Shen, Liang; Jiang, Xiuli; Chen, Zheng; Fu, Dun; Li, Qingbiao; Ouyang, Tong; Wang, Yuanpeng

    2017-06-01

    Layered double hydroxides (LDHs) intercalated with amino acids such as methionine (Met) were synthesized as new adsorbents to remediate arsenic-polluted water. This Zn2Al-Met-LDHs, identified with the formula of Zn0.7Al0.3(OH)2(Met)0.3·0.32H2O, has good thermal stability. Adsorption experiments with Zn2Al-Met-LDHs showed that the residual arsenic in solution could be reduced below the regulation limit, and this adsorption process fitted Langmuir isotherm and the pseudo-second-order kinetics well. A remarkably high removal efficiency and the maximum adsorption capacity for As(III) were achieved, 96.7% and 94.1 mg/g, respectively, at 298 K. The desorption efficiency of As(III) from the arsenic-saturated Zn2Al-Met-LDHs (<8.7%), far less than that of As(V), promises a specific and reliable uptake of As(III) in sorts of solutions. More importantly, a complete and in-depth spectra analysis through FTIR, XPS and NMR was conducted to explain the excellent performance of Zn2Al-Met-LDHs in arsenic removal. Herein, two special chemical reactions were proposed as the dominant mechanisms, i.e., hydrogen bonding between the carboxyl group of the host Met and the hydroxyl group of As(III) or As(V), and the formation of a chelate ring between the guest As(III) and the S, N bidentate ligands of the intercalated Met in the LDHs.

  5. Novel Lipophilic Probe for Detecting Near-Membrane Reactive Oxygen Species Responses and Its Application for Studies of Pancreatic Acinar Cells: Effects of Pyocyanin and L-Ornithine

    PubMed Central

    Chvanov, Michael; Huang, Wei; Jin, Tao; Wen, Li; Armstrong, Jane; Elliot, Vicky; Alston, Ben; Burdyga, Alex; Criddle, David N.; Sutton, Robert

    2015-01-01

    Abstract Aims: The aim of this study was to develop a fluorescent reactive oxygen species (ROS) probe, which is preferentially localized in cellular membranes and displays a strong change in fluorescence upon oxidation. We also aimed to test the performance of this probe for detecting pathophysiologically relevant ROS responses in isolated cells. Results: We introduced a novel lipophilic ROS probe dihydrorhodamine B octadecyl ester (H2RB-C18). We then applied the new probe to characterize the ROS changes triggered by inducers of acute pancreatitis in pancreatic acinar cells. We resolved ROS changes produced by L-ornithine, L-arginine, cholecystokinin-8, acetylcholine, taurolithocholic acid 3-sulfate, palmitoleic acid ethyl ester, and the bacterial toxin pyocyanin. Particularly prominent ROS responses were induced by pyocyanin and L-ornithine. These ROS responses were accompanied by changes in cytosolic Ca2+concentration ([Ca2+]i), mitochondrial membrane potential (ΔΨ), and NAD(P)H concentration. Innovation: The study describes a novel sensitive lipophilic ROS probe. The probe is particularly suitable for detecting ROS in near-membrane regions and therefore for reporting the ROS environment of plasma membrane channels and pumps. Conclusions: In our experimental conditions, the novel probe was more sensitive than 5-(and-6)-chloromethyl-2′,7′-dichlorodihydrofluorescein (CM-H2DCF) and dihydrorhodamine123 (H2R123) and allowed us to resolve ROS responses to secretagogues, pyocyanin, and L-ornithine. Changes in the fluorescence of the new probe were particularly prominent in the peripheral plasma membrane-associated regions. Our findings suggest that the new probe will be a useful tool in studies of the contribution of ROS to the pathophysiology of exocrine pancreas and other organs/tissues. Antioxid. Redox Signal. 22, 451–464. PMID:24635199

  6. Inverse Reactive Transport Simulator (Inverts): An Inverse Model for Contaminant Transport with Nonlinear Adsorption and Source Terms

    SciTech Connect

    McGrail, B. Peter

    2001-10-31

    A numerically based simulator was developed to assist in the interpretation of complex laboratory experiments examining transport processes of chemical and biological contaminants subject to nonlinear adsorption and/or source terms. The inversion is performed with any of three nonlinear regression methods, Marquardt-Levenberg, conjugate gradient, or quasi-Newton. The governing equations for the problem are solved by the method of finite-differences including any combination of three boundary conditions: (1) Dirichlet, (2) Neumann, and (3) Cauchy. The dispersive terms in the transport equations were solved using the second-order accurate in time and space Crank-Nicolson scheme, while the advective terms were handled using a third-order in time and space, total variation diminishing (TVD) scheme that damps spurious oscillations around sharp concentration fronts. The numerical algorithms were implemented in the computer code INVERTS, which runs on any standard personal computer. Apart from a comprehensive set of test problems, INVERTS was also used to model the elution of a nonradioactive tracer, {sup 185}Re, in a pressurized unsaturated flow (PUF) experiment with a simulated waste glass for low-activity waste immobilization. Interpretation of the elution profile was best described with a nonlinear kinetic model for adsorption.

  7. Quantum-mechanical parameters for the risk assessment of multi-walled carbon-nanotubes: A study using adsorption of probe compounds and its application to biomolecules.

    PubMed

    Chayawan; Vikas

    2016-11-01

    This work forwards new insights into the risk-assessment of multi-walled carbon-nanotubes (MWCNTs) while analysing the role of quantum-mechanical interactions between the electrons in the adsorption of probe compounds and biomolecules by MWCNTs. For this, the quantitative models are developed using quantum-chemical descriptors and their electron-correlation contribution. The major quantum-chemical factors contributing to the adsorption are found to be mean polarizability, electron-correlation energy, and electron-correlation contribution to the absolute electronegativity and LUMO energy. The proposed models, based on only three quantum-chemical factors, are found to be even more robust and predictive than the previously known five or four factors based linear free-energy and solvation-energy relationships. The proposed models are employed to predict the adsorption of biomolecules including steroid hormones and DNA bases. The steroid hormones are predicted to be strongly adsorbed by the MWCNTs, with the order: hydrocortisone > aldosterone > progesterone > ethinyl-oestradiol > testosterone > oestradiol, whereas the DNA bases are found to be relatively less adsorbed but follow the order as: guanine > adenine > thymine > cytosine > uracil. Besides these, the developed electron-correlation based models predict several insecticides, pesticides, herbicides, fungicides, plasticizers and antimicrobial agents in cosmetics, to be strongly adsorbed by the carbon-nanotubes. The present study proposes that the instantaneous inter-electronic interactions may be quite significant in various physico-chemical processes involving MWCNTs, and can be used as a reliable predictor for their risk assessment.

  8. Probing Defect Sites on CeO2 Nanocrystals with Well-Defined Surface Planes by Raman Spectroscopy and O2 Adsorption

    SciTech Connect

    Wu, Zili; Li, Meijun; Howe, Jane Y; Meyer III, Harry M; Overbury, Steven {Steve} H

    2010-01-01

    Defect sites play an essential role in ceria catalysis. In this study, ceria nanocrystals with well defined surface planes have been synthesized and utilized for studying defect sites with both Raman spectroscopy and O2 adsorption. Ceria nanorods ({110} + {100}), nanocubes ({100}), and nano-octahedrons ({111}) are employed to analyze the quantity and quality of defect sites on different ceria surfaces. On oxidized surface, nanorods have the most abundant intrinsic defect sites, followed by nanocubes and nano-octahedrons. When reduced, the induced defect sites are more clustered on nanorods than on nanocubes although similar amount (based on surface area) of such defect sites are produced on the two surfaces. Very few defect sites can be generated on the nano-octahedrons due to the least reducibility. These differences can be rationalized by the crystallographic surface terminations of the ceria nanocrystals. The different defect sites on these nanocrystals lead to the adsorption of different surface dioxygen species. Superoxide on one-electron defect sites and peroxide on two-electron defect sites with different clustering degree are identified on the ceria nanocrystals depending on their morphology. Furthermore, the stability and reactivity of these oxygen species are also found to be surface-dependent, which is of significance for ceria-catalyzed oxidation reactions.

  9. Cation location in microporous zeolite, SSZ-13, probed with xenon adsorption measurement and 129Xe NMR spectrum.

    PubMed

    Shin, Na Ra; Kim, Su Hyun; Shin, Hye Sun; Jang, Ik Jun; Cho, Sung June

    2013-06-01

    The location of metal ion, Ag2+, Ca2+, Cu2+ and Y3+ in the SSZ-13 has been investigated with xenon adsorption measurement and 129Xe NMR spectrum. It was referred that the location of the metal ion varies depending on the corresponding charge. The ion-exchanged Ag ion was located in the alpha-cage to interact directly with xenon. Others multivalent cation contributed little with xenon because these were present near the six membered rings where xenon cannot access.

  10. Probing the adsorption mechanism in thiamazole bound to the silver surface with Surface-enhanced Raman Scattering and DFT

    NASA Astrophysics Data System (ADS)

    Biswas, Nandita; Thomas, Susy; Sarkar, Anjana; Mukherjee, Tulsi; Kapoor, Sudhir

    2009-09-01

    Surface-enhanced Raman scattering (SERS) of thiamazole have been investigated in aqueous solution. Thiamazole is an important anti-thyroid drug that is used in the treatment of hyperthyroidism (over activity of the thyroid gland). Due to its medicinal importance, the surface adsorption properties of thiamazole have been studied. The experimental Raman and SERS data are supported with DFT calculations using B3LYP functional with LANL2DZ basis set. From the SERS spectra as well as theoretical calculations, it has been inferred that thiamazole is chemisorbed to the silver surface directly through the sulphur atom and the ring N atom, with a tilted orientation.

  11. Comparative Study on Synergetic Degradation of a Reactive Dye Using Different Types of Fly Ash in Combined Adsorption and Photocatalysis

    NASA Astrophysics Data System (ADS)

    Giri Babu, P. V. S.; Swaminathan, G.

    2016-09-01

    A comprehensive study was carried out on four different fly ashes used as a catalyst for the degradation of Acid Red 1 using ultraviolet rays. These fly ashes are collected from different thermal power stations located at various places in India and having different chemical compositions. Three fly ashes are from lignite-based thermal power plants, and one is from the coal-based power plant. One fly ash is classified as Class F, two fly ashes are classified as Class C and remaining one is not conforming to ASTM C618 classification. X-Ray Fluorescence analysis was used to identify the chemical composition of fly ashes and SiO2, Al2O3, CaO, Fe2O3 and TiO2 were found to be the major elements present in different proportions. Various analysis were carried out on all the fly ashes like Scanning Electron Microscopy to identify the microphysical properties, Energy Dispersive X-Ray spectroscopy to quantify the elements present in the catalyst and X-Ray Diffraction to identify the catalyst phase analysis. The radical generated during the reaction was identified by Electron paramagnetic resonance spectroscopy. The parameters such as initial pH of the dye solution, catalyst dosage and initial dye concentration which influence the dye degradation efficiency were studied and optimised. In 60 min duration, the dye degradation efficiency at optimum parametric values of pH 2.5, initial dye concentration of 10 mg/L and catalyst dosage of 1.0 g/L using various fly ashes, i.e., Salam Power Plant, Barmer Lignite Power Plant, Kutch Lignite Power Plant and Neyveli Lignite Thermal Power plant (NLTP) were found to be 40, 60, 67 and 95 % respectively. The contribution of adsorption alone was 18 % at the above mentioned optimum parametric values. Among the above four fly ash NLTP fly ashes proved to be most efficient.

  12. CdS/TiO2-fluorescein isothiocyanate nanoparticles as fluorescence resonance energy transfer probe for the determination of trace alkaline phosphatase based on affinity adsorption assay.

    PubMed

    Liu, Jia-Ming; Lin, Li-ping; Jiao, Li; Cui, Ma-Lin; Wang, Xin-Xing; Zhang, Li-Hong; Zheng, Zhi-Yong

    2012-08-30

    The CdS/TiO(2)-fluorescein isothiocyanate (FITC) luminescent nanoparticles (CdS/TiO(2)-FITC) with the particle size of 20 nm have been synthesized by sol-gel method. CdS/TiO(2)-FITC could emit the fluorescence of both FITC and CdS/TiO(2). The fluorescence resonance energy transfer (FRET) occurred between the donor CdS/TiO(2) and the acceptor FITC in the CdS/TiO(2)-FITC. Taking advantages of the excellent characteristics of FRET, a new CdS/TiO(2)-FITC FRET labeling reagent and a CdS/TiO(2)-FITC-wheat germ agglutinin (CdS/TiO(2)-FITC-WGA) fluorescent probe have been developed. The FRET occurring between the donor CdS/TiO(2) and the acceptor FITC in the labelled product CdS/TiO(2)-FITC-WGA-AP, formed in the affinity adsorption reaction between the WGA in this CdS/TiO(2)-FITC-WGA fluorescent probe and alkaline phosphatase (AP), sharply enhanced the fluorescence signal of FITC and quench the fluorescence signal of CdS/TiO(2). Moreover, the ΔF (the change of the fluorescence signal) of FITC and CdS/TiO(2) were proportional to the content of AP, respectively. Thus, a new method that CdS/TiO(2)-fluorescein isothiocyanate nanoparticles for the determination of trace AP based on FRET-affinity adsorption assay has been established. The limit of quantification (LOQ) of the method was 1.3×10(-17) g AP mL(-1) for CdS/TiO(2) and 1.1×10(-17) g AP mL(-1) for FITC, respectively. This sensitive, rapid, high selective and precise method has been applied to the determination of AP in human serum and the prediction of human disease with the results agreed well with enzyme-linked immunosorbent assay (ELISA) in Zhangzhou Municipal Hospital of Fujian Province. Simultaneously, the reaction mechanism for the determination of AP was also discussed.

  13. PREDICTING CHEMICAL REACTIVITY OF HUMIC SUBSTANCES FOR MINERALS AND XENOBIOTICS: USE OF COMPUTATIONAL CHEMISTRY, SCANNING PROBE MICROSCOPY AND VIRTUAL REALITY

    EPA Science Inventory

    In this chapter we review the literature on scanning probe microscopy (SPM), virtual reality (VR), and computational chemistry and our earlier work dealing with modeling lignin, lignin-carbohydrate complexes (LCC), humic substances (HSs) and non-bonded organo-mineral interactions...

  14. Azobenzene-caged sulforhodamine dyes: a novel class of ‘turn-on’ reactive probes for hypoxic tumor cell imaging

    NASA Astrophysics Data System (ADS)

    Chevalier, Arnaud; Piao, Wen; Hanaoka, Kenjiro; Nagano, Tetsuo; Renard, Pierre-Yves; Romieu, Anthony

    2015-12-01

    New sulforhodamine-based fluorescent ‘turn-on’ probes have been developed for the direct imaging of cellular hypoxia. Rapid access to this novel class of water-soluble ‘azobenzene-caged’ fluorophores was made possible through an easily-implementable azo-coupling reaction between a fluorescent primary arylamine derived from a sulforhodamine 101 scaffold (named SR101-NaphtNH 2 ) and a tertiary aniline whose N-substituents are neutral, cationic, or zwitterionic. The detection mechanism is based on the bioreductive cleavage of the azo bond that restores strong far-red fluorescence (emission maximum at 625 nm) by regenerating the original sulforhodamine SR101-NaphtNH 2 . This valuable fluorogenic response was obtained for the three ‘smart’ probes studied in this work, as shown by an in vitro assay using rat liver microsomes placed under aerobic and then under hypoxic conditions. Most importantly, the probe namely SR101-NaphtNH 2 -Hyp-diMe was successfully applied for imaging the hypoxic status of tumor cells (A549 cells).

  15. Surface sites on Pt-CeO2 mixed oxide catalysts probed by CO adsorption: a synchrotron radiation photoelectron spectroscopy study.

    PubMed

    Neitzel, Armin; Lykhach, Yaroslava; Skála, Tomáš; Tsud, Nataliya; Vorokhta, Mykhailo; Mazur, Daniel; Prince, Kevin C; Matolín, Vladimír; Libuda, Jörg

    2014-12-07

    By means of synchrotron radiation photoemission spectroscopy, we have investigated Pt-CeO2 mixed oxide films prepared on CeO2(111)/Cu(111). Using CO molecules as a probe, we associate the corresponding surface species with specific surface sites. This allows us to identify the changes in the composition and morphology of Pt-CeO2 mixed oxide films caused by annealing in an ultrahigh vacuum. Specifically, two peaks in C 1s spectra at 289.4 and 291.2 eV, associated with tridentate and bidentate carbonate species, are formed on the nanostructured stoichiometric CeO2 film. The peak at 290.5-291.0 eV in the C 1s spectra indicates the onset of restructuring, i.e. coarsening, of the Pt-CeO2 film. This peak is associated with a carbonate species formed near an oxygen vacancy. The onset of cerium oxide reduction is indicated by the peak at 287.8-288.0 eV associated with carbonite species formed near Ce(3+) cations. The development of surface species on the Pt-CeO2 mixed oxides suggests that restructuring of the films occurs above 300 K irrespective of Pt loadings. We do not find any adsorbed CO species associated with Pt(4+) or Pt(2+). The onset of Pt(2+) reduction is indicated by the peak at 286.9 eV in the C 1s spectra due to CO adsorption on metallic Pt particles. The thermal stability of Pt(2+) in Pt-CeO2 mixed oxide depends on Pt loading. We find excellent stability of Pt(2+) for 12% Pt content in the CeO2 film, whereas at a Pt concentration of 25% in the CeO2 film, a large fraction of the Pt(2+) is converted into metallic Pt particles above 300 K.

  16. Adsorption with biodegradation for decolorization of reactive black 5 by Funalia trogii 200800 on a fly ash-chitosan medium in a fluidized bed bioreactor-kinetic model and reactor performance.

    PubMed

    Lin, Yen-Hui; Lin, Wen-Fan; Jhang, Kai-Ning; Lin, Pei-Yu; Lee, Mong-Chuan

    2013-02-01

    A non-steady-state mathematical model system for the kinetics of adsorption and biodegradation of reactive black 5 (RB5) by Funalia trogii (F. trogii) ATCC 200800 biofilm on fly ash-chitosan bead in the fluidized bed process was derived. The mechanisms in the model system included adsorption by fly ash-chitosan beads, biodegradation by F. trogii cells and mass transport diffusion. Batch kinetic tests were independently performed to determine surface diffusivity of RB5, adsorption parameters for RB5 and biokinetic parameters of F. trogii ATCC 200800. A column test was conducted using a continuous-flow fluidized bed reactor with a recycling pump to approximate a completely-mixed flow reactor for model verification. The experimental results indicated that F. trogii biofilm bioregenerated the fly ash-chitosan beads after attached F. trogii has grown significantly. The removal efficiency of RB5 was about 95 % when RB5 concentration in the effluent was approximately 0.34 mg/L at a steady-state condition. The concentration of suspended F. trogii cells reached up to about 1.74 mg/L while the thickness of attached F. trogii cells was estimated to be 80 μm at a steady-state condition by model prediction. The comparisons of experimental data and model prediction show that the model system for adsorption and biodegradation of RB5 can predict the experimental results well. The approaches of experiments and mathematical modeling in this study can be applied to design a full-scale fluidized bed process to treat reactive dye in textile wastewater.

  17. Different Adsorption Behavior of Rare Earth and Metallic Ion Complexes on Langmuir Mono layers Probed by Sum-Frequency Generation Spectroscopy

    SciTech Connect

    Song, Woongmo; Vaknin, David; Kim, Doseok

    2013-02-25

    Adsorption behavior of counterions under a Langmuir monolayer was investigated by sum-frequency generation (SFG) spectroscopy. By comparing SFG spectra of arachidic acid (AA) Langmuir monolayer/water interface with and without added salt, it was found that the simple trivalent cation La3+ adsorbed on AA monolayer only when the carboxylic headgroups are charged (deprotonated), implying that counterion adsorption is induced by Coulomb interaction. On the other hand, metal hydroxide complex Fe(OH)3 adsorbed even on a charge-neutral AA monolayer, indicating that the adsorption of iron hydroxide is due to chemical interaction such as covalent or hydrogen bonding to the headgroup of the molecules at the monolayer.

  18. Phosphate-based glass fiber vs. bulk glass: Change in fiber optical response to probe in vitro glass reactivity.

    PubMed

    Massera, J; Ahmed, I; Petit, L; Aallos, V; Hupa, L

    2014-04-01

    This paper investigates the effect of fiber drawing on the thermal and structural properties as well as on the glass reactivity of a phosphate glass in tris(hydroxymethyl)aminomethane-buffered (TRIS) solution and simulated body fluid (SBF). The changes induced in the thermal properties suggest that the fiber drawing process leads to a weakening and probable re-orientation of the POP bonds. Whereas the fiber drawing did not significantly impact the release of P and Ca, an increase in the release of Na into the solution was noticed. This was probably due to small structural reorientations occurring during the fiber drawing process and to a slight diffusion of Na to the fiber surface. Both the powders from the bulk and the glass fibers formed a Ca-P surface layer when immersed in SBF and TRIS. The layer thickness was higher in the calcium and phosphate supersaturated SBF than in TRIS. This paper for the first time presents the in vitro reactivity and optical response of a phosphate-based bioactive glass (PBG) fiber when immersed in SBF. The light intensity remained constant for the first 48h after which a decrease with three distinct slopes was observed: the first decrease between 48 and 200h of immersion could be correlated to the formation of the Ca-P layer at the fiber surface. After this a faster decrease in light transmission was observed from 200 to ~425h in SBF. SEM analysis suggested that after 200h, the surface of the fiber was fully covered by a thin Ca-P layer which is likely to scatter light. For immersion times longer than ~425h, the thickness of the Ca-P layer increased and thus acted as a barrier to the dissolution process limiting further reduction in light transmission. The tracking of light transmission through the PBG fiber allowed monitoring of the fiber dissolution in vitro. These results are essential in developing new bioactive fiber sensors that can be used to monitor bioresponse in situ.

  19. Infrared spectroscopic and thermodynamic assessment of extraframework cationic adsorption sites in the zeolite K-L by using CO as probe molecule

    NASA Astrophysics Data System (ADS)

    Delgado, Montserrat R.; de Yuso, Alicia Martínez; Bulánek, Roman; Arean, Carlos O.

    2015-10-01

    Zeolites are often used as the host material for holding and organizing adsorbed molecules and supramolecular species inside their void channels and cages, in order to exploit space confinement and host-guest interaction for engineering composite materials having novel electronic and optical properties. That endeavour would benefit from improved knowledge about the type and strength of the zeolite adsorption sites. To this end, variable temperature infrared spectroscopy (a technique capable of giving simultaneous information on the type and strength of gas-adsorption complexes) was used herein to characterize the zeolite K-L by means of adsorbed CO. Two types of cationic adsorption sites (termed D‧ and D″) were found on the wall of the zeolite main channel; formation of the corresponding CO adsorption complexes was found to involve a standard enthalpy change of -23.4 and -26.7 kJ mol-1, respectively.

  20. Reactive characterization as a probe of the nature of catalytic sites. Final report, April 15, 1988--February 14, 1993

    SciTech Connect

    Brenner, A.

    1998-05-01

    The primary goal of the last year of the research program was to create a new type of selective heterogeneous catalyst. The new catalysts were synthesized, their unusual selectivity assessed by a model reaction, and some of the parameters which are important in creating unusual selectivity in these catalysts determined. Near the end of this proposal, considerable excitement was generated by the discovery of high temperature superconductors. It was decided to briefly investigate the activity of some superconductors and related cuprates. This research was done in concert with a project funded by Ford Motor Company. Catalysts were investigated for two reactions useful in pollution control: CO oxidation and NO reduction. In addition, some stoichiometric measurements of the oxygen content of superconductors and related cuprates were made using a TPR apparatus in the lab. In addition, some experiments were done with the objective of preparing novel MO-Pd/Al{sub 2}O{sub 3} catalysts in which the Mo and Pd were in close contact. These catalysts have the potential of replacing much more expensive rhodium containing catalysts which are currently used for emissions control. Progress on the following is described: H{sub 2}-D{sub 2} exchange on transition metals; New method of determining the number of active sites; New method of determining the hydroxyl content of catalysts; H{sub 2}-D{sub 2} exchange on metal oxides; Reactive characterization and atomic isolation of active sites; Site isolated catalysts synthesized by selective poisoning; Catalysts prepared from high temperature superconductors; Mixed metal Pd-Mo catalysts; and Selective reduction of nitric oxide.

  1. A first-principles study of Pt-Ni bimetallic cluster adsorption on the anatase TiO2 (1 0 1) surface: Probing electron effect of Ni in TiO2 (1 0 1)-bimetallic cluster (Pt-Ni) on the adsorption and dissociation of methanol

    NASA Astrophysics Data System (ADS)

    Liu, Feila; Xiao, Peng; Uchaker, Evan; He, Huichao; Zhou, Ming; Zhou, Xin; Zhang, Yunhuai

    2014-10-01

    A density functional theory (DFT) based method in conjunction with the projector augmented wave and pseudopotential methods have been applied to investigate the adsorption of Pt4 and Pt3Ni on the anatase TiO2 (1 0 1) surface. Two stable Pt3Ni adsorptions with considerable adsorption energies on the anatase TiO2 (1 0 1) surface were identified. Analysis of the partial density (PDOS) of states and Bader charge suggest that the electronic structure of Pt is modified by Ni due to the electron transfer from Ni to Pt atoms in the Pt3Ni clusters. The 2cO (3cO)-PtNi-5cTi conformation of the adsorbed Pt3Ni on the anatase TiO2 (1 0 1) surface provides a more feasible model for electron injection through the Pt3Ni/TiO2 interface. The reactivity of Pt3Ni/TiO2 is superior to Pt4/TiO2 and effectively manifests itself in the eased decomposition of Osbnd H bonds derived by methanol and alleviative CO adsorption.

  2. Asphaltene adsorption mechanisms on the local scale probed by neutron reflectivity: transition from monolayer to multilayer growth above the flocculation threshold.

    PubMed

    Jouault, Nicolas; Corvis, Yohann; Cousin, Fabrice; Jestin, Jacques; Barré, Loïc

    2009-04-07

    We present here a study of the adsorption of asphaltenes on hydrophilic and hydrophobic solid surfaces by coupling measurements of adsorption isotherms on the macroscopic scale on silica powder with measurements of the structure of the adsorbed asphaltene layer on the microscopic scale obtained by neutron reflectivity on flat silicon wafers. Under good-solvent conditions, if adsorption isotherms reveal that the interaction potential between asphaltenes and the surface is slightly higher for the hydrophilic surface than for the hydrophobic one, then the mechanism of adsorption is similar in both cases because all samples exhibit the same local structure of the adsorbed asphaltene layer: it is a solvated monolayer with thickness of the same order of magnitude as the size of the asphaltene aggregates in the bulk. The surface excess, gamma, is thus always of the same order (approximately 3 mg/m2). The adsorption process induces a densification of the aggregates at the interface because the adsorbed monolayer is much less solvated than aggregates in bulk solution. When a bad solvent is progressively added, the asphaltene adsorbed layer keeps its monolayer structure as long as the bulk flocculation threshold is not reached. Above the threshold, the size of the asphaltene adsorbed layer grows and forms a multilayer structure.

  3. Evaluation of the probe dihydrocalcein acetoxymethylester as an indicator of reactive oxygen species formation and comparison with oxidative DNA base modification determined by modified alkaline elution technique.

    PubMed

    Rohnstock, A; Lehmann, L

    2007-12-01

    Reactive oxygen species (ROS) play a predominant role in various diseases and the development of fast and easy methods for the quantification of intracellular ROS represents an important goal. Therefore, the aim of the present study was the evaluation of the fluorogenic probe dihydrocalcein acetoxymethylester (AM) for the detection of intracellular ROS. A flow cytometric method was developed using MCF-7 cells and the kinetics of ester hydrolysis and the cellular distribution and stability of calcein were characterized using calcein AM. Then, MCF-7 cells were challenged with model agents for the generation of singlet oxygen (illumination with visible light), peroxyl and hydroxyl radicals (tert-butylhydroperoxide, tBHP), superoxide anion radicals (potassium dioxide), and the intracellular formation of superoxide anion radicals by redox cycling (menadione) and the formation of calcein was compared with the induction of oxidative DNA base modifications assessed by modified alkaline elution technique. Every model agent significantly induced formamidopyrimidine-DNA glycosylase-sensitive sites (i.e. oxidative DNA base modifications) and most also induced DNA strand breaks. In contrast, exclusively tBHP and illumination with visible light induced the intracellular formation of calcein. In conclusion, though intracellular oxidation of dihydrocalcein represents a fast screening method, it detects a limited spectrum of ROS.

  4. Ozone adsorption on carbon nanoparticles

    NASA Astrophysics Data System (ADS)

    Chassard, Guillaume; Gosselin, Sylvie; Visez, Nicolas; Petitprez, Denis

    2014-05-01

    Carbonaceous particles produced by incomplete combustion or thermal decomposition of hydrocarbons are ubiquitous in the atmosphere. On these particles are adsorbed hundreds of chemical species. Those of great concern to health are polycyclic aromatic hydrocarbons (PAHs). During atmospheric transport, particulate PAHs react with gaseous oxidants. The induced chemical transformations may change toxicity and hygroscopicity of these potentially inhalable particles. The interaction between ozone and carbon particles has been extensively investigated in literature. However ozone adsorption and surface reaction mechanisms are still ambiguous. Some studies described a fast catalytic decomposition of ozone initiated by an atomic oxygen chemisorption followed by a molecular oxygen release [1-3]. Others suggested a reversible ozone adsorption according to Langmuir-type behaviour [4,5]. The aim of this present study is a better understanding of ozone interaction with carbon surfaces. An aerosol of carbon nanoparticles was generated by flowing synthetic air in a glass tube containing pure carbon (primary particles < 50 nm), under magnetic stirring. The aerosol was then mixed with ozone in an aerosol flow tube. Ozone uptake experiments were performed with different particles concentrations with a fixed ozone concentration. The influence of several factors on kinetics was examined: initial ozone concentration, particle size (50 nm ≤ Dp ≤ 200 nm) and competitive adsorption (with probe molecule and water). The effect of initial ozone concentration was first studied. Accordingly to literature, it has been observed that the number of gas-phase ozone molecules lost per unit particle surface area tends towards a plateau for high ozone concentration suggesting a reversible ozone adsorption according to a Langmuir mechanism. We calculated the initial reaction probability between O3 and carbon particles.An initial uptake coefficient of 1.10-4 was obtained. Similar experiments were

  5. Synthesis Of Reactive Nano-Fe/Pd Bimetallic System-Impregnated Activated Carbon For The Simultaneous Adsorption And Dechlorination Of PCBs

    EPA Science Inventory

    Synthesis and use of reactive metal particles have shown significant environmental implications for the remediation of groundwater and sediment contaminated with chlorinated compounds. Herein, we have developed an effective strategy, employing a series of innovative granular act...

  6. MnCl2 and MgCl2 for the removal of reactive dye Levafix Brilliant Blue EBRA from synthetic textile wastewaters: an adsorption/aggregation mechanism.

    PubMed

    Bouyakoub, A Z; Lartiges, B S; Ouhib, R; Kacha, S; El Samrani, A G; Ghanbaja, J; Barres, O

    2011-03-15

    Two divalent cation-based coagulants, magnesium chloride and manganese chloride, were used to treat synthetic textile wastewaters containing the azo-dye pigment Levafix Brilliant Blue EBRA. The jar-tests were performed in the presence or absence of auxiliary dyeing chemicals. They proved that (i) both divalent cation-based coagulants were effective in the treatment of those alkaline effluents, (ii) better performances in terms of color removal, residual turbidity, and settled volume, were achieved with manganese chloride, and (iii) the presence of dyeing auxiliaries significantly increases the required coagulant demand for treating the textile effluent. The dye removal mechanisms were investigated by combining observations of freeze-dried sediments with transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy and selected area electron diffraction, Fourier transform infrared spectroscopy, adsorption experiments, and aggregates size measurements with a laser sizer under cyclic shear conditions. The results show that brucite (Mg(OH)(2)) particles are formed when applying MgCl(2) to the textile wastewaters, whereas a mixture of feitknechite (β-MnOOH) and hausmannite (Mn(3)O(4)) is obtained when using MnCl(2). More poorly crystallized particles are formed in presence of auxiliary dyeing chemicals. The adsorption experiments suggested that the azo-dye pigment adsorbs onto the surface of precipitating phases, whereas the aggregation dynamics indicated that a charge-neutralization mechanism underlies the formation of aggregates. The dye removal is then consistent with a precipitation/adsorption mechanism.

  7. Detection of reactive oxygen species (ROS) by the oxidant-sensing probe 2',7'-dichlorodihydrofluorescein diacetate in the cyanobacterium Anabaena variabilis PCC 7937

    SciTech Connect

    Rastogi, Rajesh P.; Singh, Shailendra P.; Haeder, Donat-P.; Sinha, Rajeshwar P.

    2010-07-02

    The generation of reactive oxygen species (ROS) under simulated solar radiation (UV-B: 0.30 Wm{sup -2}, UV-A: 25.70 Wm{sup -2} and PAR: 118.06 Wm{sup -2}) was studied in the cyanobacterium Anabaena variabilis PCC 7937 using the oxidant-sensing fluorescent probe 2',7'-dichlorodihydrofluorescein diacetate (DCFH-DA). DCFH-DA is a nonpolar dye, converted into the polar derivative DCFH by cellular esterases that are nonfluorescent but switched to highly fluorescent DCF when oxidized by intracellular ROS and other peroxides. The images obtained from the fluorescence microscope after 12 h of irradiation showed green fluorescence from cells covered with 295, 320 or 395 nm cut-off filters, indicating the generation of ROS in all treatments. However, the green/red fluorescence ratio obtained from fluorescence microscopic analysis showed the highest generation of ROS after UV-B radiation in comparison to PAR or UV-A radiation. Production of ROS was also measured by a spectrofluorophotometer and results obtained supported the results of fluorescence microscopy. Low levels of ROS were detected at the start (0 h) of the experiment showing that they are generated even during normal metabolism. This study also showed that UV-B radiation causes the fragmentation of the cyanobacterial filaments which could be due to the observed oxidative stress. This is the first report for the detection of intracellular ROS in a cyanobacterium by fluorescence microscopy using DCFH-DA and thereby suggesting the applicability of this method in the study of in vivo generation of ROS.

  8. Uptake and bio-reactivity of polystyrene nanoparticles is affected by surface modifications, ageing and LPS adsorption: in vitro studies on neural tissue cells

    NASA Astrophysics Data System (ADS)

    Murali, Kumarasamy; Kenesei, Kata; Li, Yang; Demeter, Kornél; Környei, Zsuzsanna; Madarász, Emilia

    2015-02-01

    Because of their capacity of crossing an intact blood-brain barrier and reaching the brain through an injured barrier or via the nasal epithelium, nanoparticles have been considered as vehicles to deliver drugs and as contrast materials for brain imaging. The potential neurotoxicity of nanoparticles, however, is not fully explored. Using particles with a biologically inert polystyrene core material, we investigated the role of the chemical composition of particle surfaces in the in vitro interaction with different neural cell types. PS NPs within a size-range of 45-70 nm influenced the metabolic activity of cells depending on the cell-type, but caused toxicity only at extremely high particle concentrations. Neurons did not internalize particles, while microglial cells ingested a large amount of carboxylated but almost no PEGylated NPs. PEGylation reduced the protein adsorption, toxicity and cellular uptake of NPs. After storage (shelf-life >6 months), the toxicity and cellular uptake of NPs increased. The altered biological activity of ``aged'' NPs was due to particle aggregation and due to the adsorption of bioactive compounds on NP surfaces. Aggregation by increasing the size and sedimentation velocity of NPs results in increased cell-targeted NP doses. The ready endotoxin adsorption which cannot be prevented by PEG coating, can render the particles toxic. The age-dependent changes in otherwise harmless NPs could be the important sources for variability in the effects of NPs, and could explain the contradictory data obtained with ``identical'' NPs.Because of their capacity of crossing an intact blood-brain barrier and reaching the brain through an injured barrier or via the nasal epithelium, nanoparticles have been considered as vehicles to deliver drugs and as contrast materials for brain imaging. The potential neurotoxicity of nanoparticles, however, is not fully explored. Using particles with a biologically inert polystyrene core material, we investigated the

  9. Probing the reactivation process of sarin-inhibited acetylcholinesterase with α-nucleophiles: hydroxylamine anion is predicted to be a better antidote with DFT calculations.

    PubMed

    Khan, Md Abdul Shafeeuulla; Lo, Rabindranath; Bandyopadhyay, Tusar; Ganguly, Bishwajit

    2011-08-01

    Inactivation of acetylcholinesterase (AChE) due to inhibition by organophosphorus (OP) compounds is a major threat to human since AChE is a key enzyme in neurotransmission process. Oximes are used as potential reactivators of OP-inhibited AChE due to their α-effect nucleophilic reactivity. In search of more effective reactivating agents, model studies have shown that α-effect is not so important for dephosphylation reactions. We report the importance of α-effect of nucleophilic reactivity towards the reactivation of OP-inhibited AChE with hydroxylamine anion. We have demonstrated with DFT [B3LYP/6-311G(d,p)] calculations that the reactivation process of sarin-serine adduct 2 with hydroxylamine anion is more efficient than the other nucleophiles reported. The superiority of hydroxylamine anion to reactivate the sarin-inhibited AChE with sarin-serine adducts 3 and 4 compared to formoximate anion was observed in the presence and absence of hydrogen bonding interactions of Gly121 and Gly122. The calculated results show that the rates of reactivation process of adduct 4 with hydroxylamine anion are 261 and 223 times faster than the formoximate anion in the absence and presence of such hydrogen bonding interactions. The DFT calculated results shed light on the importance of the adjacent carbonyl group of Glu202 for the reactivation of sarin-serine adduct, in particular with formoximate anion. The reverse reactivation reaction between hydroxylamine anion and sarin-serine adduct was found to be higher in energy compared to the other nucleophiles, which suggests that this α-nucleophile can be a good antidote agent for the reactivation process.

  10. Self-healable and reversible liposome leakage by citrate-capped gold nanoparticles: probing the initial adsorption/desorption induced lipid phase transition

    NASA Astrophysics Data System (ADS)

    Wang, Feng; Liu, Juewen

    2015-09-01

    We herein report that the adsorption/desorption of citrate-capped gold nanoparticles (AuNPs) transiently causes leakage in fluid phase DOPC liposomes, while the liposomes do not leak with AuNPs capped with mercaptopropionic acid (MPA). Leakage also fails to occur for gel phase DPPC liposomes. Citrate-capped (but not MPA-capped) AuNPs raise the phase transition temperature of DPPC. We conclude that citrate-capped AuNPs interact with the PC liposomes very strongly, inducing a local fluid-to-gel lipid phase transition for DOPC. Leakage takes place during this transition, and the membrane integrity is resumed after the transition. Citrate-capped AuNPs allow stronger van der Waals forces than MPA-capped AuNPs with PC liposomes, since the latter are separated from the liposome surface by the ~0.3 nm MPA layer.We herein report that the adsorption/desorption of citrate-capped gold nanoparticles (AuNPs) transiently causes leakage in fluid phase DOPC liposomes, while the liposomes do not leak with AuNPs capped with mercaptopropionic acid (MPA). Leakage also fails to occur for gel phase DPPC liposomes. Citrate-capped (but not MPA-capped) AuNPs raise the phase transition temperature of DPPC. We conclude that citrate-capped AuNPs interact with the PC liposomes very strongly, inducing a local fluid-to-gel lipid phase transition for DOPC. Leakage takes place during this transition, and the membrane integrity is resumed after the transition. Citrate-capped AuNPs allow stronger van der Waals forces than MPA-capped AuNPs with PC liposomes, since the latter are separated from the liposome surface by the ~0.3 nm MPA layer. Electronic supplementary information (ESI) available: Methods, TEM, UV-vis and DLS data. See DOI: 10.1039/c5nr04805b

  11. Probing the Properties of the Molecular Adlayers on Metal Substrates: Scanning Tunneling Microscopy Study of Amine Adsorption on Gold(111) and Graphene Nanoislands on Cobalt(0001)

    NASA Astrophysics Data System (ADS)

    Zhou, Hui

    In this thesis, we present our findings on two major topics, both of which are studies of molecules on metal surfaces by scanning tunneling microscopy (STM). The first topic is on adsorption of a model amine compound, 1,4-benzenediamine (BDA), on the reconstructed Au(111) surface, chosen for its potential application as a molecular electronic device. The molecules were deposited in the gas phase onto the substrate in the vacuum chamber. Five different patterns of BDA molecules on the surface at different coverages, and the preferred adsorption sites of BDA molecules on reconstructed Au(111) surface, were observed. In addition, BDA molecules were susceptible to tip-induced movement, suggesting that BDA molecules on metal surfaces can be a potential candidate in STM molecular manipulations. We also studied graphene nanoislands on Co(0001) in the hope of understanding interaction of expitaxially grown graphene and metal substrates. This topic can shed a light on the potential application of graphene as an electronic device, especially in spintronics. The graphene nanoislands were formed by annealing contorted hexabenzocoronene (HBC) on the Co(0001) surface. In our experiments, we have determined atop registry of graphene atoms with respect to the underlying Co surface. We also investigated the low-energy electronic structures of graphene nanoislands by scanning tunneling spectroscopy. The result was compared with a first-principle calculation using density functional theory (DFT) which suggested strong coupling between graphene pi-bands and cobalt d-electrons. We also observed that the islands exhibit zigzag edges, which exhibits unique electronic structures compared with the center areas of the islands.

  12. Reactivity of a Thick BaO Film Supported on Pt(111): Adsorption and Reaction of NO2, H2O and CO2

    SciTech Connect

    Mudiyanselage, Kumudu; Yi, Cheol-Woo W.; Szanyi, Janos

    2009-09-15

    Reactions of NO2, H2O, and CO2 with a thick (> 20 MLE) BaO film supported on Pt(111) were studied with temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). NO2 reacts with a thick BaO to form surface nitrite-nitrate ion pairs at 300 K, while only nitrates form at 600 K. In the thermal decomposition process of nitrite–nitrate ion pairs, first nitrites decompose and desorb as NO. Then nitrates decompose in two steps : at lower temperature with the release of NO2 and at higher temperature, nitrates dissociate to NO + O2. The thick BaO layer converts completely to Ba(OH)2 following the adsorption of H2O at 300 K. Dehydration/dehydroxylation of this hydroxide layer can be fully achieved by annealing to 550 K. CO2 also reacts with BaO to form BaCO3 that completely decomposes to regenerate BaO upon annealing to 825 K. However, the thick BaO film cannot be converted completely to Ba(NOx)2 or BaCO3 under the experimental conditions employed in this study.

  13. Selective photo-deposition of Cu onto the surface of monodisperse oleic acid capped TiO2 nanorods probed by FT-IR CO-adsorption studies.

    PubMed

    Hikov, Todor; Schroeter, Marie-Katrin; Khodeir, Lamma; Chemseddine, Abdelkrim; Muhler, Martin; Fischer, Roland A

    2006-04-07

    A novel, non-aqueous, organometallic route to nanocomposite Cu@TiO2 materials is presented. TiO2 nanorods stabilized with oleic acid (OLA) were used as support for the photo-assisted deposition of Cu using the organometallic Cu(II) precursor [Cu(OCH(CH3)CH2N(CH3)2)2] (1). The copper precursor penetrates through the shell of OLA and is photo reduced to deposit Cu0 directly at the surface of the TiO2 rods. The obtained Cu decorated nanorods were still soluble in nonpolar organic solvents without change of the morphology of nanorods. The Cu@TiO2 colloid was characterized by means of UV-VIS, XRD, AAS, and HRTEM. FTIR CO adsorption studies provide evidence for Cu0 anchored at the titania surface by a characteristic absorption at 2084 cm-1. Comparative studies of Cu-deposition were performed using CuCl2 as simple Cu source which proved that the concept of organometallic disguise of the metal centre results in a higher reaction rate and the circumvention of non-selective reduction, parasitic side reactions and undesired agglomeration of the OLA stabilized titania nanorods.

  14. Probing the Role of Zr Addition versus Textural Properties in Enhancement of CO 2 Adsorption Performance in Silica/PEI Composite Sorbents

    DOE PAGES

    Sakwa-Novak, Miles A.; Holewinski, Adam; Hoyt, Caroline B.; ...

    2015-08-08

    Polymeric amines such as poly(ethylenimine) (PEI) supported on mesoporous oxides are promising candidate adsorbents for CO2 capture processes. One important aspect to the design and optimization of these materials is a fundamental understanding of how the properties of the oxide support such as pore structure, particle morphology, and surface properties affect the efficiency of the guest polymer in its interactions with CO2. Previously, the efficiency of impregnated PEI to adsorb CO2 was shown to increase upon the addition of Zr as a surface modifier in SBA-15. But, the efficacy of this method to tune the adsorption performance has not beenmore » explored in materials of differing textural and morphological nature. These issues are directly addressed via the preparation of an array of SBA-15 support materials with varying textural and morphological properties, as well as varying content of zirconium doped into the material. Zirconium is incorporated into the SBA-15 either during the synthesis of the SBA-15, or postsynthetically via deposition of Zr species onto pure-silica SBA-15. The method of Zr incorporation alters the textural and morphological properties of the parent SBA-15 in different ways. Importantly, the CO2 capacity of SBA-15 impregnated with PEI increases by a maximum of ~60% with the quantity of doped Zr for a “standard” SBA-15 containing significant microporosity, while no increase in the CO2 capacity is observed upon Zr incorporation for an SBA-15 with reduced microporosity and a larger pore size, pore volume, and particle size. Finally, adsorbents supported on SBA-15 with controlled particle morphology show only modest increases in CO2 capacity upon inclusion of Zr to the silica framework. The data demonstrate that the textural and morphological properties of the support have a more significant impact on the ability of PEI to capture CO2 than the support surface composition.« less

  15. In silico studies in probing the role of kinetic and structural effects of different drugs for the reactivation of tabun-inhibited AChE.

    PubMed

    Lo, Rabindranath; Chandar, Nellore Bhanu; Kesharwani, Manoj K; Jain, Aastha; Ganguly, Bishwajit

    2013-01-01

    We have examined the reactivation mechanism of the tabun-conjugated AChE with various drugs using density functional theory (DFT) and post-Hartree-Fock methods. The electronic environments and structural features of neutral oximes (deazapralidoxime and 3-hydroxy-2-pyridinealdoxime) and charged monopyridinium oxime (2-PAM) and bispyridinium oxime (Ortho-7) are different, hence their efficacy varies towards the reactivation process of tabun-conjugated AChE. The calculated potential energy surfaces suggest that a monopyridinium reactivator is less favorable for the reactivation of tabun-inhibited AChE compared to a bis-quaternary reactivator, which substantiates the experimental study. The rate determining barrier with neutral oximes was found to be ∼2.5 kcal/mol, which was ∼5.0 kcal/mol lower than charged oxime drugs such as Ortho-7. The structural analysis of the calculated geometries suggest that the charged oximes form strong O(…)H and N(…)H hydrogen bonding and C-H(…)π non-bonding interaction with the tabun-inhibited enzyme to stabilize the reactant complex compared to separated reactants, which influences the activation barrier. The ability of neutral drugs to cross the blood-brain barrier was also found to be superior to charged antidotes, which corroborates the available experimental observations. The calculated activation barriers support the superiority of neutral oximes for the activation of tabun-inhibited AChE compared to charged oximes. However, they lack effective interactions with their peripheral sites. Docking studies revealed that the poor binding affinity of simple neutral oxime drugs such as 3-hydroxy-2-pyridinealdoxime inside the active-site gorge of AChE was significantly augmented with the addition of neutral peripheral units compared to conventional charged peripheral sites. The newly designed oxime drug 2 appears to be an attractive candidate as efficient antidote to kinetically and structurally reactivate the tabun

  16. In Silico Studies in Probing the Role of Kinetic and Structural Effects of Different Drugs for the Reactivation of Tabun-Inhibited AChE

    PubMed Central

    Lo, Rabindranath; Chandar, Nellore Bhanu; Kesharwani, Manoj K.; Jain, Aastha; Ganguly, Bishwajit

    2013-01-01

    We have examined the reactivation mechanism of the tabun-conjugated AChE with various drugs using density functional theory (DFT) and post-Hartree-Fock methods. The electronic environments and structural features of neutral oximes (deazapralidoxime and 3-hydroxy-2-pyridinealdoxime) and charged monopyridinium oxime (2-PAM) and bispyridinium oxime (Ortho-7) are different, hence their efficacy varies towards the reactivation process of tabun-conjugated AChE. The calculated potential energy surfaces suggest that a monopyridinium reactivator is less favorable for the reactivation of tabun-inhibited AChE compared to a bis-quaternary reactivator, which substantiates the experimental study. The rate determining barrier with neutral oximes was found to be ∼2.5 kcal/mol, which was ∼5.0 kcal/mol lower than charged oxime drugs such as Ortho-7. The structural analysis of the calculated geometries suggest that the charged oximes form strong O…H and N…H hydrogen bonding and C-H…π non-bonding interaction with the tabun-inhibited enzyme to stabilize the reactant complex compared to separated reactants, which influences the activation barrier. The ability of neutral drugs to cross the blood-brain barrier was also found to be superior to charged antidotes, which corroborates the available experimental observations. The calculated activation barriers support the superiority of neutral oximes for the activation of tabun-inhibited AChE compared to charged oximes. However, they lack effective interactions with their peripheral sites. Docking studies revealed that the poor binding affinity of simple neutral oxime drugs such as 3-hydroxy-2-pyridinealdoxime inside the active-site gorge of AChE was significantly augmented with the addition of neutral peripheral units compared to conventional charged peripheral sites. The newly designed oxime drug 2 appears to be an attractive candidate as efficient antidote to kinetically and structurally reactivate the tabun-inhibited enzyme

  17. Optically probing Al—O and O—H vibrations to characterize water adsorption and surface reconstruction on α-alumina: An experimental and theoretical study

    SciTech Connect

    Tong, Yujin Kirsch, Harald; Wolf, Martin; Campen, R. Kramer; Wirth, Jonas; Saalfrank, Peter

    2015-02-07

    Oxide/water interfaces are ubiquitous in a wide variety of applications and the environment. Despite this ubiquity, and attendant decades of study, gaining molecular level insight into water/oxide interaction has proven challenging. In part, this challenge springs from a lack of tools to concurrently characterize changes in surface structure (i.e., water/oxide interaction from the perspective of the solid) and O—H population and local environment (i.e., water/oxide interaction from the water perspective). Here, we demonstrate the application of surface specific vibrational spectroscopy to the characterization of the interaction of the paradigmatic α-Al{sub 2}O{sub 3}(0001) surface and water. By probing both the interfacial Al—O (surface phonon) and O—H spectral response, we characterize this interaction from both perspectives. Through electronic structure calculation, we assign the interfacial Al—O response and rationalize its changes on surface dehydroxylation and reconstruction. Because our technique is all-optical and interface specific, it is equally applicable to oxide surfaces in vacuum, ambient atmospheres and at the solid/liquid interface. Application of this approach to additional alumina surfaces and other oxides thus seems likely to significantly expand our understanding of how water meets oxide surfaces and thus the wide variety of phenomena this interaction controls.

  18. Quantitation of bacteria through adsorption of intracellular biomolecules on carbon paste and screen-printed carbon electrodes and voltammetry of redox-active probes.

    PubMed

    Obuchowska, Agnes

    2008-03-01

    A new electrochemical method for the quantitation of bacteria that is rapid, inexpensive, and amenable to miniaturization is reported. Cyclic voltammetry was used to quantitate M. luteus, C. sporogenes, and E. coli JM105 in exponential and stationary phases, following exposure of screen-printed carbon working electrodes (SPCEs) to lysed culture samples. Ferricyanide was used as a probe. The detection limits (3s) were calculated and the dynamic ranges for E. coli (exponential and stationary phases), M. luteus (exponential and stationary phases), and C. sporogenes (exponential phase) lysed by lysozyme were 3 x 10(4) to 5 x 10(6) colony-forming units (CFU) mL(-1), 5 x 10(6) to 2 x 10(8) CFU mL(-1) and 3 x 10(3) to 3 x 10(5) CFU mL(-1), respectively. Good overlap was obtained between the calibration curves when the electrochemical signal was plotted against the dry bacterial weight, or between the protein concentration in the bacterial lysate. In contrast, unlysed bacteria did not change the electrochemical signal of ferricyanide. The results indicate that the reduction of the electrochemical signal in the presence of the lysate is mainly due to the fouling of the electrode by proteins. Similar results were obtained with carbon-paste electrodes although detection limits were better with SPCEs. The method described herein was applied to quantitation of bacteria in a cooling tower water sample.

  19. Probing the Role of Zr Addition versus Textural Properties in Enhancement of CO 2 Adsorption Performance in Silica/PEI Composite Sorbents

    SciTech Connect

    Sakwa-Novak, Miles A.; Holewinski, Adam; Hoyt, Caroline B.; Yoo, Chun-Jae; Chai, Song-Hai; Dai, Sheng; Jones, Christopher W.

    2015-08-08

    Polymeric amines such as poly(ethylenimine) (PEI) supported on mesoporous oxides are promising candidate adsorbents for CO2 capture processes. One important aspect to the design and optimization of these materials is a fundamental understanding of how the properties of the oxide support such as pore structure, particle morphology, and surface properties affect the efficiency of the guest polymer in its interactions with CO2. Previously, the efficiency of impregnated PEI to adsorb CO2 was shown to increase upon the addition of Zr as a surface modifier in SBA-15. But, the efficacy of this method to tune the adsorption performance has not been explored in materials of differing textural and morphological nature. These issues are directly addressed via the preparation of an array of SBA-15 support materials with varying textural and morphological properties, as well as varying content of zirconium doped into the material. Zirconium is incorporated into the SBA-15 either during the synthesis of the SBA-15, or postsynthetically via deposition of Zr species onto pure-silica SBA-15. The method of Zr incorporation alters the textural and morphological properties of the parent SBA-15 in different ways. Importantly, the CO2 capacity of SBA-15 impregnated with PEI increases by a maximum of ~60% with the quantity of doped Zr for a “standard” SBA-15 containing significant microporosity, while no increase in the CO2 capacity is observed upon Zr incorporation for an SBA-15 with reduced microporosity and a larger pore size, pore volume, and particle size. Finally, adsorbents supported on SBA-15 with controlled particle morphology show only modest increases in CO2 capacity upon inclusion of Zr to the silica framework. The data demonstrate that the textural and morphological properties of the support have a more significant impact on the ability of PEI to capture CO2 than the support surface composition.

  20. Tailoring bifunctional hybrid organic–inorganic nanoadsorbents by the choice of functional layer composition probed by adsorption of Cu2+ ions

    PubMed Central

    Tomina, Veronika V; Melnyk, Inna V; Zub, Yuriy L; Kareiva, Aivaras; Vaclavikova, Miroslava; Kessler, Vadim G

    2017-01-01

    Spherical silica particles with bifunctional (≡Si(CH2)3NH2/≡SiCH3, ≡Si(CH2)3NH2/≡Si(CH2)2(CF2)5CF3) surface layers were produced by a one-step approach using a modified Stöber method in three-component alkoxysilane systems, resulting in greatly increased contents of functional components. The content of functional groups and thermal stability of the surface layers were analyzed by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, and 13C and 29Si solid-state NMR spectroscopy revealing their composition and organization. The fine chemical structure of the surface in the produced hybrid adsorbent particles and the ligand distribution were further investigated by electron paramagnetic resonance (EPR) and electron spectroscopy of diffuse reflectance (ESDR) spectroscopy using Cu2+ ion coordination as a probe. The composition and structure of the emerging surface complexes were determined and used to provide an insight into the molecular structure of the surfaces. It was demonstrated that the introduction of short hydrophobic (methyl) groups improves the kinetic characteristics of the samples during the sorption of copper(II) ions and promotes fixation of aminopropyl groups on the surface of silica microspheres. The introduction of long hydrophobic (perfluoroctyl) groups changes the nature of the surface, where they are arranged in alternately hydrophobic/hydrophilic patches. This makes the aminopropyl groups huddled and less active in the sorption of metal cations. The size and aggregation/morphology of obtained particles was optimized controlling the synthesis conditions, such as concentrations of reactants, basicity of the medium, and the process temperature. PMID:28243572

  1. Color removal of reactive dyes from water by clinoptilolite.

    PubMed

    Armağan, Bülent; Turan, Mustafa; Ozdemir, Orhan; Celik, Mehmet S

    2004-01-01

    The adsorption of reactive dyes on Gordes (Turkey) clinoptilolite was investigated by a series of batch and column adsorption experiments. Three reactive dyes (Everzol Black, Everzol Red, Everzol Yellow) were used in laboratory studies. Synthetic wastewaters were used and the ability of natural zeolite (clinoptilolite) and their modified form were examined. The adsorption results, in batch and column reactor, indicate that natural zeolite have limited adsorption capacities of the reactive dyes but are substantially improved upon modifying their surfaces with quaternary amines (HTAB). The degree of hydrophilicity is found to play an important role in the uptake of reactive dyes.

  2. Developing an Acidic Residue Reactive and Sulfoxide-Containing MS-Cleavable Homobifunctional Cross-Linker for Probing Protein–Protein Interactions

    PubMed Central

    2016-01-01

    Cross-linking mass spectrometry (XL-MS) has become a powerful strategy for defining protein–protein interactions and elucidating architectures of large protein complexes. However, one of the inherent challenges in MS analysis of cross-linked peptides is their unambiguous identification. To facilitate this process, we have previously developed a series of amine-reactive sulfoxide-containing MS-cleavable cross-linkers. These MS-cleavable reagents have allowed us to establish a common robust XL-MS workflow that enables fast and accurate identification of cross-linked peptides using multistage tandem mass spectrometry (MSn). Although amine-reactive reagents targeting lysine residues have been successful, it remains difficult to characterize protein interaction interfaces with little or no lysine residues. To expand the coverage of protein interaction regions, we present here the development of a new acidic residue-targeting sulfoxide-containing MS-cleavable homobifunctional cross-linker, dihydrazide sulfoxide (DHSO). We demonstrate that DHSO cross-linked peptides display the same predictable and characteristic fragmentation pattern during collision induced dissociation as amine-reactive sulfoxide-containing MS-cleavable cross-linked peptides, thus permitting their simplified analysis and unambiguous identification by MSn. Additionally, we show that DHSO can provide complementary data to amine-reactive reagents. Collectively, this work not only enlarges the range of the application of XL-MS approaches but also further demonstrates the robustness and applicability of sulfoxide-based MS-cleavability in conjunction with various cross-linking chemistries. PMID:27417384

  3. Binding hotspots on K-ras: consensus ligand binding sites and other reactive regions from probe-based molecular dynamics analysis.

    PubMed

    Prakash, Priyanka; Hancock, John F; Gorfe, Alemayehu A

    2015-05-01

    We have used probe-based molecular dynamics (pMD) simulations to search for interaction hotspots on the surface of the therapeutically highly relevant oncogenic K-Ras G12D. Combining the probe-based query with an ensemble-based pocket identification scheme and an analysis of existing Ras-ligand complexes, we show that (i) pMD is a robust and cost-effective strategy for binding site identification, (ii) all four of the previously reported ligand binding sites are suitable for structure-based ligand design, and (iii) in some cases probe binding and expanded sampling of configurational space enable pocket expansion and increase the likelihood of site identification. Furthermore, by comparing the distribution of hotspots in nonpocket-like regions with known protein- and membrane-interacting interfaces, we propose that pMD has the potential to predict surface patches responsible for protein-biomolecule interactions. These observations have important implications for future drug design efforts and will facilitate the search for potential interfaces responsible for the proposed transient oligomerization or interaction of Ras with other biomolecules in the cellular milieu.

  4. Binding hotspots on K-Ras: consensus ligand binding sites and other reactive regions from probe-based molecular dynamics analysis

    PubMed Central

    Prakash, Priyanka; Hancock, John F.; Gorfe, Alemayehu A.

    2015-01-01

    We have used probe-based molecular dynamics (pMD) simulations to search for interaction hotspots on the surface of the therapeutically highly relevant oncogenic K-Ras G12D. Combining the probe-based query with an ensemble-based pocket identification scheme and an analysis of existing Ras-ligand complexes, we show that (i) pMD is a robust and cost-effective strategy for binding site identification, (ii) all four of the previously reported ligand binding sites are suitable for structure-based ligand design, and (iii) in some cases probe binding and expanded sampling of configurational space enable pocket expansion and increase the likelihood of site identification. Furthermore, by comparing the distribution of hotspots in non-pocket-like regions with known protein- and membrane-interacting interfaces, we propose that pMD has the potential to predict surface patches responsible for protein-biomolecule interactions. These observations have important implications for future drug design efforts and will facilitate the search for potential interfaces responsible for the proposed transient oligomerization or interaction of Ras with other biomolecules in the cellular milieu. PMID:25740554

  5. Differential scanning calorimetry (DSC) as a tool for probing the reactivity of polyynes relevant to hexadehydro-Diels-Alder (HDDA) cascades.

    PubMed

    Woods, Brian P; Hoye, Thomas R

    2014-12-19

    The differential scanning calorimetry (DSC) behavior of a number of alkyne-rich compounds is described. The DSC trace for each compound exhibits an exothermic event at a characteristic onset temperature. For the tri- and tetraynes whose [4 + 2] HDDA reactivity in solution has been determined, these onset temperatures show a strong correlation with the cyclization activation energy. The studies reported here exemplify how the data available through this operationally simple analytical technique can give valuable insights into the thermal behavior of small molecules.

  6. A water soluble glucopyranosyl conjugate as a selective and reactive probe for cysteine in a buffer and its application to living cells.

    PubMed

    Areti, Sivaiah; Teotia, Rohit; Rao, Chebrolu Pulla

    2015-11-07

    A water soluble and biocompatible glucopyranosyl conjugate (L) has been synthesized and characterized by various techniques. The L has been employed to recognize Cys selectively among the naturally occurring amino acids in HEPES buffer at physiological pH. A minimum detection limit of 2.5 × 10(-7) M was shown by L for Cys in the buffer at pH = 7.4. The reactivity of L towards biological thiols as demonstrated by emission and absorption is supported by the observed increase in the fluorescence intensity; however, Cys shows a maximum increase owing to its better nucleophilicity. The reactivity of Cys on L is demonstrated by (1)H NMR, ESI MS, emission and absorption spectroscopy, and the formation of the binary complex was supported by ESI MS. The control molecular study revealed the necessity of the glyco-moiety to bring water solubility and biological adaptability. The cellular studies support that the conjugate L is biologically adaptable and shows effective intracellular fluorescence emission upon reacting with intracellular thiols.

  7. Accessible reactive surface area and abiotic redox reactivity of iron oxyhydroxides in acidic brines

    NASA Astrophysics Data System (ADS)

    Strehlau, Jennifer H.; Toner, Brandy M.; Arnold, William A.; Penn, R. Lee

    2017-01-01

    The reactivity of iron oxyhydroxide nanoparticles in low pH and high ionic strength solutions was quantified to assess abiotic contributions to oxidation-reduction chemistry in acidic brine environments, such as mine groundwater seepage, lakes in Western Australia, and acid mine drainage settings, which are of global interest for their environmental impacts and unique geomicrobiology. Factors expected to influence accessible and reactive surface area, including Fe(II) adsorption and aggregate size, were measured as a function of pH and CaCl2 concentration and related to the kinetics of redox reactions in aqueous suspensions of synthetic goethite (α-FeOOH), akaganeite (β-FeOOH), and ferrihydrite (Fe10O14(OH)2) nanoparticles. Aqueous conditions and iron oxyhydroxides were chosen based on characterization of natural iron-rich mine microbial mats located in Soudan Underground Mine State Park, Minnesota, USA. Quinone species were used as redox sensors because they are well-defined probes and are present in natural organic matter. Fe(II) adsorption to the iron oxyhydroxide mineral surfaces from aqueous solution was measurable only at pH values above 4 and either decreased or was not affected by CaCl2 concentration. Concentrations at or above 0.020 M CaCl2 in acetate buffer (pH 4.5) induced particle aggregation. Assessment of Fe(II) adsorption and particle aggregation in acidic brine suggested that accessible reactive surface area may be limited in acidic brines. This was supported by observations of decreasing benzoquinone reduction rate by adsorbed Fe(II) at high CaCl2 concentration. In contrast, the hydroquinone oxidation rate increased at high CaCl2 concentrations, which may be due to suppressed adsorption of Fe(II) generated by the reaction. Results suggest that iron geochemical cycling in acidic brine environments will be substantially different than for iron oxyhydroxides in low-saline waters with circumneutral pH. These findings have implications for acidic

  8. Use of cysteine-reactive crosslinkers to probe conformational flexibility of human DJ-1 demonstrates that Glu18 mutations are dimers

    PubMed Central

    Prahlad, Janani; Hauser, David N.; Milkovic, Nicole M.; Cookson, Mark R.; Wilson, Mark A.

    2014-01-01

    The oxidation of a key cysteine residue (Cys106) in the parkinsonism-associated protein DJ-1 regulates its ability to protect against oxidative stress and mitochondrial damage. Cys106 interacts with a neighboring protonated Glu18 residue, stabilizing the Cys106-SO2− (sulfinic acid) form of DJ-1. To study this important post-translational modification, we previously designed several Glu18 mutations (E18N, E18D, E18Q) that alter the oxidative propensity of Cys106. However, recent results suggest these Glu18 mutations cause loss of DJ-1 dimerization, which would severely compromise the protein’s function. The purpose of this study was to conclusively determine the oligomerization state of these mutants using X-ray crystallography, NMR spectroscopy, thermal stability analysis, CD spectroscopy, sedimentation equilibrium ultracentrifugation, and crosslinking. We found that all of the Glu18 DJ-1 mutants were dimeric. Thiol crosslinking indicates that these mutant dimers are more flexible than the wild-type protein and can form multiple crosslinked dimeric species due to the transient exposure of cysteine residues that are inaccessible in the wild-type protein. The enhanced flexibility of Glu18 DJ-1 mutants provides a parsimonious explanation for their lower observed crosslinking efficiency in cells. In addition, thiol crosslinkers may have an underappreciated value as qualitative probes of protein conformational flexibility. PMID:24832775

  9. Fluorescence imaging of reactive oxygen species by confocal laser scanning microscopy for track analysis of synchrotron X-ray photoelectric nanoradiator dose: X-ray pump-optical probe.

    PubMed

    Jeon, Jae Kun; Han, Sung Mi; Kim, Jong Ki

    2016-09-01

    Bursts of emissions of low-energy electrons, including interatomic Coulomb decay electrons and Auger electrons (0-1000 eV), as well as X-ray fluorescence produced by irradiation of large-Z element nanoparticles by either X-ray photons or high-energy ion beams, is referred to as the nanoradiator effect. In therapeutic applications, this effect can damage pathological tissues that selectively take up the nanoparticles. Herein, a new nanoradiator dosimetry method is presented that uses probes for reactive oxygen species (ROS) incorporated into three-dimensional gels, on which macrophages containing iron oxide nanoparticles (IONs) are attached. This method, together with site-specific irradiation of the intracellular nanoparticles from a microbeam of polychromatic synchrotron X-rays (5-14 keV), measures the range and distribution of OH radicals produced by X-ray emission or superoxide anions ({\\rm{O}}_2^-) produced by low-energy electrons. The measurements are based on confocal laser scanning of the fluorescence of the hydroxyl radical probe 2-[6-(4'-amino)phenoxy-3H-xanthen-3-on-9-yl] benzoic acid (APF) or the superoxide probe hydroethidine-dihydroethidium (DHE) that was oxidized by each ROS, enabling tracking of the radiation dose emitted by the nanoradiator. In the range 70 µm below the irradiated cell, ^\\bullet{\\rm{OH}} radicals derived mostly from either incident X-ray or X-ray fluorescence of ION nanoradiators are distributed along the line of depth direction in ROS gel. In contrast, {\\rm{O}}_2^- derived from secondary electron or low-energy electron emission by ION nanoradiators are scattered over the ROS gel. ROS fluorescence due to the ION nanoradiators was observed continuously to a depth of 1.5 mm for both oxidized APF and oxidized DHE with relatively large intensity compared with the fluorescence caused by the ROS produced solely by incident primary X-rays, which was limited to a depth of 600 µm, suggesting dose enhancement as well as more

  10. Adsorption and functionality of fibrinogen on triblock copolymer-coated surfaces

    NASA Astrophysics Data System (ADS)

    O'Connor, Stephen Moss

    To assess the influence of the surface microenvironment on the adsorption and biologic activity of fibrinogen, a series of poly(ethylene oxide)/poly(propylene oxide) triblock copolymers were adsorbed to solid, hydrophobic polystyrene-divinylbenzene beads. The copolymers, which were of the form PEOsb{b}PPOsb{a}PEOsb{b}, varied in their hydrophile/lipophile balances (HLB) due only to differences in their PEO chain length (5 to 129 EO units) as the hydrophobic PPO core segment was of fixed length (56 or 69 PO units). The surface coverage of copolymers was determined first and after exposing the beads to fibrinogen or to human plasma, the total amount of protein adsorbed to their surface was measured. The functionality of fibrinogen bound to copolymer-modified beads was assessed in terms of fibrin clot formation and by the adherence of macrophages (THP-1 tumor cells). Enzymatic processing was used to probe the surface orientation of fibrinogen. The copolymers appear to adsorb in an expanded fashion, a conclusion supported by surface pressure-area isotherms of the copolymers spread at the air-water interface. As compared to copolymer-free surfaces, protein adsorption decreases by up to 90% as the PEO chain length of the copolymers increases. The copolymer coatings appear to lower fibrinogen adsorption by limiting the available surface area. On surfaces coated with the hydrophobic versions of the copolymers, the biologic assays demonstrate that fibrinogen is as reactive/coagulable as for surfaces with saturated coverages of fibrin despite that these copolymer-coated surfaces have 60% less fibrinogen adsorbed to them. When adsorbed at the same low surface concentration in the absence of copolymer, fibrinogen is not active. Enzymatic processing of bound fibrinogen suggests that the presence of the copolymers promote the adsorption of the protein in end-on fashion. It is proposed here, that when adsorbed end-on, fibrinogen is functional because its reactive sites are

  11. Spectrophotometric probe

    DOEpatents

    Prather, W.S.; O'Rourke, P.E.

    1994-08-02

    A support structure is described bearing at least one probe for making spectrophotometric measurements of a fluid using a source of light and a spectrophotometer. The probe includes a housing with two optical fibers and a planoconvex lens. A sleeve bearing a mirror surrounds the housing. The lens is separated from the mirror by a fixed distance, defining an interior space for receiving a volume of the fluid sample. A plurality of throughholes extending through the sleeve communicate between the sample volume and the exterior of the probe, all but one hole bearing a screen. A protective jacket surrounds the probe. A hollow conduit bearing a tube is formed in the wall of the probe for venting any air in the interior space when fluid enters. The probe is held at an acute angle so the optic fibers carrying the light to and from the probe are not bent severely on emergence from the probe. 3 figs.

  12. Spectrophotometric probe

    DOEpatents

    Prather, William S.; O'Rourke, Patrick E.

    1994-01-01

    A support structure bearing at least one probe for making spectrophotometric measurements of a fluid using a source of light and a spectrophotometer. The probe includes a housing with two optical fibers and a planoconvex lens. A sleeve bearing a mirror surrounds the housing. The lens is separated from the mirror by a fixed distance, defining an interior space for receiving a volume of the fluid sample. A plurality of throughholes extending through the sleeve communicate between the sample volume and the exterior of the probe, all but one hole bearing a screen. A protective jacket surrounds the probe. A hollow conduit bearing a tube is formed in the wall of the probe for venting any air in the interior space when fluid enters. The probe is held at an acute angle so the optic fibers carrying the light to and from the probe are not bent severely on emergence from the probe.

  13. Influence of LaFeO 3 Surface Termination on Water Reactivity

    DOE PAGES

    Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.; ...

    2017-02-16

    The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. In comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecular watermore » at lower relative humidity than its FeO2-terminated counterpart. But, the FeO2-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate–adsorbate interactions may impact reactivity. These results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.« less

  14. Cantilevered probe detector with piezoelectric element

    SciTech Connect

    Adams, Jesse D; Sulchek, Todd A; Feigin, Stuart C

    2014-04-29

    A disclosed chemical detection system for detecting a target material, such as an explosive material, can include a cantilevered probe, a probe heater coupled to the cantilevered probe, and a piezoelectric element disposed on the cantilevered probe. The piezoelectric element can be configured as a detector and/or an actuator. Detection can include, for example, detecting a movement of the cantilevered probe or a property of the cantilevered probe. The movement or a change in the property of the cantilevered probe can occur, for example, by adsorption of the target material, desorption of the target material, reaction of the target material and/or phase change of the target material. Examples of detectable movements and properties include temperature shifts, impedance shifts, and resonant frequency shifts of the cantilevered probe. The overall chemical detection system can be incorporated, for example, into a handheld explosive material detection system.

  15. Cantilevered probe detector with piezoelectric element

    DOEpatents

    Adams, Jesse D.; Sulchek, Todd A.; Feigin, Stuart C.

    2010-04-06

    A disclosed chemical detection system for detecting a target material, such as an explosive material, can include a cantilevered probe, a probe heater coupled to the cantilevered probe, and a piezoelectric element disposed on the cantilevered probe. The piezoelectric element can be configured as a detector and/or an actuator. Detection can include, for example, detecting a movement of the cantilevered probe or a property of the cantilevered probe. The movement or a change in the property of the cantilevered probe can occur, for example, by adsorption of the target material, desorption of the target material, reaction of the target material and/or phase change of the target material. Examples of detectable movements and properties include temperature shifts, impedance shifts, and resonant frequency shifts of the cantilevered probe. The overall chemical detection system can be incorporated, for example, into a handheld explosive material detection system.

  16. Cantilevered probe detector with piezoelectric element

    DOEpatents

    Adams, Jesse D; Sulchek, Todd A; Feigin, Stuart C

    2013-04-30

    A disclosed chemical detection system for detecting a target material, such as an explosive material, can include a cantilevered probe, a probe heater coupled to the cantilevered probe, and a piezoelectric element disposed on the cantilevered probe. The piezoelectric element can be configured as a detector and/or an actuator. Detection can include, for example, detecting a movement of the cantilevered probe or a property of the cantilevered probe. The movement or a change in the property of the cantilevered probe can occur, for example, by adsorption of the target material, desorption of the target material, reaction of the target material and/or phase change of the target material. Examples of detectable movements and properties include temperature shifts, impedance shifts, and resonant frequency shifts of the cantilevered probe. The overall chemical detection system can be incorporated, for example, into a handheld explosive material detection system.

  17. Cantilevered probe detector with piezoelectric element

    DOEpatents

    Adams, Jesse D [Reno, NV; Sulchek, Todd A [Oakland, CA; Feigin, Stuart C [Reno, NV

    2012-07-10

    A disclosed chemical detection system for detecting a target material, such as an explosive material, can include a cantilevered probe, a probe heater coupled to the cantilevered probe, and a piezoelectric element disposed on the cantilevered probe. The piezoelectric element can be configured as a detector and/or an actuator. Detection can include, for example, detecting a movement of the cantilevered probe or a property of the cantilevered probe. The movement or a change in the property of the cantilevered probe can occur, for example, by adsorption of the target material, desorption of the target material, reaction of the target material and/or phase change of the target material. Examples of detectable movements and properties include temperature shifts, impedance shifts, and resonant frequency shifts of the cantilevered probe. The overall chemical detection system can be incorporated, for example, into a handheld explosive material detection system.

  18. Magnetic modification of microporous carbon for dye adsorption.

    PubMed

    Kyzas, George Z; Deliyanni, Eleni A; Lazaridis, Nikolaos K

    2014-09-15

    In this study, impregnation of microporous activated carbon with magnetite was achieved by co-precipitation of iron salts onto activated carbon. The evaluation of the adsorption ability of this material was examined using the anionic dye Reactive Black 5 as model dye pollutant (adsorbate). The effect of pH, ionic strength, contact time and initial dye concentration were also studied. It was found that high pH and high ionic strength favor the adsorption of Reactive Black 5. The adsorption kinetics and isotherms were well fitted by the fractal BS model and Langmuir model, respectively. The impregnation with magnetite decreases the adsorption capacity of activated carbon. Thermal re-activation of dye-loaded activated carbons was also succeeded. The characterization of the magnetic carbons was investigated by various techniques (SEM/EDAX, VSM, BET, FTIR, XRD, DTG) revealing many possible interactions in the carbon-dye system.

  19. Probing the role of P dbnd O stretching mode enhancement in nerve-agent sensors: Simulation of the adsorption of diisopropylfluorophosphate on the model MgO and CaO surfaces

    NASA Astrophysics Data System (ADS)

    Kolodziejczyk, Wojciech; Majumdar, D.; Roszak, Szczepan; Leszczynski, Jerzy

    2007-12-01

    The interactions of diisopropylfluorophosphate (DFP) with model MgO and CaO surfaces have been investigated using density functional (DFT) and Møller-Plesset second order perturbation techniques. The geometries were fully optimized at the DFT level. The calculated interaction energies and the corresponding thermodynamic properties show that DFP is physisorbed on these two model oxide surfaces and adsorption on the MgO surface is stronger. Analyses of the calculated IR and Raman spectra point to the enhancement of the P dbnd O stretching mode with respect to the isolated DFP and this property could be used to detect nerve-agents using surface-enhanced Raman spectroscopy.

  20. Characterization and reactivity of sodium aluminoborosilicate glass fiber surfaces

    NASA Astrophysics Data System (ADS)

    Ortiz Rivera, Lymaris; Bakaev, Victor A.; Banerjee, Joy; Mueller, Karl T.; Pantano, Carlo G.

    2016-05-01

    Multicomponent complex oxides, such as sodium aluminoborosilicate glass fibers, are important materials used for thermal insulation in buildings and homes. Although the surface properties of single oxides, such as silica, have been extensively studied, less is known about the distribution of reactive sites at the surface of multicomponent oxides. Here, we investigated the reactivity of sodium aluminoborosilicate glass fiber surfaces for better understanding of their interface chemistry and bonding with acrylic polymers. Acetic acid (with and without a 13C enrichment) was used as a probe representative of the carboxylic functional groups in many acrylic polymers and adhesives. Inverse gas chromatography coupled to a mass spectrometer (IGC-MS), and solid state nuclear magnetic resonance (NMR), were used to characterize the fiber surface reactions and surface chemical structure. In this way, we discovered that both sodium ions in the glass surface, as well as sodium carbonate salts that formed on the surface due to the intrinsic reactivity of this glass in humid air, are primary sites of interaction with the carboxylic acid. Surface analysis by X-ray photoelectron spectroscopy (XPS) confirmed the presence of sodium carbonates on these surfaces. Computer simulations of the interactions between the reactive sites on the glass fiber surface with acetic acid were performed to evaluate energetically favorable reactions. The adsorption reactions with sodium in the glass structure provide adhesive bonding sites, whereas the reaction with the sodium carbonate consumes the acid to form sodium-carboxylate, H2O and CO2 without any contribution to chemical bonding at the interface.

  1. Ionization characteristics of the Cys-25/His-159 interactive system and of the modulatory group of papain: resolution of ambiguity by electronic perturbation of the quasi-2-mercaptopyridine leaving group in a new pyrimidyl disulphide reactivity probe.

    PubMed Central

    Mellor, G W; Thomas, E W; Topham, C M; Brocklehurst, K

    1993-01-01

    1. A new thiol-specific reactivity probe 4,4'-dipyrimidyl disulphide [compound (VII), m.p. 110 degrees C, pKa of its monohydronated form 0.91] was synthesized and used to resolve the ambiguity of interpretation of the behaviour of papain (EC 3.4.22.2) in alkaline media known to depend to varying extents on two ionizations with pKa values approx. 8.0-8.5 and > or = 9.5 respectively. 2. A new extensive pH-second-order rate constant (k) data set for the reaction of papain with 2-(acetamido)-ethyl 2'-pyridyl disulphide (IV) demonstrated the existence of a striking rate maximum at pH approx. 4, the independence of k around pH 8 and the increase in k with increase in pH across a pKa value of 10.0, behaviour similar to that of other 2-pyridyl disulphides (R-S-S-2-Py) that lack key substrate-like binding sites in R. 3. Although the simplest interpretation of the pKa value of 10.0 assigns it to the formation of (Cys-25)-S-/(His-159)-Im from the ion-pair state of the papain catalytic site, another interpretation may be conceived in which this pKa value is assigned to another group remote from the catalytic site, the state of ionization of which modulates catalytic-site behaviour. This alternative assignment is shown to require compensating effects in the pH region around 8 such that the formation of (Cys-25)-S-/(His-159)-Im across pKa 8.0-8.5 is without net kinetic effect in the reactions of simple 2-pyridyl disulphides such as compound (IV) and 2,2'-dipyridyl disulphide (II). 4. The lower basicity of compound (VII) relative to that of compound (II) (pKa 2.45) was predicted to diminish or abolish the compensation postulated as a possibility in reactions of 2-pyridyl disulphides because of the decreased effectiveness of reaction via a (His-159)-Im+H-assisted transition state. The characteristics of the pH-dependence of the reaction of papain with compound (VII) which are quite different from those for its reaction with compound (II) support both this prediction and the

  2. Optical probe

    DOEpatents

    Hencken, Kenneth; Flower, William L.

    1999-01-01

    A compact optical probe is disclosed particularly useful for analysis of emissions in industrial environments. The instant invention provides a geometry for optically-based measurements that allows all optical components (source, detector, rely optics, etc.) to be located in proximity to one another. The geometry of the probe disclosed herein provides a means for making optical measurements in environments where it is difficult and/or expensive to gain access to the vicinity of a flow stream to be measured. Significantly, the lens geometry of the optical probe allows the analysis location within a flow stream being monitored to be moved while maintaining optical alignment of all components even when the optical probe is focused on a plurality of different analysis points within the flow stream.

  3. Adsorption and diffusion of water on graphene from first principles

    NASA Astrophysics Data System (ADS)

    Ma, Jie; Michaelides, Angelos; Alfè, Dario; Schimka, Laurids; Kresse, Georg; Wang, Enge

    2011-07-01

    Water monomer adsorption on graphene is examined with state-of-the-art electronic structure approaches. The adsorption energy determinations on this system from quantum Monte Carlo and the random-phase approximation yield small values of <100 meV. These benchmarks provide a deeper understanding of the reactivity of graphene that may underpin the development of improved more approximate methods enabling the accurate treatment of more complex processes at wet-carbon interfaces. As an example, we show how dispersion-corrected density functional theory, which we show gives a satisfactory description of this adsorption system, predicts that water undergoes ultra-fast diffusion on graphene at low temperatures.

  4. Adsorption Refrigeration System

    SciTech Connect

    Wang, Kai; Vineyard, Edward Allan

    2011-01-01

    Adsorption refrigeration is an environmentally friendly cooling technology which could be driven by recovered waste heat or low-grade heat such as solar energy. In comparison with absorption system, an adsorption system has no problems such as corrosion at high temperature and salt crystallization. In comparison with vapor compression refrigeration system, it has the advantages of simple control, no moving parts and less noise. This paper introduces the basic theory of adsorption cycle as well as the advanced adsorption cycles such as heat and mass recovery cycle, thermal wave cycle and convection thermal wave cycle. The types, characteristics, advantages and drawbacks of different adsorbents used in adsorption refrigeration systems are also summarized. This article will increase the awareness of this emerging cooling technology among the HVAC engineers and help them select appropriate adsorption systems in energy-efficient building design.

  5. Reactive sintering and reactive hot

    NASA Astrophysics Data System (ADS)

    Murray, J. C.; German, R. M.

    1992-09-01

    NbAl3 has been synthesized from elemental powders by reactive sintering (RS) and reactive hot isostatic pressing (RHIP). Both processes involve a self-propagating exothermic reaction between the constituent powders to form an intermetallic compound. The RHIP approach uses simultaneous external pressurization to make a higher density product. This study focused on developing a method to use reactive synthesis to form high-density NbAl3 compacts. High RS and RHIP densities were possible with the appropriate raw materials and processing parameters. These include powder purity, particle sizes, degassing, heating rate, furnace temperature, and compaction pressures. Near full density was attained with RHIP, and up to 95 pct density was attained with RS.

  6. Problems affecting the fidelity of pressure measuring instruments for planetary probes

    NASA Technical Reports Server (NTRS)

    Hudson, J. B.

    1972-01-01

    Determination is made of the nature and magnitude of surface-related effects that cause errors in pressure measuring instruments, with special reference being made to instruments intended for use in planetary probes. The interaction of gases with clean surfaces of metals likely to be used as gage construction materials was studied. Special emphasis was placed on the adsorption, chemical reaction, and electron-induced desorption processes. The results indicated that all metals tested were subject to surface processes which would degrade gage fidelity. It was also found, however, that the formation of inert adsorbed layers on these metal surfaces, such as carbon on platinum, greatly reduced or eliminated these effects. This process, combined with a system design which avoids contact between reactive gases and hot filaments, appears to offer the most promising solution to the gage fidelity problem.

  7. Surface-enhanced Raman scattering (SERS) dosimeter and probe

    DOEpatents

    Vo-Dinh, Tuan

    1995-01-01

    A dosimeter and probe for measuring exposure to chemical and biological compounds is disclosed. The dosimeter or probe includes a collector which may be analyzed by surface-enhanced Raman spectroscopy. The collector comprises a surface-enhanced Raman scattering-active material having a coating applied thereto to improve the adsorption properties of the collector. The collector may also be used in automated sequential devises, in probe array devices.

  8. Surface-enhanced Raman scattering (SERS) dosimeter and probe

    DOEpatents

    Vo-Dinh, T.

    1995-03-21

    A dosimeter and probe for measuring exposure to chemical and biological compounds is disclosed. The dosimeter or probe includes a collector which may be analyzed by surface-enhanced Raman spectroscopy. The collector comprises a surface-enhanced Raman scattering-active material having a coating applied thereto to improve the adsorption properties of the collector. The collector may also be used in automated sequential devices, in probe array devices. 10 figures.

  9. A Simple Adsorption Experiment

    ERIC Educational Resources Information Center

    Guirado, Gonzalo; Ayllon, Jose A.

    2011-01-01

    The study of adsorption phenomenon is one of the most relevant and traditional physical chemistry experiments performed by chemistry undergraduate students in laboratory courses. In this article, we describe an easy, inexpensive, and straightforward way to experimentally determine adsorption isotherms using pieces of filter paper as the adsorbent…

  10. Silicon-doping in carbon nanotubes: formation energies, electronic structures, and chemical reactivity.

    PubMed

    Bian, Ruixin; Zhao, Jingxiang; Fu, Honggang

    2013-04-01

    By carrying out density functional theory (DFT) calculations, we have studied the effects of silicon (Si)-doping on the geometrical and electronic properties, as well as the chemical reactivity of carbon nanotubes (CNTs). It is found that the formation energies of these nanotubes increase with increasing tube diameters, indicating that the embedding of Si into narrower CNTs is more energetically favorable. For the given diameters, Si-doping in a (n, 0) CNT is slightly easier than that of in (n, n) CNT. Moreover, the doped CNTs with two Si atoms are easier to obtain than those with one Si atom. Due to the introduction of impurity states after Si-doping, the electronic properties of CNTs have been changed in different ways: upon Si-doping into zigzag CNTs, the band gap of nanotube is decreased, while the opening of band gap in armchair CNTs is found. To evaluate the chemical reactivity of Si-doped CNTs, the adsorption of NH3 and H2O on this kind of material is explored. The results show that N-H bond of NH3 and O-H bond of H2O can be easily split on the surface of doped CNTs. Of particular interest, the novel reactivity makes it feasible to use Si-doped CNT as a new type of splitter for NH3 and H2O bond, which is very important in chemical and biological processes. Future experimental studies are greatly desired to probe such interesting processes.

  11. Pollution Probe.

    ERIC Educational Resources Information Center

    Chant, Donald A.

    This book is written as a statement of concern about pollution by members of Pollution Probe, a citizens' anti-pollution group in Canada. Its purpose is to create public awareness and pressure for the eventual solution to pollution problems. The need for effective government policies to control the population explosion, conserve natural resources,…

  12. Gas sampling system for reactive gas-solid mixtures

    DOEpatents

    Daum, Edward D.; Downs, William; Jankura, Bryan J.; McCoury, Jr., John M.

    1990-01-01

    An apparatus and method for sampling gas containing a reactive particulate solid phase flowing through a duct and for communicating a representative sample to a gas analyzer. A sample probe sheath 32 with an angular opening 34 extends vertically into a sample gas duct 30. The angular opening 34 is opposite the gas flow. A gas sampling probe 36 concentrically located within sheath 32 along with calibration probe 40 partly extends in the sheath 32. Calibration probe 40 extends further in the sheath 32 than gas sampling probe 36 for purging the probe sheath area with a calibration gas during calibration.

  13. Gas sampling system for reactive gas-solid mixtures

    DOEpatents

    Daum, Edward D.; Downs, William; Jankura, Bryan J.; McCoury, Jr., John M.

    1989-01-01

    An apparatus and method for sampling a gas containing a reactive particulate solid phase flowing through a duct and for communicating a representative sample to a gas analyzer. A sample probe sheath 32 with an angular opening 34 extends vertically into a sample gas duct 30. The angular opening 34 is opposite the gas flow. A gas sampling probe 36 concentrically located within sheath 32 along with calibration probe 40 partly extend in the sheath 32. Calibration probe 40 extends further in the sheath 32 than gas sampling probe 36 for purging the probe sheath area with a calibration gas during calibration.

  14. Impact of interactions between metal oxides to oxidative reactivity of manganese dioxide.

    PubMed

    Taujale, Saru; Zhang, Huichun

    2012-03-06

    Manganese oxides typically exist as mixtures with other metal oxides in soil-water environments; however, information is only available on their redox activity as single oxides. To bridge this gap, we examined three binary oxide mixtures containing MnO(2) and a secondary metal oxide (Al(2)O(3), SiO(2) or TiO(2)). The goal was to understand how these secondary oxides affect the oxidative reactivity of MnO(2). SEM images suggest significant heteroaggregation between Al(2)O(3) and MnO(2) and to a lesser extent between SiO(2)/TiO(2) and MnO(2). Using triclosan and chlorophene as probe compounds, pseudofirst-order kinetic results showed that Al(2)O(3) had the strongest inhibitory effect on MnO(2) reactivity, followed by SiO(2) and then TiO(2). Al(3+) ion or soluble SiO(2) had comparable inhibitory effects as Al(2)O(3) or SiO(2), indicating the dominant inhibitory mechanism was surface complexation/precipitation of Al/Si species on MnO(2) surfaces. TiO(2) inhibited MnO(2) reactivity only when a limited amount of triclosan was present. Due to strong adsorption and slow desorption of triclosan by TiO(2), precursor-complex formation between triclosan and MnO(2) was much slower and likely became the new rate-limiting step (as opposed to electron transfer in all other cases). These mechanisms can also explain the observed adsorption behavior of triclosan by the binary oxide mixtures and single oxides.

  15. What Is Reactive Arthritis?

    MedlinePlus

    ... Arthritis PDF Version Size: 69 KB November 2014 What is Reactive Arthritis? Fast Facts: An Easy-to- ... Information About Reactive Arthritis and Other Related Conditions What Causes Reactive Arthritis? Sometimes, reactive arthritis is set ...

  16. Mediation of the nanotribological properties of cellulose by chitosan adsorption.

    PubMed

    Nordgren, Niklas; Eronen, Paula; Osterberg, Monika; Laine, Janne; Rutland, Mark W

    2009-03-09

    Cellulosic model surfaces functionalized with chitosan, a naturally occurring cationic biomacromolecule, by in situ adsorption have been studied with an atomic force microscope (AFM) in colloidal probe configuration. The interaction forces on approach and separation, as well as the nanotribological properties, were shown to be highly pH-dependent, and a significant difference in the behavior was seen before and after chitosan adsorption. In general, all forces on approach showed a highly repulsive interaction at shorter distances due to deformation of the probe. At high pH, before chitosan adsorption, a long-range electrostatic repulsion was observed, consistent with DLVO theory. However, at low pH no electrostatic contribution was found before adsorption, probably due to charge neutralization of carboxyl groups. After chitosan adsorption, repulsive forces acting over a much longer distance than predicted by DLVO theory were present at low pH. This effect was ascribed to chain extension of the chitosan species of which the magnitude and the range of the force increased dramatically with higher charge at low pH. In all cases, a typical saw-tooth patterned adhesion was present, with pull-off events occurring at different separations. The frequency of these events after chitosan adsorption was greatly increased at longer distances. Additionally, the adsorbed chitosan markedly reduced the friction, where the largest effect was a 7-fold decrease of the friction coefficient observed at low pH.

  17. Scanning probe microscopy in catalysis.

    PubMed

    Yeung, King Lun; Yao, Nan

    2004-09-01

    This review discusses the recent progress in the application of scanning probe microscopy (SPM) in catalysis. SPM proves to be an invaluable technique for imaging catalytic surfaces and interfaces. Most SPM research is related to the structural and morphological transformation associated with catalyst preparation and use. Real-time SPM observation of surface dynamics including adsorption, diffusion and reaction, provides invaluable insights to the mechanism of catalysis. SPM is also used to shape and manipulate surfaces and surface processes. Fabrication of nanostructured catalysts, direct manipulation of adsorbed atoms and molecules and tip-mediated reactions are some examples of new SPM approach in catalyst research.

  18. LOCATION AND CHARACTERIZATION OF SUBSURFACE ANOMALIES USING A SOIL CONDUCTIVITY PROBE

    EPA Science Inventory

    An electrical conductivity probe, designed for use with "direct push" technology, has been successfully used to locate buried drums, contaminant plumes, and to precisely locate and characterize a previously installed permeable reactive iron wall. The conductivity probe was desig...

  19. Hybrid adsorptive membrane reactor

    NASA Technical Reports Server (NTRS)

    Tsotsis, Theodore T. (Inventor); Sahimi, Muhammad (Inventor); Fayyaz-Najafi, Babak (Inventor); Harale, Aadesh (Inventor); Park, Byoung-Gi (Inventor); Liu, Paul K. T. (Inventor)

    2011-01-01

    A hybrid adsorbent-membrane reactor in which the chemical reaction, membrane separation, and product adsorption are coupled. Also disclosed are a dual-reactor apparatus and a process using the reactor or the apparatus.

  20. Generalized random sequential adsorption

    NASA Astrophysics Data System (ADS)

    Tarjus, G.; Schaaf, P.; Talbot, J.

    1990-12-01

    Adsorption of hard spherical particles onto a flat uniform surface is analyzed by using generalized random sequential adsorption (RSA) models. These models are defined by releasing the condition of immobility present in the usual RSA rules to allow for desorption or surface diffusion. Contrary to the simple RSA case, generalized RSA processes are no longer irreversible and the system formed by the adsorbed particles on the surface may reach an equilibrium state. We show by using a distribution function approach that the kinetics of such processes can be described by means of an exact infinite hierarchy of equations reminiscent of the Kirkwood-Salsburg hierarchy for systems at equilibrium. We illustrate the way in which the systems produced by adsorption/desorption and by adsorption/diffusion evolve between the two limits represented by ``simple RSA'' and ``equilibrium'' by considering approximate solutions in terms of truncated density expansions.

  1. Hybrid adsorptive membrane reactor

    SciTech Connect

    Tsotsis, Theodore T.; Sahimi, Muhammad; Fayyaz-Najafi, Babak; Harale, Aadesh; Park, Byoung-Gi; Liu, Paul K. T.

    2011-03-01

    A hybrid adsorbent-membrane reactor in which the chemical reaction, membrane separation, and product adsorption are coupled. Also disclosed are a dual-reactor apparatus and a process using the reactor or the apparatus.

  2. Adsorption of Atmospheric Gases on Pu Surfaces

    SciTech Connect

    Nelson, A J; Holliday, K S; Stanford, J A; Grant, W K; Erler, R G; Allen, P G; McLean, W; Roussel, P

    2012-03-29

    Surface adsorption represents a competition between collision and scattering processes that depend on surface energy, surface structure and temperature. The surface reactivity of the actinides can add additional complexity due to radiological dissociation of the gas and electronic structure. Here we elucidate the chemical bonding of gas molecules adsorbed on Pu metal and oxide surfaces. Atmospheric gas reactions were studied at 190 and 300 K using x-ray photoelectron spectroscopy. Evolution of the Pu 4f and O 1s core-level states were studied as a function of gas dose rates to generate a set of Langmuir isotherms. Results show that the initial gas dose forms Pu{sub 2}O{sub 3} on the Pu metal surface followed by the formation of PuO{sub 2} resulting in a layered oxide structure. This work represents the first steps in determining the activation energy for adsorption of various atmospheric gases on Pu.

  3. A review on chitosan-based adsorptive membranes.

    PubMed

    Salehi, Ehsan; Daraei, Parisa; Arabi Shamsabadi, Ahmad

    2016-11-05

    Membrane adsorbents have emerged as powerful and attractive tools for the removal of hazardous materials such as dyes and heavy metal ions, mainly in trace amounts, from water resources. Among membrane adsorbents, those prepared from or modified with chitosan biopolymer and its derivatives are cases of interest because of chitosan advantages including biocompatibility, biodegradability, nontoxicity, reactivity, film and fiber forming capacity and favorable hydrophilicity. This review is oriented to provide a framework for better insight into fabrication methods and applications of chitosan-based adsorptive membranes. Critical aspects including thermokinetic analyses of adsorption and regeneration capacity of the membrane adsorbents have been also overviewed. Future of chitosan-based adsorptive membranes might include efforts for the improvement of mechanical stability and reusability and also most targeted application of appropriate copolymers as well as nanostructures in preparing high performance adsorptive membranes.

  4. Modeling the 3D structure of wheat subtilisin/chymotrypsin inhibitor (WSCI). Probing the reactive site with two susceptible proteinases by time-course analysis and molecular dynamics simulations.

    PubMed

    Facchiano, Angelo M; Costantini, Susan; Di Maro, Antimo; Panichi, Daniela; Chambery, Angela; Parente, Augusto; Di Gennaro, Simone; Poerio, Elia

    2006-07-01

    Comparative modeling and time-course hydrolysis experiments have been applied to investigate two enzyme-inhibitor complexes formed between the wheat subtilisin-chymotrypsin inhibitor (WSCI) and two susceptible proteinases. WSCI represents the first case of a wheat protein inhibitor active against animal chymotrypsins and bacterial subtilisins. The model was created using as template structure that of the CI-2A inhibitor from barley (PDB code: 2CI2), which shares 87% sequence identity with WSCI. Under these conditions of high similarity, the comparative modeling approach can be successfully applied. We predicted the WSCI 3D model and used it to investigate enzyme-inhibitor complex systems. Experimental observations indicated that chymotrypsin, but not subtilisin, in addition to cleavage at the primary reactive site Met48-Glu49, is able to hydrolyze a second peptide bond between Phe58 and Val59. Here, we report on cleavage of the peptide bond at the inhibitor's reactive site (Met48-Glu49) determined using time-course hydrolysis experiments; the same event was investigated for both subtilisin/WSCI and chymotrypsin/WSCI complexes using molecular dynamics simulations. The molecular details of the initial inhibitor-enzyme interactions, as well as of the changes observed during the simulations, allow us to speculate on the different fates of the two WSCI-proteinase complexes.

  5. Silsesquioxane nanoparticles with reactive internal functional groups

    NASA Astrophysics Data System (ADS)

    Brozek, Eric M.; Washton, Nancy M.; Mueller, Karl T.; Zharov, Ilya

    2017-02-01

    A series of silsesquioxane nanoparticles containing reactive internal organic functionalities throughout the entire particle body have been synthesized using a surfactant-free method with organosilanes as the sole precursors and a base catalyst. The organic functional groups incorporated are vinyl, allyl, mercapto, cyanoethyl, and cyanopropyl groups. The sizes and morphologies of the particles were characterized using SEM and nitrogen adsorption, while the compositions were confirmed using TGA, FT-IR, solid state NMR, and elemental analysis. The accessibility and reactivity of the functional groups inside the particles were demonstrated by performing bromination and reduction reactions in the interior of the particles.

  6. ICES ON TITAN: LABORATORY MEASUREMENTS THAT COMPLEMENT THE HUYGENS PROBE

    SciTech Connect

    J. ROBINSON; ET AL

    2000-08-01

    This is the final report of a three-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The composition of the cold bodies in the outer solar system may hold some of the key molecular clues concerning the composition of the prestellax molecular cloud that gave rise to the solar system. We studied the physical chemistry and heterogeneous (gas/surface) reactivity of extraterrestrial ice analogs of the surfaces of Saturn's moon Titan. This program coupled our surface spectroscopic techniques with physical adsorption measurements. We addressed several of the pressing questions regarding Titan such as: Is storage of hydrocarbons in Titan's water ice crust feasible? Do heterogeneous processes influence the atmospheric chemical composition of Titan? Are phase transitions to be expected? These data can be incorporated into photochemical models with the goal of improved modeling of the chemical composition and meteorology of Titan's atmosphere. Titan will be probed by the Cassini-Huygens Mission. Our results on Titan ice analogs can be used to help interpret the mission data.

  7. The 'reactive

    NASA Astrophysics Data System (ADS)

    Battista Piccardo, Giovanni; Guarnieri, Luisa

    2010-05-01

    The Ligurian ophiolitic peridotites [South Lanzo, Erro-Tobbio, Internal Ligurides and Corsica] are characterized by the abundance of spinel(Sp) peridotites showing depleted compositions and ranging from Cpx-poor Sp lherzolites to Sp harzburgites. They were recognized in the last decades as refractory residua by MORB-forming partial melting of the asthenosphere, and were similar to abyssal peridotites. Recent structural and compositional studies promoted a better understanding of their structural and compositional features and their genetic processes. In the field these depleted peridotites replace with primary contacts pyroxenite-bearing fertile Sp lherzolites that have been recognized as sub-continental lithospheric mantle. Field relationships evidence that decametric-hectometric bodies of pristine pyroxenite-veined lithospheric Sp lherzolites are preserved as structural remnants within the km-scale masses of depleted peridotites. The depleted peridotites show coarse-grained recrystallized textures and reaction micro-structures indicating pyroxene dissolution and olivine precipitation that have been considered as records of melt/peridotite interaction during reactive diffuse porous flow of undersaturated melts. They show, moreover, contrasting bulk and mineral chemistries that cannot be produced by simple partial melting and melt extraction. In particular, their bulk compositions are depleted in SiO2 and enriched in FeO with respect to refractory residua after any kind of partial melting, as calculated by Niu (1997), indicating that they cannot be formed by simple partial melting and melt extraction processes. Moreover, TiO2 content in Sp is usually significantly higher (up to 0.8-1.0 wt%) than typical TiO2 contents of spinels (usually < 0.1-0.2 wt %) in fertile mantle peridotites and melting refractory residua, indicating that spinel attained element equilibration with a Ti-bearing basaltic melt. The depleted peridotites usually show strongly variable Cpx modal

  8. Adsorption of star polymers

    NASA Astrophysics Data System (ADS)

    Halperin, A.; Joanny, J. F.

    1991-06-01

    The adsorption of star polymers on a flat solid surface is analyzed by means of scalling arguments based on the Daoud-Cotton blob model. For the adsorption of a single star, consisting of f arms comprising each N monomers, we distinguish three regimes determined by the adsorption energy of a monomer at the surface, δ kT. 1) Strong adsorption characterized by the full adsorption of all arms occurs for δ > (f/N)^{3/5}. 2) A “Sombrero” like structure comprising f_ads fully adsorbed arms and f{-}f_ads free arms is obtained for (f/N)^{3/5}> δ > f^{9/20}/N^{3/5}. 3) Weakly adsorbed stars retain, essentially, the structure of a free star. This regime occurs for δ < f^{9/20}/N^{3/5}. The weakly adsorbed structure may also exist as a metastable state if δ > f^{9/5}/N^{3/5}. Nous étudions l'adsorption de polymères en étoile sur une surface solide en utilisant une approche de lois d'échelles basée sur le modèle de blobs de Daoud et Cotton. Pour une étoile formée de f bras contenant chacun N monomères, nous distinguons trois régimes suivant la valeur de l'énergie d'adsorption d'un monomère sur la surface δ kT. 1) L'adsorption forte caractérisée par une adsorption complète de tous les bras se produit lorsque δ > (f/N)^{3/5}. 2) Une structure en “sombrero” avec f_ads bras adsorbés et f{-}f_ads bras libres est obtenue si f^{9/20}/N^{3/5}δ < (f/N)^{3/5}. 3) Les étoiles faiblement adsorbées gardent une structure très similaire à celle des étoiles libres en solution. Ce régime existe si δ < f^{9/20}/N^{3/5}. La structure correspondant aux étoiles faiblement adsorbées peut aussi exister comme un état métastable si δ > f^{9/5}/N^{3/5}.

  9. The influence of CO adsorption on the surface composition of cobalt/palladium alloys

    NASA Astrophysics Data System (ADS)

    Murdoch, A.; Trant, A. G.; Gustafson, J.; Jones, T. E.; Noakes, T. C. Q.; Bailey, P.; Baddeley, C. J.

    2016-04-01

    Segregation induced by the adsorption of gas phase species can strongly influence the composition of bimetallic surfaces and can therefore play an important role in influencing heterogeneous catalytic reactions. The addition of palladium to cobalt catalysts has been shown to promote Fischer Tropsch catalysis. We investigate the adsorption of CO onto bimetallic CoPd surfaces on Pd{111} using a combination of reflection absorption infrared spectroscopy and medium energy ion scattering. The vibrational frequency of adsorbed CO provides crucial information on the adsorption sites adopted by CO and medium energy ion scattering probes the surface composition before and after CO exposure. We show that cobalt segregation is induced by CO adsorption and rationalise these observations in terms of the strength of adsorption of CO in various surface adsorption sites.

  10. Study of char gasification in a reaction/adsorption apparatus

    SciTech Connect

    Sotirchos, S.V.; Crowley, J.A.

    1987-09-01

    The reaction of an activated carbon (coconut char) with CO/sub 2/ was studied in a reaction/adsorption apparatus which allows successive reactivity and physical adsorption measurements to be made on the same solid sample. Reaction and surface area evolution data were obtained in the temperature range from 800 to 900/sup 0/C. All reaction rate trajectories obtained in this study showed a maximum in the reaction rate, 2-3 times higher than the initial rate, at about 85% conversion. There was no correlation between these results and the evolution of the internal surface area although the reaction appeared to take place initially in the kinetically controlled regime.

  11. Gas surface Interactions with Nanocatalysts: Particle Size Effects in the Adsorption Dynamics of CO on Supported Gold Cluster

    SciTech Connect

    Kadossov, E.; Lu, M.; Justin, J.; Rosenmann, D.; Ocola, L.E.; Cabrini, S.; Burghaus, U.

    2009-12-01

    We present evidence that adsorption probabilities (gas-surface adsorption dynamics) of CO depend distinctly on the Au cluster size, with a reactivity maximum at {approx}3 nm. This cluster size is consistent with the legendary reactivity enhancement seen for the CO-oxidation reaction. Electron beam lithography has been used to fabricate some of the samples (down to 12 nm) as well as physical vapor deposition.

  12. Modeling oxyanion adsorption on ferralic soil, part 2: chromate, selenate, molybdate, and arsenate adsorption.

    PubMed

    Pérez, Claudio; Antelo, Juan; Fiol, Sarah; Arce, Florencio

    2014-10-01

    High levels of oxyanions are found in the soil environment, often as a result of human activity. At high concentrations, oxyanions can be harmful to both humans and wildlife. Information about the interactions between oxyanions and natural samples is essential for understanding the bioavailability, toxicity, and transport of these compounds in the environment. In the present study, the authors investigated the reactivity of different oxyanions (AsO4 , MoO4 , SeO4 , and CrO4 ) at different pH values in 2 horizons of a ferralic soil. By combining available microscopic data on iron oxides with the macroscopic data obtained, the authors were able to use the charge distribution model to accurately describe the adsorption of these 4 oxyanions and thus to determine the surface speciation. The charge distribution model was previously calibrated and evaluated using phosphate adsorption/desorption data. The adsorption behavior on ferralic soil is controlled mainly by the natural iron oxides present, and it is qualitatively analogous to that exhibited by synthetic iron oxides. The highest adsorption was found for arsenate ions, whereas the lowest was found for selenate, with chromate and molybdate ions showing an intermediate behavior.

  13. New Adsorption Methods.

    ERIC Educational Resources Information Center

    Wankat, Phillip C.

    1984-01-01

    Discusses a simple method for following the movement of a solute in an adsorption or ion exchange system. This movement is used to study a variety of operational methods, including continuous flow and pulsed flow counter-current operations and simulated counter-current systems. Effect of changing thermodynamic variables is also considered. (JM)

  14. SEPARATION BY ADSORPTION

    DOEpatents

    Lowe, C.S.

    1959-06-16

    Separation of Pu from fission products by adsorption on hydrous aluminum silicate is described. The Pu in a HNO/sub 3/ solution is oxidized to the hexavalent state and contacted with the silicate which adsorbs fission products. (T.R.H.)

  15. Acidity characterization of heterogeneous catalysts by solid-state NMR spectroscopy using probe molecules.

    PubMed

    Zheng, Anmin; Liu, Shang-Bin; Deng, Feng

    2013-01-01

    Characterization of the surface acidic properties of solid acid catalysts is a key issue in heterogeneous catalysis. Important acid features of solid acids, such as their type (Brønsted vs. Lewis acid), distribution and accessibility (internal vs. external sites), concentration (amount), and strength of acid sites are crucial factors dictating their reactivity and selectivity. This short review provides information on different solid-state NMR techniques used for acidity characterization of solid acid catalysts. In particular, different approaches using probe molecules containing a specific nucleus of interest, such as pyridine-d5, 2-(13)C-acetone, trimethylphosphine, and trimethylphosphine oxide, are compared. Incorporation of valuable information (such as the adsorption structure, deprotonation energy, and NMR parameters) from density functional theory (DFT) calculations can yield explicit correlations between the chemical shift of adsorbed probe molecules and the intrinsic acid strength of solid acids. Methods that combine experimental NMR data with DFT calculations can therefore provide both qualitative and quantitative information on acid sites.

  16. Influence of the pore structure and surface chemical properties of activated carbon on the adsorption of mercury from aqueous solutions.

    PubMed

    Lu, Xincheng; Jiang, Jianchun; Sun, Kang; Wang, Jinbiao; Zhang, Yanping

    2014-01-15

    Reactivation and chemical modification were used to obtain modified activated carbons with different pore structure and surface chemical properties. The samples were characterized by nitrogen absorption-desorption, Fourier transform infrared spectroscopy and the Bothem method. Using mercury chloride as the target pollutant, the Hg(2+) adsorption ability of samples was investigated. The results show that the Hg(2+) adsorption capacity of samples increased significantly with increases in micropores and acidic functional groups and that the adsorption process was exothermic. Different models and thermodynamic parameters were evaluated to establish the mechanisms. It was concluded that the adsorption occurred through a monolayer mechanism by a two-speed process involving both rapid adsorption and slow adsorption. The adsorption rate was determined by chemical reaction.

  17. Arsenate adsorption mechanisms at the allophane - Water interface

    USGS Publications Warehouse

    Arai, Y.; Sparks, D.L.; Davis, J.A.

    2005-01-01

    We investigated arsenate (As(V)) reactivity and surface speciation on amorphous aluminosilicate mineral (synthetic allophane) surfaces using batch adsorption experiments, powder X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The adsorption isotherm experiments indicated that As(V) uptake increased with increasing [As(V)]0 from 50 to 1000 ??M (i.e., Langmuir type adsorption isotherm) and that the total As adsorption slightly decreased with increasing NaCl concentrations from 0.01 to 0.1 M. Arsenate adsorption was initially (0-10 h) rapid followed by a slow continuum uptake, and the adsorption processes reached the steady state after 720 h. X-ray absorption spectroscopic analyses suggest that As(V) predominantly forms bidentate binuclear surface species on aluminum octahedral structures, and these species are stable up to 11 months. Solubility calculations and powder XRD analyses indicate no evidence of crystalline AI-As(V) precipitates in the experimental systems. Overall, macroscopic and spectroscopic evidence suggest that the As(V) adsorption mechanisms at the allophane-water interface are attributable to ligand exchange reactions between As(V) and surface-coordinated water molecules and hydroxyl and silicate ions. The research findings imply that dissolved tetrahedral oxyanions (e.g., H2PO42- and H2AsO42-) are readily retained on amorphous aluminosilicate minerals in aquifer and soils at near neutral pH. The innersphere adsorption mechanisms might be important in controlling dissolved arsenate and phosphate in amorphous aluminosilicate-rich low-temperature geochemical environments. ?? 2005 American Chemical Society.

  18. Orbitalwise Coordination Number for Predicting Adsorption Properties of Metal Nanocatalysts

    NASA Astrophysics Data System (ADS)

    Ma, Xianfeng; Xin, Hongliang

    2017-01-01

    We present the orbitalwise coordination number CNα (α =s or d ) as a reactivity descriptor for metal nanocatalysts. With the noble metal Au (5 d106 s1 ) as a specific case, the CNs computed using the two-center s -electron hopping integrals to neighboring atoms provides an accurate and robust description of the trends in CO and O adsorption energies on extended surfaces terminated with different facets and nanoparticles of varying size and shape, outperforming existing bond-counting methods. Importantly, the CNs has a solid physiochemical basis via a direct connection to the moment characteristics of the projected density of states onto the s orbital of a Au adsorption site. Furthermore, the CNs shows promise as a viable descriptor for predicting adsorption properties of Au alloy nanoparticles with size-dependent lattice strains and coinage metal ligands.

  19. Orbitalwise Coordination Number for Predicting Adsorption Properties of Metal Nanocatalysts.

    PubMed

    Ma, Xianfeng; Xin, Hongliang

    2017-01-20

    We present the orbitalwise coordination number CN^{α} (α=s or d) as a reactivity descriptor for metal nanocatalysts. With the noble metal Au (5d^{10}6s^{1}) as a specific case, the CN^{s} computed using the two-center s-electron hopping integrals to neighboring atoms provides an accurate and robust description of the trends in CO and O adsorption energies on extended surfaces terminated with different facets and nanoparticles of varying size and shape, outperforming existing bond-counting methods. Importantly, the CN^{s} has a solid physiochemical basis via a direct connection to the moment characteristics of the projected density of states onto the s orbital of a Au adsorption site. Furthermore, the CN^{s} shows promise as a viable descriptor for predicting adsorption properties of Au alloy nanoparticles with size-dependent lattice strains and coinage metal ligands.

  20. Structural characteristics of modified activated carbons and adsorption of explosives.

    PubMed

    Tomaszewski, W; Gun'ko, V M; Skubiszewska-Zieba, J; Leboda, R

    2003-10-15

    Several series of activated carbons prepared by catalytic and noncatalytic gasification and subsequent deposition of pyrocarbon by pyrolysis of methylene chloride or n-amyl alcohol were studied by FTIR, chromatography, and adsorption methods using nitrogen and probe organics (explosives). The relationships between the textural characteristics of carbon samples and the recovery rates (eta) of explosives on solid-phase extraction (SPE) using different solvents for their elution after adsorption were analyzed using experimental and quantum chemical calculation results. The eta values for nitrate esters, cyclic nitroamines, and nitroaromatics only partially correlate with different adsorbent parameters (characterizing microporosity, mesoporosity, pore size distributions, etc.), polarity of eluting solvents, or characteristics of probe molecules, since there are many factors strongly affecting the recovery rates. Some of the synthesized carbons provide higher eta values than those for such commercial adsorbents as Hypercarb and Envicarb.

  1. Regenerable adsorption system

    NASA Technical Reports Server (NTRS)

    Roychoudhury, Subir (Inventor); Perry, Jay (Inventor); Walsh, Dennis (Inventor)

    2006-01-01

    A method for regenerable adsorption includes providing a substrate that defines at least one layer of ultra short channel length mesh capable of conducting an electrical current therethrough, coating at least a portion of the substrate with a desired sorbent for trace contaminant control or CO.sub.2 sorption, resistively heating the substrate, and passing a flowstream through the substrate and in contact with the sorbent.

  2. Diffusion Influenced Adsorption Kinetics.

    PubMed

    Miura, Toshiaki; Seki, Kazuhiko

    2015-08-27

    When the kinetics of adsorption is influenced by the diffusive flow of solutes, the solute concentration at the surface is influenced by the surface coverage of solutes, which is given by the Langmuir-Hinshelwood adsorption equation. The diffusion equation with the boundary condition given by the Langmuir-Hinshelwood adsorption equation leads to the nonlinear integro-differential equation for the surface coverage. In this paper, we solved the nonlinear integro-differential equation using the Grünwald-Letnikov formula developed to solve fractional kinetics. Guided by the numerical results, analytical expressions for the upper and lower bounds of the exact numerical results were obtained. The upper and lower bounds were close to the exact numerical results in the diffusion- and reaction-controlled limits, respectively. We examined the validity of the two simple analytical expressions obtained in the diffusion-controlled limit. The results were generalized to include the effect of dispersive diffusion. We also investigated the effect of molecular rearrangement of anisotropic molecules on surface coverage.

  3. Spectroscopic study of amino acids adsorption on pyrite surface: From vacuum to solution conditions.

    NASA Astrophysics Data System (ADS)

    Mateo-Marti, E.; Sanchez-Arenillas, M.

    2015-10-01

    We characterized the adsorption of cystine molecules among other amino acids on pyrite surface via X-ray photoelectron spectroscopy. A novel comparative analysis revealed remarkable differences with respect to molecular adsorption and surface chemistry induced by environmental conditions. Pyrite is a highly reactive surface and contains two crucial types of surface functional groups that drive molecular chemistry on the surface depending on the surrounding conditions. Therefore, the systems explored in this study hold interesting implications for supporting catalyzed prebiotic chemistry reactions.

  4. Effect Of Reaction Environments On The Reactivity Of PCB (2-Chlorobiphenyl) Over Activated Carbon Impregnated With Palladized Iron

    EPA Science Inventory

    Reactive activated carbon (RAC) impregnated with palladized iron nanoparticles has been developed to treat polychlorinated biphenyls (PCBs). In this study, we evaluated the effects of various reaction environments on the adsorption-mediated dechlorination of 2-chlorobiphenyl (2-...

  5. Hydrodynamic ultrasonic probe

    DOEpatents

    Day, Robert A.; Conti, Armond E.

    1980-01-01

    An improved probe for in-service ultrasonic inspection of long lengths of a workpiece, such as small diameter tubing from the interior. The improved probe utilizes a conventional transducer or transducers configured to inspect the tubing for flaws and/or wall thickness variations. The probe utilizes a hydraulic technique, in place of the conventional mechanical guides or bushings, which allows the probe to move rectilinearly or rotationally while preventing cocking thereof in the tube and provides damping vibration of the probe. The probe thus has lower friction and higher inspection speed than presently known probes.

  6. Probe tip heating assembly

    SciTech Connect

    Schmitz, Roger William; Oh, Yunje

    2016-10-25

    A heating assembly configured for use in mechanical testing at a scale of microns or less. The heating assembly includes a probe tip assembly configured for coupling with a transducer of the mechanical testing system. The probe tip assembly includes a probe tip heater system having a heating element, a probe tip coupled with the probe tip heater system, and a heater socket assembly. The heater socket assembly, in one example, includes a yoke and a heater interface that form a socket within the heater socket assembly. The probe tip heater system, coupled with the probe tip, is slidably received and clamped within the socket.

  7. Adsorption kinetics, thermodynamics and desorption of natural dissolved organic matter by multiwalled carbon nanotubes.

    PubMed

    Su, Fengsheng; Lu, Chungsying

    2007-09-01

    Multiwalled carbon nanotubes (CNTs) were thermally treated and were employed as adsorbents to study their adsorption kinetics and thermodynamics of natural dissolved organic matter (NDOM) from aqueous solutions. The adsorption kinetics follows the first-order rate law while the adsorption thermodynamics indicates the exothermic and spontaneous nature. A comparative study on the adsorption/desorption properties of NDOM between CNTs and granular activated carbon (GAC) was also conducted and revealed that the CNTs possess more NDOM adsorption capacities and show less weight loss through 10 cycles of water treatment and reactivation than the GAC. This suggests that the CNTs are promising NDOM adsorbents for preventing the microbiological degradation of drinking water quality as well as the formation of disinfection by products in water treatment.

  8. On the physical adsorption of vapors by microporous carbons

    SciTech Connect

    Bradley, R.H. . Inst. of Surface Science and Technology); Rand, B. . Division of Ceramics)

    1995-01-01

    The physical adsorption of nonpolar and polar vapors by active carbons is discussed in relation to pore structure and pore wall chemistry. For nonpolar vapors the Dubinin-Radushkevich equation is used to derive micropore volumes (W[sub 0]), average adsorption energies (E[sub 0]), and micropore widths (L) for a number of systems. These parameters are used to interpret the adsorption behavior of nitrogen which, because it is a relatively small molecule, is frequently used at 77 K to probe porosity and surface area. Results are presented for three carbons from differing precursors, namely, coal, coconut shells, and polyvinylidene chloride (PVDC) to illustrate the applicability of the technique. For the latter carbon increases in micropore size, induced by activation in carbon dioxide, and reductions in accessible pore volume caused by heat treatment in argon are also characterized and related to structural changes. The approach is then extended to the adsorption of larger hydrogen vapors, where the resulting W[sub 0] values may require correction for molecular packing effects which occur in the lower relative pressure regions of the isotherms, i.e., during the filling of ultramicropores. These packing effects are shown to limit the use of the Polanyi characteristic curve for correlating isotherm data for several vapors, of differing molecular size, by one adsorbent. Data for the adsorption of water, which is a strongly polar liquid, have been interpreted using the Dubinin-Serpinsky equation.

  9. Modeling diffusion and adsorption in compacted bentonite: a critical review

    NASA Astrophysics Data System (ADS)

    Bourg, Ian C.; Bourg, Alain C. M.; Sposito, Garrison

    2003-03-01

    The current way of describing diffusive transport through compacted clays is a simple diffusion model coupled to a linear adsorption coefficient ( Kd). To fit the observed results of cation diffusion, this model is usually extended with an adjustable "surface diffusion" coefficient. Description of the negative adsorption of anions calls for a further adjustment through the use of an "effective porosity". The final model thus includes many fitting parameters. This is inconvenient where predictive modeling is called for (e.g., for waste confinement using compacted clay liners). The diffusion/adsorption models in current use have been derived from the common hydrogeological equation of advection/dispersion/adsorption. However, certain simplifications were also borrowed without questioning their applicability to the case of compacted clays. Among these simplifications, the assumption that the volume of the adsorbed phase is negligible should be discussed. We propose a modified diffusion/adsorption model that accounts for the volume of the adsorbed phase. It suggests that diffusion through highly compacted clay takes place through the interlayers (i.e., in the adsorbed phase). Quantitative prediction of the diffusive flux will necessitate more detailed descriptions of surface reactivity and of the mobility of interlayer species.

  10. Adsorption of dyes using different types of clay: a review

    NASA Astrophysics Data System (ADS)

    Adeyemo, Aderonke Ajibola; Adeoye, Idowu Olatunbosun; Bello, Olugbenga Solomon

    2015-09-01

    Increasing amount of dyes in the ecosystem particularly in wastewater has propelled the search for more efficient low-cost adsorbents. The effective use of the sorption properties (high surface area and surface chemistry, lack of toxicity and potential for ion exchange) of different clays as adsorbents for the removal of different type of dyes (basic, acidic, reactive) from water and wastewater as potential alternatives to activated carbons has recently received widespread attention because of the environmental-friendly nature of clay materials. Insights into the efficiencies of raw and modified/activated clay adsorbents and ways of improving their efficiencies to obtain better results are discussed. Acid-modified clay resulted in higher rate of dye adsorption and an increased surface area and porosity (49.05 mm2 and 53.4 %). Base-modified clay has lower adsorption capacities, while ZnCl2-modified clay had the least rate of adsorption with a surface area of 44.3 mm2 and porosity of 43.4 %. This review also explores the grey areas of the adsorption properties of the raw clays and the improved performance of activated/modified clay materials with particular reference to the effects of pH, temperature, initial dye concentration and adsorbent dosage on the adsorption capacities of the clays. Various challenges encountered in using clay materials are highlighted and a number of future prospects for the adsorbents are proposed.

  11. Hyperpolarized NMR Probes for Biological Assays

    PubMed Central

    Meier, Sebastian; Jensen, Pernille R.; Karlsson, Magnus; Lerche, Mathilde H.

    2014-01-01

    During the last decade, the development of nuclear spin polarization enhanced (hyperpolarized) molecular probes has opened up new opportunities for studying the inner workings of living cells in real time. The hyperpolarized probes are produced ex situ, introduced into biological systems and detected with high sensitivity and contrast against background signals using high resolution NMR spectroscopy. A variety of natural, derivatized and designed hyperpolarized probes has emerged for diverse biological studies including assays of intracellular reaction progression, pathway kinetics, probe uptake and export, pH, redox state, reactive oxygen species, ion concentrations, drug efficacy or oncogenic signaling. These probes are readily used directly under natural conditions in biofluids and are often directly developed and optimized for cellular assays, thus leaving little doubt about their specificity and utility under biologically relevant conditions. Hyperpolarized molecular probes for biological NMR spectroscopy enable the unbiased detection of complex processes by virtue of the high spectral resolution, structural specificity and quantifiability of NMR signals. Here, we provide a survey of strategies used for the selection, design and use of hyperpolarized NMR probes in biological assays, and describe current limitations and developments. PMID:24441771

  12. Reactive compatibilizer-tracer: A powerful tool for designing, scaling up and optimizing reactive blending processes

    NASA Astrophysics Data System (ADS)

    Ji, Wei-Yun; Feng, Lian-Fang; Zhang, Cai-Liang; Hu, Guo-Hua

    2015-05-01

    A concept of reactive compatibilizer-tracer is developed to study reactive polymer blending processes in a twin screw extruder. It is summarized as follows. Fluorescent moieties such as anthracene are attached to a reactive compatibilizer so that the latter can be served both as a compatibilizer and a tracer. When evaluating its compatibilizing efficiency for a polymer blending system, unlike the polymer components of the blend which are continuously fed to the extruder, the reactive compatibilizer-tracer is added as a pulse. The concentration of the reactive compatibilizer-tracer in the polymer blend at the die exit is measured, in-line and in real time, using probes capable of detecting the signal of the emission of fluorescent moieties of the reactive compatibilizer-tracer. In the meantime, the corresponding size of the dispersed phase domains of the blend is determined off-line. These two pieces of information allow assessing the compatibilizing efficiency of a reactive compatibilizer in a much easier manner and using a much smaller amount of compatibilizer. Consequently, the concept of reactive compatibilizer-tracer can help select most appropriate compatibilizers under real industrial polymer blending conditions as well as scaling up and/or optimizing them.

  13. System for reactivating catalysts

    SciTech Connect

    Ginosar, Daniel M.; Thompson, David N.; Anderson, Raymond P.

    2010-03-02

    A method of reactivating a catalyst, such as a solid catalyst or a liquid catalyst is provided. The method comprises providing a catalyst that is at least partially deactivated by fouling agents. The catalyst is contacted with a fluid reactivating agent that is at or above a critical point of the fluid reactivating agent and is of sufficient density to dissolve impurities. The fluid reactivating agent reacts with at least one fouling agent, releasing the at least one fouling agent from the catalyst. The at least one fouling agent becomes dissolved in the fluid reactivating agent and is subsequently separated or removed from the fluid reactivating agent so that the fluid reactivating agent may be reused. A system for reactivating a catalyst is also disclosed.

  14. Numerical estimation of adsorption energy distributions from adsorption isotherm data with the expectation-maximization method

    SciTech Connect

    Stanley, B.J.; Guiochon, G. |

    1993-08-01

    The expectation-maximization (EM) method of parameter estimation is used to calculate adsorption energy distributions of molecular probes from their adsorption isotherms. EM does not require prior knowledge of the distribution function or the isotherm, requires no smoothing of the isotherm data, and converges with high stability towards the maximum-likelihood estimate. The method is therefore robust and accurate at high iteration numbers. The EM algorithm is tested with simulated energy distributions corresponding to unimodal Gaussian, bimodal Gaussian, Poisson distributions, and the distributions resulting from Misra isotherms. Theoretical isotherms are generated from these distributions using the Langmuir model, and then chromatographic band profiles are computed using the ideal model of chromatography. Noise is then introduced in the theoretical band profiles comparable to those observed experimentally. The isotherm is then calculated using the elution-by-characteristic points method. The energy distribution given by the EM method is compared to the original one. Results are contrasted to those obtained with the House and Jaycock algorithm HILDA, and shown to be superior in terms of robustness, accuracy, and information theory. The effect of undersampling of the high-pressure/low-energy region of the adsorption is reported and discussed for the EM algorithm, as well as the effect of signal-to-noise ratio on the degree of heterogeneity that may be estimated experimentally.

  15. Parameters estimation for reactive transport: A way to test the validity of a reactive model

    NASA Astrophysics Data System (ADS)

    Aggarwal, Mohit; Cheikh Anta Ndiaye, Mame; Carrayrou, Jérôme

    The chemical parameters used in reactive transport models are not known accurately due to the complexity and the heterogeneous conditions of a real domain. We will present an efficient algorithm in order to estimate the chemical parameters using Monte-Carlo method. Monte-Carlo methods are very robust for the optimisation of the highly non-linear mathematical model describing reactive transport. Reactive transport of tributyltin (TBT) through natural quartz sand at seven different pHs is taken as the test case. Our algorithm will be used to estimate the chemical parameters of the sorption of TBT onto the natural quartz sand. By testing and comparing three models of surface complexation, we show that the proposed adsorption model cannot explain the experimental data.

  16. Chemical reactivity of Ni-Rh nanowires.

    PubMed

    Schoiswohl, J; Mittendorfer, F; Surnev, S; Ramsey, M G; Andersen, J N; Netzer, F P

    2006-09-22

    The properties of bimetallic Ni-Rh nanowires, fabricated by decorating the steps of vicinal Rh(111) surfaces by stripes of self-assembled Ni adatoms, have been probed by STM, photoemission, and ab initio density functional theory calculations. These Ni-Rh nanowires have specific electronic properties that lead to a significantly enhanced chemical reactivity towards oxygen. As a result, the Ni-Rh nanowires can be oxidized exclusively, generating novel quasi-one-dimensional oxide structures.

  17. Adsorption of fulvic acid on goethite

    SciTech Connect

    Filius, J.D.; Lumsdon, D.G.; Meeussen, J.C.L.; Hiemstra, T.; Riemsduk, W.H. van

    2000-01-01

    The adsorption of fulvic acid by goethite was determined experimentally as a function of concentration, pH, and ionic strength. The data were described with the CD-MUSIC model of Hiemstra and Van Riemsdijk (1996), which allows the distribution of charge of the bound fulvate molecule over a surface region. Simultaneously, the concentration, pH, and salt dependency of the binding of fulvic acid can be described. Using the same parameters, the basic charging behavior of the goethite in the absence of fulvic acid could be described well. The surface species used in the model indicate that inner sphere coordination of carboxylic groups of the fulvate molecule is important at low pH, whereas at high pH the outer sphere coordination with reactive groups of the fulvate molecule with high proton affinity is important.

  18. Gold Supported on La2O3: Structure and Reactivity with CO2 and Implicatinos for CO Oxidation Catalysis

    SciTech Connect

    Mihaylov, M.; Ivanova, E; Hao, Y; Hadjiivanov, K; Knozinger, H; Gates, B

    2008-01-01

    A sample consisting of gold dispersed on high-area porous lanthanum oxide was prepared by adsorption of dimethylgold acetylacetonate. X-ray absorption spectroscopy and infrared (IR) spectroscopy were used to characterize the gold species and their ligands, and CO as a probe molecule was used with IR spectroscopy to follow the changes in the gold species under various reaction conditions, with a focus on oxidation?reduction processes. Gold on the initially prepared sample was present as Au{sup 3+} species, but only a small fraction of them were apparently reactive with the CO probe molecule. After evacuation at elevated temperatures, the gold was first reduced to give clusters incorporating positively charged gold species, which in turn were converted to neutral gold species. CO and O{sub 2} reacted with the reduced sample in a process that appears to be autocatalytic and related to the existence of oxidized gold species that facilitate oxygen activation and CO oxidation catalysis. Surprisingly, it was also established that - although they are inert toward O{sub 2} at room temperature - the supported gold nanoparticles are readily oxidized by CO{sub 2}, a result that suggests that CO{sub 2} may be the actual oxidant of gold in CO oxidation catalysis. The supported zerovalent gold nanoparticles are also easily oxidized by NO and by NO{sub 2}.

  19. First principle study of the surface reactivity of layered lithium oxides LiMO2 (M = Ni, Mn, Co)

    NASA Astrophysics Data System (ADS)

    Vallverdu, Germain; Minvielle, Marie; Andreu, Nathalie; Gonbeau, Danielle; Baraille, Isabelle

    2016-07-01

    LiNixMnyCo1 - x - yO2 compounds (NMC) are layered oxides widely used in commercial lithium-ion batteries at the positive electrode. Nevertheless surface reactivity of this material is still not well known. As a first step, based on first principle calculations, this study deals with the electronic properties and the surface reactivity of LiMO2 (M = Co, Ni, Mn) compounds, considering the behavior of each transition metal separately in the same R 3 ̅ mα-NaFeO2-type structure, the one of LiCoO2 and NMC. For each compound, after a brief description of the bare slab electronic properties, we explored the acido-basic and redox properties of the (110) and (104) surfaces by considering the adsorption of a gaseous probe. The chemisorption of SO2 produces both sulfite or sulfate species associated respectively to an acido-basic or a reduction process. These processes are localized on the transition metals of the first two layers of the surface. Although sulfate species are globally favored, a different behavior is obtained depending on both the surface and the transition metal considered. We conclude with a simple scheme which describes the reduction processes on the both surfaces in terms of formal oxidation degrees of transition metals.

  20. Probing Nanoparticle Reactivity at the Single-Molecule Level

    DTIC Science & Technology

    2014-02-15

    doi: Xiaochun Zhou, Weilin Xu, Guokun Liu, Debashis Panda , Peng Chen. Size-Dependent Catalytic Activity and Dynamics of Gold Nanoparticles at the...Debashis Panda , Peng Chen. Size Dependent Catalytic Activity and Dynamics of Gold Nanoparticles at the Single-Molecule Level, (12 2009) Books...Bibliography 1 X. Zhou, W. Xu, G. Liu, D. Panda & P. Chen. Size dependent catalytic activity and dynamics of gold nanoparticles at the single

  1. Chemical Reactivity as a Probe of Ionic-Liquid Surfaces

    DTIC Science & Technology

    2009-04-30

    Fernandez de la Mora, and M. Gamero-Castaño, J. Appl. Phys., 2003, 94, 3599. 10 N. V. Plechkova and K. R. Seddon , Chem. Soc. Rev., 2008, 37, 123. 11 G ...Costen and Kenneth G McKendrick* School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, UK k.g.mckendrick@hw.ac.uk...synthesizing the ionic liquids for these experiments. REFERENCES 1 J. D. Holbrey and K. R. Seddon , Clean Products and Processes, 1999, 1, 223. 2

  2. Magic Numbers in Molecular Clusters: A Probe for Chemical Reactivity

    DTIC Science & Technology

    1992-05-29

    gas phase reactions of DME with DME + or any of its frag- ment ions giving rise to methanol ions. The reaction (s) giving rise to the { DME )nCH 3 OH 2... methanol to give DME but to date, the mechanism of the initial C-C bond formation remains to be unequivocally established. 2 0 The initial step of...in proto- nated cluster ions. Several ion/molecule reactions in the DME system have been reported in 10 which methanol was suggested as the neutral

  3. Magic Numbers in Molecular Clusters: A Probe for Chemical Reactivity

    DTIC Science & Technology

    1992-06-01

    known that the initial step in this process involves dehydration of methanol to give DME but to date, the mechanism of the initial C-C bond formation...remains to be unequivocally established. 2 0 The initial step of the catalytic conversion, i.e. dehydration of methanol to DME , has been observed in...have proposed9 , 19 that the 46n + 33 ions may be as- signed as methanol ions solvated by DME ions, i.e. {DMEnCH 3 OH 2 + . The observation of these

  4. Sulfur-bonded thiophenes in organometallic rhenium complexes and adsorption of isocyanides on gold

    SciTech Connect

    Robertson, Mitchell Joe

    1993-08-01

    This dissertation contains results of research conducted in two different areas: (1) organometallic synthesis and reactivity, and (2) organometallic surface chemistry. In the synthesis and reactivity studies, sulfur coordination of thiophene and benzo[b]thiophene to the metal center in organometallic rhenium complexes is examined. In the surface chemistry studies, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) is used to analyze the adsorption of several isocyanides on the surface of gold powder. Results are compared and contrasted to known organometallic chemistry.

  5. Liquid-Phase Adsorption Fundamentals.

    ERIC Educational Resources Information Center

    Cooney, David O.

    1987-01-01

    Describes an experiment developed and used in the unit operations laboratory course at the University of Wyoming. Involves the liquid-phase adsorption of an organic compound from aqueous solution on activated carbon, and is relevant to adsorption processes in general. (TW)

  6. Hot-wire probe

    NASA Technical Reports Server (NTRS)

    Mikulla, V.

    1976-01-01

    High-temperature platinum probe measures turbulence and Reynolds shear stresses in high-temperature compressible flows. Probe does not vibrate at high velocities and does not react like strain gage on warmup.

  7. Comparison of two strategies for detection of reactive oxygen species

    NASA Astrophysics Data System (ADS)

    Gao, Weidong; Zhou, Yuanshu; Gu, Yueqing

    2014-09-01

    Photodynamic therapy (PDT) is a clinically approved treatment that was applied to oncology , dermatology, and ophthalmology. Reactive oxygen species (ROS) play a important role in the efficacy of PDT. Online monitoring of reactive oxygen species is the key to understand effect of PDT treatment. We used Fluorescence probes DPBF and luminescent probe luminal to measure the ROS in cells. And we revaluate the relationship between the amount of light and cell survival. There is strongly correlated between the amount of light and cell kill.

  8. Protein Adsorption to Titanium and Zirconia Using a Quartz Crystal Microbalance Method.

    PubMed

    Kusakawa, You; Yoshida, Eiji; Hayakawa, Tohru

    2017-01-01

    Protein adsorption onto titanium (Ti) or zirconia (ZrO2) was evaluated using a 27 MHz quartz crystal microbalance (QCM). As proteins, fibronectin (Fn), a cell adhesive protein, and albumin (Alb), a cell adhesion-inhibiting protein, were evaluated. The Ti and ZrO2 sensors for QCM were characterized by atomic force microscopy and electron probe microanalysis observation, measurement of contact angle against water, and surface roughness. The amounts of Fn and Alb adsorbed onto the Ti and ZrO2 sensors and apparent reaction rate were obtained using QCM measurements. Ti sensor showed greater adsorption of Fn and Alb than the ZrO2 sensor. In addition, amount of Fn adsorbed onto the Ti or ZrO2 sensors was higher than that of Alb. The surface roughness and hydrophilicity of Ti or ZrO2 may influence the adsorption of Fn or Alb. With regard to the adsorption rate, Alb adsorbed more rapidly than Fn onto Ti. Comparing Ti and ZrO2, Alb adsorption rate to Ti was faster than that to ZrO2. Fn adsorption will be effective for cell activities, but Alb adsorption will not. QCM method could simulate in vivo Fn and Alb adsorption to Ti or ZrO2.

  9. Protein Adsorption to Titanium and Zirconia Using a Quartz Crystal Microbalance Method

    PubMed Central

    Kusakawa, You

    2017-01-01

    Protein adsorption onto titanium (Ti) or zirconia (ZrO2) was evaluated using a 27 MHz quartz crystal microbalance (QCM). As proteins, fibronectin (Fn), a cell adhesive protein, and albumin (Alb), a cell adhesion-inhibiting protein, were evaluated. The Ti and ZrO2 sensors for QCM were characterized by atomic force microscopy and electron probe microanalysis observation, measurement of contact angle against water, and surface roughness. The amounts of Fn and Alb adsorbed onto the Ti and ZrO2 sensors and apparent reaction rate were obtained using QCM measurements. Ti sensor showed greater adsorption of Fn and Alb than the ZrO2 sensor. In addition, amount of Fn adsorbed onto the Ti or ZrO2 sensors was higher than that of Alb. The surface roughness and hydrophilicity of Ti or ZrO2 may influence the adsorption of Fn or Alb. With regard to the adsorption rate, Alb adsorbed more rapidly than Fn onto Ti. Comparing Ti and ZrO2, Alb adsorption rate to Ti was faster than that to ZrO2. Fn adsorption will be effective for cell activities, but Alb adsorption will not. QCM method could simulate in vivo Fn and Alb adsorption to Ti or ZrO2. PMID:28246591

  10. Galileo Probe Battery System

    NASA Technical Reports Server (NTRS)

    Dagarin, B. P.; Taenaka, R. K.; Stofel, E. J.

    1997-01-01

    The conclusions of the Galileo probe battery system are: the battery performance met mission requirements with margin; extensive ground-based and flight tests of batteries prior to probe separation from orbiter provided good prediction of actual entry performance at Jupiter; and the Li-SO2 battery was an important choice for the probe's main power.

  11. A Magnetoresistance Measuring Probe.

    DTIC Science & Technology

    The in line four point probe, commonly used for measuring the sheet resistance in a conductor, cannot measure the anisotropic ferromagnetic magnetoresistance. However, the addition of two contact points that are not collinear with the current contacts give the probe the ability to non-destructively measure the anistropic magnetoresistance. Keywords: Magnetoresistance; Anisotropic; Thin-Film; Permalloy; Four Point Probe; Anisotropic Resistance.

  12. Chromium adsorption by lignin

    SciTech Connect

    Lalvani, S.B.; Huebner, A.; Wiltowski, T.S.

    2000-01-01

    Hexavalent chromium is a known carcinogen, and its maximum contamination level in drinking water is determined by the US Environmental Protection Agency (EPA). Chromium in the wastewaters from plating and metal finishing, tanning, and photographic industries poses environmental problems. A commercially available lignin was used for the removal of hexavalent as well as trivalent chromium from aqueous solution. It is known that hexavalent chromium is present as an anionic species in the solution. It was found that lignin can remove up to 63% hexavalent and 100% trivalent chromium from aqueous solutions. The removal of chromium ions was also investigated using a commercially available activated carbon. This absorbent facilitated very little hexavalent and almost complete trivalent chromium removal. Adsorption isotherms and kinetics data on the metal removal by lignin and activated carbon are presented and discussed.

  13. High temperature adsorption measurements

    SciTech Connect

    Bertani, R.; Parisi, L.; Perini, R.; Tarquini, B.

    1996-12-31

    Adsorption phenomena are a rich and rather new field of study in geothermal research, in particular at very high temperature. ENEL is interested in the exploitation of geothermal regions with super-heated steam, and it is important to understand the behavior of water-rock interaction. We have analyzed in the 170-200{degrees}C temperature range four samples of Monteverdi cuttings; the next experimental effort will be at 220{degrees}C and over in 1996. The first results of the 1995 runs are collected in this paper. We can highlight four main items: (1) At relative pressures over 0.6 the capillarity forces are very important. (2) There is no significant temperature effect. (3) Adsorbed water can be present, and it is able to multiply by a factor of 15 the estimated reserve of super-heated steam only. (4) Pores smaller than 15 {Angstrom} do not contribute to the adsorbed mass.

  14. High temperature adsorption measurements

    SciTech Connect

    Bertani, R.; Parisi, L.; Perini, R.; Tarquini, B.

    1996-01-24

    Adsorption phenomena are a rich and rather new field of study in geothermal research, in particular at very high temperature. ENEL is interested in the exploitation of geothermal regions with superheated steam, and it is important to understand the behavior of water-rock interaction. We have analyzed in the 170-200 °C temperature range four samples of Monteverdi cuttings; the next experimental effort will be at 220 °C and over in 1996. The first results of the 1995 runs are collected in this paper. We can highlight four main items: 1. At relative pressures over 0.6 the capillarity forces are very important. 2. There is no significant temperature effect. 3. Adsorbed water can be present, and it is able to multiply by a factor of 15 the estimated reserve of super-heated steam only. 4. Pores smaller than 15 Å do not contribute to the adsorbed mass.

  15. Mobilization and re-adsorption of arsenate on ferrihydrite and hematite in the presence of oxalate.

    PubMed

    Yu, Bo; Jia, Shao-Yi; Liu, Yong; Wu, Song-Hai; Han, Xu

    2013-11-15

    In this study, mobilization and re-adsorption of arsenate on 2-line ferrihydrite and hematite in the presence of oxalate was investigated. Our results showed that arsenate could be mobilized during the dissolution of ferrihydrite and hematite. After reaching the maximum values, the released arsenate could re-adsorb on the residual ferrihydrite, whereas such an observation was not significant in hematite system. More reactive sites exposed during the dissolution of ferrihydrite could contribute to the re-adsorption of the released arsenate at pH 3.0, while the insignificant re-adsorption of arsenate on hematite could be explained by the inhibitory adsorption effect of oxalate on arsenate. Although dissolution rates of iron oxides decreased with the increase of arsenate on both ferrihydrite and hematite, dissolution rate was mainly determined by the reactivity of iron oxides, and ferrihydrite showed a higher reactivity than hematite in the presence of oxalate. Mathematic model proposed in our study further indicated that arsenate loading showed a more significant effect on arsenate mobilization in hematite system, while it was more effective in arsenate re-adsorption in ferrihydrite system.

  16. Alloimmunization in autoimmune hemolytic anemia patient: The differential adsorption approach

    PubMed Central

    Dara, Ravi C.; Tiwari, Aseem Kumar; Arora, Dinesh; Mitra, Subhasis; Acharya, Devi Prasad; Aggarwal, Geet; Sharma, Jyoti

    2017-01-01

    Patients of β-thalassemia major are dependent on regular blood transfusions for their entire lifetime. Development of antibodies against red blood cell (RBC) antigen which may be alloantibody or autoantibody, several times as a result of frequent red cell component transfusions, further complicates the subsequent transfusion therapy. Among the autoantibodies, warm-reactive autoantibodies are commoner and interfere in the pretransfusion testing. These RBC autoantibodies present in patient's serum potentially react with all the cells of antibody identification panel giving “pan-reactive” picture and making alloantibody identification complex. In this report, we present our approach in a thalassemia patient who presented with warm-type autoimmune hemolytic anemia, low hemoglobin of 5.8 g/dl, and three significant alloantibodies (anti-D, anti-S, and anti-Jkb) which were masked by pan-reactive warm autoantibody(s). Differential adsorption was used to unmask underlying alloantibodies. We suggest that differential adsorption procedure is an effective and efficient method for autoantibody adsorption, detection, and identification of masked alloantibody(s), especially in patients with low hemoglobin and history of recent blood transfusion. PMID:28316442

  17. Phenylethynyl reactive diluents

    NASA Technical Reports Server (NTRS)

    Bryant, Robert G. (Inventor); Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor)

    1995-01-01

    A composition of matter having a specified general structure is employed to terminate a nucleophilic reagent, resulting in the exclusive production of phenylethynyl terminated reactive oligomers which display unique thermal characteristics. A reactive diluent having a specified general structure is employed to decrease the melt viscosity of a phenylethynyl terminated reactive oligomer and to subsequently react with to provide a thermosetting material of enhanced density. These materials have features which make them attractive candidates for use as composite matrices and adhesives.

  18. Chemical modeling of boron adsorption by humic materials using the constant capacitance model

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The constant capacitance surface complexation model was used to describe B adsorption behavior on reference Aldrich humic acid, humic acids from various soil environments, and dissolved organic matter extracted from sewage effluents. The reactive surface functional groups on the humic materials wer...

  19. Ultrafast scanning probe microscopy

    DOEpatents

    Weiss, Shimon; Chemla, Daniel S.; Ogletree, D. Frank; Botkin, David

    1995-01-01

    An ultrafast scanning probe microscopy method for achieving subpicosecond-temporal resolution and submicron-spatial resolution of an observation sample. In one embodiment of the present claimed invention, a single short optical pulse is generated and is split into first and second pulses. One of the pulses is delayed using variable time delay means. The first pulse is then directed at an observation sample located proximate to the probe of a scanning probe microscope. The scanning probe microscope produces probe-sample signals indicative of the response of the probe to characteristics of the sample. The second pulse is used to modulate the probe of the scanning probe microscope. The time delay between the first and second pulses is then varied. The probe-sample response signal is recorded at each of the various time delays created between the first and second pulses. The probe-sample response signal is then plotted as a function of time delay to produce a cross-correlation of the probe sample response. In so doing, the present invention provides simultaneous subpicosecond-temporal resolution and submicron-spatial resolution of the sample.

  20. Traversing probe system

    DOEpatents

    Mashburn, Douglas N.; Stevens, Richard H.; Woodall, Harold C.

    1977-01-01

    This invention comprises a rotatable annular probe-positioner which carries at least one radially disposed sensing probe, such as a Pitot tube having a right-angled tip. The positioner can be coaxially and rotatably mounted within a compressor casing or the like and then actuated to orient the sensing probe as required to make measurements at selected stations in the annulus between the positioner and compressor casing. The positioner can be actuated to (a) selectively move the probe along its own axis, (b) adjust the yaw angle of the right-angled probe tip, and (c) revolve the probe about the axis common to the positioner and casing. A cam plate engages a cam-follower portion of the probe and normally rotates with the positioner. The positioner includes a first-motor-driven ring gear which effects slidable movement of the probe by rotating the positioner at a time when an external pneumatic cylinder is actuated to engage the cam plate and hold it stationary. When the pneumatic cylinder is not actuated, this ring gear can be driven to revolve the positioner and thus the probe to a desired circumferential location about the above-mentioned common axis. A second motor-driven ring gear included in the positioner can be driven to rotate the probe about its axis, thus adjusting the yaw angle of the probe tip. The positioner can be used in highly corrosive atmosphere, such as gaseous uranium hexafluoride.

  1. Ultrafast scanning probe microscopy

    DOEpatents

    Weiss, S.; Chemla, D.S.; Ogletree, D.F.; Botkin, D.

    1995-05-16

    An ultrafast scanning probe microscopy method is described for achieving subpicosecond-temporal resolution and submicron-spatial resolution of an observation sample. In one embodiment of the present claimed invention, a single short optical pulse is generated and is split into first and second pulses. One of the pulses is delayed using variable time delay means. The first pulse is then directed at an observation sample located proximate to the probe of a scanning probe microscope. The scanning probe microscope produces probe-sample signals indicative of the response of the probe to characteristics of the sample. The second pulse is used to modulate the probe of the scanning probe microscope. The time delay between the first and second pulses is then varied. The probe-sample response signal is recorded at each of the various time delays created between the first and second pulses. The probe-sample response signal is then plotted as a function of time delay to produce a cross-correlation of the probe sample response. In so doing, the present invention provides simultaneous subpicosecond-temporal resolution and submicron-spatial resolution of the sample. 6 Figs.

  2. Material Exhibiting Efficient CO2 Adsorption at Room Temperature for Concentrations Lower Than 1000 ppm: Elucidation of the State of Barium Ion Exchanged in an MFI-Type Zeolite.

    PubMed

    Itadani, Atsushi; Oda, Akira; Torigoe, Hiroe; Ohkubo, Takahiro; Sato, Mineo; Kobayashi, Hisayoshi; Kuroda, Yasushige

    2016-04-06

    Carbon dioxide (CO2) gas is well-known as a greenhouse gas that leads to global warming. Many efforts have been made to capture CO2 from coal-fired power plants, as well as to reduce the amounts of excess CO2 in the atmosphere to around 400 ppm. However, this is not a simple task, particularly in the lower pressure region than 1000 ppm. This is because the CO2 molecule is chemically stable and has a relatively low reactivity. In the present study, the CO2 adsorption at room temperature on MFI-type zeolites exchanged with alkaline-earth-metal ions, with focus on CO2 concentrations <1000 ppm, was investigated both experimentally and by calculation. These materials exhibited a particularly efficient adsorption capability for CO2, compared with other presented samples, such as the sodium-form and transition-metal ion-exchanged MFI-type zeolites. Ethyne (C2H2) was used as a probe molecule. Analyses were carried out with IR spectroscopy and X-ray absorption, and provided significant information regarding the presence of the M(2+)-O(2-)-M(2+) (M(2+): alkaline-earth-metal ion) species formed in the samples. It was subsequently determined that this species acts as a highly efficient site for CO2 adsorption at room temperature under very low pressure, compared to a single M(2+) species. A further advantage is that this material can be easily regenerated by a treatment, e.g., through the application of the temperature swing adsorption process, at relatively low temperatures (300-473 K).

  3. Electrical resistivity probes

    DOEpatents

    Lee, Ki Ha; Becker, Alex; Faybishenko, Boris A.; Solbau, Ray D.

    2003-10-21

    A miniaturized electrical resistivity (ER) probe based on a known current-voltage (I-V) electrode structure, the Wenner array, is designed for local (point) measurement. A pair of voltage measuring electrodes are positioned between a pair of current carrying electrodes. The electrodes are typically about 1 cm long, separated by 1 cm, so the probe is only about 1 inch long. The electrodes are mounted to a rigid tube with electrical wires in the tube and a sand bag may be placed around the electrodes to protect the electrodes. The probes can be positioned in a borehole or on the surface. The electrodes make contact with the surrounding medium. In a dual mode system, individual probes of a plurality of spaced probes can be used to measure local resistance, i.e. point measurements, but the system can select different probes to make interval measurements between probes and between boreholes.

  4. Random sequential adsorption on fractals.

    PubMed

    Ciesla, Michal; Barbasz, Jakub

    2012-07-28

    Irreversible adsorption of spheres on flat collectors having dimension d < 2 is studied. Molecules are adsorbed on Sierpinski's triangle and carpet-like fractals (1 < d < 2), and on general Cantor set (d < 1). Adsorption process is modeled numerically using random sequential adsorption (RSA) algorithm. The paper concentrates on measurement of fundamental properties of coverages, i.e., maximal random coverage ratio and density autocorrelation function, as well as RSA kinetics. Obtained results allow to improve phenomenological relation between maximal random coverage ratio and collector dimension. Moreover, simulations show that, in general, most of known dimensional properties of adsorbed monolayers are valid for non-integer dimensions.

  5. Galactose adsorption on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Alatalo, Matti; Puisto, Mikko

    2014-03-01

    In order to understand the valorisation of biomass, it is essential to study the behavior of sugar molecules on catalytic surfaces. We have studied the adsorption of galactose molecules on the Ru(0001) surface using first principles calculations. We present results for the fully relaxed configurations of the molecule at different adsorption sites. We also compare the effect of the inclusion of the van der Waals interactions on both the energetics of the free galactose molecule and the adsorption energy of galactose on Ru(0001). We compare our results, obtained using periodically repeated supercells, to those obtained with cluster calculations.

  6. Effect of tribology processes on adsorption of albumin

    NASA Astrophysics Data System (ADS)

    Yan, Yu; Yang, Hongjuan; Wang, Linghe; Su, Yanjing; Qiao, Lijie

    2016-03-01

    As soon as artificial joint replacements are implanted into patients, the adsorption of proteins can occur. Joint implants operate in a protein-rich and relatively corrosive environment under tribological contact. The contacted area acted as an anodic part and the rest of the surface was more cathodic. Therefore, the adsorption of proteins is different in and outside the wear track. Adsorbed proteins would denature during rubbing and a tribofilm could form. The tribofilm can lubricate the surface and act as a barrier to corrosion damage. However, to observe the adsorption of proteins in situ has always been a challenge. Scanning Kelvin probe force microscope (SKPFM) was used to study the adsorption of albumin on the surface of CoCrMo alloy under simulated tribology movement. Fluorescence microscopy (FM) was employed to reveal the protein molecules in the wear scar. It was found that albumin molecules can decrease the surface potential and accelerate the corrosion process. In the wear track, albumin denatured and changed the surface potential as time progressed.

  7. Evaluation of confinement effects in zeolites under Henry's adsorption regime

    NASA Astrophysics Data System (ADS)

    Pera-Titus, Marc; Llorens, Joan

    2010-06-01

    This paper provides a detailed thermodynamic analysis of gas/vapour adsorption in zeolites at low pressures. At these conditions, we show first that Henry's isotherm can be conveniently rewritten using the thermodynamic isotherm model developed in a previous study [J. Llorens, M. Pera-Titus, Description of gas adsorption on microporous materials: evaluation of energy heterogeneity, J. Colloid Interface Sci. 331, 2009, 302-311], linking the integral free energy of adsorption relative to saturation, Ψ/ RT, expressed as a Kiselev integral, with the variable Z = 1/-ln( Π), being Π the relative pressure. Relevant information about sorbate confinement effects in zeolites can be inferred using strong sorbates under Henry's adsorption regime using the thermodynamic formulation provided here. The confining level of zeolites can be characterized by a parameter ( m1), whose value depends on the zeolite framework, but remains essentially unchanged with the sorbate probe molecule and temperature. We illustrate the application of these concepts using a collection of MFI and MTW-type zeolites as model systems.

  8. Protein Adsorption in Three Dimensions

    PubMed Central

    Vogler, Erwin A.

    2011-01-01

    Recent experimental and theoretical work clarifying the physical chemistry of blood-protein adsorption from aqueous-buffer solution to various kinds of surfaces is reviewed and interpreted within the context of biomaterial applications, especially toward development of cardiovascular biomaterials. The importance of this subject in biomaterials surface science is emphasized by reducing the “protein-adsorption problem” to three core questions that require quantitative answer. An overview of the protein-adsorption literature identifies some of the sources of inconsistency among many investigators participating in more than five decades of focused research. A tutorial on the fundamental biophysical chemistry of protein adsorption sets the stage for a detailed discussion of the kinetics and thermodynamics of protein adsorption, including adsorption competition between two proteins for the same adsorbent immersed in a binary-protein mixture. Both kinetics and steady-state adsorption can be rationalized using a single interpretive paradigm asserting that protein molecules partition from solution into a three-dimensional (3D) interphase separating bulk solution from the physical-adsorbent surface. Adsorbed protein collects in one-or-more adsorbed layers, depending on protein size, solution concentration, and adsorbent surface energy (water wettability). The adsorption process begins with the hydration of an adsorbent surface brought into contact with an aqueous-protein solution. Surface hydration reactions instantaneously form a thin, pseudo-2D interface between the adsorbent and protein solution. Protein molecules rapidly diffuse into this newly-formed interface, creating a truly 3D interphase that inflates with arriving proteins and fills to capacity within milliseconds at mg/mL bulk-solution concentrations CB. This inflated interphase subsequently undergoes time-dependent (minutes-to-hours) decrease in volume VI by expulsion of either-or-both interphase water and

  9. Tracking thermal fronts with temperature-sensitive, chemically reactive tracers

    SciTech Connect

    Robinson, B.A.; Birdsell, S.A.

    1987-01-01

    Los Alamos is developing tracer techniques using reactive chemicals to track thermal fronts in fractured geothermal reservoirs. If a nonadsorbing tracer flowing from the injection to production well chemically reacts, its reaction rate will be a strong function of temperature. Thus the extent of chemical reaction will be greatest early in the lifetime of the system, and less as the thermal front progresses from the injection to production well. Early laboratory experiments identified tracers with chemical kinetics suitable for reservoirs in the temperature range of 75 to 100/sup 0/C. Recent kinetics studies have focused on the kinetics of hydrolysis of derivatives of bromobenzene. This class of reactions can be used in reservoirs ranging in temperature from 150 to 275/sup 0/C, which is of greater interest to the geothermal industry. Future studies will include laboratory adsorption experiments to identify possibly unwanted adsorption on granite, development of sensitive analytical techniques, and a field demonstration of the reactive tracer concept.

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

    NASA Astrophysics Data System (ADS)

    Matos, Jeronimo; Kara, Abdelkader

    2015-03-01

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

  11. Bromide Adsorption by Reference Minerals and Soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bromide, Br-, adsorption behavior was investigated on amorphous Al and Fe oxide, montmorillonite, kaolinite, and temperate and tropical soils. Bromide adsorption decreased with increasing solution pH with minimal adsorption occurring above pH 7. Bromide adsorption was higher for amorphous oxides t...

  12. Site-Specific Reactivity of Ethylene at Distorted Dangling-Bond Configurations on Si(001).

    PubMed

    Pecher, Josua; Mette, Gerson; Dürr, Michael; Tonner, Ralf

    2017-02-17

    Differences in adsorption and reaction energetics for ethylene on Si(001) are reported with respect to distorted dangling-bond configurations induced by hydrogen precoverage, as obtained by DFT calculations. This can help to understand the influence of surface defects and precoverage on the reactivity of organic molecules on semiconductor surfaces in general. The results show that the reactivity of surface dimers fully enclosed by hydrogen-covered atoms is essentially unchanged compared to the clean surface. This is confirmed by scanning tunneling microscopy measurements. On the contrary, adsorption sites with partially covered surface dimers show a drastic increase in reactivity. This is due to a lowering of the reaction barrier by more than 50 % relative to the clean surface, which is in line with previous experiments. Adsorption on dimers enclosed by molecule (ethylene)-covered surface atoms is reported to have a strongly decreased reactivity, as a result of destabilization of the intermediate state due to steric repulsion; this is quantified through periodic energy decomposition analysis. Furthermore, an approach for the calculation of Gibbs energies of adsorption based on statistical thermodynamics considerations is applied to the system. The results show that the loss in molecular entropy leads to a significant destabilization of adsorption states.

  13. Centrifugal Adsorption Cartridge System

    NASA Technical Reports Server (NTRS)

    Gonda, Steve R.; Tsao, Yow-Min D.; Lee, Wenshan

    2004-01-01

    The centrifugal adsorption cartridge system (CACS) is an apparatus that recovers one or more bioproduct(s) from a dilute aqueous solution or suspension flowing from a bioreactor. The CACS can be used both on Earth in unit gravity and in space in low gravity. The CACS can be connected downstream from the bioreactor; alternatively, it can be connected into a flow loop that includes the bioreactor so that the liquid can be recycled. A centrifugal adsorption cartridge in the CACS (see figure) includes two concentric cylinders with a spiral ramp between them. The volume between the inner and outer cylinders, and between the turns of the spiral ramp is packed with an adsorbent material. The inner cylinder is a sieve tube covered with a gas-permeable, hydrophobic membrane. During operation, the liquid effluent from the bioreactor is introduced at one end of the spiral ramp, which then constrains the liquid to flow along the spiral path through the adsorbent material. The spiral ramp also makes the flow more nearly uniform than it would otherwise be, and it minimizes any channeling other than that of the spiral flow itself. The adsorbent material is formulated to selectively capture the bioproduct(s) of interest. The bioproduct(s) can then be stored in bound form in the cartridge or else eluted from the cartridge. The centrifugal effect of the spiral flow is utilized to remove gas bubbles from the liquid. The centrifugal effect forces the bubbles radially inward, toward and through the membrane of the inner cylinder. The gas-permeable, hydrophobic membrane allows the bubbles to enter the inner cylinder while keeping the liquid out. The bubbles that thus enter the cylinder are vented to the atmosphere. The spacing between the ramps determines rate of flow along the spiral, and thereby affects the air-bubble-removal efficiency. The spacing between the ramps also determines the length of the fluid path through the cartridge adsorbent, and thus affects the bioproduct

  14. Capability of defective graphene-supported Pd13 and Ag13 particles for mercury adsorption

    NASA Astrophysics Data System (ADS)

    Meeprasert, Jittima; Junkaew, Anchalee; Rungnim, Chompoonut; Kunaseth, Manaschai; Kungwan, Nawee; Promarak, Vinich; Namuangruk, Supawadee

    2016-02-01

    Reactivity of single-vacancy defective graphene (DG) and DG-supported Pdn and Agn (n = 1, 13) for mercury (Hg0) adsorption has been studied using density functional theory calculation. The results show that Pdn binds defective site of DG much stronger than the Agn, while metal nanocluster binds DG stronger than single metal atom. Metal clustering affects the adsorption ability of Pd composite while that of Ag is comparatively less. The binding strength of -8.49 eV was found for Pd13 binding on DG surface, indicating its high stability. Analyses of structure, energy, partial density of states, and d-band center (ɛd) revealed that the adsorbed metal atom or cluster enhances the reactivity of DG toward Hg adsorption. In addition, the Hg adsorption ability of Mn-DG composite is found to be related to the ɛd of the deposited Mn, in which the closer ɛd of Mn to the Fermi level correspond to the higher adsorption strength of Hg on Mn-DG composite. The order of Hg adsorption strength on Mn-DG composite are as follows: Pd13 (-1.68 eV) >> Ag13 (-0.67 eV) ∼ Ag1 (-0.69 eV) > Pd1 (-0.62 eV). Pd13-DG composite is therefore more efficient sorbent for Hg0 removal in terms of high stability and high adsorption reactivity compared to the Ag13. Further design of highly efficient carbon based sorbents should be focused on tailoring the ɛd of deposited metals.

  15. Cationic polyelectrolyte/bentonite prepared by ultrasonic technique and its use as adsorbent for Reactive Blue K-GL dye.

    PubMed

    Li, Qian; Yue, Qin-Yan; Su, Yuan; Gao, Bao-Yu; Fu, Lin

    2007-08-17

    In this study, the cationic polyelectrolyte polyepicholorohydrin-dimethylamine (EPI-DMA) was intercalated into bentonite using ultrasonic. The structure of EPI-DMA/bentonite and its adsorption of Reactive Blue K-GL (RB K-GL) dye were investigated. Compared with raw bentonite, the EPI-DMA/bentonite had larger interlayer spacing and was more hydrophobic, providing with better surface properties for adsorption. The adsorption of RB K-GL on EPI-DMA/bentonite was described by the adsorption models of Langmuir, Freundlich and Dubinin-Radushkevic. The adsorption kinetics was analyzed using pseudo-first- and second-order kinetic models and intraparticle diffusion model. Results showed that both the intraparticle diffusion and first-order adsorption occur in the initial period of adsorption, and that pseudo-second-order kinetic model was more suitable for describing the whole adsorption process. The reaction rates were also calculated. The changes of free energy, enthalpy and entropy of adsorption were evaluated for the adsorption of RB K-GL onto EPI-DMA/bentonite, suggesting that the adsorption process was spontaneous and exothermic.

  16. Chiral segregation driven by a dynamical response of the adsorption footprint to the local adsorption environment: bitartrate on Cu(110).

    PubMed

    Darling, G R; Forster, M; Lin, C; Liu, N; Raval, R; Hodgson, A

    2017-03-15

    Local or global ordering of chiral molecules at a surface is a key step in both chiral separation and heterogeneous enantioselective catalysis. Using density functional theory and scanning probe microscopy results, we find that the accepted structural model for the well known bitartrate on Cu(110) chiral system cannot account for the chiral segregation observed. Instead, we show that this strongly bound, chiral adsorbate changes its adsorption footprint in response to the local environment. The flexible adsorption geometry allows bitartrate to form stable homochiral trimer chains in which the central molecule restructures from a rectangular to an oblique footprint, breaking its internal hydrogen bonds in order to form strong intermolecular hydrogen bonds to neighbouring adsorbates. Racemic structures containing mixed enantiomers do not form strong hydrogen bonds, providing the thermodynamic driving force for the chiral separation that is observed experimentally. This result shows the importance of considering the dynamical response of molecular adsorption footprints at the surface in directing chiral assembly and segregation. The ability of strongly-chemisorbed enantiomers to change footprint depending on the local adsorption environment indicates that supramolecular assemblies at surfaces may exhibit more complex dynamical behaviour than hitherto suspected, which, ultimately, could be tailored to lead to environment and stimuli-responsive chiral surfaces.

  17. Probing Surface Sites of TiO2: Reactions with [HRe(CO)5] and [CH3Re(CO)5

    SciTech Connect

    Lobo-Lapidus, R.; Gates, B

    2010-01-01

    Two carbonyl complexes of rhenium, [HRe(CO){sub 5}] and [CH{sub 3}Re(CO){sub 5}], were used to probe surface sites of TiO{sub 2} (anatase). These complexes were adsorbed from the gas phase onto anatase powder that had been treated in flowing O{sub 2} or under vacuum to vary the density of surface OH sites. Infrared (IR) spectra demonstrate the variation in the number of sites, including Ti{sup +3} {double_bond} OH and Ti{sup +4} {double_bond} OH. IR and extended X-ray absorption fine structure (EXAFS) spectra show that chemisorption of the rhenium complexes led to their decarbonylation, with formation of surface-bound rhenium tricarbonyls, when [HRe(CO){sub 5}] was adsorbed, or rhenium tetracarbonyls, when [CH{sub 3}Re(CO){sub 5}] was adsorbed. These reactions were accompanied by the formation of water and surface carbonates and removal of terminal hydroxyl groups associated with Ti{sup +3} and Ti{sup +4} ions on the anatase. Data characterizing the samples after adsorption of [HRe(CO){sub 5}] or [CH{sub 3}Re(CO){sub 5}] determined a ranking of the reactivity of the surface OH sites, with the Ti{sup +3}OH groups being the more reactive towards the rhenium complexes but the less likely to be dehydroxylated. The two rhenium pentacarbonyl probes provided complementary information, suggesting that the carbonate species originate from carbonyl ligands initially bonded to the rhenium and from hydroxyl groups of the titania surface, with the reaction leading to the formation of water and bridging hydroxyl groups on the titania. The results illustrate the value of using a family of organometallic complexes as probes of oxide surface sites.

  18. Multilayer adsorption on fractal surfaces.

    PubMed

    Vajda, Péter; Felinger, Attila

    2014-01-10

    Multilayer adsorption is often observed in liquid chromatography. The most frequently employed model for multilayer adsorption is the BET isotherm equation. In this study we introduce an interpretation of multilayer adsorption measured on liquid chromatographic stationary phases based on the fractal theory. The fractal BET isotherm model was successfully used to determine the apparent fractal dimension of the adsorbent surface. The nonlinear fitting of the fractal BET equation gives us the estimation of the adsorption equilibrium constants and the monolayer saturation capacity of the adsorbent as well. In our experiments, aniline and proline were used as test molecules on reversed phase and normal phase columns, respectively. Our results suggest an apparent fractal dimension 2.88-2.99 in the case of reversed phase adsorbents, in the contrast with a bare silica column with a fractal dimension of 2.54.

  19. Molecular diffusion between walls with adsorption and desorption

    NASA Astrophysics Data System (ADS)

    Levesque, Maximilien; Bénichou, Olivier; Rotenberg, Benjamin

    2013-01-01

    The time dependency of the diffusion coefficient of particles in porous media is an efficient probe of their geometry. The analysis of this quantity, measured, e.g., by nuclear magnetic resonance, can provide rich information pertaining to porosity, pore size distribution, permeability, and surface-to-volume ratio of porous materials. Nevertheless, in numerous if not all practical situations, transport is confined by walls where adsorption and desorption processes may occur. In this article, we derive explicitly the expression of the time-dependent diffusion coefficient between two confining walls in the presence of adsorption and desorption. We show that they strongly modify the time-dependency of the diffusion coefficient, even in this simple geometry. We finally propose several applications, from sorption rates measurements to the use as a reference for numerical implementations for more complex geometries.

  20. Theoretical investigations of the CO adsorption on ZnF2 surfaces

    NASA Astrophysics Data System (ADS)

    Kaawar, Zeinab; Müller, Carsten; Paulus, Beate

    2017-02-01

    Periodic density functional theory calculations were performed to investigate the Lewis acidity of unsaturated surface cations of ZnF2, using CO as probe molecule at different coverages. We have calculated adsorption energies for CO on all low index ZnF2 surfaces using DFT with the B3LYP functional and subsequent dispersion correction. Additionally local second order Møller-Plesset perturbation theory (LMP2) calculations were performed. In most of the cases, the adsorption of CO on different surfaces is described well using B3LYP. Dispersion correction to B3LYP is found to overestimate the adsorption energy. The interaction among adsorbed CO molecules appears to have a significant effect on the adsorption energies at full coverage.

  1. Spectroscopic study of cystine adsorption on pyrite surface: From vacuum to solution conditions

    NASA Astrophysics Data System (ADS)

    Sanchez-Arenillas, M.; Mateo-Marti, E.

    2015-09-01

    We characterized the adsorption of cystine molecules on pyrite surface via X-ray photoelectron spectroscopy. Anoxic conditions were simulated under ultra-high-vacuum conditions. In contrast, to simulate oxidation conditions, the molecules were adsorbed on pyrite surface from solution. A novel comparative analysis revealed remarkable differences with respect to molecular adsorption and surface chemistry induced by environmental conditions. Molecular adsorption under anoxic conditions was observed to be more favorable, concentrating a large number of molecules on the surface and two different chemical species. In contrast, the presence of oxygen induced an autocatalytic oxidation process on the pyrite surface, which facilitated water binding on pyrite surface and partially blocked molecular adsorption. Pyrite is a highly reactive surface and contains two crucial types of surface functional groups that drive molecular chemistry on the surface depending on the surrounding conditions. Therefore, the system explored in this study holds interesting implications for supporting catalyzed prebiotic chemistry reactions.

  2. Short-Cycle Adsorption Refrigerator

    NASA Technical Reports Server (NTRS)

    Chan, C. K.

    1988-01-01

    Modular adsorption/Joule-Thomson-effect refrigerator offers fast regeneration; adsorption/desorption cycle time expected to be 1 minute. Pressurized hydrogen generated by bank of compressor modules during heating phase passes through system of check valves and expands in Joule-Thomson junction as it enters refrigeration chamber. Hydrogen absorbs heat from load before it is sucked out by another bank of compressor modules in cooling phase.

  3. Adsorption hysteresis in nanopores

    PubMed

    Neimark; Ravikovitch; Vishnyakov

    2000-08-01

    Capillary condensation hysteresis in nanopores is studied by Monte Carlo simulations and the nonlocal density functional theory. Comparing the theoretical results with the experimental data on low temperature sorption of nitrogen and argon in cylindrical channels of mesoporous siliceous molecular sieves of MCM-41 type, we have revealed four qualitatively different sorption regimes depending on the temperature and pore size. As the pore size increases at a given temperature, or as the temperature decreases at a given pore size, the following regimes are consequently observed: volume filling without phase separation, reversible stepwise capillary condensation, irreversible capillary condensation with developing hysteresis, and capillary condensation with developed hysteresis. We show that, in the regime of developed hysteresis (pores wider than 5 nm in the case of nitrogen sorption at 77 K), condensation occurs spontaneously at the vaporlike spinodal while desorption takes place at the equilibrium. A quantitative agreement is found between the modeling results and the experimental hysteresis loops formed by the adsorption-desorption isotherms. The results obtained provide a better understanding of the general behavior of confined fluids and the specifics of sorption and phase transitions in nanomaterials.

  4. Surfactant adsorption kinetics in microfluidics

    PubMed Central

    Riechers, Birte; Maes, Florine; Akoury, Elias; Semin, Benoît; Gruner, Philipp; Baret, Jean-Christophe

    2016-01-01

    Emulsions are metastable dispersions. Their lifetimes are directly related to the dynamics of surfactants. We design a microfluidic method to measure the kinetics of adsorption of surfactants to the droplet interface, a key process involved in foaming, emulsification, and droplet coarsening. The method is based on the pH decay in the droplet as a direct measurement of the adsorption of a carboxylic acid surfactant to the interface. From the kinetic measurement of the bulk equilibration of the pH, we fully determine the adsorption process of the surfactant. The small droplet size and the convection during the droplet flow ensure that the transport of surfactant through the bulk is not limiting the kinetics of adsorption. To validate our measurements, we show that the adsorption process determines the timescale required to stabilize droplets against coalescence, and we show that the interface should be covered at more than 90% to prevent coalescence. We therefore quantitatively link the process of adsorption/desorption, the stabilization of emulsions, and the kinetics of solute partitioning—here through ion exchange—unraveling the timescales governing these processes. Our method can be further generalized to other surfactants, including nonionic surfactants, by making use of fluorophore–surfactant interactions. PMID:27688765

  5. Surfactant adsorption kinetics in microfluidics

    NASA Astrophysics Data System (ADS)

    Riechers, Birte; Maes, Florine; Akoury, Elias; Semin, Benoît; Gruner, Philipp; Baret, Jean-Christophe

    2016-10-01

    Emulsions are metastable dispersions. Their lifetimes are directly related to the dynamics of surfactants. We design a microfluidic method to measure the kinetics of adsorption of surfactants to the droplet interface, a key process involved in foaming, emulsification, and droplet coarsening. The method is based on the pH decay in the droplet as a direct measurement of the adsorption of a carboxylic acid surfactant to the interface. From the kinetic measurement of the bulk equilibration of the pH, we fully determine the adsorption process of the surfactant. The small droplet size and the convection during the droplet flow ensure that the transport of surfactant through the bulk is not limiting the kinetics of adsorption. To validate our measurements, we show that the adsorption process determines the timescale required to stabilize droplets against coalescence, and we show that the interface should be covered at more than 90% to prevent coalescence. We therefore quantitatively link the process of adsorption/desorption, the stabilization of emulsions, and the kinetics of solute partitioning—here through ion exchange—unraveling the timescales governing these processes. Our method can be further generalized to other surfactants, including nonionic surfactants, by making use of fluorophore-surfactant interactions.

  6. High temperature probe

    DOEpatents

    Swan, Raymond A.

    1994-01-01

    A high temperature probe for sampling, for example, smokestack fumes, and is able to withstand temperatures of 3000.degree. F. The probe is constructed so as to prevent leakage via the seal by placing the seal inside the water jacket whereby the seal is not exposed to high temperature, which destroys the seal. The sample inlet of the probe is also provided with cooling fins about the area of the seal to provide additional cooling to prevent the seal from being destroyed. Also, a heated jacket is provided for maintaining the temperature of the gas being tested as it passes through the probe. The probe includes pressure sensing means for determining the flow velocity of an efficient being sampled. In addition, thermocouples are located in various places on the probe to monitor the temperature of the gas passing there through.

  7. Adsorption and absorption of boron, nitrogen, aluminum, and phosphorus on silicene: Stability and electronic and phonon properties

    NASA Astrophysics Data System (ADS)

    Sivek, J.; Sahin, H.; Partoens, B.; Peeters, F. M.

    2013-02-01

    Ab initio calculations within the density-functional theory formalism are performed to investigate the chemical functionalization of a graphene-like monolayer of silicon—silicene—with B, N, Al, or P atoms. The structural, electronic, magnetic, and vibrational properties are reported. The most preferable adsorption sites are found to be valley, bridge, valley and hill sites for B, N, Al, and P adatoms, respectively. All the relaxed systems with adsorbed/substituted atoms exhibit metallic behavior with strongly bonded B, N, Al, and P atoms accompanied by an appreciable electron transfer from silicene to the B, N, and P adatom/substituent. The Al atoms exhibit opposite charge transfer, with n-type doping of silicene and weaker bonding. The adatoms/substituents induce characteristic branches in the phonon spectrum of silicene, which can be probed by Raman measurements. Using molecular dynamics, we found that the systems under study are stable up to at least T=500 K. Our results demonstrate that silicene has a very reactive and functionalizable surface.

  8. Dye Adsorption Behavior of Polyvinyl Alcohol/Glutaraldehyde/β-Cyclodextrin Polymer Membranes

    NASA Astrophysics Data System (ADS)

    Ghemati, Dj.; Aliouche, Dj.

    2014-05-01

    Crosslinked polyvinyl alcohol/glutaraldehyde (PVA/GA) membranes were prepared, and attempts to obtain hydrophilic crosslinked PVA membranes were made by adding various amounts of β-cyclodexrin (β-CD), which is a typical cyclic oligosaccharide able to form inclusion complexes with organic host molecules (host-guest complexes). Thus, membranes of PVA/GA/β-CD were synthesized. The membranes were characterized by infrared spectroscopy (FTIR) and swelling measurements. The ability of cyclodextrin to include a wide variety of chemicals was also exploited for the dye adsorption to show the potentialities of the membranes in textile liquid waste processing. Adsorption of reactive methyl orange, and methylene blue dyes on PVA/GA/β-CD membranes was consequently studied using UV-Vis spectroscopy at wavelengths of 547, 463, and 660 nm. Adsorption reached equilibrium after 24 h. Results indicated that there is no covalent bond formation between PVA and β-CD; the β-CD is completely mixed into the PVA matrix polymer. The adsorption capacity increases with increasing amounts of cyclodextrin; the maximum adsorption capacity was obtained with 8% β-CD. Therefore, the change in adsorption capacities may be due to the dye structure effect, and the negative value of free energy indicated the spontaneous nature of adsorption.

  9. Transient internal probe

    NASA Astrophysics Data System (ADS)

    Jarboe, Thomas R.; Mattick, Arthur T.

    1993-12-01

    The Transient Internal Probe (TIP) diagnostic is a novel method for probing the interior of hot magnetic fusion plasmas that are inaccessible with ordinary stationary probes. A small probe of magneto-optic (Verdet) material is fired through a plasma at speeds of several km/sec, illuminated by a laser beam. The beam's polarization is rotated in the probe by the local magnetic field and retroreflection back to a polarimetry detector allows determination of the B-field profile across the diameter of a plasma at a spatial resolution of better than 1-cm and an absolute B-field resolution of a few tens of Gauss. The principal components of a TIP diagnostic system were developed and tested. A two-stage light gas gun was constructed that accelerates 30-caliber projectiles to 3 km/sec, and methods were examined for stripping a lexan sabot from a probe prior to entry into a plasma. Probes of CdMnTe and FR-5 Verdet glass were fabricated, and a polarimetry system was constructed for resolving polarization to within 0.25 deg. The diagnostic was validated by measuring a static B-field with a moving (dropped) TIP probe, and finding agreement with Hall-probe measurements to within experimental accuracy (40 Gauss).

  10. Macroscopic and spectroscopic investigations of the adsorption of nitroaromatic compounds on graphene oxide, reduced graphene oxide, and graphene nanosheets.

    PubMed

    Chen, Xiaoxiao; Chen, Baoliang

    2015-05-19

    The surface properties and adsorption mechanisms of graphene materials are important for potential environmental applications. The adsorption of m-dinitrobenzene, nitrobenzene, and p-nitrotoluene onto graphene oxide (GO), reduced graphene oxide (RGO), and graphene (G) nanosheets was investigated using IR spectroscopy to probe the molecular interactions of graphene materials with nitroaromatic compounds (NACs). The hydrophilic GO displayed the weakest adsorption capability. The adsorption of RGO and G was significantly increased due to the recovery of hydrophobic π-conjugation carbon atoms as active sites. RGO nanosheets, which had more defect sites than did GO or G nanosheets, resulted in the highest adsorption of NACs which was 10-50 times greater than the reported adsorption of carbon nanotubes. Superior adsorption was dominated by various interaction modes including π-π electron donor-acceptor interactions between the π-electron-deficient phenyls of the NACs and the π-electron-rich matrix of the graphene nanosheets, and the charge electrostatic and polar interactions between the defect sites of graphene nanosheets and the -NO2 of the NAC. The charge transfer was initially proved by FTIR that a blue shift of asymmetric -NO2 stretching was observed with a concomitant red shift of symmetric -NO2 stretching after m-dinitrobenzene was adsorbed. The multiple interaction mechanisms of the adsorption of NAC molecule onto flat graphene nanosheets favor the adsorption, detection, and transformation of explosives.

  11. Adsorption of mercury in coal-fired power plants gypsum slurry on TiO2/chitosan composite material

    NASA Astrophysics Data System (ADS)

    Gao, P.; Gao, B. B.; Gao, J. Q.; Zhang, K.; Chen, Y. J.; Yang, Y. P.; Chen, H. W.

    2016-07-01

    In this study, a simple method was used to prepare a chitosan adsorbent to mix with KI and TiO2. Gravimetric analysis (TG), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were used to characterize the samples before and after adsorption of Hg2+. A mercury adsorption experiment was also conducted in the gypsum slurry. The results show that using hydrobromic acid as a solvent of adsorbent resulted in a better adsorption effect than using acetic acid alone. Also, the sample (CS-KI/TiO2-HBr) had a maximum mercury adsorption capacity when the pH=5 and the t=50°C. The characterization experiments showed that the thermal stability of composite materials declined and the TiO2 uniformly dispersed in the surface of the samples with a lamellar structure, generating a lot of cracks and recesses that increased the reactive sites. Furthermore, when the TiO2 reacted with CS, it resulted in Ti-C, Ti-O and Ti-N bonds. The Br- can prevent the growth of TiO2 crystal grains and strengthen the ability of I- to remove mercury. The adsorption isotherm and kinetic results indicated that the adsorption behaviour of CS-KI/TiO2-HBr as it removes Hg2+ is an inhomogeneous multilayer adsorption process. The surface adsorption and intraparticle diffusion effects are both important in the Hg2+ adsorption process.

  12. Removal of dorzolamide from biomedical wastewaters with adsorption onto graphite oxide/poly(acrylic acid) grafted chitosan nanocomposite.

    PubMed

    Kyzas, George Z; Bikiaris, Dimitrios N; Seredych, Mykola; Bandosz, Teresa J; Deliyanni, Eleni A

    2014-01-01

    A novel graphite oxide/poly(acrylic acid) grafted chitosan nanocomposite (GO/CSA) was prepared and used as biosorbent for the removal of pharmaceutical compound (dorzolamide) from biomedical synthetic wastewaters. The performance was evaluated taking into account pH, kinetics and thermodynamics of adsorption. GO/CSA presented higher adsorption capacity in comparison with the parent materials (graphite oxide and poly(acrylic acid) grafted chitosan). All adsorbents prepared were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and potentiometric titration. The surface features were also evaluated after the dorzolamide adsorption in order to derive the adsorption mechanism. It was suggested that the reactive groups of GO and CSA can interact with the amino groups of dorzolamide and mainly the abundance of carboxyl groups of GO/CSA composite was the main reason for its enhanced adsorption capacity.

  13. Fluorescent probes for hydrogen sulfide detection and bioimaging.

    PubMed

    Yu, Fabiao; Han, Xiaoyue; Chen, Lingxin

    2014-10-21

    In comparison with other biological detection technologies, fluorescence bioimaging technology has become a powerful supporting tool for intracellular detection, and can provide attractive facilities for investigating physiological and pathological processes of interest with high spatial and temporal resolution, less invasiveness, and a rapid response. Due to the versatile roles of hydrogen sulfide (H2S) in cellular signal transduction and intracellular redox status regulation, fluorescent probes for the detection of this third signalling gasotransmitter have rapidly increased in number in recent years. These probes can offer powerful means to investigate the physiological actions of H2S in its native environments without disturbing its endogenous distribution. In this feature article, we address the synthesis and design strategies for the development of fluorescent probes for H2S based on the reaction type between H2S and the probes. Moreover, we also highlight fluorescent probes for other reactive sulfur species, such as sulfane sulfurs and SO2 derivatives.

  14. Adsorption and desorption of chlorpyrifos to soils and sediments.

    PubMed

    Gebremariam, Seyoum Yami; Beutel, Marc W; Yonge, David R; Flury, Markus; Harsh, James B

    2012-01-01

    ,439 and 15,500 L/kg for sediipents. This variation may result from several factors, including various experimental artifacts, variation in quality of soil organic matter, and inconsistencies in experimental methodologies. Based on this review, there appears to be no definitive quantification of chlorpyrifos adsorption or desorption characteristics. Thus, it is difficult to predict its adsorptive behavior with certainty, without resorting to experimental methods specific to the soil or sediment of interest. This limitation should be recognized in the context of current efforts to predict the risk, fate, and transport of chlorpyrifos based upon published partition coefficients. Based on a comprehensive review of the peer-reviewed literature related to adsorption and desorption of chlorpyrifos, we propose the following key areas for future research. From this review, it becomes increasingly evident that pesticide partitioning cannot be fully accounted for by the fraction of soil or solid-matrix organic matter or carbon content. Therefore, research that probes the variation in the nature and quality of soil organic matter on pesticide adsorption is highly desirable. Pesticide persistence and bioavailability depend on insights into desorption capacity. Therefore, understanding the fate and environmental impact of hydrophobic pesticides is incomplete without new research being performed to improve insights into pesticide desorption from soils and sediments. There is also a need for greater attention and consistency in developing experimental methods aimed at estimating partition coefficients. Moreover, in such testing, choosing initial concentrations and liquid-solid ratios that are more representative of environmental conditions could improve usefulness and interpretation of data that are obtained. Future monitoring efforts should include the sampling and analysis of suspended particulates to account for suspended solid-phase CPF, a commonly underestimated fraction in surface

  15. Electrokinetic investigation of surfactant adsorption.

    PubMed

    Bellmann, C; Synytska, A; Caspari, A; Drechsler, A; Grundke, K

    2007-05-15

    Fuerstenau [D.W. Fuerstenau, in: M.L. Hair (Ed.), Dekker, New York, 1971, p. 143] has already discussed the role of hydrocarbon chain of surfactants, the effect of alkyl chain length, chain structure and the pH of the solution on the adsorption process of surfactants. Later Kosmulski [M. Kosmulski, Chemical Properties of Material Surfaces, Surfactant Science Series, vol. 102, Dekker, New York, Basel, 2001] included the effect of surfactant concentration, equilibration time, temperature and electrolyte in his approaches. Certainly, the character of the head groups of the surfactant and the properties of the adsorbent surface are the basis for the adsorption process. Different surfactants and adsorbents cause different adsorption mechanisms described firstly by Rosen [M.J. Rosen, Surfactants and Interfacial Phenomena, second ed., Wiley, New York, 1989]. These adsorption mechanisms and their influencing factors were studied by electrokinetic investigations. Here only changes of the charges at the surfaces could be detected. To control the results of electrokinetic investigations they were compared with results from ellipsometric measurements. In the case of surfactant adsorption the chain length was vitally important. It could be shown by the adsorption of alkyl trimethyl ammonium bromides onto polymer films spin coated at wafer surfaces. The influence of the chain length depending on surface properties of the polymer film was studied. Streaming potential measurements were applied for these investigations. The obtained results enabled us to calculate the molar cohesive free energy per mol of CH2-group in the alkaline chain of the surfactant if all other specific adsorption effects were neglected.

  16. A Quantitative Mass-Spectrometry Platform to Monitor Changes in Cysteine Reactivity

    PubMed Central

    Qian, Yu; Weerapana, Eranthie

    2017-01-01

    Summary Cysteine residues on proteins serve diverse functional roles in catalysis and regulation and are susceptible to numerous posttranslational modifications. Methods to monitor the reactivity of cysteines within the context of a complex proteome have facilitated the identification and functional characterization of cysteine residues on disparate proteins. Here, we describe the use of a cysteine-reactive iodoacetamide probe coupled to isotopically labeled, cleavable linkers to identify and quantify cysteine-reactivity changes from two biological samples. PMID:27778278

  17. Adsorption of oxygen on W/100/ - Adsorption kinetics and structure

    NASA Technical Reports Server (NTRS)

    Bauer, E.; Poppa, H.; Viswanath, Y.

    1976-01-01

    The adsorption of oxygen on W(100) single-crystal surfaces is studied by Auger electron spectroscopy (AES), flash desorption, low-energy electron diffraction (LEED), and retarding-field work-function measurements. The AES results reveal stepwise changes in the sticking coefficients in the coverage range 0 to 1 and activated adsorption at higher coverages. Upon room-temperature adsorption, a series of complex LEED patterns is observed. In layers adsorbed at 1050 K and cooled to room temperature, the p(2 x 1) structure is the first ordered structure observed. This structure shows a reversible order-disorder transition between 700 and 1000 K and is characterized by a work function which is lower than that of the clean surface. Heating room-temperature adsorbates changes their structure irreversibly. At temperatures below 750 K, some new structures are observed.

  18. Formative Assessment Probes

    ERIC Educational Resources Information Center

    Eberle, Francis; Keeley, Page

    2008-01-01

    Formative assessment probes can be effective tools to help teachers build a bridge between students' initial ideas and scientific ones. In this article, the authors describe how using two formative assessment probes can help teachers determine the extent to which students make similar connections between developing a concept of matter and a…

  19. Probing Skills for Tutors.

    ERIC Educational Resources Information Center

    Brown, Beryl E.

    The Office of Academic Support and Instructional Services (OASIS) at the University of California at San Diego sponsors a workshop that teaches tutors to use five types of probing skills. The use of the skills is fundamental to the student learner's acquisition of complex relationships and problem solving skills. The five types of probes are:…

  20. Adsorption of thiophene on silica-supported Mo clusters

    NASA Astrophysics Data System (ADS)

    Komarneni, M.; Kadossov, E.; Justin, J.; Lu, M.; Burghaus, U.

    2010-07-01

    The adsorption/decomposition kinetics/dynamics of thiophene has been studied on silica-supported Mo and MoS x clusters. Two-dimensional cluster formation at small Mo exposures and three-dimensional cluster growth at larger exposures would be consistent with the Auger electron spectroscopy (AES) data. Thermal desorption spectroscopy (TDS) indicates two reaction pathways. H 4C 4S desorbs molecularly at 190-400 K. Two TDS features were evident and could be assigned to molecularly on Mo sites, and S sites adsorbed thiophene. Assuming a standard preexponential factor (ν = 1 × 10 13/s) for first-order kinetics, the binding energies for adsorption on Mo (sulfur) sites amount to 90 (65) kJ/mol for 0.4 ML Mo exposure and 76 (63) kJ/mol for 2 ML Mo. Thus, smaller clusters are more reactive than larger clusters for molecular adsorption of H 4C 4S. The second reaction pathway, the decomposition of thiophene, starts at 250 K. Utilizing multimass TDS, H 2, H 2S, and mostly alkynes are detected in the gas phase as decomposition products. H 4C 4S bond activation results in partially sulfided Mo clusters as well as S and C residuals on the surface. S and C poison the catalyst. As a result, with an increasing number of H 4C 4S adsorption/desorption cycles, the uptake of molecular thiophene decreases as well as the H 2 and H 2S production ceases. Thus, silica-supported sulfided Mo clusters are less reactive than metallic clusters. The poisoned catalyst can be partially reactivated by annealing in O 2. However, Mo oxides also appear to form, which passivate the catalyst further. On the other hand, while annealing a used catalyst in H/H 2, it is poisoned even more (i.e., the S AES signal increases). By means of adsorption transients, the initial adsorption probability, S0, of C 4H 4S has been determined. At thermal impact energies ( Ei = 0.04 eV), S0 for molecular adsorption amounts to 0.43 ± 0.03 for a surface temperature of 200 K. S0 increases with Mo cluster size, obeying the

  1. Adsorptive desulfurization by activated alumina.

    PubMed

    Srivastav, Ankur; Srivastava, Vimal Chandra

    2009-10-30

    This study reports usage of commercial grade activated alumina (aluminum oxide) as adsorbent for the removal of sulfur from model oil (dibenthiophene (DBT) dissolved in n-hexane). Bulk density of alumina was found to be 1177.77 kg/m(3). The BET surface area of alumina was found to decrease from 143.6 to 66.4 m(2)/g after the loading of DBT at optimum conditions. The carbon-oxygen functional groups present on the surface of alumina were found to be effective in the adsorption of DBT onto alumina. Optimum adsorbent dose was found to be 20 g/l. The adsorption of DBT on alumina was found to be gradual process, and quasi-equilibrium reached in 24 h. Langmuir isotherm best represented the equilibrium adsorption data. The heat of adsorption and change in entropy for DBT adsorption onto alumina was found to be 19.5 kJ/mol and 139.2 kJ/mol K, respectively.

  2. Reduced protein adsorption by osmolytes.

    PubMed

    Evers, Florian; Steitz, Roland; Tolan, Metin; Czeslik, Claus

    2011-06-07

    Osmolytes are substances that affect osmosis and are used by cells to adapt to environmental stress. Here, we report a neutron reflectivity study on the influence of some osmolytes on protein adsorption at solid-liquid interfaces. Bovine ribonuclease A (RNase) and bovine insulin were used as model proteins adsorbing at a hydrophilic silica and at a hydrophobic polystyrene surface. From the neutron reflectivity data, the adsorbed protein layers were characterized in terms of layer thickness, protein packing density, and adsorbed protein mass in the absence and presence of urea, trehalose, sucrose, and glycerol. All data point to the clear effect of these nonionic cosolvents on the degree of protein adsorption. For example, 1 M sucrose leads to a reduction of the adsorbed amount of RNase by 39% on a silica surface and by 71% on a polystyrene surface. Trehalose was found to exhibit activity similar to that of sucrose. The changes in adsorbed protein mass can be attributed to a decreased packing density of the proteins in the adsorbed layers. Moreover, we investigated insulin adsorption at a hydrophobic surface in the absence and presence of glycerol. The degree of insulin adsorption is decreased by even 80% in the presence of 4 M of glycerol. The results of this study demonstrate that nonionic cosolvents can be used to tune and control nonspecific protein adsorption at aqueous-solid interfaces, which might be relevant for biomedical applications.

  3. A biological oil adsorption filter.

    PubMed

    Pasila, Antti

    2004-12-01

    A new oil adsorption method called adsorption filtration (AF) has been developed. It is a technology where by oil residues can be cleaned from water by running it through a simple filter made from freeze treated, dried, milled and then fragmented plant material. By choosing suitable plants and fragmentation sizes it is possible to produce filters, which pass water but adsorb oil. The aim of this study was to investigate the possibilities of manufacturing oil adsorbing filter materials from reed canary grass (Phalaris arundinacea), flax (Linum usitatissimum L.) or hemp fibre (Cannabis sativa L.). The oil (80 ml) was mixed with de-ionised water (200 ml) and this mixture was filtered through 10 or 20 g adsorption filters. Fine spring harvested hemp fibre (diameter less than 1 mm) and reed canary grass fragments adsorb 2-4 g of oil per gram of adsorption material compared to 1-3 g of water. Adsorption filtration is thus a novel way of gathering spilled oil in shallow coastal waters before the oil reaches the shore.

  4. Rational Design of a Fluorescent Hydrogen Peroxide Probe Based on the Umbelliferone Fluorophore

    PubMed Central

    Du, Lupei; Li, Minyong; Zheng, Shilong; Wang, Binghe

    2008-01-01

    In this study, we report a novel water-soluble umbelliferone-based fluorescent probe for hydrogen peroxide. This probe shows very large increases (up to 100 fold) in fluorescent intensity upon reaction with hydrogen peroxide, and good selectivity over other reactive oxygen species (ROS). PMID:19081820

  5. Circumferential pressure probe

    NASA Technical Reports Server (NTRS)

    Holmes, Harlan K. (Inventor); Moore, Thomas C. (Inventor); Fantl, Andrew J. (Inventor)

    1989-01-01

    A probe for measuring circumferential pressure inside a body cavity is disclosed. In the preferred embodiment, a urodynamic pressure measurement probe for evaluating human urinary sphincter function is disclosed. Along the length of the probe are disposed a multiplicity of deformable wall sensors which typically comprise support tube sections with flexible side wall areas. These are arranged along the length of the probe in two areas, one just proximal to the tip for the sensing of fluid pressure inside the bladder, and five in the sensing section which is positioned within the urethra at the point at which the urinary sphincter constricts to control the flow of urine. The remainder of the length of the probe comprises multiple rigid support tube sections interspersed with flexible support tube sections in the form of bellows to provide flexibility.

  6. Electron temperature probe

    NASA Astrophysics Data System (ADS)

    Oyama, K.-I.; Cheng, C. Z.

    2013-11-01

    The electron temperature probe (ETP) was invented in Japan in 1970's. The probe measures the electron temperature accurately and the measurement is not influenced by the electrode contamination. The instrument has low weight, low data transmission bit rate and low power consumption. The probe has been deployed in many sounding rockets, Earth orbiting scientific satellites, and Mars exploration spacecraft in Japan. The probe has also been deployed in sounding rockets in West Germany, India, Canada, USA, and Brazil. The probe has also been deployed in Brazilian satellites, Korean satellites, and recently as a Taiwan satellite payload. The manuscript describes the principle of the ETP instrument, the system configuration, the mechanical interface with respect to the sensor location, the control timing between data processing units; some useful information, the interference with other instruments, and future improvements and tasks. Some useful information for conducting performance check after the instrument fabrication and before the flight deployment is also presented in Appendix A.

  7. Inflatable traversing probe seal

    NASA Technical Reports Server (NTRS)

    Trimarchi, Paul A.

    1991-01-01

    An inflatable seal acts as a pressure-tight zipper to provide traversing capability for instrumentation rakes and probes. A specially designed probe segment with a teardrop cross-section in the vicinity of the inflatable seal minimizes leakage at the interface. The probe is able to travel through a lengthwise slot in a pressure vessel or wind tunnel section, while still maintaining pressure integrity. The design uses two commercially available inflatable seals, opposing each other, to cover the probe slot in a wind tunnel wall. Proof-of-concept tests were conducted at vessel pressures up to 30 psig, with seals inflated to 50 psig, showing no measurable leakage along the seal's length or around the probe teardrop cross-section. This seal concept can replace the existing technology of sliding face plate/O-ring systems in applications where lengthwise space is limited.

  8. When is arthritis reactive?

    PubMed Central

    Hamdulay, S S; Glynne, S J; Keat, A

    2006-01-01

    Reactive arthritis is an important cause of lower limb oligoarthritis, mainly in young adults. It is one of the spondyloarthropathy family; it is distinguishable from other forms of inflammatory arthritis by virtue of the distribution of affected sites and the high prevalence of characteristic extra‐articular lesions. Many terms have been used to refer to this and related forms of arthritis leading to some confusion. Reactive arthritis is precipitated by an infection at a distant site and genetic susceptibility is marked by possession of the HLA‐B27 gene, although the mechanism remains uncertain. Diagnosis is a two stage process and requires demonstration of a temporal link with a recognised “trigger” infection. The identification and management of “sexually acquired” and “enteric” forms of reactive arthritis are considered. Putative links with HIV infection are also discussed. The clinical features, approach to investigation, diagnosis, and management of reactive arthritis are reviewed. PMID:16822921

  9. Metal adsorption on mosses: Toward a universal adsorption model.

    PubMed

    González, A G; Pokrovsky, O S

    2014-02-01

    This study quantifies the adsorption of heavy metals on 4 typical moss species used for environmental monitoring in the moss bag technique. The adsorption of Cu(2+), Cd(2+), Ni(2+), Pb(2+) and Zn(2+) onto Hypnum sp., Sphagnum sp., Pseudoscleropodium purum and Brachytecium rutabulum has been investigated using a batch reactor in a wide range of pH (1.3-11.0) and metal concentrations in solution (1.6μM-3.8mM). A Linear Programming Model (LPM) was applied for the experimental data to derive equilibrium constants and the number of surface binding sites. The surface acid-base titration performed for 4 mosses at a pH range of 3-10 in 0.1M NaNO3 demonstrated that Sphagnum sp. is the most efficient adsorbent as it has the maximal number of proton-binding sites on the surface (0.65mmol g(-1)). The pKa computed for all the moss species suggested the presence of 5 major functional groups: phosphodiester, carboxyl, phosphoryl, amine and polyphenols. The results of pH-edge experiments demonstrated that B. rutabulum exhibits the highest percentage of metal adsorption and has the highest number of available sites for most of the metals studied. However, according to the results of the constant pH "Langmuirian" isotherm, Sphagnum sp. can be considered as the strongest adsorbent, although the relative difference from other mosses is within 20%. The LPM was found to satisfactorily fit the experimental data in the full range of the studied solution parameters. The results of this study demonstrate a rather similar pattern of five metal adsorptions on mosses, both as a function of pH and as a metal concentration, which is further corroborated by similar values of adsorption constants. Therefore, despite the species and geographic differences between the mosses, a universal adsorption edge and constant pH adsorption isotherm can be recommended for 4 studied mosses. The quantitative comparison of metal adsorption with other common natural organic and inorganic materials demonstrates

  10. Application of probe manipulator to repair probe cards

    NASA Astrophysics Data System (ADS)

    Konno, Takeshi; Kobayashi, Mikihiko; Egashira, Mitsuru; Machida, Kazumichi; Urata, Atsuo

    2006-03-01

    We fabricated an apparatus for manipulation and welding of fine metal objects using a probe. The apparatus is composed of a work probe of a tungsten alloy needle, stages, a DC power supply, and an observation system. The work probe is held vertically above a gold substrate placed on stages to control the relative position against the work probe. The DC power supply is equipped to apply voltage of 0-10kV between the work probe and the substrate. One application of the apparatus is to repair probe cards. Thousands of contact probes (needles) are mounted on the printed circuit board (PCB) in the probe card. The contact probes are mounted one by one by the hands. Recently, an array of the contact probe on the PCB is produced by the LIGA process in response to narrower semiconductor pitch length. The problem is that there are no methods to repair a wrong contact probe. Whole of the contact probes should be a waste owing to one wrong contact probe. We propose to replace a wrong contact probe with a good one using our apparatus. Experiments to remove a contact probe by the apparatus is carried out using the specimen of a mimic probe card, where a cantilever type contact probes are arranged with a pitch of 25 micrometers. Removal of the wrong contact probe is carried out by a non-contact discharge and a contact discharge using the apparatus. High voltage of about 1-2kV is applied after the work probe is moved to above the target contact probe for the non-contact discharge. While high voltage of about10kV is applied after the work probe is positioned in contact with the target contact probe for the contact discharge. The target contact probe is removed by both methods, though the neighboring contact probes are damaged. The latter method is hopeful for removal for repair of the probe card.

  11. Removal of Chemazol Reactive Red 195 from aqueous solution by dehydrated beet pulp carbon.

    PubMed

    Dursun, Arzu Y; Tepe, Ozlem

    2011-10-30

    An agricultural low-cost by-product, dehydrated beet pulp carbon (DBPC) was used as an adsorbent for removal of Chemazol Reactive Red 195 (CRR 195) from aqueous solution. The surface area of DBPC was measured as 9.5m(2)g(-1) by using BET method. The results indicated that adsorption was strongly pH-dependent and optimum pH was determined as 1.0. The maximum dye adsorption capacity was obtained as 58.0 mg g(-1)at the temperature of 50°C at this pH value. The Freundlich and Langmuir adsorption models were used for the mathematical description of the adsorption equilibrium and it was reported that, experimental data fitted very well to Freundlich model. Mass transfer and kinetic models were applied to the experimental data to examine the mechanisms of adsorption and potential rate-controlling steps. It was found that both external mass transfer and intra-particle diffusion played an important role in the adsorption mechanisms of dye and adsorption kinetics followed the pseudo-first-order type kinetic model. The thermodynamic parameters such as, Gibbs free energy changes (ΔG°), standard enthalpy change (ΔH°) and standard entropy change (ΔS°) had been determined. The results show that adsorption of CRR 195 on DBPC is endothermic and spontaneous in nature.

  12. Pioneer Jupiter orbiter probe mission 1980, probe description

    NASA Technical Reports Server (NTRS)

    Defrees, R. E.

    1974-01-01

    The adaptation of the Saturn-Uranus Atmospheric Entry Probe (SUAEP) to a Jupiter entry probe is summarized. This report is extracted from a comprehensive study of Jovian missions, atmospheric model definitions and probe subsystem alternatives.

  13. Ligand-incorporation site in 5-methylcytosine-detection probe modulating the site of osmium complexation with the target DNA.

    PubMed

    Sugizaki, Kaori; Nakamura, Akiko; Yanagisawa, Hiroyuki; Okamoto, Akimitsu

    2012-09-01

    ICON Probes, short DNA strands containing an adenine linked to a bipyridine ligand, formed an interstrand cross-link with 5-methylcytosine located opposite the modified adenine in the presence of an osmium oxidant. The location of a bipyridine-tethered adenine in the probes varied the selectivity of the reactive base. An ICON probe where the modified adenine was located at the probe center showed a 5-methylcytosine-selective osmium complexation, whereas an ICON probe with the modified adenine at the strand end exhibited high reactivity towards thymine as well as 5-methylcytosine. The modulation of reactive bases by the incorporation of a bipyridine-tethered adenine site made facilitates design of ICON probes for the fluorometric detection of 5-methylcytosine.

  14. Preliminary investigation of phosphorus adsorption onto two types of iron oxide-organic matter complexes.

    PubMed

    Yan, Jinlong; Jiang, Tao; Yao, Ying; Lu, Song; Wang, Qilei; Wei, Shiqiang

    2016-04-01

    Iron oxide (FeO) coated by natural organic matter (NOM) is ubiquitous. The associations of minerals with organic matter (OM) significantly changes their surface properties and reactivity, and thus affect the environmental fate of pollutants, including nutrients (e.g., phosphorus (P)). In this study, ferrihydrite/goethite-humic acid (FH/GE-HA) complexes were prepared and their adsorption characteristics on P at various pH and ionic strength were investigated. The results indicated that the FeO-OM complexes showed a decreased P adsorption capacity in comparison with bare FeO. The maximum adsorption capacity (Qmax) decreased in the order of FH (22.17 mg/g)>FH-HA (5.43 mg/g)>GE (4.67 mg/g)>GE-HA (3.27 mg/g). After coating with HA, the amorphous FH-HA complex still showed higher P adsorption than the crystalline GE-HA complex. The decreased P adsorption observed might be attributed to changes of the FeO surface charges caused by OM association. The dependence of P adsorption on the specific surface area of adsorbents suggests that the FeO component in the complexes is still the main contributor for the adsorption surfaces. The P adsorptions on FeO-HA complexes decreased with increasing initial pH or decreasing initial ionic strength. A strong dependence of P adsorption on ionic strength and pH may demonstrate that outer-sphere complexes between the OM component on the surface and P possibly coexist with inner-sphere surface complexes between the FeO component and P. Therefore, previous over-emphasis on the contributions of original minerals to P immobilization possibly over-estimates the P loading capacity of soils, especially in humic-rich areas.

  15. Powerful greenhouse gas nitrous oxide adsorption onto intrinsic and Pd doped Single walled carbon nanotube

    NASA Astrophysics Data System (ADS)

    Yoosefian, Mehdi

    2017-01-01

    Density functional studies on the adsorption behavior of nitrous oxide (N2O) onto intrinsic carbon nanotube (CNT) and Pd-doped (5,5) single-walled carbon nanotube (Pd-CNT) have been reported. Introduction of Pd dopant facilitates in adsorption of N2O on the otherwise inert nanotube as observed from the adsorption energies and global reactivity descriptor values. Among three adsorption features of N2O onto CNT, the horizontal adsorption with Eads = -0.16 eV exhibits higher adsorption energy. On the other hand the Pd-CNT exhibit strong affinity toward gas molecule and would cause a huge increase in N2O adsorption energies. Chemical and electronic properties of CNT and Pd-CNT in the absence and presence of N2O were investigated. Adsorption of N2O gas molecule would affect the electronic conductance of Pd-CNT that can serve as a signal of gas sensors and the increased energy gaps demonstrate the formation of more stable systems. The atoms in molecules (AIM) theory and the natural bond orbital (NBO) calculations were performed to get more details about the nature and charge transfers in intermolecular interactions within adsorption process. As a final point, the density of states (DOSs) calculations was achieved to confirm previous results. According to our results, intrinsic CNT cannot act as a suitable adsorbent while Pd-CNT can be introduced as novel detectable complex for designing high sensitive, fast response and high efficient carbon nanotube based gas sensor to detect N2O gas as an air pollutant. Our results could provide helpful information for the design and fabrication of the N2O sensors.

  16. Adsorption isotherms of charged nanoparticles.

    PubMed

    Dos Santos, Alexandre P; Bakhshandeh, Amin; Diehl, Alexandre; Levin, Yan

    2016-10-19

    We present theory and simulations which allow us to quantitatively calculate the amount of surface adsorption excess of charged nanoparticles onto a charged surface. The theory is very accurate for weakly charged nanoparticles and can be used at physiological concentrations of salt. We have also developed an efficient simulation algorithm which can be used for dilute suspensions of nanoparticles of any charge, even at very large salt concentrations. With the help of the new simulation method, we are able to efficiently calculate the adsorption isotherms of highly charged nanoparticles in suspensions containing multivalent ions, for which there are no accurate theoretical methods available.

  17. Thermodynamic features of dioxins' adsorption.

    PubMed

    Prisciandaro, Marina; Piemonte, Vincenzo; di Celso, Giuseppe Mazziotti; Ronconi, Silvia; Capocelli, Mauro

    2017-02-15

    In this paper, the six more poisonous species among all congeners of dioxin group are taken into account, and the P-T diagram for each of them is developed. Starting from the knowledge of vapour tensions and thermodynamic parameters, the theoretical adsorption isotherms are calculated according to the Langmuir's model. In particular, the Langmuir isotherm parameters (K and wmax) have been validated through the estimation of the adsorption heat (ΔHads), which varies in the range 20-24kJ/mol, in agreement with literature values. This result will allow to put the thermodynamical basis for a rational design of different process units devoted to dioxins removal.

  18. Counterion release and electrostatic adsorption

    PubMed

    Sens; Joanny

    2000-05-22

    The effective charge of a rigid polyelectrolyte (PE) approaching an oppositely charged surface is studied. The cases of a weak (annealed) and strongly charged PE with condensed counterions (such as DNA) are discussed. In the most interesting case of the adsorption onto a substrate of low dielectric constant (such as a lipid membrane or a mica sheet) the condensed counterions are not always released as the PE approaches the substrate, because of the major importance of the image-charge effect. For the adsorption onto a surface with freely moving charges, the image-charge effect becomes less important and full release is often expected.

  19. Powder-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

    DOEpatents

    Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

    2016-05-03

    A powder-based adsorbent and a related method of manufacture are provided. The powder-based adsorbent includes polymer powder with grafted side chains and an increased surface area per unit weight to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. A method for forming the powder-based adsorbent includes irradiating polymer powder, grafting with polymerizable reactive monomers, reacting with hydroxylamine, and conditioning with an alkaline solution. Powder-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

  20. Foam-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

    DOEpatents

    Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

    2015-06-02

    Foam-based adsorbents and a related method of manufacture are provided. The foam-based adsorbents include polymer foam with grafted side chains and an increased surface area per unit weight to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. A method for forming the foam-based adsorbents includes irradiating polymer foam, grafting with polymerizable reactive monomers, reacting with hydroxylamine, and conditioning with an alkaline solution. Foam-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

  1. Reactive Power Compensator.

    DOEpatents

    El-Sharkawi, M.A.; Venkata, S.S.; Chen, M.; Andexler, G.; Huang, T.

    1992-07-28

    A system and method for determining and providing reactive power compensation for an inductive load. A reactive power compensator (50,50') monitors the voltage and current flowing through each of three distribution lines (52a, 52b, 52c), which are supplying three-phase power to one or more inductive loads. Using signals indicative of the current on each of these lines when the voltage waveform on the line crosses zero, the reactive power compensator determines a reactive power compensator capacitance that must be connected to the lines to maintain a desired VAR level, power factor, or line voltage. Alternatively, an operator can manually select a specific capacitance for connection to each line, or the capacitance can be selected based on a time schedule. The reactive power compensator produces control signals, which are coupled through optical fibers (102/106) to a switch driver (110, 110') to select specific compensation capacitors (112) for connections to each line. The switch driver develops triggering signals that are supplied to a plurality of series-connected solid state switches (350), which control charge current in one direction in respect to ground for each compensation capacitor. During each cycle, current flows from ground to charge the capacitors as the voltage on the line begins to go negative from its positive peak value. The triggering signals are applied to gate the solid state switches into a conducting state when the potential on the lines and on the capacitors reaches a negative peak value, thereby minimizing both the potential difference and across the charge current through the switches when they begin to conduct. Any harmonic distortion on the potential and current carried by the lines is filtered out from the current and potential signals used by the reactive power compensator so that it does not affect the determination of the required reactive compensation. 26 figs.

  2. Reactive power compensator

    DOEpatents

    El-Sharkawi, Mohamed A.; Venkata, Subrahmanyam S.; Chen, Mingliang; Andexler, George; Huang, Tony

    1992-01-01

    A system and method for determining and providing reactive power compensation for an inductive load. A reactive power compensator (50,50') monitors the voltage and current flowing through each of three distribution lines (52a, 52b, 52c), which are supplying three-phase power to one or more inductive loads. Using signals indicative of the current on each of these lines when the voltage waveform on the line crosses zero, the reactive power compensator determines a reactive power compensator capacitance that must be connected to the lines to maintain a desired VAR level, power factor, or line voltage. Alternatively, an operator can manually select a specific capacitance for connection to each line, or the capacitance can be selected based on a time schedule. The reactive power compensator produces control signals, which are coupled through optical fibers (102/106) to a switch driver (110, 110') to select specific compensation capacitors (112) for connections to each line. The switch driver develops triggering signals that are supplied to a plurality of series-connected solid state switches (350), which control charge current in one direction in respect to ground for each compensation capacitor. During each cycle, current flows from ground to charge the capacitors as the voltage on the line begins to go negative from its positive peak value. The triggering signals are applied to gate the solid state switches into a conducting state when the potential on the lines and on the capacitors reaches a negative peak value, thereby minimizing both the potential difference and across the charge current through the switches when they begin to conduct. Any harmonic distortion on the potential and current carried by the lines is filtered out from the current and potential signals used by the reactive power compensator so that it does not affect the determination of the required reactive compensation.

  3. BEAM CONTROL PROBE

    DOEpatents

    Chesterman, A.W.

    1959-03-17

    A probe is described for intercepting a desired portion of a beam of charged particles and for indicating the spatial disposition of the beam. The disclosed probe assembly includes a pair of pivotally mounted vanes moveable into a single plane with adjacent edges joining and a calibrated mechanical arrangement for pivoting the vancs apart. When the probe is disposed in the path of a charged particle beam, the vanes may be adjusted according to the beam current received in each vane to ascertain the dimension of the beam.

  4. Foldable polymers as probes

    DOEpatents

    Li, Alexander D. Q.; Wang, Wei

    2007-07-03

    Disclosed herein are novel probes, which can be used to detect and identify target molecules of interest in a sample. The disclosed probes can be used to monitor conformational changes induced by molecular recognition events in addition to providing signaling the presence and/or identity of a target molecule. Methods, including solid phase synthesis techniques, for making probe molecules that exhibit changes in their optical properties upon target molecule binding are described in the disclosure. Also disclosed herein are novel chromophore moieties, which have tailored fluorescent emission spectra.

  5. Foldable polymers as probes

    DOEpatents

    Li, Alexander D. Q.; Wang, Wei

    2009-07-07

    Disclosed herein are novel probes, which can be used to detect and identify target molecules of interest in a sample. The disclosed probes can be used to monitor conformational changes induced by molecular recognition events in addition to providing signaling the presence and/or identity of a target molecule. Methods, including solid phase synthesis techniques, for making probe molecules that exhibit changes in their optical properties upon target molecule binding are described in the disclosure. Also disclosed herein are novel chromophore moieties, which have tailored fluorescent emission spectra.

  6. Focus: DNA probes

    SciTech Connect

    Not Available

    1986-11-01

    Progress in the development of DNA probes for the identification and quantitation of specific genetic sequences in biological samples is reviewed. Current research efforts in the development of DNA probes for the diagnosis of a wide variety of bacterial, viral, and other infectious diseases, such as herpes simplex and cytomegalovirus, and inherited genetic diseases such as cystic fibrosis and sickle cell anemia are discussed. Progress in development of DNA probe assays for cancer diagnosis, detection of Salmonella food poisoning, tissue typing (detection of histocompatibility antigens), mutagen screening, and animal diseases, among other applications is included.

  7. Adsorption of Organics from Domestic Water Supplies.

    ERIC Educational Resources Information Center

    McGuire, Michael J.; Suffet, Irwin H.

    1978-01-01

    This article discusses the current state of the art of organics removal by adsorption. Various theoretical explanations of the adsorption process are given, along with practical results from laboratory, pilot-scale, and full-scale applications. (CS)

  8. CONTAMINANT ADSORPTION AND OXIDATION VIA FENTON REACTION

    EPA Science Inventory

    A ground water treatment process is proposed involving two cgemical processes: adsorption and oxidation. Adsorption of an organic compound onto granulated activated carbon (GAC) containing iron conveniently results in immobilizing and concentrating contaminants from the ground w...

  9. Jupiter probe heatshield configuration optimization

    NASA Technical Reports Server (NTRS)

    Dirling, R. B., Jr.; Binder, J. D.

    1978-01-01

    The effect of initial probe heatshield shape on the total probe mass loss during Jovian entry is considered. Modification of the aerothermal environment and probe entry trajectory due to changing probe heatshield shape is included in a computerized technique designed for rapid assessment of the effect of probe initial shape on heatshield mass loss. Results obtained indicate the importance of trajectory and heating distribution coupling with probe shape and mass change.

  10. Adsorption of proteins from plasma at polyester non-wovens.

    PubMed

    Klomp, A J; Engbers, G H; Mol, J; Terlingen, J G; Feijen, J

    1999-07-01

    Polyester non-wovens in filters for the removal of leukocytes from platelet concentrates (PCs) must be platelet compatible. In PC filtration, the adsorption of proteins at the plasma-non-woven interface can be of great importance with respect to the yield of platelets. Unmodified and radio frequency glow discharge (RFGD) treated poly(ethylene terephthalate) non-woven (NW-PET) and two commercial surface-modified non-wovens were contacted with human plasma. Protein desorption by sodium dodecyl sulphate (SDS) was evaluated by X-ray photoelectron spectroscopy (XPS). The desorbed proteins were characterized by gel electrophoresis and immunoblotting. Compared to the commercial surface-modified non-wovens, unmodified and RFGD-treated NW-PETs adsorbed a relatively high amount of protein. Significantly more protein was removed from the hydrophobic NW-PET by SDS than from the hydrophilic RFGD-treated non-wovens. RFGD treatment of NW-PET reduces the reversibility of protein adsorption. Less albumin and fibrinogen were removed from the RFGD-treated non-wovens than from NW-PET. In addition, a large amount of histidine-rich glycoprotein was removed from RFGD-treated non-wovens, but not from NW-PET. The different behaviour of RFGFD-treated non-wovens towards protein adsorption is probably caused by differences in the chemical reactivity of the non-woven surfaces.

  11. Variations in Reactivity on Different Crystallographic Orientations of Cerium Oxide

    SciTech Connect

    Mullins, David R; Albrecht, Peter M; Calaza, Florencia C

    2013-01-01

    Cerium oxide is a principal component in many heterogeneous catalytic processes. One of its key characteristics is the ability to provide or remove oxygen in chemical reactions. The different crystallographic faces of ceria present significantly different surface structures and compositions that may alter the catalytic reactivity. The structure and composition determine the number of coordination vacancies surrounding surface atoms, the availability of adsorption sites, the spacing between adsorption sites and the ability to remove O from the surface. To investigate the role of surface orientation on reactivity, CeO2 films were grown with two different orientations. CeO2(100) films were grown ex situ by pulsed laser deposition on Nb-doped SrTiO3(100). CeO2(111) films were grown in situ by thermal deposition of Ce metal onto Ru(0001) in an oxygen atmosphere. The chemical reactivity was characterized by the adsorption and decomposition of various molecules such as alcohols, aldehydes and organic acids. In general the CeO2(100) surface was found to be more active, i.e. molecules adsorbed more readily and reacted to form new products, especially on a fully oxidized substrate. However the CeO2(100) surface was less selective with a greater propensity to produce CO, CO2 and water as products. The differences in chemical reactivity are discussed in light of possible structural terminations of the two surfaces. Recently nanocubes and nano-octahedra have been synthesized that display CeO2(100) and CeO2(111) faces, respectively. These nanoparticles enable us to correlate reactions on high surface area model catalysts at atmospheric pressure with model single crystal films in a UHV environment.

  12. Molecular insights into the pH-dependent adsorption and removal of ionizable antibiotic oxytetracycline by adsorbent cyclodextrin polymers.

    PubMed

    Zhang, Yu; Cai, Xiyun; Xiong, Weina; Jiang, Hao; Zhao, Haitong; Yang, Xianhai; Li, Chao; Fu, Zhiqiang; Chen, Jingwen

    2014-01-01

    Effects of pH on adsorption and removal efficiency of ionizable organic compounds (IOCs) by environmental adsorbents are an area of debate, because of its dual mediation towards adsorbents and adsorbate. Here, we probe the pH-dependent adsorption of ionizable antibiotic oxytetracycline (comprising OTCH2 (+), OTCH(±), OTC(-), and OTC(2-)) onto cyclodextrin polymers (CDPs) with the nature of molecular recognition and pH inertness. OTCH(±) commonly has high adsorption affinity, OTC(-) exhibits moderate affinity, and the other two species have negligible affinity. These species are evidenced to selectively interact with structural units (e.g., CD cavity, pore channel, and network) of the polymers and thus immobilized onto the adsorbents to different extents. The differences in adsorption affinity and mechanisms of the species account for the pH-dependent adsorption of OTC. The mathematical equations are derived from the multiple linear regression (MLR) analysis of quantitatively relating adsorption affinity of OTC at varying pH to adsorbent properties. A combination of the MLR analysis for OTC and molecular recognition of adsorption of the species illustrates the nature of the pH-dependent adsorption of OTC. Based on this finding, γ-HP-CDP is chosen to adsorb and remove OTC at pH 5.0 and 7.0, showing high removal efficiency and strong resistance to the interference of coexisting components.

  13. Reactive Simulations for Biochemical Processes

    NASA Astrophysics Data System (ADS)

    Boero, M.

    After a brief review of the hybrid QM/MM molecular dynamics scheme and its coupling to the metadynamics method, I will show how such a combination of computational tools can be used to study chemical reactions of general biological interest. Specifically, by using such a reactive hybrid paradigm, where the QM driver is a Car-Parrinello Lagrangian dynamics, we have inspected the ATP hydrolysis reaction in the anti-freezing protein known as heat shock cognate protein (Hsc70) and the unconventional propagation of protons across peptide groups in the H-path of the bovine cytochrome c oxidase. While the former represents a fundamental reaction operated by all living beings in a wealth of processes and functions, the second one is involved in cell respiration. For both systems accurate X-ray data are available, yet the actual reaction mechanism escapes experimental probes. The simulations presented here provide the complementary information missing in experiments, offer a direct insight into the reaction mechanisms at a molecular level, and allow to understand which pathways nature can follow to realize these processes fundamental to living organisms.

  14. Comparison of quartz sand, anthracite, shale and biological ceramsite for adsorptive removal of phosphorus from aqueous solution.

    PubMed

    Jiang, Cheng; Jia, Liyue; Zhang, Bo; He, Yiliang; Kirumba, George

    2014-02-01

    The choice of substrates with high phosphorus adsorption capacity is vital for sustainable phosphorus removal from waste water in constructed wetlands. In this study, four substrates were used: quartz sand, anthracite, shale and biological ceramsite. These substrate samples were characterized by Xray diffractometry and scanning electron microscopy studies for their mineral components (chemical components) and surface characteristics. The dynamic experimental results revealed the following ranking order for total phosphorus (TP) removal efficiency: anthracite > biological ceramsite > shale > quartz sand. The adsorptive removal capacities for TP using anthracite, biological ceramsite, shale and quartz sand were 85.87, 81.44, 59.65, and 55.98 mg/kg, respectively. Phosphorus desorption was also studied to analyze the substrates' adsorption efficiency in wastewater treatment as well as the substrates' ability to be reused for treatment. It was noted that the removal performance for the different forms of phosphorus was dependent on the nature of the substrate and the adsorption mechanism. A comparative analysis showed that the removal of particulate phosphorus was much easier using shale. Whereas anthracite had the highest soluble reactive phosphorus (SRP) adsorptive capacity, biological ceramsite had the highest dissolved organic phosphorus (DOP) removal capacity. Phosphorus removal by shale and biological ceramsite was mainly through chemical adsorption, precipitation or biological adsorption. On the other hand, phosphorus removal through physical adsorption (electrostatic attraction or ion exchange) was dominant in anthracite and quartz sand.

  15. Mechanism and energetics of O and O2 adsorption on polar and non-polar ZnO surfaces

    NASA Astrophysics Data System (ADS)

    Gorai, Prashun; Seebauer, Edmund G.; Ertekin, Elif

    2016-05-01

    Polar surfaces of semiconducting metal oxides can exhibit structures and chemical reactivities that are distinct from their non-polar surfaces. Using first-principles calculations, we examine O adatom and O2 molecule adsorption on 8 different known ZnO reconstructions including Zn-terminated (Zn-ZnO) and O-terminated (O-ZnO) polar surfaces, and non-polar surfaces. We find that adsorption tendencies are largely governed by the thermodynamic environment, but exhibit variations due to the different surface chemistries of various reconstructions. The Zn-ZnO surface reconstructions which appear under O-rich and H-poor environments are found to be most amenable to O and O2 adsorption. We attribute this to the fact that on Zn-ZnO, the O-rich environments that promote O adsorption also simultaneously favor reconstructions that involve adsorbed O species. On these Zn-ZnO surfaces, O2 dissociatively adsorbs to form O adatoms. By contrast, on O-ZnO surfaces, the O-rich conditions required for O or O2 adsorption tend to promote reconstructions involving adsorbed H species, making further O species adsorption more difficult. These insights about O2 adsorption on ZnO surfaces suggest possible design rules to understand the adsorption properties of semiconductor polar surfaces.

  16. A new strategy for site-specific alkylation of DNA using oligonucleotides containing an abasic site and alkylating probes.

    PubMed

    Sato, Norihiro; Tsuji, Genichiro; Sasaki, Yoshihiro; Usami, Akira; Moki, Takuma; Onizuka, Kazumitsu; Yamada, Ken; Nagatsugi, Fumi

    2015-10-14

    Selective chemical reactions with DNA, such as its labelling, are very useful in many applications. In this paper, we discuss a new strategy for the selective alkylation of DNA using an oligonucleotide containing an abasic site and alkylating probes. We designed three probes consisting of 2-AVP as a reactive moiety and three kinds of binding moiety with high affinity to duplex DNA. Among these probes, Hoechst-AVP probe exhibited high selectivity and efficient reactivity to thymine bases at the site opposite an abasic site in DNA. Our method is potentially useful for inducing site-directed reactions aimed at inhibiting polymerase reactions.

  17. Enhanced adsorption of humic acids on ordered mesoporous carbon compared with microporous activated carbon.

    PubMed

    Liu, Fengling; Xu, Zhaoyi; Wan, Haiqin; Wan, Yuqiu; Zheng, Shourong; Zhu, Dongqiang

    2011-04-01

    Humic acids are ubiquitous in surface and underground waters and may pose potential risk to human health when present in drinking water sources. In this study, ordered mesoporous carbon was synthesized by means of a hard template method and further characterized by X-ray diffraction, N2 adsorption, transition electron microscopy, elemental analysis, and zeta-potential measurement. Batch experiments were conducted to evaluate adsorption of two humic acids from coal and soil, respectively, on the synthesized carbon. For comparison, a commercial microporous activated carbon and nonporous graphite were included as additional adsorbents; moreover, phenol was adopted as a small probe adsorbate. Pore size distribution characterization showed that the synthesized carbon had ordered mesoporous structure, whereas the activated carbon was composed mainly of micropores with a much broader pore size distribution. Accordingly, adsorption of the two humic acids was substantially lower on the activated carbon than on the synthesized carbon, because of the size-exclusion effect. In contrast, the synthesized carbon and activated carbon showed comparable adsorption for phenol when the size-exclusion effect was not in operation. Additionally, we verified by size-exclusion chromatography studies that the synthesized carbon exhibited greater adsorption for the large humic acid fraction than the activated carbon. The pH dependence of adsorption on the three carbonaceous adsorbents was also compared between the two test humic acids. The findings highlight the potential of using ordered mesoporous carbon as a superior adsorbent for the removal of humic acids.

  18. Dibenzothiophene adsorption at boron doped carbon nanoribbons studied within density functional theory

    NASA Astrophysics Data System (ADS)

    López-Albarrán, P.; Navarro-Santos, P.; Garcia-Ramirez, M. A.; Ricardo-Chávez, J. L.

    2015-06-01

    The adsorption of dibenzothiophene (DBT) on bare and boron-doped armchair carbon nanoribbons (ACNRs) is being investigated in the framework of the density functional theory by implementing periodic boundary conditions that include corrections from dispersion interactions. The reactivity of the ACNRs is characterized by using the Fukui functions as well as the electrostatic potential as local descriptors. Non-covalent adsorption mechanism is found when using the local Perdew-Becke-Ernzerhof functional, regardless of the DBT orientation and adsorption location. The dispersion interactions addition is a milestone to describe the adsorption process. The charge defects introduced in small number (i.e., by doping with B atoms), within the ACNRs increases the selectivity towards sulfur mainly due to the charge depletion at B sites. The DBT magnitude in the adsorption energy shows non-covalent interactions. As a consequence, the configurations where the DBT is adsorbed on a BC3 island increase the adsorption energy compared to random B arrangements. The stability of these configurations can be explained satisfactorily in terms of dipole interactions. Nevertheless, from the charge-density difference analysis and the weak Bader charge-distribution interactions cannot be ruled out completely. This is why the electronic properties of the ribbons are analyzed in order to elucidate the key role played by the B and DBT states in the adsorbed configurations.

  19. A DFT study of hydrogen adsorption on Be, Mg and Ca frameworks in erionite zeolite

    NASA Astrophysics Data System (ADS)

    Fellah, Mehmet Ferdi

    2017-02-01

    The molecular hydrogen adsorption was investigated on additional frameworks with earth alkaline metal atoms (Be, Mg and Ca) in 24T ERI zeolite cluster model by means of Density Functional Theory study. HOMO and LUMO energy values, chemical potential, chemical hardness, electronegativity, adsorption energy and adsorption enthalpy values have been calculated in this study. Mg-ERI and Ca-ERI clusters have much lower chemical potentials with much lower adsorption energy values when compared to the value of Be-ERI cluster. Additionally, they are softer than Be-ERI cluster with respect to their lower chemical hardness values. Hydrogen adsorption enthalpy values were computed as -3.6 and -3.9 kJ/mol on Mg-ERI and Ca-ERI clusters, respectively. These adsorption enthalpy values are significantly larger than the enthalpy value of liquefaction for hydrogen molecule. This consequently specifies that Mg-ERI and Ca-ERI zeolite structures which have higher chemical reactivity appear to be a promising candidate cryoadsorbent for hydrogen storage.

  20. Adsorption of Cu(II), Ni(II) and Zn(II) on modified jute fibres.

    PubMed

    Shukla, S R; Pai, Roshan S

    2005-09-01

    The potential of a lignocellulosic fibre, jute, was assessed for adsorption of heavy metal ions like Cu(II), Ni(II) and Zn(II) from their aqueous solutions. The fibre was also used as adsorbent after chemically modifying it by two different techniques viz, loading of a dye with specific structure, C.I. Reactive Orange 13, and oxidising with hydrogen peroxide. Both the modified jute fibres gave higher metal ion adsorption. Thus, the dye loaded jute fibres showed metal ion uptake values of 8.4, 5.26 and 5.95 mg/g for Cu(II), Ni(II) and Zn(II), respectively, while the corresponding values for oxidised jute fibres were 7.73, 5.57 and 8.02 mg/g, as against 4.23, 3.37 and 3.55 mg/g for unmodified jute fibres. Adsorption isotherm models indicated best fit for Langmuir model for the modified jute fibres. The adsorption values decreased with lowering of pH. The desorption efficiency, regenerative and reuse capacity of these adsorbents were also assessed for three successive adsorption-desorption cycles. The adsorptive capacity was retained only when the caustic soda regeneration is carried out as an intermediate step after desorption. Possible mechanism has been given.

  1. Dibenzothiophene adsorption at boron doped carbon nanoribbons studied within density functional theory

    SciTech Connect

    López-Albarrán, P.; Navarro-Santos, P.; Garcia-Ramirez, M. A.; Ricardo-Chávez, J. L.

    2015-06-21

    The adsorption of dibenzothiophene (DBT) on bare and boron-doped armchair carbon nanoribbons (ACNRs) is being investigated in the framework of the density functional theory by implementing periodic boundary conditions that include corrections from dispersion interactions. The reactivity of the ACNRs is characterized by using the Fukui functions as well as the electrostatic potential as local descriptors. Non-covalent adsorption mechanism is found when using the local Perdew-Becke-Ernzerhof functional, regardless of the DBT orientation and adsorption location. The dispersion interactions addition is a milestone to describe the adsorption process. The charge defects introduced in small number (i.e., by doping with B atoms), within the ACNRs increases the selectivity towards sulfur mainly due to the charge depletion at B sites. The DBT magnitude in the adsorption energy shows non-covalent interactions. As a consequence, the configurations where the DBT is adsorbed on a BC{sub 3} island increase the adsorption energy compared to random B arrangements. The stability of these configurations can be explained satisfactorily in terms of dipole interactions. Nevertheless, from the charge-density difference analysis and the weak Bader charge-distribution interactions cannot be ruled out completely. This is why the electronic properties of the ribbons are analyzed in order to elucidate the key role played by the B and DBT states in the adsorbed configurations.

  2. An Ultrasonographic Periodontal Probe

    NASA Astrophysics Data System (ADS)

    Bertoncini, C. A.; Hinders, M. K.

    2010-02-01

    Periodontal disease, commonly known as gum disease, affects millions of people. The current method of detecting periodontal pocket depth is painful, invasive, and inaccurate. As an alternative to manual probing, an ultrasonographic periodontal probe is being developed to use ultrasound echo waveforms to measure periodontal pocket depth, which is the main measure of periodontal disease. Wavelet transforms and pattern classification techniques are implemented in artificial intelligence routines that can automatically detect pocket depth. The main pattern classification technique used here, called a binary classification algorithm, compares test objects with only two possible pocket depth measurements at a time and relies on dimensionality reduction for the final determination. This method correctly identifies up to 90% of the ultrasonographic probe measurements within the manual probe's tolerance.

  3. Geological assessment probe

    NASA Astrophysics Data System (ADS)

    Collins, E. R.

    1980-04-01

    A probe is described which can be installed in a side hole that extends from a bore hole in the Earth, to assess the permeability of the strata surrounding the borehole. The probe is elongated and has a plurality of seals spaced therealong and sealed to the walls of the side hole to form a plurality of chambers sealed from one another. A tracer fluid injector on the probe can inject a tracer fluid into one of the chambers, while a tracer fluid detector located in another chamber can detect the tracer fluid, to thereby sense the permeability of the strata surrounding the side hole. The probe can include a train of modules, with each module having an inflatable packer which is inflated by the difference between the borehole pressure and the strata pressure.

  4. Technology for Entry Probes

    NASA Technical Reports Server (NTRS)

    Cutts, James A.; Arnold, James; Venkatapathy, Ethiraj; Kolawa, Elizabeth; Munk, Michelle; Wercinski, Paul; Laub, Bernard

    2005-01-01

    A viewgraph describing technologies for entry probes is presented. The topics include: 1) Entry Phase; 2) Descent Phase; 3) Long duration atmospheric observations; 4) Survivability at high temperatures; and 5) Summary.

  5. ADSORPTION OF SURFACTANT ON CLAYS

    EPA Science Inventory

    Surfactants used to enhance remediation of soils by soil washing are often lost in the process. Neither the amount nor the cause of this loss is known. It is assumed that clays present in the soil are responsible for the loss of the surfactant. In this papere, adsorption prope...

  6. Adsorption of pesticides on resins.

    PubMed

    Kyriakopoulos, Grigorios; Hourdakis, Adamadia; Doulia, Danae

    2003-03-01

    The objective of this work was to assess the capability of organic hydrophobic polymeric resins Amberlite XAD-4 and XAD-7 to remove the pesticides alachlor and amitrole from water. The pesticides adsorption on the two different adsorbents was measured by batch equilibrium technique and isotherm types and parameters were estimated. Two theoretical models were applied based on a Freundlich and a Langmuir isotherms. The effect of pesticides chemical composition and structure as well as the nature of solid surface on the efficiency of adsorption was evaluated. The influence of pH also was studied. In low pH solutions adsorption of amitrole was higher upon the nonionic aliphatic acrylic ester copolymer XAD-7 in comparison to the nonionic, crosslinked macroreticular copolymer of styrene divinylbenzene XAD-4. In neutral and intermediate pH solutions the polar acrylic ester copolymer XAD-7 was more effective to the retention of alachlor. The acrylic ester copolymer showed at pH 3 the lower effectiveness in alachlor removal from water. The data of the adsorption isotherms of pesticides upon the examined polymeric resins seemed to conform to both the Freundlich and the Langmuir isotherm models.

  7. Engineering and Design: Adsorption Design Guide

    DTIC Science & Technology

    2001-03-01

    adsorptive media addressed in- clude granular activated carbon (GAC) and other alternative adsorption carbon media, such as powdered activated carbon (PAC... Adsorption Media. a. Activated Carbon . Activated carbon can be manufactured from carbonaceous material, in- cluding coal (bituminous, subbituminous...information contained in Corps of Engineers Guide Specification 11225: Downflow Liquid Granular Activated Carbon

  8. Cryogenic Optoelectronic Probe Station

    DTIC Science & Technology

    2012-08-01

    capability is very important for a few on- going projects under DOD support. Selected Examples of Research Using COPS Example 1: sheet resistance measurement...donor concentration of this thin film contact material, we need to know the sheet resistance . As shown in Fig. 1, four electric probes are landed...voltage of 62.4 mV across probe 2 and 3. Therefore we can determine the sheet resistance by using Eq: = ( ) . This gives the sheet

  9. Adjustable Pitot Probe

    NASA Technical Reports Server (NTRS)

    Ashby, George C., Jr.; Robbins, W. Eugene; Horsley, Lewis A.

    1991-01-01

    Probe readily positionable in core of uniform flow in hypersonic wind tunnel. Formed of pair of mating cylindrical housings: transducer housing and pitot-tube housing. Pitot tube supported by adjustable wedge fairing attached to top of pitot-tube housing with semicircular foot. Probe adjusted both radially and circumferentially. In addition, pressure-sensing transducer cooled internally by water or other cooling fluid passing through annulus of cooling system.

  10. Phenylethynyl terminated reactive oligomer

    NASA Technical Reports Server (NTRS)

    Bryant, Robert G. (Inventor); Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor)

    1995-01-01

    A composition of matter having the general structure: ##STR1## (wherein X is F, Cl, or NO.sub.2, and Y is CO, SO.sub.2 or C(CF.sub.3).sub.2) is employed to terminate a nucleophilic reagent, resulting in the exclusive production of phenylethynyl terminated reactive oligomers which display unique thermal characteristics. A reactive diluent having the general structure: ##STR2## (wherein R is any aliphatic or aromatic moiety) is employed to decrease the melt viscosity of a phenylethynyl terminated reactive oligomer and to subsequently react therewith to provide a thermosetting material of enhanced density. These materials have features which make them attractive candidates for use as composite matrices and adhesives.

  11. Interactive chemical reactivity exploration.

    PubMed

    Haag, Moritz P; Vaucher, Alain C; Bosson, Maël; Redon, Stéphane; Reiher, Markus

    2014-10-20

    Elucidating chemical reactivity in complex molecular assemblies of a few hundred atoms is, despite the remarkable progress in quantum chemistry, still a major challenge. Black-box search methods to find intermediates and transition-state structures might fail in such situations because of the high-dimensionality of the potential energy surface. Here, we propose the concept of interactive chemical reactivity exploration to effectively introduce the chemist's intuition into the search process. We employ a haptic pointer device with force feedback to allow the operator the direct manipulation of structures in three dimensions along with simultaneous perception of the quantum mechanical response upon structure modification as forces. We elaborate on the details of how such an interactive exploration should proceed and which technical difficulties need to be overcome. All reactivity-exploration concepts developed for this purpose have been implemented in the samson programming environment.

  12. Adsorption of aqueous Zn(II) species on synthetic zeolites

    NASA Astrophysics Data System (ADS)

    Badillo-Almaraz, Véronica; Trocellier, Patrick; Dávila-Rangel, Ignacio

    2003-09-01

    To supply a good quality drinkable water tends to become a strategic task in both developed and under development countries in the world due to the number of potential contamination sources. One of the major problems is derived from the presence of heavy toxic metals like zinc or lead resulting from industrial activities. Zeolites are known as very efficient mineral substrates for fixing aqueous ionic species through their wide range of channels present in the crystalline structure and due to their strong surface reactivity. MicroPIXE coupled with microRBS (3.05 MeV 4He + ions) have been used to quantify the incorporation of zinc within two commercial zeolites containing alkali elements (zeolite X and clinoptilolite) in the concentration range of: 0.0002-0.05 M at neutral pH. At the beginning of the interaction between zeolite and Zn(II) solution, the adsorption process exhibits a direct proportionality between the content of zinc fixed on the mineral substrate and the aqueous concentration up to 0.01 M. Beyond this point a saturation effect seems to occur, indicating the strong decrease of available adsorption sites. Sodium or potassium ions are probably exchanged with Zn(II) ions during this process. The compared behaviour of the two zeolites is then discussed in terms of kinetic effects based on ionic radius values. A co-adsorption test carried on with a 50-50% Zn(II) 0.001 M-Pb(II) 0.001 M solution shows that lead does not occupy the same sites as zinc because the content of zinc fixed on the zeolite sample exactly corresponds to the result obtained with a pure 0.001 M Zn(II) solution. All these data clearly showed that zeolite surface reactivity is greatly influenced by the mineral cage-like structure and particularly the presence of pockets, spaces and channels.

  13. Probing magnetic and gold nanoparticles by using MAClevers® as ultrasensitive sensors.

    PubMed

    Nakamura, Marcelo; Araki, Koiti; Toma, Henrique E

    2010-12-01

    Magnetic AFM probes known as MAClevers® were employed for sensing picogram amounts of magnetic nanoparticles, based on the cantilever frequency shifts resulting from the magnetically induced adsorption of mass. By using organothiol functionalized magnetic nanoparticles, this analytical strategy was successfully extended to the detection of gold nanoparticles, as confirmed by confocal Raman microscopy.

  14. Effect of Doping on Surface Reactivity and Conduction Mechanism in Sm-doped CeO2 Thin Films

    SciTech Connect

    Yang, Nan; Belianinov, Alex; Strelcov, Evgheni; Tebano, Antonello; Daniele, Di Castro; Schlueter, Christoph; Lee, Tien-Lin; Baddorf, Arthur P.; Wisinger, Nina; Jesse, Stephen; Kalinin, Sergei V; Balestrino, Giuseppe; Aruta, Carmela

    2014-11-21

    Scanning probe microscopy measurements show irreversible surface electrochemistry in Sm-doped CeO2 thin films, which depends on humidity, temperature and doping concentration. A systematic study by electrochemical strain microscopy (ESM) in samples with two different Sm content and in several working conditions allows disclosing the microscopic mechanism underlying the difference in water adsorption and splitting with subsequent proton liberation. We measure the behavior of the hysteresis loops by changing temperature and humidity, both in standard ESM configuration and using the first order reversal curve (FORC) method. Complementing our study with spectroscopic measurements by hard x-ray photoemission spectroscopy we find that water incorporation is favored until the doping with Sm is too high to allow the presence of Ce3+. The influence of doping on the surface reactivity and conduction mechanism clearly emerges from all of our experimental results. We find that at lower Sm concentration proton conduction is prevalent, featured by lower activation energy and higher mobility. Defect concentrations determine the type of the prevalent charge carrier in a doping dependent manner.

  15. Effect of Doping on Surface Reactivity and Conduction Mechanism in Sm-doped CeO2 Thin Films

    DOE PAGES

    Yang, Nan; Belianinov, Alex; Strelcov, Evgheni; ...

    2014-11-21

    Scanning probe microscopy measurements show irreversible surface electrochemistry in Sm-doped CeO2 thin films, which depends on humidity, temperature and doping concentration. A systematic study by electrochemical strain microscopy (ESM) in samples with two different Sm content and in several working conditions allows disclosing the microscopic mechanism underlying the difference in water adsorption and splitting with subsequent proton liberation. We measure the behavior of the hysteresis loops by changing temperature and humidity, both in standard ESM configuration and using the first order reversal curve (FORC) method. Complementing our study with spectroscopic measurements by hard x-ray photoemission spectroscopy we find that watermore » incorporation is favored until the doping with Sm is too high to allow the presence of Ce3+. The influence of doping on the surface reactivity and conduction mechanism clearly emerges from all of our experimental results. We find that at lower Sm concentration proton conduction is prevalent, featured by lower activation energy and higher mobility. Defect concentrations determine the type of the prevalent charge carrier in a doping dependent manner.« less

  16. Reactivity of dicoordinated stannylones (Sn0) versus stannylenes (SnII): an investigation using DFT-based reactivity indices.

    PubMed

    Broeckaert, Lies; Frenking, Gernot; Geerlings, Paul; De Proft, Frank

    2013-10-07

    The reactivity of dicoordinated Sn(0) compounds, stannylones, is probed using density functional theory (DFT)-based reactivity indices and compared with the reactivity of dicoordinated Sn(II) compounds, stannylenes. For the former compounds, the influence of different types of electron-donating ligands, such as cyclic and acyclic carbenes, stannylenes and phosphines, on the reactivity of the central Sn atom is analyzed in detail. Sn(0) compounds are found to be relatively soft systems with a high nucleophilicity, and the plots of the Fukui function f(-) for an electrophilic attack consistently predict the highest reactivity on the Sn atom. Next, complexes of dicoordinated Sn compounds with different Lewis acids of variable hardness are computed. In a first part, the double-base character of stannylones is demonstrated in interactions with the hardest Lewis acid H(+). Both the first and second proton affinities (PAs) are high and are well correlated with the atomic charge on the Sn atom, probing its local hardness. These observations are also in line with electrostatic potential plots that demonstrate that the tin atom in Sn(0) compounds bears a higher negative charge in comparison to Sn(II) compounds. Stannylones and stannylenes can be distinguished from each other by the partial charges at Sn and by various reactivity indices. It also becomes clear that there is a smooth transition between the two classes of compounds. We furthermore demonstrate both from DFT-based reactivity indices and from energy decomposition analysis, combined with natural orbitals for chemical valence (EDA-NOCV), that the monocomplexed stannylones are still nucleophilic and as reactive towards a second Lewis acid as towards the first one. The dominating interaction is a strong σ-type interaction from the Sn atom towards the Lewis acid. The interaction energy is higher for complexes with the cation Ag(+) than with the non-charged electrophiles BH(3), BF(3), and AlCl(3).

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

    ERIC Educational Resources Information Center

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

    2008-01-01

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

  18. Huygens probe on target

    NASA Astrophysics Data System (ADS)

    1995-07-01

    In October 1997, a Titan/Centaur rocket lifting-off from Cape Canaveral will boost the spacecraft into a 6.7 year trajectory to reach Saturn. The trajectory will use two swing-bys of Venus in April 1998 and June 1999, followed by an Earth swing-by in August 1999 and a Jupiter swing-by in December 2000 to boost speed and reach Saturn in July 2004. A few months after going into orbit around Saturn, the Cassini spacecraft will release the Huygens probe for its descent through the atmosphere of Titan, the largest satellite of Saturn. The Huygens probe will measure the abundance of elements and compounds in Titan's atmosphere, the distribution of trace gases and aerosols, winds, temperature, pressure and surface state and its composition. A multi-spectral camera on the probe will provide images of the landscape of Titan. Titan is a unique planetary body in the solar system. It has an atmosphere which is primarily nitrogen. but is also rich in hydrocarbons. Due to the vast distance of the Saturnian system from the Sun, this atmosphere is at a very low temperature, thus greatly slowing down all the chemical processes. A study of this atmosphere will throw light on the development of our own atmosphere and contribute to our understanding of the origins of life on Earth. The Huygens probe is being developed by ESA with Aerospatiale (F) as the industrial prime contractor. Since the start of the programme in April 1990, very good progress has been made in design and hardware development. The entry into the Titan atmosphere will result in a very high surface temperature on the probe, generated as it decelerates due to the friction of the upper atmospheric layers. After the probe has slowed down sufficiently, a system of parachutes ensures a slow descent to the surface of Titan in approximately two and a half hours. The scientific measurements can only begin after the heat shield, which is needed to protect the probe during the high temperature entry phase, has been ejected

  19. Adsorption and desorption of arsenic to aquifer sediment on the Red River floodplain at Nam Du, Vietnam

    PubMed Central

    Thi Hoa Mai, Nguyen; Postma, Dieke; Thi Kim Trang, Pham; Jessen, Søren; Hung Viet, Pham; Larsen, Flemming

    2016-01-01

    The adsorption of arsenic onto aquifer sediment from the Red River floodplain, Vietnam, was determined in a series of batch experiments. Due to water supply pumping, river water infiltrates into the aquifer at the field site and has leached the uppermost aquifer sediments. The leached sediments, remain anoxic but contain little reactive arsenic and iron, and are used in our experiments. The adsorption and desorption experiments were carried out by addition or removal of arsenic from the aqueous phase in sediment suspensions under strictly anoxic conditions. Also the effects of HCO3, Fe(II), PO4 and Si on arsenic adsorption were explored. The results show much stronger adsorption of As(V) as compared to As(III), full reversibility for As(III) adsorption and less so for As(V). The presence or absence of HCO3 did not influence arsenic adsorption. Fe(II) enhanced As(V) sorption but did not influence the adsorption of As(III) in any way. During simultaneous adsorption of As(III) and Fe(II), As(III) was found to be fully desorbable while Fe(II) was completely irreversibly adsorbed and clearly the two sorption processes are uncoupled. Phosphate was the only solute that significantly could displace As(III) from the sediment surface. Compiling literature data on arsenic adsorption to aquifer sediment in Vietnam and Bangladesh revealed As(III) isotherms to be almost identical regardless of the nature of the sediment or the site of sampling. In contrast, there was a large variation in As(V) adsorption isotherms between studies. A tentative conclusion is that As(III) and As(V) are not adsorbing onto the same sediment surface sites. The adsorption behavior of arsenic onto aquifer sediments and synthetic Fe-oxides is compared. Particularly, the much stronger adsorption of As(V) than of As(III) onto Red River as well as on most Bangladesh aquifer sediments, indicates that the perception that arsenic, phosphate and other species compete for the same surface sites of iron oxides in

  20. Adsorption and desorption of arsenic to aquifer sediment on the Red River floodplain at Nam Du, Vietnam

    NASA Astrophysics Data System (ADS)

    Thi Hoa Mai, Nguyen; Postma, Dieke; Thi Kim Trang, Pham; Jessen, Søren; Hung Viet, Pham; Larsen, Flemming

    2014-10-01

    The adsorption of arsenic onto aquifer sediment from the Red River floodplain, Vietnam, was determined in a series of batch experiments. Due to water supply pumping, river water infiltrates into the aquifer at the field site and has leached the uppermost aquifer sediments. The leached sediments remain anoxic but contain little reactive arsenic and iron, and are used in our experiments. The adsorption and desorption experiments were carried out by addition or removal of arsenic from the aqueous phase in sediment suspensions under strictly anoxic conditions. Also the effects of HCO3, Fe(II), PO4 and Si on arsenic adsorption were explored. The results show much stronger adsorption of As(V) as compared to As(III), full reversibility for As(III) adsorption and less so for As(V). The presence or absence of HCO3 did not influence arsenic adsorption. Fe(II) enhanced As(V) sorption but did not influence the adsorption of As(III) in any way. During simultaneous adsorption of As(III) and Fe(II), As(III) was found to be fully desorbable while Fe(II) was completely irreversibly adsorbed and clearly the two sorption processes are uncoupled. Phosphate was the only solute that significantly could displace As(III) from the sediment surface. Compiling literature data on arsenic adsorption to aquifer sediment in Vietnam and Bangladesh revealed As(III) isotherms to be almost identical regardless of the nature of the sediment or the site of sampling. In contrast, there was a large variation in As(V) adsorption isotherms between studies. A tentative conclusion is that As(III) and As(V) are not adsorbing onto the same sediment surface sites. The adsorption behavior of arsenic onto aquifer sediments and synthetic Fe-oxides is compared. Particularly, the much stronger adsorption of As(V) than of As(III) onto Red River as well as on most Bangladesh aquifer sediments, indicates that the perception that arsenic, phosphate and other species compete for the same surface sites of iron oxides in

  1. Electric-Assisted Capillary Rise Adsorption of Polar and Nonpolar Solvents by Cellulose and Chitosan.

    PubMed

    Yan, Qi; Wang, Min-Yan; Wu, Yu-Hang; Jiang, Lin-Hai; Shen, Qing

    2016-02-18

    Electric-assisted capillary rise adsorption of polar and nonpolar solvents by cellulose and chitosan was studied by employing an electrostatic generator to assist a common capillary rise wetting by taking the anode and cathode electrodes respectively linked to a metal tube charged with samples and the probe solvent. To vary the voltage at 0, 100, 200, and 300 V, respectively, the recorded dynamic adsorption results showed that the cellulose and chitosan both kept a stable adsorption of the nonpolar hexane and diiodomethane, obviously ignoring the voltage increase. Moreover, the hexane amount adsorbed by cellulose and chitosan is similar, while the diiodomethane amount was adsorbed to a greater amount by cellulose as compared with the chitosan corresponding to these two biomaterials-based nonpolar components, for example, greater for cellulose and smaller for chitosan. Results also showed that the adsorption of polar water and formamide was gradually increased with the voltage increase, especially for chitosan, to correspond to the polar component of these materials, for example, greater for chitosan and smaller for cellulose. These adsorption behaviors suggested that the application of an extra electric field can only enhance the adsorption of polar solvent, and the molecular structure, for exmaple, the β-(1-4)-linked d-glucosamine units of chitosan, has sensitive electric field responses in polar solvent adsorption as compared with those of the β(1-4)-linked d-glucose units of cellulose. The reason for the electric adsorption behaviors was known due to the presence of an extra electric-field-induced reduction of the total surface tension of solvent and mainly the polar component.

  2. Adsorption site analysis of impurity embedded single-walled carbon nanotube bundles

    USGS Publications Warehouse

    Agnihotri, S.; Mota, J.P.B.; Rostam-Abadi, M.; Rood, M.J.

    2006-01-01

    Bundle morphology and adsorptive contributions from nanotubes and impurities are studied both experimentally and by simulation using a computer-aided methodology, which employs a small physisorbed probe molecule to explore the porosity of nanotube samples. Grand canonical Monte Carlo simulation of nitrogen adsorption on localized sites of a bundle is carried out to predict adsorption in its accessible internal pore volume and on its external surface as a function of tube diameter. External adsorption is split into the contributions from the clean surface of the outermost nanotubes of the bundle and from the surface of the impurities. The site-specific isotherms are then combined into a global isotherm for a given sample using knowledge of its tube-diameter distribution obtained by Raman spectroscopy. The structural parameters of the sample, such as the fraction of open-ended nanotubes and the contributions from impurities and nanotube bundles to total external surface area, are determined by fitting the experimental nitrogen adsorption data to the simulated isotherm. The degree of closure between experimental and calculated adsorption isotherms for samples manufactured by two different methods, to provide different nanotube morphology and contamination level, further strengthens the validity and resulting interpretations based on the proposed approach. The average number of nanotubes per bundle and average bundle size, within a sample, are also quantified. The proposed method allows for extrapolation of adsorption properties to conditions where the purification process is 100% effective at removing all impurities and opening access to all intrabundle adsorption sites. ?? 2006 Elsevier Ltd. All rights reserved.

  3. Waste metal hydroxide sludge as adsorbent for a reactive dye.

    PubMed

    Santos, Sílvia C R; Vílar, Vítor J P; Boaventura, Rui A R

    2008-05-30

    An industrial waste sludge mainly composed by metal hydroxides was used as a low-cost adsorbent for removing a reactive textile dye (Remazol Brilliant Blue) in solution. Characterization of this waste material included chemical composition, pH(ZPC) determination, particle size distribution, physical textural properties and metals mobility under different pH conditions. Dye adsorption equilibrium isotherms were determined at 25 and 35 degrees C and pH of 4, 7 and 10 revealing reasonably fits to Langmuir and Freundlich models. At 25 degrees C and pH 7, Langmuir fit indicates a maximum adsorption capacity of 91.0mg/g. An adsorptive ion-exchange mechanism was identified from desorption studies. Batch kinetic experiments were also conducted at different initial dye concentration, temperature, adsorbent dosage and pH. A pseudo-second-order model showed good agreement with experimental data. LDF approximation model was used to estimate homogeneous solid diffusion coefficients and the effective pore diffusivities. Additionally, a simulated real effluent containing the selected dye, salts and dyeing auxiliary chemicals, was also used in equilibrium and kinetic experiments and the adsorption performance was compared with aqueous dye solutions.

  4. O(2) adsorption and dissociation on neutral, positively and negatively charged Au(n) (n = 5-79) clusters.

    PubMed

    Roldán, Alberto; Ricart, Josep Manel; Illas, Francesc; Pacchioni, Gianfranco

    2010-09-28

    The adsorption and dissociation of an O(2) molecule on gas-phase gold clusters of size varying from 5 to 79 atoms have been investigated by means of first principles density functional theory calculations. The adsorption energies and dissociation barriers have been determined for neutral, positively and negatively charged gold clusters in order to analyze in a systematic way the role of the charge on the cluster reactivity. While there is beneficial effect on O(2) activation of an extra electron on the small gold clusters (Au(5) and Au(13)), the effect is absent for positively charged clusters. The effect of the charge vanishes rapidly by increasing the cluster size and is not visible for clusters containing about 40 atoms or more. Au(38) appears to be the most reactive among the clusters considered and strong oscillations in adsorption energies and dissociation barriers are found even for clusters containing several tens of atoms like Au(38), Au(55), and Au(79).

  5. Phosphate adsorption on lanthanum loaded biochar.

    PubMed

    Wang, Zhanghong; Shen, Dekui; Shen, Fei; Li, Tianyu

    2016-05-01

    To attain a low-cost and high-efficient phosphate adsorbent, lanthanum (La) loaded biochar (La-BC) prepared by a chemical precipitation method was developed. La-BC and its pristine biochar (CK-BC) were comparatively characterized using zeta potential, BET surface area, scanning electron microscopy/energy dispersive spectrometer (SEM-EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR). The adsorption ability and the mechanisms during adsorption process for the La-BC samples were also investigated. La loaded on the surface of biochar can be termed as La-composites (such as LaOOH, LaONO3 and La(OH)3), leading to the decrease of negative charge and surface area of biochar. La-BC exhibited the high adsorption capacity to phosphate compared to CK-BC. Adsorption isotherm and adsorption kinetic studies showed that the Langmuir isotherm and second order model could well describe the adsorption process of La-BC, indicating that the adsorption was dominated by a homogeneous and chemical process. The calculated maximum adsorption capacity was as high as 46.37 mg g(-1) (computed in P). Thermodynamic analysis revealed that the adsorption was spontaneous and endothermic. SEM, XRD, XPS and FT-IR analysis suggested that the multi-adsorption mechanisms including precipitation, ligand exchange and complexation interactions can be evidenced during the phosphate adsorption process by La-composites in La-BC.

  6. Adsorption of organic chemicals in soils.

    PubMed Central

    Calvet, R

    1989-01-01

    This paper presents a review on adsorption of organic chemicals on soils sediments and their constituents. The first part of this review deals with adsorption from gas and liquid phases and gives a discussion on the physical meaning of the shape of adsorption isotherms. Results show that no general rules can be proposed to describe univocally the relation between the shape of isotherms and the nature of adsorbate-adsorbent system. Kinetics of adsorption is discussed through the description of various models. Theoretical developments exist both for the thermodynamics and the kinetics of adsorption, but there is a strong need for experimental results. Possible adsorption mechanisms are ion exchange, interaction with metallic cations, hydrogen bonds, charge transfers, and London-van der Waals dispersion forces/hydrophobic effect. However, direct proofs of a given mechanism are rare. Several factors influence adsorption behavior. Electronic structure of adsorbed molecules, properties of adsorbents, and characteristics of the liquid phase are discussed in relation to adsorption. Such properties as water solubility, organic carbon content of adsorbing materials, and the composition of the liquid phase are particularly important. Evaluation of adsorption can be obtained through either laboratory measurements or use of several correlations. Adsorption measurements must be interpreted, taking into account treatment of adsorbent materials, experimental conditions, and secondary phenomena such as degradations. Correlations between adsorption coefficients and water-octanol partition coefficient or water solubility are numerous. They may be useful tools for prediction purposes. Relations with transport, bioavailability, and degradation are described. PMID:2695323

  7. Chemical Reactivity Test (CRT)

    SciTech Connect

    Zaka, F.

    2016-12-13

    The Chemical Reactivity Test (CRT) is used to determine the thermal stability of High Explosives (HEs) and chemical compatibility between (HEs) and alien materials. The CRT is one of the small-scale safety tests performed on HE at the High Explosives Applications Facility (HEAF).

  8. Reactive power compensating system

    DOEpatents

    Williams, Timothy J.; El-Sharkawi, Mohamed A.; Venkata, Subrahmanyam S.

    1987-01-01

    The reactive power of an induction machine is compensated by providing fixed capacitors on each phase line for the minimum compensation required, sensing the current on one line at the time its voltage crosses zero to determine the actual compensation required for each phase, and selecting switched capacitors on each line to provide the balance of the compensation required.

  9. Reactive Sensor Networks (RSN)

    DTIC Science & Technology

    2003-10-01

    Networks,” Distributed Autonomous Robotic Systems DARS 2000, pp. 471-472, Springer Verlag, Tokyo. R. R. Brooks. “Stigmergy an intelligence metric...Paper, March 2003. • R. Brooks, et al. “Reactive Sensor Networks: Mobile Code Support for Autonomous Sensor Networks,” Distributed Autonomous Robotic Systems DARS

  10. Reactive transport modeling

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This special section in the Vadose Zone Journal focusing on reactive transport modeling was developed from a special symposium jointly sponsored by the Soil Physics and Soil Chemistry Divisions of the Soil Science Society of America at the 2010 annual meetings held in Long Beach, CA. It contains eig...

  11. Reactive Power Compensating System.

    DOEpatents

    Williams, Timothy J.; El-Sharkawi, Mohamed A.; Venkata, Subrahmanyam S.

    1985-01-04

    The circuit was designed for the specific application of wind-driven induction generators. It has great potential for application in any situation where a varying reactive power load is present, such as with induction motors or generators, or for transmission network compensation.

  12. Modeling Atmospheric Reactive Nitrogen

    EPA Science Inventory

    Nitrogen is an essential building block of all proteins and thus an essential nutrient for all life. Reactive nitrogen, which is naturally produced via enzymatic reactions, forest fires and lightning, is continually recycled and cascades through air, water, and soil media. Human ...

  13. Model for resonant plasma probe.

    SciTech Connect

    Warne, Larry Kevin; Johnson, William Arthur; Hebner, Gregory Albert; Jorgenson, Roy E.; Coats, Rebecca Sue

    2007-04-01

    This report constructs simple circuit models for a hairpin shaped resonant plasma probe. Effects of the plasma sheath region surrounding the wires making up the probe are determined. Electromagnetic simulations of the probe are compared to the circuit model results. The perturbing effects of the disc cavity in which the probe operates are also found.

  14. Adsorption modeling for macroscopic contaminant dispersal analysis

    SciTech Connect

    Axley, J.W.

    1990-05-01

    Two families of macroscopic adsorption models are formulated, based on fundamental principles of adsorption science and technology, that may be used for macroscopic (such as whole-building) contaminant dispersal analysis. The first family of adsorption models - the Equilibrium Adsorption (EA) Models - are based upon the simple requirement of equilibrium between adsorbent and room air. The second family - the Boundary Layer Diffusion Controlled Adsorption (BLDC) Models - add to the equilibrium requirement a boundary layer model for diffusion of the adsorbate from the room air to the adsorbent surface. Two members of each of these families are explicitly discussed, one based on the linear adsorption isotherm model and the other on the Langmuir model. The linear variants of each family are applied to model the adsorption dynamics of formaldehyde in gypsum wall board and compared to measured data.

  15. Potential use of cotton plant wastes for the removal of Remazol Black B reactive dye.

    PubMed

    Tunç, Ozlem; Tanaci, Hacer; Aksu, Zümriye

    2009-04-15

    In this study, the potential use of cotton plant wastes - stalk (CS) and hull (CH) - as sorbents for the removal of Remazol Black B (RB5), a vinyl sulfone type reactive dye, was investigated. The results indicated that adsorption was strongly pH-dependent but slightly temperature-dependent for each sorbent-dye system. The Freundlich, Langmuir, Redlich-Peterson and Langmuir-Freundlich adsorption models were used for the mathematical description of adsorption equilibrium and isotherm constants were evaluated at 25 degrees C. All models except the Freundlich model were applicable for the description of dye adsorption by both sorbents in the concentration range studied. According to the Langmuir model, CS and CH sorbents exhibited the highest RB5 dye uptake capacities of 35.7 and 50.9 mg g(-1), respectively, at an initial pH value of 1.0. Simple mass transfer and kinetic models were applied to the experimental data to examine the mechanisms of adsorption and potential rate-controlling steps. It was found that both external mass transfer and intra-particle diffusion played an important role in the adsorption mechanisms of dye, and adsorption kinetics followed the pseudo second-order type kinetic model for each sorbent. Using the Langmuir model parameters, thermodynamic constant DeltaG degrees was also evaluated for each sorption system.

  16. Adsorption Behavior of Nonplanar Phthalocyanines: Competition of Different Adsorption Conformations

    PubMed Central

    2016-01-01

    Using density functional theory augmented with state-of-the-art van der Waals corrections, we studied the geometric and electronic properties of nonplanar chlorogallium-phthalocyanine GaClPc molecules adsorbed on Cu(111). Comparing these results with published experimental data for adsorption heights, we found indications for breaking of the metal–halogen bond when the molecule is heated during or after the deposition process. Interestingly, the work-function change induced by this dissociated geometry is the same as that computed for an intact adsorbate layer in the “Cl-down” configuration, with both agreeing well with the experimental photoemission data. This is unexpected, as the chemical natures of the adsorbates and the adsorption distances are markedly different in the two cases. The observation is explained as a consequence of Fermi-level pinning due to fractional charge transfer at the interface. Our results show that rationalizing the adsorption configurations on the basis of electronic interface properties alone can be ambiguous and that additional insight from dispersion-corrected DFT simulations is desirable. PMID:27066160

  17. Isolation and Reactivity of Trifluoromethyl Iodonium Salts

    PubMed Central

    2016-01-01

    The strategic incorporation of the trifluoromethyl (CF3) functionality within therapeutic or agrochemical agents is a proven strategy for altering their associated physicochemical properties (e.g., metabolic stability, lipophilicity, and bioavailability). Electrophilic trifluoromethylation has emerged as an important methodology for installing the CF3 moiety onto an array of molecular architectures, and, in particular, CF3 λ3-iodanes have garnered significant interest because of their unique reactivity and ease of handling. Trifluoromethylations mediated by these hypervalent iodine reagents often require activation through an exogenous Lewis or Brønsted acid; thus, putative intermediates invoked in these transformations are cationic CF3 iodoniums. These iodoniums have, thus far, eluded isolation and investigation of their innate reactivity (which has encouraged speculation that such species cannot be accessed). A more complete understanding of the mechanistic relevance of CF3 iodoniums is paramount for the development of new trifluoromethylative strategies involving λ3-iodanes. Here, we demonstrate that CF3 iodonium salts are readily prepared from common λ3-iodane precursors and exhibit remarkable persistence under ambient conditions. These reagents are competent electrophiles for a variety of trifluoromethylation reactions, and their reactivity is reminiscent of that observed when CF3 iodanes are activated using Lewis acids. As such, our results suggest the mechanistic relevance of CF3 iodonium intermediates in trifluoromethylative processes mediated by λ3-iodanes. The isolation of CF3 iodonium salts also presents the unique opportunity to employ them more generally as mechanistic probes. PMID:27280169

  18. In-situ Raman spectroscopy to elucidate the influence of adsorption in graphene electrochemistry

    PubMed Central

    van den Beld, Wesley T. E.; Odijk, Mathieu; Vervuurt, René H. J.; Weber, Jan-Willem; Bol, Ageeth A.; van den Berg, Albert; Eijkel, Jan C. T.

    2017-01-01

    Electrochemistry on graphene is of particular interest due to graphene’s high surface area, high electrical conductivity and low interfacial capacitance. Because the graphene Fermi level can be probed by its strong Raman signal, information on the graphene doping can be obtained which in turn can provide information on adsorbed atoms or molecules. For this paper, the adsorption analysis was successfully performed using three electroactive substances with different electrode interaction mechanisms: hexaammineruthenium(III) chloride (RuHex), ferrocenemethanol (FcMeOH) and potassium ferricyanide/potassium ferrocyanide (Fe(CN)6). The adsorption state was probed by analysing the G-peak position in the measured in-situ Raman spectrum during electrochemical experiments. We conclude that electrochemical Raman spectroscopy on graphene is a valuable tool to obtain in-situ information on adsorbed species on graphene, isolated from the rest of the electrochemical behaviour. PMID:28338094

  19. In-situ Raman spectroscopy to elucidate the influence of adsorption in graphene electrochemistry

    NASA Astrophysics Data System (ADS)

    van den Beld, Wesley T. E.; Odijk, Mathieu; Vervuurt, René H. J.; Weber, Jan-Willem; Bol, Ageeth A.; van den Berg, Albert; Eijkel, Jan C. T.

    2017-03-01

    Electrochemistry on graphene is of particular interest due to graphene’s high surface area, high electrical conductivity and low interfacial capacitance. Because the graphene Fermi level can be probed by its strong Raman signal, information on the graphene doping can be obtained which in turn can provide information on adsorbed atoms or molecules. For this paper, the adsorption analysis was successfully performed using three electroactive substances with different electrode interaction mechanisms: hexaammineruthenium(III) chloride (RuHex), ferrocenemethanol (FcMeOH) and potassium ferricyanide/potassium ferrocyanide (Fe(CN)6). The adsorption state was probed by analysing the G-peak position in the measured in-situ Raman spectrum during electrochemical experiments. We conclude that electrochemical Raman spectroscopy on graphene is a valuable tool to obtain in-situ information on adsorbed species on graphene, isolated from the rest of the electrochemical behaviour.

  20. Adsorption of various alcohols on Illinois No. 6 coal in aqueous solutions

    SciTech Connect

    Kwon, K.C.; Rigby, R.R.

    1993-07-01

    Hydrophilicity, hydrophobicity and aromacity of Illinois {number_sign}6 coal in water are relatively determined by evaluating equilibrium physical/chemical adsorption of probe compounds on the coal. Experiments on equilibrium adsorption loadings of various additives on 60--200 mesh Illinois {number_sign}6 coal (DECS-2; Randolph county) were performed to investigate relatively surface properties of the coal at 25{degree}C. The additives include various alcohols, alkanes and aromatic compounds. The main objectives of this research are to evaluate relatively surface properties of raw coals, treated coals and coal minerals with the inverse liquid chromatography technique, using various probe compounds, to analyze flotation recoveries of coals with a micro-flotation apparatus in order to relate coal floatability to evaluated coal surface properties, and to delineate roles of coal-cleaning/handling additives with the inverse liquid chromatography technique.

  1. Convective heat flow probe

    DOEpatents

    Dunn, J.C.; Hardee, H.C.; Striker, R.P.

    1984-01-09

    A convective heat flow probe device is provided which measures heat flow and fluid flow magnitude in the formation surrounding a borehole. The probe comprises an elongate housing adapted to be lowered down into the borehole; a plurality of heaters extending along the probe for heating the formation surrounding the borehole; a plurality of temperature sensors arranged around the periphery of the probe for measuring the temperature of the surrounding formation after heating thereof by the heater elements. The temperature sensors and heater elements are mounted in a plurality of separate heater pads which are supported by the housing and which are adapted to be radially expanded into firm engagement with the walls of the borehole. The heat supplied by the heater elements and the temperatures measured by the temperature sensors are monitored and used in providing the desired measurements. The outer peripheral surfaces of the heater pads are configured as segments of a cylinder and form a full cylinder when taken together. A plurality of temperature sensors are located on each pad so as to extend along the length and across the width thereof, with a heating element being located in each pad beneath the temperature sensors. An expansion mechanism driven by a clamping motor provides expansion and retraction of the heater pads and expandable packet-type seals are provided along the probe above and below the heater pads.

  2. Surgical force detection probe

    NASA Technical Reports Server (NTRS)

    Tcheng, Ping; Roberts, Paul; Scott, Charles; Prass, Richard

    1991-01-01

    The development progress of a precision electro-mechanical instrument which allows the detection and documentation of the forces and moment applied to human tissue during surgery (under actual operation room conditions), is reported. The pen-shaped prototype probe which measures 1/2 inch in diameter and 7 inches in length was fabricated using an aerodynamic balance. The aerodynamic balance, a standard wind tunnel force and moment sensing transducer, measures the forces and the moments transmitted through the surgeon's hand to the human tissue during surgery. The prototype probe which was fabricated as a development tool was tested successfully. The final version of the surgical force detection probe will be designed based on additional laboratory tests in order to establish the full scale loads. It is expected that the final product will require a simplified aerodynamic balance with two or three force components and one moment component with lighter full scale loads. A signal conditioner was fabricated to process and display the outputs from the prototype probe. This unit will be interfaced with a PC-based data system to provide automatic data acquisition, data processing, and graphics display. The expected overall accuracy of the probe is better than one percent full scale.

  3. Synthesizing mixed phase titania nanocomposites with enhanced photoactivity and redshifted photoresponse by reactive DC magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Chen, Le

    Recent work points out the importance of the solid-solid interface in explaining the high photoactivity of mixed phase TiO2 catalysts. The goal of this research was to probe the synthesis-structure-function relationships of the solid-solid interfaces created by the reactive direct current (DC) magnetron sputtering of titanium dioxide. I hypothesize that the reactive DC magnetron sputtering is a useful method for synthesizing photo-catalysts with unique structure including solid-solid interfaces and surface defects that are associated with enhanced photoreactivity as well as a photoresponse shifted to longer wavelengths of light. I showed that sputter deposition provides excellent control of the phase and interface formation as well as the stoichiometry of the films. I explored the effects exerted by the process parameters of pressure, oxygen partial pressure, target power, substrate bias (RF), deposition incidence angle, and post annealing treatment on the structural and functional characteristics of the catalysts. I have successfully made pure and mixed phase TiO2 films. These films were characterized with UV-Vis, XPS, AFM, SEM, TEM, XRD and EPR, to determine optical properties, elemental stoichiometry, surface morphology, phase distribution and chemical coordination. Bundles of anatase-rutile nano-columns having high densities of dual-scale of interfaces among and within the columns are fabricated. Photocatalytic performance of the sputtered films as measured by the oxidation of the pollutant, acetaldehyde, and the reduction of CO2 for fuel (CH4) production was compared (normalized for surface area) to that of mixed phase TiO2 fabricated by other methods, including flame hydrolysis powders, and solgel deposited TiO 2 films. The sputtered mixed phase materials were far superior to the commercial standard (Degussa P25) and solgel TiO2 based on gas phase reaction of acetaldehyde oxidation under UV light and CO2 reduction under both UV and visible illuminations. The

  4. Synthesis of porous chitosan-polyaniline/ZnO hybrid composite and application for removal of reactive orange 16 dye.

    PubMed

    Kannusamy, Pandiselvi; Sivalingam, Thambidurai

    2013-08-01

    For the first time, chitosan-polyaniline/ZnO hybrids were prepared through a polymerization of aniline hydrochloride in the presence of ZnCl2 and chitosan. The hybrid materials were characterized by FT-IR, BET, SEM, UV-vis spectra and XRD analysis. From the BET and SEM micrographs, the introduction of ZnO nanoparticles into chitosan-polyaniline hybrid could obviously increase the porosity due to good possibility for dye adsorption. Adsorption experiments were carried out as a function of contact time, concentration of dye, adsorbent dosage and pH using reactive orange 16 as a model pollutant. The adsorption equilibrium data were fitted well to the Langmuir isotherm equation, with maximum adsorption capacity value was found to be 476.2mgg(-1). Adsorption kinetics was best described by the pseudo-second-order model agreed well with the experimental data and good correlation (R(2)>0.999). Photocatalytic degradation of dye under UV irradiation at pH 5.8 has also been examined. FT-IR spectrum clearly indicates that before adsorption of hybrid showed the functional groups of chitosan and polyaniline, whereas the dye adsorbed hybrid only present the dye molecules and ZnO. Based on the results of present investigation, the introduction of ZnCl2 into chitosan-polyaniline hybrid will enhance the adsorption of reactive dyes and photocatalytic degradation.

  5. Surface reactivity in the pathogenic response to particulates.

    PubMed Central

    Fubini, B

    1997-01-01

    The peculiar characteristics of dust toxicity are discussed in relation to the processes taking place at the particle-biological medium interface. Because of surface reactivity, toxicity of solids is not merely predictable from chemical composition and molecular structure, as with water soluble compounds. With particles having the same bulk composition, micromorphology (the thermal and mechanical history of dust and adsorption from the environment) determines the kind and abundance of active surface sites, thus modulating reactivity toward cells and tissues. The quantitative evaluation of doses is discussed in comparisons of dose-response relationships obtained with different materials. Responses related to the surface of the particle are better compared on a per-unit surface than per-unit weight basis. The role of micromorphology, hydrophilicity, and reactive surface cations in determining the pathogenicity of inhaled particles is described with reference to silica and asbestos toxicity. Heating crystalline silica decreases hydrophilicity, with consequent modifications in membranolytic potential, retention, and transport. Transition metal ions exposed at the surface generate free radicals in aqueous suspensions. Continuous redox cycling of iron, with consequent activation-reactivation of the surface sites releasing free radicals, could account for the long-term pathogenicity caused by the inhalation of iron-containing fibers. In various pathogenicities caused by mixed dusts, the contact between components modifies toxicity. Hard metal lung disease is caused by exposure to mixtures of metals and carbides, typically cobalt (Co) and tungsten carbide (WC), but not to single components. Toxicity stems from reactive oxygen species generation in a mechanism involving both Co metal and WC in mutual contact. A relationship between the extent of water adsorption and biopersistence is proposed for vitreous fibers. Modifications of the surface taking place in vivo are

  6. Adsorption of organic acids on TiO2 nanoparticles: effects of pH, nanoparticle size, and nanoparticle aggregation.

    PubMed

    Pettibone, John M; Cwiertny, David M; Scherer, Michelle; Grassian, Vicki H

    2008-06-01

    In this study, the adsorption of two organic acids, oxalic acid and adipic acid, on TiO2 nanoparticles was investigated at room temperature, 298 K. Solution-phase measurements were used to quantify the extent and reversibility of oxalic acid and adipic acid adsorption on anatase nanoparticles with primary particle sizes of 5 and 32 nm. At all pH values considered, there were minimal differences in measured Langmuir adsorption constants, K ads, or surface-area-normalized maximum adsorbate-surface coverages, Gamma max, between 5 and 32 nm particles. Although macroscopic differences in the reactivity of these organic acids as a function of nanoparticle size were not observed, ATR-FTIR spectroscopy showed some distinct differences in the absorption bands present for oxalic acid adsorbed on 5 nm particles compared to 32 nm particles, suggesting different adsorption sites or a different distribution of adsorption sites for oxalic acid on the 5 nm particles. These results illustrate that molecular-level differences in nanoparticle reactivity can still exist even when macroscopic differences are not observed from solution phase measurements. Our results also allowed the impact of nanoparticle aggregation on acid uptake to be assessed. It is clear that particle aggregation occurs at all pH values and that organic acids can destabilize nanoparticle suspensions. Furthermore, 5 nm particles can form larger aggregates compared to 32 nm particles under the same conditions of pH and solid concentrations. The relative reactivity of 5 and 32 nm particles as determined from Langmuir adsorption parameters did not appear to vary greatly despite differences that occur in nanoparticle aggregation for these two different size nanoparticles. Although this potentially suggests that aggregation does not impact organic acid uptake on anatase particles, these data clearly show that challenges remain in assessing the available surface area for adsorption in nanoparticle aqueous suspensions

  7. Reactivity Network: Secondary Sources for Inorganic Reactivity Information.

    ERIC Educational Resources Information Center

    Mellon, E. K.

    1989-01-01

    Provides an eclectic annotated bibliography of secondary sources for inorganic reactivity information of interest to reactivity network review authors and to anyone seeking information about simple inorganic reactions in order to develop experiments and demonstrations. Gives 119 sources. (MVL)

  8. Ice-Borehole Probe

    NASA Technical Reports Server (NTRS)

    Behar, Alberto; Carsey, Frank; Lane, Arthur; Engelhardt, Herman

    2006-01-01

    An instrumentation system has been developed for studying interactions between a glacier or ice sheet and the underlying rock and/or soil. Prior borehole imaging systems have been used in well-drilling and mineral-exploration applications and for studying relatively thin valley glaciers, but have not been used for studying thick ice sheets like those of Antarctica. The system includes a cylindrical imaging probe that is lowered into a hole that has been bored through the ice to the ice/bedrock interface by use of an established hot-water-jet technique. The images acquired by the cameras yield information on the movement of the ice relative to the bedrock and on visible features of the lower structure of the ice sheet, including ice layers formed at different times, bubbles, and mineralogical inclusions. At the time of reporting the information for this article, the system was just deployed in two boreholes on the Amery ice shelf in East Antarctica and after successful 2000 2001 deployments in 4 boreholes at Ice Stream C, West Antarctica, and in 2002 at Black Rapids Glacier, Alaska. The probe is designed to operate at temperatures from 40 to +40 C and to withstand the cold, wet, high-pressure [130-atm (13.20-MPa)] environment at the bottom of a water-filled borehole in ice as deep as 1.6 km. A current version is being outfitted to service 2.4-km-deep boreholes at the Rutford Ice Stream in West Antarctica. The probe (see figure) contains a sidelooking charge-coupled-device (CCD) camera that generates both a real-time analog video signal and a sequence of still-image data, and contains a digital videotape recorder. The probe also contains a downward-looking CCD analog video camera, plus halogen lamps to illuminate the fields of view of both cameras. The analog video outputs of the cameras are converted to optical signals that are transmitted to a surface station via optical fibers in a cable. Electric power is supplied to the probe through wires in the cable at a

  9. Experimental and theoretical study using DFT method for the competitive adsorption of two cationic dyes from wastewaters

    NASA Astrophysics Data System (ADS)

    Regti, Abdelmajid; Ayouchia, Hicham Ben El; Laamari, My Rachid; Stiriba, Salah Eddine; Anane, Hafid; Haddad, Mohammadine El

    2016-12-01

    The adsorption of cationic dyes, Basic Yellow (BY28) and Methylene Blue (MB) on a new activated carbon from medlar species were studied in both single and binary system. Some experimental parameters, namely, pH, amount of adsorbent and contact time are studied. Quantum chemical results indicate that the adsorption efficiency was directly related to the dye electrophilicity power. Some theorical parameters were calculated and proved that MB is more electrophilic than BY28, than greatest interaction with surface sites. Kinetic study showed that the adsorption follows the pseudo-second-order model and Freundlich was the best model to describe the phenomenon in the single and binary system. According to the local reactivity results using Parr functions, the sulphur and nitrogen atoms will be the main adsorption sites.

  10. Multispectral imaging probe

    SciTech Connect

    Sandison, David R.; Platzbecker, Mark R.; Descour, Michael R.; Armour, David L.; Craig, Marcus J.; Richards-Kortum, Rebecca

    1999-01-01

    A multispectral imaging probe delivers a range of wavelengths of excitation light to a target and collects a range of expressed light wavelengths. The multispectral imaging probe is adapted for mobile use and use in confined spaces, and is sealed against the effects of hostile environments. The multispectral imaging probe comprises a housing that defines a sealed volume that is substantially sealed from the surrounding environment. A beam splitting device mounts within the sealed volume. Excitation light is directed to the beam splitting device, which directs the excitation light to a target. Expressed light from the target reaches the beam splitting device along a path coaxial with the path traveled by the excitation light from the beam splitting device to the target. The beam splitting device directs expressed light to a collection subsystem for delivery to a detector.

  11. Multispectral imaging probe

    DOEpatents

    Sandison, D.R.; Platzbecker, M.R.; Descour, M.R.; Armour, D.L.; Craig, M.J.; Richards-Kortum, R.

    1999-07-27

    A multispectral imaging probe delivers a range of wavelengths of excitation light to a target and collects a range of expressed light wavelengths. The multispectral imaging probe is adapted for mobile use and use in confined spaces, and is sealed against the effects of hostile environments. The multispectral imaging probe comprises a housing that defines a sealed volume that is substantially sealed from the surrounding environment. A beam splitting device mounts within the sealed volume. Excitation light is directed to the beam splitting device, which directs the excitation light to a target. Expressed light from the target reaches the beam splitting device along a path coaxial with the path traveled by the excitation light from the beam splitting device to the target. The beam splitting device directs expressed light to a collection subsystem for delivery to a detector. 8 figs.

  12. Studies on Vapor Adsorption Systems

    NASA Technical Reports Server (NTRS)

    Shamsundar, N.; Ramotowski, M.

    1998-01-01

    The project consisted of performing experiments on single and dual bed vapor adsorption systems, thermodynamic cycle optimization, and thermal modeling. The work was described in a technical paper that appeared in conference proceedings and a Master's thesis, which were previously submitted to NASA. The present report describes some additional thermal modeling work done subsequently, and includes listings of computer codes developed during the project. Recommendations for future work are provided.

  13. Homogenous and heterogenous advanced oxidation of two commercial reactive dyes.

    PubMed

    Balcioglu, I A; Arslan, I; Sacan, M T

    2001-07-01

    Two commercial reactive dyes, the azo dye Reactive Black 5 and the copper phythalocyanine dye Reactive Blue 21, have been treated at a concentration of 75 mg l(-1) by titanium dioxide mediated photocatalytic (TiO2/UV), dark and UV-light assisted Fenton (Fe2+/H2O2) and Fenton-like (Fe3+/H2O2) processes in acidic medium. For the treatment of Reactive Black 5, all investigated advanced oxidation processes were quite effective in terms of colour, COD as well as TOC removal. Moreover, the relative growth inhibition of the azo dye towards the marine algae Dunaliella tertiolecta that was initially 70%, did not exhibit an increase during the studied advanced oxidation reactions and complete detoxification at the end of the treatment period could be achieved for all investigated treatment processes. However, for Reactive Blue 21, abatement in COD and UV-VIS absorbance values was mainly due to the adsorption of the dye on the photocatalyst surface and/or the coagulative effect of Fe3+/Fe2+ ions. Although only a limited fraction of the copper phythalocyanine dye underwent oxidative degradation, 47% of the total copper in the dye was already released after 1 h photocatalytic treatment.

  14. Chromatographic determination of the differential isosteric adsorption enthalpies and differential entropies on ordered silica materials.

    PubMed

    Grajek, H; Paciura-Zadrozna, J; Witkiewicz, Z

    2008-06-13

    The adsorption properties of the ordered mesoporous siliceous materials: MCM-41C16 (denoted as C16), MCM-41C16-SH and MCM-41C16-NH(2) (known as MCMs) having different surface functionalities were studied by inverse gas chromatography to assess their suitability for adsorption of analytes from gas and liquid phases. Polar and non-polar adsorbates were employed. The differential isosteric enthalpies, -DeltaH(ads), and differential entropies, -DeltaS(ads), of adsorption of different 'molecular probes' were determined chromatographically. A mathematical link between the -DeltaH(ads), and -DeltaS(ads) magnitudes and experimental data was derived through an Antoine-type equation. The present studies have been entirely restricted to the region of low adsorbate concentration. The problem of the interrelationship between the -DeltaH(ads), and -DeltaS(ads) values, known as the 'thermodynamic compensation effect', and interpretation of chromatographic data for the adsorption of different adsorbates on the MCMs have been considered in the light of both experimental data obtained in the present studies and the data available in the literature for siliceous adsorbents with randomly ordered structures. It was shown chromatographically that there is substantial parallelism between the magnitudes of the differential isosteric enthalpy and differential entropy for some 'molecular probes' chromatographed on C16 and its derivatives. Complementary information was obtained by atomic-force microscopy (AFM), X-ray photoelectron spectroscopy and X-ray diffraction (XRD) spectroscopy.

  15. Enthalpies of proton adsorption onto Bacillus licheniformis at 25, 37, 50, and 75 °C

    NASA Astrophysics Data System (ADS)

    Gorman-Lewis, Drew

    2011-03-01

    Understanding bacterial surface reactivity requires many different lines of investigation. Toward this end, we used isothermal titration calorimetry to measure heats of proton adsorption onto a Gram positive thermophile Bacillus licheniformis at 25, 37, 50, and 75 °C. Proton adsorption under all conditions exhibited exothermic heat production. Below pH 4.5, exothermic heats decreased as temperature increased above 37 °C; above pH 4.5, there was no significant difference in heats evolved at the temperatures investigated. Total proton uptake did not vary significantly with temperature. Site-specific enthalpies and entropies were calculated by applying a 4-site, non-electrostatic surface complexation model to the calorimetric data. Interpretation of site-specific enthalpies and entropies of proton adsorption for site L1, L2, and L4 are consistent with previous interpretations of phosphoryl, carboxyl, and hydroxyl/amine site-identities, respectively, and with previous calorimetric measurements of proton adsorption onto mesophilic species. Enthalpies and entropies for surface site L3 are not consistent with the commonly inferred phosphoryl site-identity and are more consistent with sulfhydryl functional groups. These results reveal intricacies of surface reactivity that are not detectable by other methods.

  16. Hydrogen Adsorption in Carbon nanoparticles

    NASA Astrophysics Data System (ADS)

    Cabrera, A. L.; Rojas, S.; Dias-Droguett, D. E.; Bhuyan, H.; Aomoa, N.; Kakati, M.

    2013-03-01

    We have studied hydrogen adsorption in carbon nanoparticles using a quartz crystal microbalance. The carbon nanoparticles were synthesized from a thermal plasma jet at different pressure (15 - 263 torr) of the reactants and different current (50 - 250 A) to generate the plasma. The as-prepared carbon nanoparticles were directly deposited on top of the gold electrode of a quartz crystal and we monitored in-situ the changes in resonance frequency while the chamber was pressurized at different hydrogen pressures. These changes enabled determination of absorbed hydrogen mass in order to get H/C mass ratio curves as a function of H2 pressure. Adsorption curves obtained in some carbon nanoparticles indicated the formation of hydrogen monolayer inside the pores of the carbon nanoparticles. Using the value of the jump due to the formation of a H2\\ monolayer, a surface area was estimated between 40-60 m2/g for hydrogen adsorption. In other carbon samples, hydrogen uptake curves indicated that H2 was filling the sample's pores when pore volume was large. These observations will be discussed in detail for several carbon nanoparticles samples. Funds provided by VRI Puente 9/2012 and 10/2012

  17. Adsorption of Gemini surfactants onto clathrate hydrates.

    PubMed

    Salako, O; Lo, C; Couzis, A; Somasundaran, P; Lee, J W

    2013-12-15

    This work addresses the adsorption of two Gemini surfactants at the cyclopentane (CP) hydrate-water interface. The Gemini surfactants investigated here are Dowfax C6L and Dowfax 2A1 that have two anionic head groups and one hydrophobic tail group. The adsorption of these surfactants was quantified using adsorption isotherms and the adsorption isotherms were determined using liquid-liquid titrations. Even if the Gemini surfactant adsorption isotherms show multi-layer adsorption, they possess the first Langmuir layer with the second adsorption layer only evident in the 2A1 adsorption isotherm. Zeta potentials of CP hydrate particles in the surfactant solution of various concentrations of Dowfax C6L and Dowfax 2A1 were measured to further explain their adsorption behavior at the CP hydrate-water interface. Zeta potentials of alumina particles as a model particle system in different concentrations of sodium dodecyl sulfate (SDS), Dowfax C6L and Dowfax 2A1 were also measured to confirm the configuration of all the surfactants at the interface. The determination of the isotherms and zeta-potentials provides an understanding framework for the adsorption behavior of the two Gemini surfactants at the hydrate-water interface.

  18. Phenylethynyl Containing Reactive Additives

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Smith, Joseph G., Jr. (Inventor); Hergenrother, Paul M. (Inventor)

    2002-01-01

    Phenylethynyl containing reactive additives were prepared from aromatic diamine, containing phenylethvnvl groups and various ratios of phthalic anhydride and 4-phenylethynviphthalic anhydride in glacial acetic acid to form the imide in one step or in N-methyl-2-pvrrolidinone to form the amide acid intermediate. The reactive additives were mixed in various amounts (10% to 90%) with oligomers containing either terminal or pendent phenylethynyl groups (or both) to reduce the melt viscosity and thereby enhance processability. Upon thermal cure, the additives react and become chemically incorporated into the matrix and effect an increase in crosslink density relative to that of the host resin. This resultant increase in crosslink density has advantageous consequences on the cured resin properties such as higher glass transition temperature and higher modulus as compared to that of the host resin.

  19. Reactive Air Aluminization

    SciTech Connect

    Choi, Jung-Pyung; Chou, Y. S.; Stevenson, Jeffry W.

    2011-10-28

    Ferritic stainless steels and other alloys are of great interest to SOFC developers for applications such as interconnects, cell frames, and balance of plant components. While these alloys offer significant advantages (e.g., low material and manufacturing cost, high thermal conductivity, and high temperature oxidation resistance), there are challenges which can hinder their utilization in SOFC systems; these challenges include Cr volatility and reactivity with glass seals. To overcome these challenges, protective coatings and surface treatments for the alloys are under development. In particular, aluminization of alloy surfaces offers the potential for mitigating both evaporation of Cr from the alloy surface and reaction of alloy constituents with glass seals. Commercial aluminization processes are available to SOFC developers, but they tend to be costly due to their use of exotic raw materials and/or processing conditions. As an alternative, PNNL has developed Reactive Air Aluminization (RAA), which offers a low-cost, simpler alternative to conventional aluminization methods.

  20. Phenylethynyl Containing Reactive Additives

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Smith, Joseph G., Jr. (Inventor); Hergenrother, Paul M. (Inventor)

    2002-01-01

    Phenylethynyl containing reactive additives were prepared from aromatic diamines containing phenylethynyl groups and various ratios of phthalic anhydride and 4-phenylethynylphthalic anhydride in glacial acetic acid to form the imide in one step or in N-methyl-2-pyrrolidi none to form the amide acid intermediate. The reactive additives were mixed in various amounts (10% to 90%) with oligomers containing either terminal or pendent phenylethynyl groups (or both) to reduce the melt viscosity and thereby enhance processability. Upon thermal cure, the additives react and become chemically incorporated into the matrix and effect an increase in crosslink density relative to that of the host resin. This resultant increase in crosslink density has advantageous consequences on the cured resin properties such as higher glass transition temperature and higher modulus as compared to that of the host resin.

  1. Nonquaternary Cholinesterase Reactivators.

    DTIC Science & Technology

    1982-08-30

    Methylphosphonyl-AChE by la, lb, 2, and 3 . .............................................. 83 Chapter III 1 Lineweaver - Burke Plot for Compound 3a...Not determined. I11 ................ ."--..-. . . .S . -. -.. .i.,...,. _. o, . ’._ -. .-. . , , I I 1 .. .! 8.08.O 1I i i 7.0 LINEWEAVER - BURKE ...10 15 20 25 30 35 40 [AcSCh] - 1 , M -1 x 10 -4 JA-1 043-23 FIGURE 1 LINEWEAVER - BURKE PLOT FOR COMPOUND 3a 112 nonquaternary reactivators with ethyl

  2. Skylab reactivation mission report

    NASA Technical Reports Server (NTRS)

    Chubb, W. B.

    1980-01-01

    On July 11, 1979, Skylab impacted the Earth's surface. The debris dispersion area stretched from the South Eastern Indian Ocean across a sparsely populated section of Western Australia. The events leading to the reentry of Skylab are discussed and a final assessment of the Skylab debris impact footprint is presented. Also included are detailed evaluations of the various Skylab systems that were reactivated when control of Skylab was regained in mid-1978 after having been powered down since February 4, 1974.

  3. Oligodeoxynucleotide Probes for Detecting Intact Cells

    NASA Technical Reports Server (NTRS)

    Rosson, Reinhardt A.; Maurina-Brunker, Julie; Langley, Kim; Pynnonen, Christine M.

    2004-01-01

    A rapid, sensitive test using chemiluminescent oligodeoxynucleotide probes has been developed for detecting, identifying, and enumerating intact cells. The test is intended especially for use in detecting and enumerating bacteria and yeasts in potable water. As in related tests that have been developed recently for similar purposes, the oligodeoxynucleotide probes used in this test are typically targeted at either singlecopy deoxyribonucleic acid (DNA) genes (such as virulence genes) or the multiple copies (10,000 to 50,000 copies per cell) of 16S ribosomal ribonucleic acids (rRNAs). Some of those tests involve radioisotope or fluorescent labeling of the probes for reporting hybridization of probes to target nucleic acids. Others of those tests involve labeling with enzymes plus the use of chemiluminescent or chromogenic substrates to report hybridization via color or the emission of light, respectively. The present test is of the last-mentioned type. The chemiluminescence in the present test can be detected easily with relatively simple instrumentation. In developing the present test, the hybridization approach was chosen because hybridization techniques are very specific. Hybridization detects stable, inheritable genetic targets within microorganisms. These targets are not dependent on products of gene expression that can vary with growth conditions or physiological states of organisms in test samples. Therefore, unique probes can be designed to detect and identify specific genera or species of bacteria or yeast (in terms of rRNA target sequences) or can be designed to detect and identify virulence genes (genomic target sequences). Because of the inherent specificity of this system, there are few problems of cross-reactivity. Hybridization tests are rapid, but hybridization tests now available commercially lack sensitivity; typically, between 10(exp 6) and 10(exp 7) cells of the target organism are needed to ensure a reliable test. Consequently, the numbers of

  4. Multiscale reactive molecular dynamics

    NASA Astrophysics Data System (ADS)

    Knight, Chris; Lindberg, Gerrick E.; Voth, Gregory A.

    2012-12-01

    Many processes important to chemistry, materials science, and biology cannot be described without considering electronic and nuclear-level dynamics and their coupling to slower, cooperative motions of the system. These inherently multiscale problems require computationally efficient and accurate methods to converge statistical properties. In this paper, a method is presented that uses data directly from condensed phase ab initio simulations to develop reactive molecular dynamics models that do not require predefined empirical functions. Instead, the interactions used in the reactive model are expressed as linear combinations of interpolating functions that are optimized by using a linear least-squares algorithm. One notable benefit of the procedure outlined here is the capability to minimize the number of parameters requiring nonlinear optimization. The method presented can be generally applied to multiscale problems and is demonstrated by generating reactive models for the hydrated excess proton and hydroxide ion based directly on condensed phase ab initio molecular dynamics simulations. The resulting models faithfully reproduce the water-ion structural properties and diffusion constants from the ab initio simulations. Additionally, the free energy profiles for proton transfer, which is sensitive to the structural diffusion of both ions in water, are reproduced. The high fidelity of these models to ab initio simulations will permit accurate modeling of general chemical reactions in condensed phase systems with computational efficiency orders of magnitudes greater than currently possible with ab initio simulation methods, thus facilitating a proper statistical sampling of the coupling to slow, large-scale motions of the system.

  5. Endocavity Ultrasound Probe Manipulators

    PubMed Central

    Stoianovici, Dan; Kim, Chunwoo; Schäfer, Felix; Huang, Chien-Ming; Zuo, Yihe; Petrisor, Doru; Han, Misop

    2014-01-01

    We developed two similar structure manipulators for medical endocavity ultrasound probes with 3 and 4 degrees of freedom (DoF). These robots allow scanning with ultrasound for 3-D imaging and enable robot-assisted image-guided procedures. Both robots use remote center of motion kinematics, characteristic of medical robots. The 4-DoF robot provides unrestricted manipulation of the endocavity probe. With the 3-DoF robot the insertion motion of the probe must be adjusted manually, but the device is simpler and may also be used to manipulate external-body probes. The robots enabled a novel surgical approach of using intraoperative image-based navigation during robot-assisted laparoscopic prostatectomy (RALP), performed with concurrent use of two robotic systems (Tandem, T-RALP). Thus far, a clinical trial for evaluation of safety and feasibility has been performed successfully on 46 patients. This paper describes the architecture and design of the robots, the two prototypes, control features related to safety, preclinical experiments, and the T-RALP procedure. PMID:24795525

  6. Laboratory plasma probe studies

    NASA Technical Reports Server (NTRS)

    Heikkila, W. J.

    1975-01-01

    Diagnostic experiments performed in a collisionless plasma using CO2 as the working gas are described. In particular, simultaneous measurements that have been performed by means of Langmuir- and RF-probes are presented. A resonance occurring above the parallel resonance in the frequency characteristic of a two electrode system is interpreted as being due to the resonant excitation of electroacoustic waves.

  7. Probing the Solar System

    ERIC Educational Resources Information Center

    Wilkinson, John

    2013-01-01

    Humans have always had the vision to one day live on other planets. This vision existed even before the first person was put into orbit. Since the early space missions of putting humans into orbit around Earth, many advances have been made in space technology. We have now sent many space probes deep into the Solar system to explore the planets and…

  8. Cervical Neoplasia Probe Control

    SciTech Connect

    Vargo, Timothy D.

    1997-01-24

    This software, which consists of a main executive and several subroutines, performs control of the optics, image acquisition, and Digital Signal Processing (DSP) of this image, of an optical based medical instrument that performs fluoresence detection of precancerous lesions (neoplasia) of the human cervix. The hardware portion of this medical instrument is known by the same name Cervical Neoplasia Probe (CNP)

  9. Ultrasonic search wheel probe

    DOEpatents

    Mikesell, Charles R.

    1978-01-01

    A device is provided for reducing internal reflections from the tire of an ultrasonic search wheel probe or from within the material being examined. The device includes a liner with an anechoic chamber within which is an ultrasonic transducer. The liner is positioned within the wheel and includes an aperture through which the ultrasonic sound from the transducer is directed.

  10. Endocavity Ultrasound Probe Manipulators.

    PubMed

    Stoianovici, Dan; Kim, Chunwoo; Schäfer, Felix; Huang, Chien-Ming; Zuo, Yihe; Petrisor, Doru; Han, Misop

    2013-06-01

    We developed two similar structure manipulators for medical endocavity ultrasound probes with 3 and 4 degrees of freedom (DoF). These robots allow scanning with ultrasound for 3-D imaging and enable robot-assisted image-guided procedures. Both robots use remote center of motion kinematics, characteristic of medical robots. The 4-DoF robot provides unrestricted manipulation of the endocavity probe. With the 3-DoF robot the insertion motion of the probe must be adjusted manually, but the device is simpler and may also be used to manipulate external-body probes. The robots enabled a novel surgical approach of using intraoperative image-based navigation during robot-assisted laparoscopic prostatectomy (RALP), performed with concurrent use of two robotic systems (Tandem, T-RALP). Thus far, a clinical trial for evaluation of safety and feasibility has been performed successfully on 46 patients. This paper describes the architecture and design of the robots, the two prototypes, control features related to safety, preclinical experiments, and the T-RALP procedure.

  11. The Phoenix Pluto Probe

    NASA Technical Reports Server (NTRS)

    Gunning, George R.; Spapperi, Jeff; Wilkinson, Jeffrey P.; Eldred, Jim; Labij, Dennis; Strinni, Meredith

    1990-01-01

    A design proposal for an unmanned probe to Pluto is presented. The topics covered include: (1) scientific instrumentation; (2) mission management, planning, and costing; (3) power and propulsion system; (4) structural subsystem; (5) command, control, and communication; and (6) attitude and articulation control.

  12. Adsorption and kinetic studies of seven different organic dyes onto magnetite nanoparticles loaded tea waste and removal of them from wastewater samples

    NASA Astrophysics Data System (ADS)

    Madrakian, Tayyebeh; Afkhami, Abbas; Ahmadi, Mazaher

    2012-12-01

    Adsorption of seven different organic dyes from aqueous solutions onto magnetite nanoparticles loaded tea waste (MNLTW) was studied. MNLTW was prepared via a simple method and was fully characterized. The properties of this magnetic adsorbent were characterized by scanning electron microscopy and X-ray diffraction. Adsorption characteristics of the MNLTW adsorbent was examined using Janus green, methylene blue, thionine, crystal violet, Congo red, neutral red and reactive blue 19 as adsorbates. Dyes adsorption process was thoroughly studied from both kinetic and equilibrium points of view for all adsorbents. The experimental isotherm data were analyzed using Langmuir, Freundlich, Sips, Redlich-Peterson, Brouers-Sotolongo and Temkin isotherms. The results from Langmuir isotherm indicated that the capacity of MNLTW for the adsorption of cationic dyes was higher than that for anionic dyes. The adsorption kinetics was tested for the pseudo-first order and pseudo-second order kinetic models at different experimental conditions.

  13. Liquid-phase separation of reactive dye by wood-rotting fungus: a biotechnological approach.

    PubMed

    Binupriya, Arthur R; Sathishkumar, Muthuswamy; Dhamodaran, Kavitha; Jayabalan, Rasu; Swaminathan, Krishnaswamy; Yun, Sei Eok

    2007-08-01

    The live and pretreated mycelial pellets/biomass of Trametes versicolor was used for the biosorption of a textile dye, reactive blue MR (RBMR) from aqueous solution. The parameters that affect the biosorption of RBMR, such as contact time, concentration of dye and pH, on the extent of RBMR adsorption were investigated. To develop an effective and accurate design model for removal of dye, adsorption kinetics and equilibrium data are essential basic requirements. Lagergren first-order, second-order and Bangham's model were used to fit the experimental data. Results of the kinetic studies showed that the second order kinetic model fitted well for the present experimental data. The Langmuir, Freundlich and Temkin adsorption models were used for the mathematical description of the biosorption equilibrium. The biosorption equilibrium data obeyed well for Langmuir isotherm and the maximum adsorption capacities were found to be 49.8, 51.6, 47.4 and 46.7 mg/g for live, autoclaved, acid- and alkali-pretreated biomass. The dye uptake capacity order of the fungal biomass was found as autoclaved > live > acid-treated > alkali-pretreated. The Freundlich and Temkin models were also able to describe the biosorption equilibrium on RBMR on live and pretreated fungal biomass. Acidic pH was favorable for the adsorption of dye. Studies on pH effect and desorption show that chemisorption seems to play a major role in the adsorption process. On comparison with fixed bed adsorption, batch mode adsorption was more efficient in adsorption of RBMR.

  14. Mechanosensitive membrane probes.

    PubMed

    Dal Molin, Marta; Verolet, Quentin; Soleimanpour, Saeideh; Matile, Stefan

    2015-04-13

    This article assembles pertinent insights behind the concept of planarizable push-pull probes. As a response to the planarization of their polarized ground state, a red shift of their excitation maximum is expected to report on either the disorder, the tension, or the potential of biomembranes. The combination of chromophore planarization and polarization contributes to various, usually more complex processes in nature. Examples include the color change of crabs or lobsters during cooking or the chemistry of vision, particularly color vision. The summary of lessons from nature is followed by an overview of mechanosensitive organic materials. Although often twisted and sometimes also polarized, their change of color under pressure usually originates from changes in their crystal packing. Intriguing exceptions include the planarization of several elegantly twisted phenylethynyl oligomers and polymers. Also mechanosensitive probes in plastics usually respond to stretching by disassembly. True ground-state planarization in response to molecular recognition is best exemplified with the binding of thoughtfully twisted cationic polythiophenes to single- and double-stranded oligonucleotides. Molecular rotors, en vogue as viscosity sensors in cells, operate by deplanarization of the first excited state. Pertinent recent examples are described, focusing on λ-ratiometry and intracellular targeting. Complementary to planarization of the ground state with twisted push-pull probes, molecular rotors report on environmental changes with quenching or shifts in emission rather than absorption. The labeling of mechanosensitive channels is discussed as a bioengineering approach to bypass the challenge to create molecular mechanosensitivity and use biological systems instead to sense membrane tension. With planarizable push-pull probes, this challenge is met not with twistome screening, but with "fluorescent flippers," a new concept to insert large and bright monomers into oligomeric

  15. DNA stickers promote polymer adsorption onto cellulose.

    PubMed

    Sato, Teruaki; Ali, Md Monsur; Pelton, Robert; Cranston, Emily D

    2012-10-08

    Adsorption of oligonucleotides onto model cellulose surfaces was investigated by comparing the Boese and Breaker's cellulose binding oligonucleotide (CBO) with a nonspecific oligonucleotide control (NSO). Measurements using the quartz crystal microbalance with dissipation technique confirmed that CBO adsorbed onto cellulose more than NSO, particularly at high ionic strengths (100 mM CaCl(2)). CBO showed a higher maximum adsorption on nanofibrillated and nanocrystalline cellulose than on regenerated cellulose, indicating a preference for the native cellulose I crystal structure under conditions that favored specific adsorption over calcium-mediated electrostatically driven adsorption. In addition, an anionic polyacrylamide (A-PAM) with grafted CBO also adsorbed onto the surface of cellulose in CaCl(2), whereas the unmodified A-PAM did not. This work shows that CBO performs as a "sticker", facilitating the adsorption of polyacrylamide onto cellulose, even under high ionic strength conditions where the adsorption of conventional polyelectrolytes is inhibited.

  16. Adsorption of goethite onto quartz and kaolinite

    USGS Publications Warehouse

    Goldberg, M.C.; Weiner, Eugene R.; Boymel, P.M.

    1984-01-01

    The adsorption of colloidal goethite onto quartz and kaolinite substrates has been studied as a function of pH and NaCl concentration. Goethite adsorption was measured quantitatively by Fourier-transform infrared spectroscopy. The results indicate that adsorption onto both substrates is due primarily to coulombic forces; however, the pH dependence of adsorption is very different for the two substrates. This is explained by the fact that the surface charge on quartz is entirely pH-dependent, while kaolinite has surface faces which carry a permanent negative charge. Adsorption of goethite on to kaolinite increases markedly with increasing NaCl concentration, while adsorption onto quartz is relatively independent of NaCl concentration. This can be explained by the influence of NaCl concentration upon the development of surface charge on the substrates. A method is described for separating surface-bound goethite from free goethite.

  17. Quantitative Understanding of van der Waals Interactions by Analyzing the Adsorption Structure and Low-Frequency Vibrational Modes of Single Benzene Molecules on Silver.

    PubMed

    Yuan, Dingwang; Han, Zhumin; Czap, Gregory; Chiang, Chi-Lun; Xu, Chen; Ho, W; Wu, Ruqian

    2016-06-16

    The combination of a sub-Kelvin scanning tunneling microscope and density functional calculations incorporating van der Waals (vdW) corrections has been used successfully to probe the adsorption structure and low-frequency vibrational modes of single benzene molecules on Ag(110). The inclusion of optimized vdW functionals and improved C6-based vdW dispersion schemes in density functional theory is crucial for obtaining the correct adsorption structure and low-energy vibrational modes. These results demonstrate the emerging capability to quantitatively probe the van der Waals interactions between a physisorbed molecule and an inert substrate.

  18. Pore size dependent molecular adsorption of cationic dye in biomass derived hierarchically porous carbon.

    PubMed

    Chen, Long; Ji, Tuo; Mu, Liwen; Shi, Yijun; Wang, Huaiyuan; Zhu, Jiahua

    2017-03-08

    Hierarchically porous carbon adsorbents were successfully fabricated from different biomass resources (softwood, hardwood, bamboo and cotton) by a facile two-step process, i.e. carbonization in nitrogen and thermal oxidation in air. Without involving any toxic/corrosive chemicals, large surface area of up to 890 m(2)/g was achieved, which is comparable to commercial activated carbon. The porous carbons with various surface area and pore size were used as adsorbents to investigate the pore size dependent adsorption phenomenon. Based on the density functional theory, effective (E-SSA) and ineffective surface area (InE-SSA) was calculated considering the geometry of used probing adsorbate. It was demonstrated that the adsorption capacity strongly depends on E-SSA instead of total surface area. Moreover, a regression model was developed to quantify the adsorption capacities contributed from E-SSA and InE-SSA, respectively. The applicability of this model has been verified by satisfactory prediction results on porous carbons prepared in this work as well as commercial activated carbon. Revealing the pore size dependent adsorption behavior in these biomass derived porous carbon adsorbents will help to design more effective materials (either from biomass or other carbon resources) targeting to specific adsorption applications.

  19. Surface plasmon resonance studies of pullulan and pullulan cinnamate adsorption onto cellulose.

    PubMed

    Kaya, Abdulaziz; Du, Xiaosong; Liu, Zelin; Lu, Jessica W; Morris, John R; Glasser, Wolfgang G; Heinze, Thomas; Esker, Alan R

    2009-09-14

    Surface plasmon resonance studies showed pullulan cinnamates (PCs) with varying degrees of substitution (DS) adsorbed onto regenerated cellulose surfaces from aqueous solutions below their critical aggregation concentrations. Results on cellulose were compared to PC adsorption onto hydrophilic and hydrophobic self-assembled thiol monolayers (SAMs) on gold to probe how different interactions affected PC adsorption. PC adsorbed onto methyl-terminated SAMs (SAM-CH(3)) > cellulose > hydroxyl-terminated SAMs (SAM-OH) for high DS and increased with DS for each surface. Data for PC adsorption onto cellulose and SAM-OH surfaces were effectively fit by Langmuir isotherms; however, Freundlich isotherms were required to fit PC adsorption isotherms for SAM-CH(3) surfaces. Atomic force microscopy images from the solid/liquid interfaces revealed PC coatings were uniform with surface roughnesses <2 nm for all surfaces. This study revealed hydrogen bonding alone could not explain PC adsorption onto cellulose and hydrophobic modification of water-soluble polysaccharides was a facile strategy for their conversion into surface modifying agents.

  20. New method for the simultaneous determination of diffusion and adsorption of dyes in silica hydrogels.

    PubMed

    Perullini, Mercedes; Jobbágy, Matías; Japas, María Laura; Bilmes, Sara A

    2014-07-01

    The fine tuning of porosity in sol gel based devices makes possible the design of novel applications in which the transport of molecules through the oxide gel plays a crucial role. In this work we develop a new method for the simultaneous analysis of diffusion and adsorption of small diffusing probes, as anionic and cationic dyes, through silica mesoporous hydrogels synthesized by sol-gel. The novelty of the work resides in the simplicity of acquisition of the experimental data (by means of a desk scanner) and further mathematical modeling, which is in line with high throughput screening procedures, enabling rapid and simultaneous determination of relevant diffusion and adsorption parameters. Net mass transport and adsorption properties of the silica based hydrogels were contrasted to dye adsorption isotherms and textural characterization of the wet gels by SAXS, as well as that of the corresponding aerogels determined by Field Emission Scanning Electron Microscopy (FESEM) and N2 adsorption. Thus, the validation of the results with well-established characterization methods demonstrates that our approach is robust enough to give reliable physicochemical information on these systems.

  1. Adsorption properties of boroxol ring doped zigzag boron nitride nanotube toward NO molecule using DFT

    NASA Astrophysics Data System (ADS)

    Zahedi, Ehsan; Babaie, Mahsa; Bahmanpour, Hooman

    2016-05-01

    In previous researches it is demonstrated that reactivity and sensitivity of boron nitride nanotubes (BNNTs) toward gas molecules can be modified by impurity. In this work, oxygen defect for three nitrogen sites was used to study the adsorption of NO molecule through the surface of boroxol ring of oxygen doped BNNT (7,0) with different adsorption patterns, including side-on and end-on. All calculations are performed using the DFT-B3LYP/6-31G∗ level of theory, and their electronic energies are corrected by gCP and D3 correction terms. High binding energies indicate that NO molecule undergoes chemical adsorption with large charge transfer from the tube which can significantly change electronic properties of the tube. Density of state (DOS) and partial DOS (PDOS) analyses revealed that adsorption of NO molecule on the boroxol ring position is covalent in nature with significant effect on the electronic properties of tube. The Laplacian of electron density, Lagrangian kinetic energy density, Hamiltonian kinetic energy density and potential energy density at bond critical points between the tube and NO indicate that the interaction between the tube and NO molecule is covalent in nature. Topological analysis of the electron localization function shows that electrons in the new formed bonds are approximately localized, meaning that the nature of adsorption process is chemical covalent. The studied nanotube is a suitable candidate to filter and eliminate NO gas molecule.

  2. Mechanism of Arsenic Adsorption on Magnetite Nanoparticles from Water: Thermodynamic and Spectroscopic Studies.

    PubMed

    Liu, Cheng-Hua; Chuang, Ya-Hui; Chen, Tsan-Yao; Tian, Yuan; Li, Hui; Wang, Ming-Kuang; Zhang, Wei

    2015-07-07

    Removal of arsenic (As) from water supplies is needed to reduce As exposure through drinking water and food consumption in many regions of the world. Magnetite nanoparticles (MNPs) are promising and novel adsorbents for As removal because of their great adsorption capacity for As and easy separation. This study aimed to investigate the adsorption mechanism of arsenate, As(V), and arsenite, As(III), on MNPs by macroscopic adsorption experiments in combination with thermodynamic calculation and microspectroscopic characterization using synchrotron-radiation-based X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). Adsorption reactions are favorable endothermic processes as evidenced by increased adsorption with increasing temperatures, and high positive enthalpy change. EXAFS spectra suggested predominant formation of bidentate binuclear corner-sharing complexes ((2)C) for As(V), and tridentate hexanuclear corner-sharing ((3)C) complexes for As(III) on MNP surfaces. The macroscopic and microscopic data conclusively identified the formation of inner-sphere complexes between As and MNP surfaces. More intriguingly, XANES and XPS results revealed complex redox transformation of the adsorbed As on MNPs exposed to air: Concomitant with the oxidation of MNPs, the oxidation of As(III) and MNPs was expected, but the observed As(V) reduction was surprising because of the role played by the reactive Fe(II).

  3. Effect of surface area and chemisorbed oxygen on the SO2 adsorption capacity of activated char

    USGS Publications Warehouse

    Lizzio, A.A.; DeBarr, J.A.

    1996-01-01

    The objective of this study was to determine whether activated char produced from Illinois coal could be used effectively to remove sulfur dioxide from coal combustion flue gas. Chars were prepared from a high-volatile Illinois bituminous coal under a wide range of pyrolysis and activation conditions. A novel char preparation technique was developed to prepare chars with SO2 adsorption capacities significantly greater than that of a commercial activated carbon. In general, there was no correlation between SO2 adsorption capacity and surface area. Temperature-programmed desorption (TPD) was used to determine the nature and extent of carbon-oxygen (C-O) complexes formed on the char surface. TPD data revealed that SO2 adsorption was inversely proportional to the amount of C-O complex. The formation of a stable C-O complex during char preparation may have served only to occupy carbon sites that were otherwise reactive towards SO2 adsorption. A fleeting C(O) complex formed during SO2 adsorption is postulated to be the reaction intermediate necessary for conversion of SO2 to H2SO4. Copyright ?? 1996 Elsevier Science Ltd.

  4. Pyrolysis of tire rubber: Porosity and adsorption characteristics of the pyrolytic chars

    SciTech Connect

    Miguel, G.S.; Fowler, G.D.; Sollars, C.J.

    1998-06-01

    Tire rubber has been pyrolyzed at various temperatures under a nitrogen atmosphere. The resulting chars have been analyzed for their porosity using nitrogen gas adsorption and for their aqueous adsorption characteristics using phenol, methylene blue, and the reactive dyes Procion Turquoise H-A and Procion Red H-E3B. Nitrogen adsorption isotherms were modeled to the BET and Dubinin-Astakhov (DA) equations to determine effective surface areas, mesopore volumes, and micropore volumes. Results showed that pyrolysis of tire rubber was essentially complete at 500 C and resulted in a char yield of approximately 42 wt%. Pyrolytic chars exhibited BET surface areas up to 85 m{sup 2}/g and micropore volumes up to 0.04 mL/g. Owing to their poorly developed micropore structure, the pyrolytic chars exhibited limited aqueous adsorption capacity for compounds of small molecular weight, such as phenol. However, the chars possessed significantly greater adsorption capacity for species of large molecular weight which was attributed to the presence of large mesopore volumes (up to 0.19 mL/g).

  5. First-principles calculations of H, O and OH adsorption on metallic layered supported thin films

    NASA Astrophysics Data System (ADS)

    Pereira, Aline O.; Miranda, Caetano R.

    2013-05-01

    In this work, the adsorption of hydrogen, oxygen and hydroxyl on metallic thin films is studied through first-principles calculations. We explore how the structural and electronic properties of palladium, platinum and gold thin films change with respect to the type of substrate. As a major result we find that Pd/Au(111) and Pt/Au(111) thin films present enhanced adsorption properties for H, O and OH. This improvement is a result of the induced tensile strain on the film due to the misfit between the lattice parameters of the film and the substrate. For these systems, the tensile strain results in a shift of the d-band center position towards to the Fermi level, with implications for the enhancement of adsorption properties. Our results suggest that the location of the unadsorbed d-band center for Pd/Au(111), Pt/Au(111) and Au thin films is a good parameter to predict the reactivity between these surfaces and H, O and OH. However, when considering different numbers of atomic monolayers, changes in adsorption energy are observed and there is no correlation for Pd/Au(111) and Au/Pt(111) films. For Pd/Pt(111) and Pt/Pd(111) films the difference between lattice parameters is relatively small, and no correlation is found, since no considerable strain is induced. In addition, our results support that a compressive strain will always lead to weaker adsorption. We also observe that the work function is strongly affected by adsorption. In particular, H adsorption results in an expansion of the interlayer distance between the topmost layers of the film. Furthermore, after atomic insertion, the interlayer distance of Pd/Pt(111) films is similar to the interlayer distance for bulk PdH0.6, which indicates that these thin films can act as precursor states for hydride formation.

  6. Surface energetics of alkaline-earth metal oxides: Trends in stability and adsorption of small molecules

    NASA Astrophysics Data System (ADS)

    Bajdich, Michal; Nørskov, Jens K.; Vojvodic, Aleksandra

    2015-04-01

    We present a systematic theoretical investigation of the surface properties, stability, and reactivity of rocksalt type alkaline-earth metal oxides including MgO, CaO, SrO, and BaO. The accuracy of commonly used exchange-correlation density functionals (LDA, PBE, RPBE, PBEsol, BEEF-vdW, and hybrid HSE) and random-phase approximation (RPA) is evaluated and compared to existing experimental values. Calculated surface energies of the four most stable surface facets under vacuum conditions, the (100) surface, the metal and oxygen terminated octopolar (111), and the (110) surfaces, exhibit a monotonic increase in stability from MgO to BaO. On the MgO(100) surface, adsorption of CO, NO, and CH4 is characterized by physisorption while H2O chemisorbs, which is in agreement with experimental findings. We further use the on-top metal adsorption of CO and NO molecules to map out the surface energetics of each alkaline-earth metal oxide surface. The considered functionals all qualitatively predict similar adsorption energy trends. The ordering between the adsorption energies on different surface facets can be attributed to differences in the local geometrical surface structure and the electronic structure of the metal constituent of the alkaline-earth metal oxide. The striking observation that CO adsorption strength is weaker than NO adsorption on the (100) terraces as the period of the alkaline-earth metal in the oxide increases is analyzed in detail in terms of charge redistribution within the σ and π channels of adsorbates. Finally, we also present oxygen adsorption and oxygen vacancy formation energies in these oxide systems.

  7. Effect of oxidation and catalytic reduction of trace organic contaminants on their activated carbon adsorption.

    PubMed

    Schoutteten, Klaas V K M; Hennebel, Tom; Dheere, Ellen; Bertelkamp, Cheryl; De Ridder, David J; Maes, Synthia; Chys, Michael; Van Hulle, Stijn W H; Vanden Bussche, Julie; Vanhaecke, Lynn; Verliefde, Arne R D

    2016-12-01

    The combination of ozonation and activated carbon (AC) adsorption is an established technology for removal of trace organic contaminants (TrOCs). In contrast to oxidation, reduction of TrOCs has recently gained attention as well, however less attention has gone to the combination of reduction with AC adsorption. In addition, no literature has compared the removal behavior of reduction vs. ozonation by-products by AC. In this study, the effect of pre-ozonation vs pre-catalytic reduction on the AC adsorption efficiency of five TrOCs and their by-products was compared. All compounds were susceptible to oxidation and reduction, however the catalytic reductive treatment proved to be a slower reaction than ozonation. New oxidation products were identified for dinoseb and new reduction products were identified for carbamazepine, bromoxynil and dinoseb. In terms of compatibility with AC adsorption, the influence of the oxidative and reductive pretreatments proved to be compound dependent. Oxidation products of bromoxynil and diatrizoic acid adsorbed better than their parent TrOCs, but oxidation products of atrazine, carbamazepine and dinoseb showed a decreased adsorption. The reductive pre-treatment showed an enhanced AC adsorption for dinoseb and a major enhancement for diatrizoic acid. For atrazine and bromoxynil, no clear influence on adsorption was noted, while for carbamazepine, the reductive pretreatment resulted in a decreased AC affinity. It may thus be concluded that when targeting mixtures of TrOCs, a trade-off will undoubtedly have to be made towards overall reactivity and removal of the different constituents, since no single treatment proves to be superior to the other.

  8. Multifractal characteristics of Nitrogen adsorption isotherms from tropical soils

    NASA Astrophysics Data System (ADS)

    Vidal Vázquez, Eva; Paz Ferreiro, Jorge

    2010-05-01

    One of the primary methods used to characterize a wide range of porous materials, including soils, are gas adsorption isotherms. An adsorption isotherm is a function relating the amount of adsorbed gas or vapour to the respective equilibrium pressure, during pressure increase at constant temperature. Adsorption data allow easily estimates of specific surface area and also can provide a characterization of pore surface heterogeneity. Most of the properties and the reactivity of soil colloids are influenced by their specific surface area and by parameters describing the surface heterogeneity. For a restricted scale range, linearity between applied pressure and volume of adsorbate holds, which is the basis for current estimations of specific surface area. However, adsorption isotherms contain also non-linear segments of pressure versus volume so that evidence of multifractal scale has been demonstrated. The aim of this study was to analyze the multifractal behaviour of nitrogen adsorption isotherms from a set of tropical soils. Samples were collected form 54 horizons belonging to 19 soil profiles in the state of Minas Gerais, Brazil. The most frequent soil type was Oxisol, according to the Soil Survey Staff, equivalent to Latossolo in the Brazilian soil classification system. Nitrogen adsorption isotherms at standard 77 K were measured using a Thermo Finnigan Sorptomatic 1990 gas sorption analyzer (Thermo Scientific, Waltham, MA). From the raw data a distributions of mass along a support was obtained to perform multifractal analysis. The probability distribution was constructed by dividing the values of the measure in a given segment by the sum of the measure in the whole scale range. The box-counting method was employed to perform multifractal analysis. All the analyzed N2 adsorption isotherms behave like a multifractal system. The singularity spectra, f(α), showed asymmetric concave down parabolic shapes, with a greater tendency toward the left side, where moments

  9. Reactivity and applications of layered silicates and layered double hydroxides.

    PubMed

    Selvam, Thangaraj; Inayat, Alexandra; Schwieger, Wilhelm

    2014-07-21

    Layered materials, such as layered sodium silicates and layered double hydroxides (LDHs), are well-known for their remarkable adsorption, intercalation and swelling properties. Their tunable interlayers offer an interesting avenue for the fabrication of pillared nanoporous materials, organic-inorganic hybrid materials and catalysts or catalyst supports. This perspective article provides a summary of the reactivity and applications of layered materials including aluminium-free layered sodium silicates (kanemite, ilerite (RUB-18 or octosilicate) and magadiite) and layered double hydroxides (LDHs). Recent developments in the use of layered sodium silicates as precursors for the preparation of various porous, functional and catalytic materials including zeolites, mesoporous materials, pillared layered silicates, organic-inorganic nanocomposites and synthesis of highly dispersed nanoparticles supported on silica are reviewed in detail. Along this perspective, we have attempted to illustrate the reactivity and transformational potential of LDHs in order to deduce the main differences and similarities between these two types of layered materials.

  10. Adsorption and isotopic fractionation of Xe

    NASA Technical Reports Server (NTRS)

    Bernatowicz, T. J.; Podosek, F. A.

    1986-01-01

    A theoretical description of the mechanisms of isotopic fractionation arising during adsorption of noble gases in a Henry's Law pressure regime is given. Experimental data on the isotopic composition of Xe adsorbed on activated charcoal in the temperature range 220 K to 350 K are presented. Both theoretical considerations and the experimental data indicate that equilibrium adsorption does not significantly alter the isotopic structure of adsorbed structure of adsorbed noble gases. Therefore, if adsorption is responsible for the elemental noble gas pattern in meteorites and the earth, the heavy noble gas isotopic fractionation between them must have been produced prior to and by a different process than equilibrium adsorption.

  11. Adsorption of water vapor on reservoir rocks

    SciTech Connect

    Not Available

    1993-07-01

    Progress is reported on: adsorption of water vapor on reservoir rocks; theoretical investigation of adsorption; estimation of adsorption parameters from transient experiments; transient adsorption experiment -- salinity and noncondensible gas effects; the physics of injection of water into, transport and storage of fluids within, and production of vapor from geothermal reservoirs; injection optimization at the Geysers Geothermal Field; a model to test multiwell data interpretation for heterogeneous reservoirs; earth tide effects on downhole pressure measurements; and a finite-difference model for free surface gravity drainage well test analysis.

  12. Adsorption of acid dye onto organobentonite.

    PubMed

    Baskaralingam, P; Pulikesi, M; Elango, D; Ramamurthi, V; Sivanesan, S

    2006-02-06

    Removal of Acid Red 151 from aqueous solution at different dye concentrations, adsorbent doses and pH has been studied. The bentonite clay has been modified using cationic surfactants, which has been confirmed using XRD and FT-IR analyses. Experimental result has shown that the acidic pH favours the adsorption. The adsorption isotherms are described by means of Langmuir and Freundlich isotherms. The adsorption capacity has been found to be 357.14 and 416.66 mg g(-1) for the cetyldimethylbenzylammonium chloride-bentonite (CDBA-bent) and cetylpyridinium chloride-bentonite (CP-bent), respectively. Kinetic studies show that the adsorption followed second-order kinetics.

  13. Method and apparatus for measuring reactivity of fissile material

    DOEpatents

    Lee, D.M.; Lindquist, L.O.

    1982-09-07

    Given are a method and apparatus for measuring nondestructively and noninvasively (i.e., using no internal probing) the burnup, reactivity, or fissile content of any material which emits neutrons and which has fissionable components. The assay is accomplished by altering the return flux of neutrons into the fuel assembly by means of changing the reflecting material. The existing passive neutron emissions in the material being assayed are used as the source of interrogating neutrons. Two measurements of either emitted neutron or emitted gamma-ray count rates are made and are then correlated to either reactivity, burnup, or fissionable content of the material being assayed, thus providing a measurement of either reactivity, burnup, or fissionable content of the material being assayed. Spent fuel which has been freshly discharged from a reactor can be assayed using this method and apparatus. Precisions of 1000 MWd/tU appear to be feasible.

  14. Interfacial Reactivity of Radionuclides: Emerging Paradigms from Molecular Level Observations

    SciTech Connect

    Felmy, Andrew R.; Ilton, Eugene S.; Rosso, Kevin M.; Zachara, John M.

    2011-08-15

    Over the past few decades use of an increasing array of molecular-level analytical probes has provided new detailed insight into mineral and radionuclide interfacial reactivity in subsurface environments. This capability has not only helped change the way mineral surface reactivity is studied but also how field-scale contaminant migration problems are addressed and ultimately resolved. Here we overview examples of relatively new interfacial reactivity paradigms with implications for future research directions. Specific examples include understanding: the role of site-to-site electron conduction at mineral surfaces and through bulk mineral phases, effects of local chemical environment on the stability of intermediate species in oxidation/reduction reactions, and the importance of mechanistic reaction pathway for defining possible reaction products and thermodynamic driving force. The discussion also includes examples of how detailed molecular/microscopic characterization of field samples has changed the way complex contaminant migration problems were conceptualized and modeled.

  15. Enabling interstellar probe

    NASA Astrophysics Data System (ADS)

    McNutt, Ralph L.; Wimmer-Schweingruber, Robert F.; International Interstellar Probe Team

    2011-04-01

    The scientific community has advocated a scientific probe to the interstellar medium for over 30 years. While the Voyager spacecraft have passed through the termination shock of the solar wind, they have limited lifetimes as their radioisotope power supplies decay. It remains unclear whether they can reach the heliopause, the boundary between shocked solar wind and interstellar plasmas, and, in any case, they will not reach the undisturbed interstellar medium. As with most exploratory space missions, their ongoing observations continue to raise even more questions about the nature of the interaction of our heliosphere and the interstellar medium. Scientific questions including: What is the nature of the nearby interstellar medium? How do the Sun and galaxy affect the dynamics of the heliosphere? What is the structure of the heliosphere? How did matter in the solar system and interstellar medium originate and evolve? can only be answered by an "interstellar precursor" probe. Such a mission is required to make in situ measurements in the interaction region and interstellar medium itself at distances far from the Sun, but in a finite mission lifetime. By launching a probe toward the incoming "interstellar wind," whose direction is known, the distance to be traveled can be minimized but is still large. The current consensus is that a scientifically compelling mission must function to at least a distance of 200 astronomical units (AU) from the Sun and return a reasonable stream of data during the voyage. The central problem is that of providing a means of propulsion to accelerate a probe from the Solar System. Even with a low-mass payload and spacecraft, achieving the high speeds needed, even with gravity assists, have remained problematic. Voyager 1, the fastest object ever to leave the system is now traveling ˜3.6 AU/yr, and a credible probe must reach at least 2-3 times this speed. The use of an Ares V is an approach for enabling a fast interstellar precursor

  16. Anion adsorption induced surface reconstructions

    NASA Astrophysics Data System (ADS)

    Tang, Lei

    2005-11-01

    Surface stress plays an important role in the behavior of solid surfaces. Potential-controlled anion adsorption in electrolytes alters the surface stress of the electrode and results in morphology changes to the surfaces. With a combination of potential-induced surface stress measurement and in situ electrochemical scanning tunneling microscopy (STM), it is demonstrated that anion adsorption induces changes in structure of thin films and modifies the growth morphology and stress evolution in epitaxially grown films. Surface structural transitions in the heteroepitaxial system consisting of one to two gold monolayers on platinum substrates were observed. By increasing the potential, structural transitions, from (1 x 1), to a striped phase, to a hexagonal structure, occurred in the gold bilayer. This hexagonal structure was related to the formation of an ordered sulfate adlayer with a ( 3x7 ) structure. Such transitions were repeatable by cycling the potential. Furthermore, the transitions between various dislocation structures were affected by anion adsorption. The surface composition of the gold bilayer on Pt was measured by underpotential deposition of copper. By subtracting the contribution of a pure Pt surface from the gold bi-layer on Pt, a stress change of -2.4 N/m was observed, which agrees with the stress change of -2.46 N/m predicted to accompany formation of 1.5 MLs of coherent Au on Pt(111) from epitaxy theory. The Cu monolayer deposited on Au(111) from an acid sulfate electrolyte was found to be pseudomorphic while the Cu monolayer formed on Au(111) in vacuum was incoherent. The stress-thickness change associated with the coherent monolayer of copper on Au(111) in electrolyte was -0.6 N/m, while conventional epitaxy theories predict a value of +7.76 N/m. STM results elucidated the sulfate adsorption on the copper monolayer caused an expansion of the layer as evidenced by a Moire Structure. For the Cu monolayer on Au(111), the sulfate-induced expansion

  17. Charcoal/Nitrogen Adsorption Cryocooler

    NASA Technical Reports Server (NTRS)

    Bard, Steven

    1987-01-01

    Refrigerator with no wear-related moving parts produces 0.5 W of cooling at 118 K. When fully developed, refrigerator needs no electrical power, and life expectancy of more than 10 yr, operates unattended to cool sensitive infrared detectors for long periods. Only moving parts in adsorption cryocooler are check valves. As charcoal is cooled in canister, gas pressure drops, allowing inlet check valve to open and admit more nitrogen. When canister is heated, pressure rises, closing inlet valve and eventually opening outlet valve.

  18. Moisture adsorption in optical coatings

    NASA Technical Reports Server (NTRS)

    Macleod, H. Angus

    1988-01-01

    The thin film filter is a very large aperture component which is exceedingly useful because of its small size, flexibility and ease of mounting. Thin film components, however, do have defects of performance and especially of stability which can cause problems in systems, particularly where long-term measurements are being made. Of all of the problems, those associated with moisture absorption are the most serious. Moisture absorption occurs in the pore-shaped voids inherent in the columnar structure of the layers. Ion-assisted deposition is a promising technique for substantially reducing moisture adsorption effects in thin film structures.

  19. Calibration Fixture For Anemometer Probes

    NASA Technical Reports Server (NTRS)

    Lewis, Charles R.; Nagel, Robert T.

    1993-01-01

    Fixture facilitates calibration of three-dimensional sideflow thermal anemometer probes. With fixture, probe oriented at number of angles throughout its design range. Readings calibrated as function of orientation in airflow. Calibration repeatable and verifiable.

  20. Adsorption of C20 on two-dimensional materials

    NASA Astrophysics Data System (ADS)

    Hussain, M. B.; Xu, L. H.; Xu, Y. X.; Wu, S. Q.; Zhu, Z. Z.

    2017-03-01

    We considered the geometric and electronic properties of C20 molecule adsorbed on various two-dimensional (2D) substrates surfaces, such as graphene, silicene, germanene, stanene, BN and MoS2 by using first-principles calculations based on the density functional theory. For each case, we have considered three adsorption configurations of C20 molecule, i.e. top-site (T), hallow-site (H) and bridge site (B), respectively. Our results show that C20's are strongly bound to silicene, germanene and stanene, however, the adsorbed C20 molecules have only weak interactions with graphene, BN and MoS2 substrates. Moreover, charge density plot implies substantial charge transfer taking place between the constituents of C20 and the substrate of silicene, germanene and stanene. Results indicate that the buckling structure of the 2D material plays important role in determining the reactivity of a 2D substrate.

  1. Covalently bound fluorescent probes as reporters for hydroxyl radical penetration into liposomal membranes.

    PubMed

    Fortier, Chanel A; Guan, Bing; Cole, Richard B; Tarr, Matthew A

    2009-05-15

    The ability of hydroxyl radicals to penetrate into liposomal model membranes (dimyristoylphosphatidylcholine) has been demonstrated. Liposomes were prepared and then characterized by digital fluorescence microscopy and dynamic light scattering after extrusion to determine liposomal lamellarity, size, and shape. Hydroxyl radicals were generated in the surrounding aqueous medium using a modified Fenton reagent (hydrogen peroxide and Fe(2+)) with the water-soluble iron chelator EDTA. High and low doses of radical were used, and the low dose was achieved with physiologically relevant iron and peroxide concentrations. Fluorescent probes covalently bound to the membrane phospholipid were used, including two lipophilic pyrenyl probes within the membrane bilayer and one polar probe at the water-membrane interface. Radical reactions with the probes were monitored by following the decrease in fluorescence and by observing oxidation products via matrix-assisted laser desorption ionization time-of-flight mass spectrometry. Differences in the probe position within the membrane were correlated with the reactivity of the probe to assess radical access to the site of the probe. For all probes, reaction rates increased with increasing temperature. Within the membrane bilayer, reaction rates were greater for the probe closest to the membrane-water interface. Cholesterol protected these probes from oxidation. Kinetic models, scavenger studies, and product identification studies indicated that hydroxyl radical reacted directly with the in-membrane probes without the mediation of a secondary radical.

  2. Experiments with probe masses

    PubMed Central

    Braginsky, V. B.

    2007-01-01

    It is reasonable to regard the experiments performed by C. Coulomb and H. Cavendish in the end of the 18th century as the beginning of laboratory experimental physics. These outstanding scientists have measured forces (accelerations) produced by electric charges and by gravitational “charges” on probe masses that were attached to torque balance. Among the variety of different research programs and projects existing today, experiments with probe masses are still playing an important role. In this short review, the achieved and planned sensitivities of very challenging LIGO (Laser Interferometer Gravitational wave Observatory) and LISA (Laser Interferometer Space Antennae) projects are described, and a list of nonsolved problems is discussed as well. The role of quantum fluctuations in high precision measurements is also outlined. Apart from these main topics, the limitations of sensitivity caused by cosmic rays and the prospects of clock frequency stability are presented. PMID:17296944

  3. Temperature averaging thermal probe

    NASA Technical Reports Server (NTRS)

    Kalil, L. F.; Reinhardt, V. (Inventor)

    1985-01-01

    A thermal probe to average temperature fluctuations over a prolonged period was formed with a temperature sensor embedded inside a solid object of a thermally conducting material. The solid object is held in a position equidistantly spaced apart from the interior surfaces of a closed housing by a mount made of a thermally insulating material. The housing is sealed to trap a vacuum or mass of air inside and thereby prevent transfer of heat directly between the environment outside of the housing and the solid object. Electrical leads couple the temperature sensor with a connector on the outside of the housing. Other solid objects of different sizes and materials may be substituted for the cylindrically-shaped object to vary the time constant of the probe.

  4. Subsurface Ice Probe

    NASA Technical Reports Server (NTRS)

    Hecht, Michael; Carsey, Frank

    2005-01-01

    The subsurface ice probe (SIPR) is a proposed apparatus that would bore into ice to depths as great as hundreds of meters by melting the ice and pumping the samples of meltwater to the surface. Originally intended for use in exploration of subsurface ice on Mars and other remote planets, the SIPR could also be used on Earth as an alternative to coring, drilling, and melting apparatuses heretofore used to sample Arctic and Antarctic ice sheets. The SIPR would include an assembly of instrumentation and electronic control equipment at the surface, connected via a tether to a compact assembly of boring, sampling, and sensor equipment in the borehole (see figure). Placing as much equipment as possible at the surface would help to attain primary objectives of minimizing power consumption, sampling with high depth resolution, and unobstructed imaging of the borehole wall. To the degree to which these requirements would be satisfied, the SIPR would offer advantages over the aforementioned ice-probing systems.

  5. Temperature averaging thermal probe

    NASA Astrophysics Data System (ADS)

    Kalil, L. F.; Reinhardt, V.

    1985-12-01

    A thermal probe to average temperature fluctuations over a prolonged period was formed with a temperature sensor embedded inside a solid object of a thermally conducting material. The solid object is held in a position equidistantly spaced apart from the interior surfaces of a closed housing by a mount made of a thermally insulating material. The housing is sealed to trap a vacuum or mass of air inside and thereby prevent transfer of heat directly between the environment outside of the housing and the solid object. Electrical leads couple the temperature sensor with a connector on the outside of the housing. Other solid objects of different sizes and materials may be substituted for the cylindrically-shaped object to vary the time constant of the probe.

  6. A highly selective fluorescent probe based on Michael addition for fast detection of hydrogen sulfide.

    PubMed

    Gao, Baozhen; Cui, Lixia; Pan, Yong; Xue, Minjie; Zhu, Boyu; Zhang, Guomei; Zhang, Caihong; Shuang, Shaomin; Dong, Chuan

    2017-02-15

    A new 4-hydroxy-1,8-naphthalimide-based compound (probe 1) has been designed and synthesized. The colorimetric and fluorescent properties of probe 1 towards hydrogen sulfide (H2S) were investigated in detail. The results show that the probe 1 could selectively and sensitively recognize H2S rather than other reactive sulfur species. The reaction mechanism of this probe is an intramolecular cyclization caused by the Michael addition of H2S to give 4-hydroxy-1,8-naphthalimide. The intramolecular charge transfer of 4-hydroxy-1,8-naphthalimide is significant. Probe 1 quickly responded to H2S and showed a 75-fold fluorescence enhancement in 5min. Moreover, probe 1 could detect H2S quantitatively with a detection limit as low as 0.23μM.

  7. A highly selective fluorescent probe based on Michael addition for fast detection of hydrogen sulfide

    NASA Astrophysics Data System (ADS)

    Gao, Baozhen; Cui, Lixia; Pan, Yong; Xue, Minjie; Zhu, Boyu; Zhang, Guomei; Zhang, Caihong; Shuang, Shaomin; Dong, Chuan

    2017-02-01

    A new 4-hydroxy-1,8-naphthalimide-based compound (probe 1) has been designed and synthesized. The colorimetric and fluorescent properties of probe 1 towards hydrogen sulfide (H2S) were investigated in detail. The results show that the probe 1 could selectively and sensitively recognize H2S rather than other reactive sulfur species. The reaction mechanism of this probe is an intramolecular cyclization caused by the Michael addition of H2S to give 4-hydroxy-1,8-naphthalimide. The intramolecular charge transfer of 4-hydroxy-1,8-naphthalimide is significant. Probe 1 quickly responded to H2S and showed a 75-fold fluorescence enhancement in 5 min. Moreover, probe 1 could detect H2S quantitatively with a detection limit as low as 0.23 μM.

  8. Space Probe Launch

    NASA Technical Reports Server (NTRS)

    1970-01-01

    Managed by Marshall Space Flight Center, the Space Tug was a reusable multipurpose space vehicle designed to transport payloads to different orbital inclinations. Utilizing mission-specific combinations of its three primary modules (crew, propulsion, and cargo) and a variety of supplementary kits, the Space Tug was capable of numerous space applications. This 1970 artist's concept depicts the Tug's propulsion module launching a space probe into lunar orbit.

  9. Gravity Probe B Inspection

    NASA Technical Reports Server (NTRS)

    2000-01-01

    The space vehicle Gravity Probe B (GP-B) is the relativity experiment developed at Stanford University to test two extraordinary predictions of Albert Einstein's general theory of relativity. The experiment will measure, very precisely, the expected tiny changes in the direction of the spin axes of four gyroscopes contained in an Earth-orbiting satellite at a 400-mile altitude. So free are the gyroscopes from disturbance that they will provide an almost perfect space-time reference system. They will measure how space and time are very slightly warped by the presence of the Earth, and, more profoundly, how the Earth's rotation very slightly drags space-time around with it. These effects, though small for the Earth, have far-reaching implications for the nature of matter and the structure of the Universe. GP-B is among the most thoroughly researched programs ever undertaken by NASA. This is the story of a scientific quest in which physicists and engineers have collaborated closely over many years. Inspired by their quest, they have invented a whole range of technologies that are already enlivening other branches of science and engineering. In this photograph, engineer Gary Reynolds is inspecting the inside of the probe neck during probe thermal repairs. GP-B is scheduled for launch in April 2004 and managed for NASA by the Marshall Space Flight Center. Development of the GP-B is the responsibility of Stanford University along with major subcontractor Lockheed Martin Corporation. (Image credit to Russ Leese, Gravity Probe B, Stanford University)

  10. Probing pathways periodically.

    PubMed

    Elston, Timothy C

    2008-10-21

    Signal transduction pathways are used by cells to process and transmit information about their external surroundings. These systems are dynamic, interconnected molecular networks. Therefore, full characterization of their behavior requires a systems-level analysis. Investigations with temporally oscillating input signals probed the dynamic properties of the high-osmolarity glycerol (HOG) pathway of the budding yeast Saccharomyces cerevisiae. These studies shed light on how the network functions as a whole to respond to changing environmental conditions.

  11. Hydrogen adsorption on functionalized nanoporous activated carbons.

    PubMed

    Zhao, X B; Xiao, B; Fletcher, A J; Thomas, K M

    2005-05-12

    There is considerable interest in hydrogen adsorption on carbon nanotubes and porous carbons as a method of storage for transport and related energy applications. This investigation has involved a systematic investigation of the role of functional groups and porous structure characteristics in determining the hydrogen adsorption characteristics of porous carbons. Suites of carbons were prepared with a wide range of nitrogen and oxygen contents and types of functional groups to investigate their effect on hydrogen adsorption. The porous structures of the carbons were characterized by nitrogen (77 K) and carbon dioxide (273 K) adsorption methods. Hydrogen adsorption isotherms were studied at 77 K and pressure up to 100 kPa. All the isotherms were Type I in the IUPAC classification scheme. Hydrogen isobars indicated that the adsorption of hydrogen is very temperature dependent with little or no hydrogen adsorption above 195 K. The isosteric enthalpies of adsorption at zero surface coverage were obtained using a virial equation, while the values at various surface coverages were obtained from the van't Hoff isochore. The values were in the range 3.9-5.2 kJ mol(-1) for the carbons studied. The thermodynamics of the adsorption process are discussed in relation to temperature limitations for hydrogen storage applications. The maximum amounts of hydrogen adsorbed correlated with the micropore volume obtained from extrapolation of the Dubinin-Radushkevich equation for carbon dioxide adsorption. Functional groups have a small detrimental effect on hydrogen adsorption, and this is related to decreased adsorbate-adsorbent and increased adsorbate-adsorbate interactions.

  12. Einstein Inflationary Probe (EIP)

    NASA Technical Reports Server (NTRS)

    Hinshaw, Gary

    2004-01-01

    I will discuss plans to develop a concept for the Einstein Inflation Probe: a mission to detect gravity waves from inflation via the unique signature they impart to the cosmic microwave background (CMB) polarization. A sensitive CMB polarization satellite may be the only way to probe physics at the grand-unified theory (GUT) scale, exceeding by 12 orders of magnitude the energies studied at the Large Hadron Collider. A detection of gravity waves would represent a remarkable confirmation of the inflationary paradigm and set the energy scale at which inflation occurred when the universe was a fraction of a second old. Even a strong upper limit to the gravity wave amplitude would be significant, ruling out many common models of inflation, and pointing to inflation occurring at much lower energy, if at all. Measuring gravity waves via the CMB polarization will be challenging. We will undertake a comprehensive study to identify the critical scientific requirements for the mission and their derived instrumental performance requirements. At the core of the study will be an assessment of what is scientifically and experimentally optimal within the scope and purpose of the Einstein Inflation Probe.

  13. Nanoscale thermal probing

    PubMed Central

    Yue, Yanan; Wang, Xinwei

    2012-01-01

    Nanoscale novel devices have raised the demand for nanoscale thermal characterization that is critical for evaluating the device performance and durability. Achieving nanoscale spatial resolution and high accuracy in temperature measurement is very challenging due to the limitation of measurement pathways. In this review, we discuss four methodologies currently developed in nanoscale surface imaging and temperature measurement. To overcome the restriction of the conventional methods, the scanning thermal microscopy technique is widely used. From the perspective of measuring target, the optical feature size method can be applied by using either Raman or fluorescence thermometry. The near-field optical method that measures nanoscale temperature by focusing the optical field to a nano-sized region provides a non-contact and non-destructive way for nanoscale thermal probing. Although the resistance thermometry based on nano-sized thermal sensors is possible for nanoscale thermal probing, significant effort is still needed to reduce the size of the current sensors by using advanced fabrication techniques. At the same time, the development of nanoscale imaging techniques, such as fluorescence imaging, provides a great potential solution to resolve the nanoscale thermal probing problem. PMID:22419968

  14. Xenon adsorption in NaA zeolite cavities

    NASA Astrophysics Data System (ADS)

    McCormick, A. V.; Chmelka, B. F.

    Adsorption of xenon atoms in the α-cages of NaA zeolite has been studied using 129Xe NMR spectroscopy to probe directly the distribution and configuration of molecules in confined, microporous environments. The 129Xe NMR spectrum is sensitive to subtle changes in xenon environment, so relative populations of α-cages containing different numbers of xenon guests can be determined and the effects of other co-adsorbed species monitored. On the basis of 129Xe NMR spectra, the distribution of xenon atoms among NaA α-cages is shown to exhibit a marked dependence on the pressure at which the xenon guests are introduced. 129Xe NMR spectra recorded at 200 K reveal that xenon atoms in the NaA α-cages experience diminished mobility (resembling condensation phenomena) at higher temperatures than in the bulk gas of equivalent density. Thus, the chemical potential of adsorbed xenon can be investigated experimentally as a function of both temperature and guest density. The density dependence of the 129Xe chemical shift in Xe/NaA and in bulk xenon gas shows that Xe-Xe interactions in the proximity of the NaA cage wall are important in α-cages containing more than five xenon guests. This trend is linked to entropic effects which may enhance xenon adsorption in the confined environment of the NaA α-cages.

  15. Bovine and human insulin adsorption at lipid monolayers: a comparison

    NASA Astrophysics Data System (ADS)

    Mauri, Sergio; Pandey, Ravindra; Rzeznicka, Izabela; Lu, Hao; Bonn, Mischa; Weidner, Tobias

    2015-07-01

    Insulin is a widely used peptide in protein research and it is utilised as a model peptide to understand the mechanics of fibril formation, which is believed to be the cause of diseases such as Alzheimer and Creutzfeld-Jakob syndrome. Insulin has been used as a model system due to its biomedical relevance, small size and relatively simple tertiary structure. The adsorption of insu lin on a variety of surfaces has become the focus of numerous studies lately. These works have helped in elucidating the consequence of surface/protein hydrophilic/hydrophobic interaction in terms of protein refolding and aggregation. Unfortunately, such model surfaces differ significantly from physiological surfaces. Here we spectroscopically investigate the adsorption of insulin at lipid monolayers, to further our understanding of the interaction of insulin with biological surfaces. In particular we study the effect of minor mutations of insulin’s primary amino acid sequence on its interaction with 1,2-Dipalmitoyl-sn-glycero-3-phosphoglycerol (DPPG) model lipid layers. We probe the structure of bovine and human insulin at the lipid/water interface using sum frequency generation spectroscopy (SFG). The SFG experiments are complemented with XPS analysis of Langmuir-Schaefer deposited lipid/insulin films. We find that bovine and human insulin, even though very similar in sequence, show a substantially different behavior when interacting with lipid films.

  16. Reactivity of Hydrogen and Methanol on (001) Surfaces of WO3, ReO3, WO3/ReO3 and ReO3/WO3

    SciTech Connect

    Ling, Sanliang; Mei, Donghai; Gutowski, Maciej S.

    2011-05-16

    Bulk tungsten trioxide (WO3) and rhenium trioxide (ReO3) share very similar structures but display different electronic properties. WO3 is a wide bandgap semiconductor while ReO3 is an electronic conductor. With the advanced molecular beam epitaxy techniques, it is possible to make heterostructures comprised of layers of WO3 and ReO3. These heterostructures might display reactivity different than pure WO3 and ReO3. The interactions of two probe molecules (hydrogen and methanol) with the (001) surfaces of WO3, ReO3, and two heterostructures ReO3/WO3 and WO3/ReO3 were investigated at the density functional theory level. Atomic hydrogen prefers to adsorb at the terminal O1C sites forming a surface hydroxyl on four surfaces. Dissociative adsorption of a hydrogen molecule at the O1C site leads to formation of a water molecule adsorbed at the surface M5C site. This is thermodynamically the most stable state. A thermodynamically less stable dissociative state involves two surface hydroxyl groups O1CH and O2CH. The interaction of molecular hydrogen and methanol with pure ReO3 is stronger than with pure WO3 and the strength of the interaction substantially changes on the WO3/ReO3 and ReO3/WO3 heterostructures. The reaction barriers for decomposition and recombination reactions are sensitive to the nature of heterostructure. The calculated adsorption energy of methanol on WO3(001) of -65.6 kJ/mol is consistent with the previous experimental estimation of -67 kJ/mol. This material is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences.

  17. Determination of Reactive Surface Area of Melt Glass

    SciTech Connect

    Bourcier,W.L.; Roberts, S.; Smith, D.K.; Hulsey, S.; Newton,L.; Sawvel, A.; Bruton, C.; Papelis, C.; Um, W.; Russell, C. E.; Chapman,J.

    2000-10-01

    A comprehensive investigation of natural and manmade silicate glasses, and nuclear melt glass was undertaken in order to derive an estimate of glass reactive surface area. Reactive surface area is needed to model release rates of radionuclides from nuclear melt glass in the subsurface. Because of the limited availability of nuclear melt glasses, natural volcanic glass samples were collected which had similar textures and compositions as those of melt glass. A flow-through reactor was used to measure the reactive surface area of the analog glasses in the presence of simplified NTS site ground waters. A measure of the physical surface area of these glasses was obtained using the BET gas-adsorption method. The studies on analog glasses were supplemented by measurement of the surface areas of pieces of actual melt glass using the BET method. The variability of the results reflect the sample preparation and measurement techniques used, as well as textural heterogeneity inherent to these samples. Based on measurements of analog and actual samples, it is recommended that the hydraulic source term calculations employ a range of 0.001 to 0.01 m{sup 2}/g for the reactive surface area of nuclear melt glass.

  18. Effects of Adsorption Constant Uncertainty on Contaminant Plume Migration: One and Two Dimensional Numerical Studies

    NASA Astrophysics Data System (ADS)

    Eliassi, M.

    2002-12-01

    In this study, we use one- and two-dimensional (1D and 2D) reactive-transport models to numerically examine variations in predictions due to uncertainty in the adsorption constants. The study specifically focuses on the hydrogeology and mineralogy of the Naturita uranium mill tailings site in Colorado. This work demonstrates the importance of selecting the appropriate adsorption constants when using reactive-transport models to evaluate risk and pollution attenuation at contaminated sites. In our model, uranium is removed from mill tailings leachate through adsorption onto smectite, an abundant clay mineral at the Naturita site. Uranium adsorbs to specific surface sites on both the basal planes and edges of the smectite. Because uranium adsorbs predominantly to the aluminum edge surface sites [>(e)AlOH], we chose to examine uncertainty only in the equilibrium constants associated with these sites. Using the Latin Hypercube Sampling method, one-hundred pairs of adsorption constant (log K) values are selected for the surface species >(e)AlO- and >(e)AlOUO2+, from normal distributions of each log K. Following a grid convergence study, 1D simulation results can be identified by two distinct groups of uranium breakthrough curves. In the first group, the breakthrough curves exhibit a classical sigmoidal shape whereas in the second group the breakthrough curves display higher uranium concentrations in solution over greater distances and times. These two groups are clearly separated by two different ranges of log K >(e)AlO- values or two different ranges for the smectite point of zero charge. Preliminary 2D simulations, in both homogeneous and randomly heterogeneous aquifers demonstrate that plume geometry and migration in longitudinal and transverse directions are also influenced by the choice of adsorption constants.

  19. Nine New Fluorescent Probes

    NASA Astrophysics Data System (ADS)

    Lin, Tsung-I.; Jovanovic, Misa V.; Dowben, Robert M.

    1989-06-01

    Absorption and fluorescence spectroscopic studies are reported here for nine new fluorescent probes recently synthesized in our laboratories: four pyrene derivatives with substituents of (i) 1,3-diacetoxy-6,8-dichlorosulfonyl, (ii) 1,3-dihydroxy-6,8-disodiumsulfonate, (iii) 1,3-disodiumsulfonate, and (iv) l-ethoxy-3,6,8-trisodiumsulfonate groups, and five [7-julolidino] coumarin derivatives with substituents of (v) 3-carboxylate-4-methyl, (vi) 3- methylcarboxylate, (vii) 3-acetate-4-methyl, (viii) 3-propionate-4-methyl, and (ix) 3-sulfonate-4-methyl groups. Pyrene compounds i and ii and coumarin compounds v and vi exhibit interesting absorbance and fluorescence properties: their absorption maxima are red shifted compared to the parent compound to the blue-green region, and the band width broadens considerably. All four blue-absorbing dyes fluoresce intensely in the green region, and the two pyrene compounds emit at such long wavelengths without formation of excimers. The fluorescence properties of these compounds are quite environment-sensitive: considerable spectral shifts and fluorescence intensity changes have been observed in the pH range from 3 to 10 and in a wide variety of polar and hydrophobic solvents with vastly different dielectric constants. The high extinction and fluorescence quantum yield of these probes make them ideal fluorescent labeling reagents for proteins, antibodies, nucleic acids, and cellular organelles. The pH and hydrophobicity-dependent fluorescence changes can be utilized as optical pH and/or hydrophobicity indicators for mapping environmental difference in various cellular components in a single cell. Since all nine probes absorb in the UV, but emit at different wavelengths in the visible, these two groups of compounds offer an advantage of utilizing a single monochromatic light source (e.g., a nitrogen laser) to achieve multi-wavelength detection for flow cytometry application. As a first step to explore potential application in

  20. Comparative evaluation of probing depth and clinical attachment level using a manual probe and Florida probe

    PubMed Central

    Kour, Amandeep; Kumar, Ashish; Puri, Komal; Khatri, Manish; Bansal, Mansi; Gupta, Geeti

    2016-01-01

    Background: To compare and evaluate the intra- and inter-examiner efficacy and reproducibility of the first-generation manual (Williams) probe and the third-generation Florida probe in terms of measuring pocket probing depth (PD) and clinical attachment level (CAL). Materials and Methods: Forty subjects/4000 sites were included in this comparative, cross-sectional study. Group- and site-wise categorizations were done. Based on gingival index, PD, and CAL, patients were divided into four groups, i.e., periodontally healthy, gingivitis, mild to moderate periodontitis, and severe periodontitis. Further, based on these parameters, a total of 4000 sites, with 1000 sites in each category randomly selected from these 40 patients, were taken. Full mouth PD and CAL measurements were recorded with two probes, by Examiner 1 and on Ramfjord teeth by Examiner 2. Results: Full mouth and Ramfjord teeth group- and site-wise PD obtained with the manual probe by both the examiners were statistically significantly deeper than that obtained with the Florida probe. The full mouth and Ramfjord teeth mean CAL measurement by Florida probe was higher as compared to manual probe in mild to moderate periodontitis group and sites, whereas in severe periodontitis group and sites, manual probe recorded higher CAL as compared to Florida probe. Conclusion: Mean PD and CAL measurements were deeper with the manual probe as compared to the Florida probe in all the groups and sites, except for the mild-moderate periodontitis group and sites where the CAL measurements with the manual probe were less than the Florida probe. Manual probe was more reproducible and showed less interexaminer variability as compared to the Florida probe. PMID:27563204

  1. Reactive Oxygen Species (ROS) generation by lunar simulants

    NASA Astrophysics Data System (ADS)

    Kaur, Jasmeet; Rickman, Douglas; Schoonen, Martin A.

    2016-05-01

    The current interest in human exploration of the Moon and past experiences of Apollo astronauts has rekindled interest into the possible harmful effects of lunar dust on human health. In comparison to the Apollo-era explorations, human explorers may be weeks on the Moon, which will raise the risk of inhalation exposure. The mineralogical composition of lunar dust is well documented, but its effects on human health are not fully understood. With the aim of understanding the reactivity of dusts that may be encountered on geologically different lunar terrains, we have studied Reactive Oxygen Species (ROS) generation by a suite of lunar simulants of different mineralogical-chemical composition dispersed in water and Simulated Lung Fluid (SLF). To further explore the reactivity of simulants under lunar environmental conditions, we compared the reactivity of simulants both in air and inert atmosphere. As the impact of micrometeorites with consequent shock-induced stresses is a major environmental factor on the Moon, we also studied the effect of mechanical stress on samples. Mechanical stress was induced by hand crushing the samples both in air and inert atmosphere. The reactivity of samples after crushing was analyzed for a period of up to nine days. Hydrogen peroxide (H2O2) in water and SLF was analyzed by an in situ electrochemical probe and hydroxyl radical (•OH) by Electron Spin Resonance (ESR) spectroscopy and Adenine probe. Out of all simulants, CSM-CL-S was found to be the most reactive simulant followed by OB-1 and then JSC-1A simulant. The overall reactivity of samples in the inert atmosphere was higher than in air. Fresh crushed samples showed a higher level of reactivity than uncrushed samples. Simulant samples treated to create agglutination, including the formation of zero-valent iron, showed less reactivity than untreated simulants. ROS generation in SLF is initially slower than in deionized water (DI), but the ROS formation is sustained for as long as 7

  2. Adsorption of beta blockers to environmental surfaces.

    PubMed

    Kibbey, Tohren C G; Paruchuri, Rajiv; Sabatini, David A; Chen, Lixia

    2007-08-01

    Beta-adrenergic blocking agents (beta blockers) are widely used pharmaceuticals which have been detected in the environment. Predicting the transport and ultimate fate of beta blockers in the environment requires understanding their adsorption to soils and sediments, something for which little information is currently available. The objective of this work was to examine the adsorption of three beta blockers, propranolol, metoprolol and nadolol, to a natural alluvial material, as well as to six minerals present as components of the alluvial material. Batch adsorption experiments indicate that, for most of the minerals studied, compound hydrophobicity is an important predictor of adsorption, with propranolol,the most hydrophobic compound studied, adsorbing to the greatest extent. Results further suggest that, for the minerals studied, electrostatic effects are not a good predictor of adsorption; adsorption extent was not well-predicted by either surface zeta potential or by the difference between experiment pH and point of zero charge, despite the cationic nature af the three beta blockers at experiment pH values. Experiments were conducted to examine the effect of an anionic surfactant, sodium dodecyl benzene sulfonate (SDBS), on adsorption. Results indicate that SDBS significantly increases the adsorption of propranolol to two different sorbents. This result is potentially important because surfactants such as SDBS are likely to be present in wastewater effluents with beta blockers and could influence their mobility in the environment.

  3. Polychelated cryogels: hemoglobin adsorption from human blood.

    PubMed

    Erol, Kadir

    2017-02-01

    The separation and purification methods are extremely important for the hemoglobin (Hb) which is a crucial biomolecule. The adsorption technique is popular among these methods and the cryogels have been used quite much due to their macropores and interconnected flow channels. In this study, the Hb adsorption onto the Cu(II) immobilized poly(2-hydroxyethyl methacrylate-glycidyl methacrylate), poly(HEMA-GMA)-Cu(II), cryogels was investigated under different conditions (pH, interaction time, initial Hb concentration, temperature and ionic strength) to optimize adsorption conditions. The swelling test, Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscope (SEM), surface area (BET), elemental and ICP-OES analysis were performed for the characterization of cryogels. Polyethyleneimine (PEI) molecule was used as a Cu(II)-chelating ligand. The Hb adsorption capacity of cryogels was determined as 193.8 mg Hb/g cryogel. The isolation of Hb from human blood was also studied under optimum adsorption conditions determined and the Hb (124.5 mg/g cryogel) was isolated. The adsorption model was investigated in the light of Langmuir and Freundlich adsorption isotherm models and it was determined to be more appropriate to the Langmuir adsorption isotherm model.

  4. Arsenate adsorption by unsaturated alluvial sediments

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Arsenate adsorption as a function of solution arsenic concentration and solution pH was investigated on five alluvial sediments from the Antelope Valley, Western Mojave Desert, California. Arsenate adsorption increased with increasing solution pH, exhibited a maximum around pH 4 to 5, and then decr...

  5. BSA adsorption on bimodal PEO brushes.

    PubMed

    Bosker, W T E; Iakovlev, P A; Norde, W; Cohen Stuart, M A

    2005-06-15

    BSA adsorption onto bimodal PEO brushes at a solid surface was measured using optical reflectometry. Bimodal brushes consist of long (N=770) and short (N=48) PEO chains and were prepared on PS surfaces, applying mixtures of PS(29)-PEO(48) and PS(37)-PEO(770) block copolymers and using the Langmuir-Blodgett technique. Pi-A isotherms of (mixtures of) the block copolymers were measured to establish the brush regime. The isotherms of PS(29)-PEO(48) show hysteresis between compression and expansion cycles, indicating aggregation of the PS(29)-PEO(48) upon compression. Mixtures of PS(29)-PEO(48) and PS(37)-PEO(770) demonstrate a similar hysteresis effect, which eventually vanishes when the ratio of PS(37)-PEO(770) to PS(29)-PEO(48) is increased. The adsorption of BSA was determined at brushes for which the grafting density of the long PEO chains was varied, while the total grafting density was kept constant. BSA adsorption onto monomodal PEO(48) and PEO(770) brushes was determined for comparison. The BSA adsorption behavior of the bimodal brushes is similar to the adsorption of BSA at PEO(770) monomodal brushes. The maximum of BSA adsorption at low grafting density of PEO(770) can be explained by ternary adsorption, implying an attraction between BSA and PEO. The contribution of primary adsorption to the total adsorbed amount is negligible.

  6. Ion Exchange and Adsorption of Inorganic Contaminants

    EPA Science Inventory

    In the first part of the chapter, the fundamentals of ion exchange and adsorption processes are explained, with the goal of demonstrating how these principles influence process design for inorganic contaminant removal. In the second part, ion exchange and adsorption processes th...

  7. Phosphoryl functionalized mesoporous silica for uranium adsorption

    NASA Astrophysics Data System (ADS)

    Xue, Guo; Yurun, Feng; Li, Ma; Dezhi, Gao; Jie, Jing; Jincheng, Yu; Haibin, Sun; Hongyu, Gong; Yujun, Zhang

    2017-04-01

    Phosphoryl functionalized mesoporous silica (TBP-SBA-15) was synthesized by modified mesoporous silica with γ-amino propyl triethoxy silane and tributyl phosphate. The obtained samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), small angle X-ray diffraction (SAXRD), thermo-gravimetric/differential thermalanalyzer (TG/DTA), N2 adsorption-desorption (BET) and Fourier transform infrared spectroscopy (FT-IR) techniques. Results showed that TBP-SBA-15 had large surface areas with ordered channel structure. Moreover, the effects of adsorption time, sorbent dose, solution pH, initial uranium concentration and temperature on the uranium adsorption behaviors were investigated. TBP-SBA-15 showed a high uranium adsorption capacity in a broad range of pH values. The U(VI) adsorption rate of TBP-SBA-15 was fast and nearly achieved completion in 10 min with the sorbent dose of 1 g/L. The U(VI) adsorption of TBP-SBA-15 followed the pseudo-second-order kinetic model and Freundlich isotherm model, indicating that the process was belonged to chemical adsorption. Furthermore, the thermodynamic parameters (ΔG0, ΔH0 and ΔS0) confirmed that the adsorption process was endothermic and spontaneous.

  8. Reactive oxygen species and redox compartmentalization.

    PubMed

    Kaludercic, Nina; Deshwal, Soni; Di Lisa, Fabio

    2014-01-01

    Reactive oxygen species (ROS) formation and signaling are of major importance and regulate a number of processes in physiological conditions. A disruption in redox status regulation, however, has been associated with numerous pathological conditions. In recent years it has become increasingly clear that oxidative and reductive modifications are confined in a spatio-temporal manner. This makes ROS signaling similar to that of Ca(2+) or other second messengers. Some subcellular compartments are more oxidizing (such as lysosomes or peroxisomes) whereas others are more reducing (mitochondria, nuclei). Moreover, although more reducing, mitochondria are especially susceptible to oxidation, most likely due to the high number of exposed thiols present in that compartment. Recent advances in the development of redox probes allow specific measurement of defined ROS in different cellular compartments in intact living cells or organisms. The availability of these tools now allows simultaneous spatio-temporal measurements and correlation between ROS generation and organelle and/or cellular function. The study of ROS compartmentalization and microdomains will help elucidate their role in physiology and disease. Here we will examine redox probes currently available and how ROS generation may vary between subcellular compartments. Furthermore, we will discuss ROS compartmentalization in physiological and pathological conditions focusing our attention on mitochondria, since their vulnerability to oxidative stress is likely at the basis of several diseases.

  9. How Surface Heterogeneity Affects Protein Adsorption: Annealing of OTS Patterns and Albumin Adsorption Kinetics*

    PubMed Central

    Hodgkinson, Gerald N.; Hlady, Vladimir

    2009-01-01

    Fluorescence microscopy and intensity histogram analysis techniques were used to monitor spatially-resolved albumin adsorption kinetics to model heterogeneous surfaces on sub-μm scales. Several distinct protein subpopulations were resolved, each represented by a normal distribution of adsorption densities on the adsorbent surface. Histogram analyses provided dynamic information of mean adsorption density, spread in adsorption density, and surface area coverage for each distinct protein subpopulation. A simple adsorption model is proposed in which individual protein binding events are predicted by the summation of multiple protein's surface sub-site interactions with different binding energy sub-sites on adsorbent surfaces. This model is predictive of the albumin adsorption on the patterns produced by one step μ-contact printing (μCP) of octadecyltrichlorosilane (OTS) on glass but fails to describe adsorption once the same patterns are altered by a thermal annealing step. PMID:19746205

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  11. Factors affecting drug adsorption on beta zeolites.

    PubMed

    Pasti, Luisa; Sarti, Elena; Cavazzini, Alberto; Marchetti, Nicola; Dondi, Francesco; Martucci, Annalisa

    2013-05-01

    The adsorption behaviour of three commonly used drugs, namely ketoprofen, hydrochlorothiazide and atenolol, from diluted aqueous solutions on beta zeolites with different SiO2/Al2O3 ratio (i.e. 25, 38 and 360) was investigated by changing the ionic strength and the pH, before and after thermal treatment of the adsorbents. The selective adsorption of drugs was confirmed by thermogravimetry and X-ray diffraction. The adsorption capacity of beta zeolites was strongly dependent on both the solution pH and the alumina content of the adsorbent. Such a remarkable difference was interpreted as a function of the interactions between drug molecules and zeolite surface functional groups. Atenolol was readily adsorbed on the less hydrophobic zeolite, under pH conditions in which electrostatic interactions were predominant. On the other hand, ketoprofen adsorption was mainly driven by hydrophobic interactions. For undissociated molecules the adsorption capability increased with the increase of hydrophobicity.

  12. Adsorption and desorption of reversible supramolecular polymers

    NASA Astrophysics Data System (ADS)

    Zweistra, Henk J. A.; Besseling, N. A. M.

    2006-08-01

    We report numerical mean-field results on the quasichemical level of approximation that describe adsorption of reversible supramolecular polymers at a flat interface. Emphasis is laid on the regime of strong adsorption from a dilute solution. There are two differences with respect to macromolecular polymer adsorption: (i) adsorption sets in at relatively high monomer concentrations of the surrounding solution, and (ii) the surface is filled within a much narrower concentration range. Contrary to macromolecular polymers, supramolecular polymers can therefore be desorbed by dilution of the equilibrium solution by solvent within an experimentally accessible concentration window. Based on simple thermodynamic arguments, we provide a quantitative explanation why supramolecular polymers adsorb at relatively high concentrations. Moreover, we discuss the (by comparison) narrow concentration window wherein filling of the surface occurs. This is attributed to the cooperative nature of supramolecular polymer adsorption. The degree of cooperativity is quantified by means of the Hill parameter n .

  13. Adsorption of xenon and krypton on shales

    NASA Technical Reports Server (NTRS)

    Podosek, F. A.; Bernatowicz, T. J.; Kramer, F. E.

    1981-01-01

    A method that uses a mass spectrometer as a manometer is employed in the measurement of Xe and Kr adsorption parameters on shales and related samples, where gas partial pressures were lower than 10 to the -11th atm, corresponding adsorption coverages are only small fractions of a monolayer, and Henry's Law behavior is expected and observed. Results show heats of adsorption in the 2-7 kcal/mol range, and Henry constants at 0-25 C of 1 cu cm STP/g per atmosphere are extrapolated. Although the adsorption properties obtained are variable by sample, the range obtained suggests that shales may be capable of an equilibrium adsorption with modern air high enough to account for a significant fraction of the atmospheric inventory of Xe, and perhaps even of Kr. This effect will nevertheless not account for the factor-of-25 defficiency of atmospheric Xe, in comparison with the planetary gas patterns observed in meteorites.

  14. Aromatics saturation over hydrotreating catalysts: Reactivity and susceptibility to poisons

    SciTech Connect

    Kokayeff, P.

    1994-12-31

    Aromatics saturation over hydrotreating catalysts has been investigated by processing a synthetic feedstock to which naphthalene, biphenyl, tetralin, and cyclohexylbenzene have been added as model aromatic compounds. The saturation reactions were successfully correlated with a kinetic model of consecutive first order reactions. The rates of saturation of the di-aromatics, naphthalene and biphenyl, were approximately 5--40 times faster than the rate of saturation of the mono-aromatics, tetralin and cyclohexylbenzene. The nature of the di-aromatic is a significant determinant of its reactivity for saturation. The rate of saturation of naphthalene is 10--20 times faster than the rate of saturation of biphenyl. The two mono-aromatics, tetralin and cyclohexylbenzene, exhibited nearly identical reactivities for saturation. An investigation of the effect of organo-nitrogen compounds on saturation activity revealed a very severe poisoning and attenuation of saturation activity. Since activity was recoverable upon the removal of the poisoning agent the chemical effect was conjectured to be due to adsorption of the poison on the active sites of the catalyst. The adsorption constants were determined for three model nitrogen compounds--quinoline, indole, and tert-butylamine. The poisoning action of an organo-nitrogen compound was found to be dependent on both basicity and chemical structure.

  15. Reactivity of small transition-metal clusters with CO

    NASA Astrophysics Data System (ADS)

    Andersson, Mats T.; Gronbeck, H.; Holmgren, L.; Rosen, Arne

    1995-09-01

    The size-dependent reactivity of several transition-metal clusters: Con, Nbn, Rhn, and Wn with CO has been investigated in a cluster beam experiment. The reactions occur at single-collision-like conditions and the results are evaluated in terms of the reaction probability (S) in a collision. For all the four metals, clusters with more than 10 - 15 atoms show a high reaction probability, S >= 0.4, rather independent of size. For smaller Nbn and Wn, the reaction probability is lower, and for Nbn, large variations in the CO reactivity are observed in the n equals 8 - 13 range with a distinct minimum at Nb10. Using an LCAO approach within the local spin density approximation (LSDA) the adsorption of molecular CO on Nbn has also been investigated theoretically. The geometries of the bare clusters were optimized and two different sites for CO were investigated. The discussion is based on a detailed analysis of Nb4. The calculations show that compact structures with high coordination numbers are the most stable ones for the bare Nb clusters and hollow sites, also maximizing the coordination, are preferred for CO adsorption. The calculations indicate that a high CO-Nbn bond strength is obtained for clusters with a high density of states close to the Fermi level and for which the HOMO level has a symmetry that allows for an efficient back-donation of electrons to the 2(pi) *-orbital of CO. A particularly low chemisorption energy was calculated for the Nb10 cluster.

  16. Development of Mackintosh Probe Extractor

    NASA Astrophysics Data System (ADS)

    Rahman, Noor Khazanah A.; Kaamin, Masiri; Suwandi, Amir Khan; Sahat, Suhaila; Jahaya Kesot, Mohd

    2016-11-01

    Dynamic probing is a continuous soil investigation technique, which is one of the simplest soil penetration test. It basically consist of repeatedly driving a metal tipped probe into the ground using a drop weight of fixed mass and travel. Testing was carried out continuously from ground level to the final penetration depth. Once the soil investigation work done, it is difficult to pull out the probe rod from the ground, due to strong soil structure grip against probe cone and prevent the probe rod out from the ground. Thus, in this case, a tool named Extracting Probe was created to assist in the process of retracting the probe rod from the ground. In addition, Extracting Probe also can reduce the time to extract the probe rod from the ground compare with the conventional method. At the same time, it also can reduce manpower cost because only one worker involve to handle this tool compare with conventional method used two or more workers. From experiment that have been done we found that the time difference between conventional tools and extracting probe is significant, average time difference is 155 minutes. In addition the extracting probe can reduce manpower usage, and also labour cost for operating the tool. With all these advantages makes this tool has the potential to be marketed.

  17. Predicting Adsorption in Natural Systems: Are We There Yet? (Invited)

    NASA Astrophysics Data System (ADS)

    Koretsky, C. M.

    2010-12-01

    databases need to be developed. In particular, improved models of adsorption on abundant constituents of natural sediments and soils, such as high surface area aluminosilicate clay minerals, are needed. SCMs for these and other sorbents need to be calibrated using broad ranges of solution conditions (e.g., pH, pCO2, sorbate/sorbent ratio, ionic strength and electrolyte composition). Testing existing SCMs using controlled laboratory systems of increasing complexity, for example, by using multiple sorbents or sorbates, through addition of natural organic matter, or by varying pCO2, will allow the limits of current SCMs to be carefully probed, providing valuable insights regarding the conditions under which such models perform poorly. Similarly, well characterized natural soils and sediments should be used in controlled laboratory settings to explore the robustness of SCMs in predicting metal adsorption on complex, natural materials. Finally, more attempts to apply SCMs to field scale settings will highlight both remaining challenges and scenarios where SCMs produce accurate predictions of metal speciation in the environment.

  18. Influence of calcite on uranium(VI) reactive transport in the groundwater–river mixing zone

    SciTech Connect

    Ma, Rui; Liu, Chongxuan; Greskowiak, Janek; Prommer, Henning; Zachara, John M.; Zheng, Chunmiao

    2014-01-23

    Calcite is an important mineral that can affect uranyl reactive transport in subsurface sediments. This study investigated the distribution of calcite and its influence on uranyl adsorption and reactive transport in the groundwater-river mixing zone at US Hanford 300A, Washington State. Simulations using a 2D reactive transport model under field-relevant hydrogeochemical conditions revealed a complex distribution of calcite concentration as a result of dynamic groundwater-river interactions. The calcite concentration distribution in turn affected the spatial and temporal changes in aqueous carbonate, calcium, and pH, which subsequently influenced U(VI) mobility and discharge rates into the river. The results implied that calcite distribution and its concentration dynamics is an important consideration for field characterization, monitoring, and reactive transport prediction.

  19. Introducing new reactivity descriptors: "Bond reactivity indices." Comparison of the new definitions and atomic reactivity indices

    NASA Astrophysics Data System (ADS)

    Sánchez-Márquez, Jesús

    2016-11-01

    A new methodology to obtain reactivity indices has been defined. This is based on reactivity functions such as the Fukui function or the dual descriptor and makes it possible to project the information of reactivity functions over molecular orbitals instead of the atoms of the molecule (atomic reactivity indices). The methodology focuses on the molecule's natural bond orbitals (bond reactivity indices) because these orbitals (with physical meaning) have the advantage of being very localized, allowing the reaction site of an electrophile or nucleophile to be determined within a very precise molecular region. This methodology gives a reactivity index for every Natural Bond Orbital (NBO), and we have verified that they have equivalent information to the reactivity functions. A representative set of molecules has been used to test the new definitions. Also, the bond reactivity index has been related with the atomic reactivity one, and complementary information has been obtained from the comparison. Finally, a new atomic reactivity index has been defined and compared with previous definitions.

  20. Two-dimensional phase transformation probed by second harmonic generation: Oscillatory transformation of the K/Al(111) system

    SciTech Connect

    Ying, Z.C.; Plummer, E.W. |

    1995-12-31

    The technique of optical second harmonic generation is used to study phase transformations at two-dimensional surfaces and interfaces. Examples are given to illustrate that changes in surface symmetry, adsorption configuration, and electronic structure can be detected by this nonlinear optical technique. An oscillatory phase transformation of potassium adsorbed atoms on Al(111) probed by second harmonic generation is analyzed in detail.

  1. Reactive attachment disorder.

    PubMed

    Hornor, Gail

    2008-01-01

    Child abuse and neglect affects the lives of many American children and can result in physical injury and disability as well as psychological trauma. Reactive attachment disorder (RAD) is one possible psychological consequence of child abuse and neglect for very young children, younger than 5 years of age. RAD is described as markedly disturbed and developmentally inappropriate social relatedness usually beginning before age 5 years. These behavioral manifestations are the direct result of and come after pathogenic care. To better understand RAD, it is first necessary to understand attachment; therefore, attachment theory is examined. Risk factors for the development of RAD are presented. Implications for pediatric nurse practitioner practice are explored. The pediatric nurse practitioner can play a vital role in recognizing RAD and ensuring that children with this disorder receive prompt mental health assessment and therapy.

  2. Reactive flow in solids

    NASA Astrophysics Data System (ADS)

    Brassart, Laurence; Suo, Zhigang

    2013-01-01

    When guest atoms diffuse into a host solid and react, the host may flow inelastically. Often a reaction can stimulate flow in a host too brittle to flow under a mechanical load alone. We formulate a theory of reactive flow in solids by regarding both flow and reaction as nonequilibrium processes, and placing the driving forces for flow and reaction on equal footing. We construct chemomechanical rate-dependent kinetic models without yield strength. In a host under constant stress and chemical potential, flow will persist indefinitely, but reaction will arrest. We also construct chemomechanical yield surface and flow rule by extending the von Mises theory of plasticity. We show that the host under a constant deviatoric stress will flow gradually in response to ramp chemical potential, and will ratchet in response to cyclic chemical potential.

  3. Adsorption and oxidation of oxalic acid on anatase TiO2 (001) surface: A density functional theory study.

    PubMed

    Sun, Tao; Wang, Yun; Zhang, Haimin; Liu, Porun; Zhao, Huijun

    2015-09-15

    Anatase TiO2 (001) surfaces have attracted great interest for photo-degradation of organic species recently due to their high reactivity. In this work, adsorption properties and oxidation mechanisms of oxalic acid on the anatase TiO2 (001) surface have been theoretically investigated using the first-principles density functional theory. Various possible adsorption configurations are considered by diversifying the connectivity of carboxylic groups with the surface. It is found that the adsorption of oxalic acid on the anatase (001) surface prefer the dissociative states. A novel double-bidentate configuration has been found due to the structural match between oxalic acid and the (001) surface. More charge is transferred from the adsorbed oxalic acid to the surface with the double-bidentate configuration when comparing with other adsorption structures. Thus, there is a positive correlation relationship between the transferred charge amount and the interfacial bond numbers when oxalic acid adsorbs on the anatase TiO2 (001) surface. The adsorption energies with dispersion corrections have demonstrated that the van der Waals interactions play an important role in the adsorption, especially when adsorbates are close to the surface.

  4. Photodegradation mechanism of two dyes: the influence of adsorption behavior on the novel TiO2 particles.

    PubMed

    Li, Wei; Wang, Yi-zhong

    2004-01-01

    The relationship between adsorption behavior and photocatalytic mechanism of the two dyes was investigated. Adsorption isotherms showed that the adsorption of cationic pink FG was Langmuir type behavior, while the reactive brilliant red k-2G was Freundlich type behavior. The increasing pH favored the adsorption of FG but have little effect on the photodegradation. The increasing pH favored the adsorption and the photodegradation of k-2G. The presence of scavenger of hvb+ and OH* radical potassium iodide inhibited the degradation of k-2G, free radicals scavenger tetranitromethane inhibited the photodegradation of FG. These results indicated that the photodegradation of FG mainly via free radicals in solution, and the photodegradation of k-2G was mainly on the catalysts surface or near the interface of solid and solution by react with hvb+ and surface-bound OH*. The different effect of SO4(2-), HCO3- on the adsorption and photodegradation of two dyes confirmed these results.

  5. PROcess Based Diagnostics PROBE

    NASA Technical Reports Server (NTRS)

    Clune, T.; Schmidt, G.; Kuo, K.; Bauer, M.; Oloso, H.

    2013-01-01

    Many of the aspects of the climate system that are of the greatest interest (e.g., the sensitivity of the system to external forcings) are emergent properties that arise via the complex interplay between disparate processes. This is also true for climate models most diagnostics are not a function of an isolated portion of source code, but rather are affected by multiple components and procedures. Thus any model-observation mismatch is hard to attribute to any specific piece of code or imperfection in a specific model assumption. An alternative approach is to identify diagnostics that are more closely tied to specific processes -- implying that if a mismatch is found, it should be much easier to identify and address specific algorithmic choices that will improve the simulation. However, this approach requires looking at model output and observational data in a more sophisticated way than the more traditional production of monthly or annual mean quantities. The data must instead be filtered in time and space for examples of the specific process being targeted.We are developing a data analysis environment called PROcess-Based Explorer (PROBE) that seeks to enable efficient and systematic computation of process-based diagnostics on very large sets of data. In this environment, investigators can define arbitrarily complex filters and then seamlessly perform computations in parallel on the filtered output from their model. The same analysis can be performed on additional related data sets (e.g., reanalyses) thereby enabling routine comparisons between model and observational data. PROBE also incorporates workflow technology to automatically update computed diagnostics for subsequent executions of a model. In this presentation, we will discuss the design and current status of PROBE as well as share results from some preliminary use cases.

  6. The removal of reactive black 5 from aqueous solutions by cotton seed shell.

    PubMed

    Uçar, Deniz; Armağan, Bülent

    2012-04-01

    This study investigated the removal of Reactive Black 5 (RB5) textile dye from aqueous solutions using cotton (Gossypium hirsutum) seed shell (CSS) as low cost adsorbents. The data were described according to the Freundlich and Langmuir isotherm models. Of these, the Langmuir model provided the best fit for the experimental data. The highest measured adsorption density was 12.19 mg/g at pH 2. An equilibrium adsorption rate of RB5 by CSS (q(e) = 11.879 mg/g) was observed at 30 minutes. In order to evaluate the adsorption kinetic mechanisms, pseudo first and second order rate kinetic models and an intraparticle diffusion model were applied, with the pseudo second order model providing an excellent fit for the data.

  7. Design and Synthesis of Near-infrared Fluorescent Probes for Imaging of Biological Nitroxyl

    PubMed Central

    Tan, Yi; Liu, Ruochuan; Zhang, Huatang; Peltier, Raoul; Lam, Yun-Wah; Zhu, Qing; Hu, Yi; Sun, Hongyan

    2015-01-01

    Nitroxyl (HNO), the reduced and protonated form of nitric oxide (NO), has recently been identified as an interesting and important signaling molecule in biological systems. However, research on its biosynthesis and bioactivities are hampered by the lack of versatile HNO detection methods applicable to living cells. In this report, two new near-infrared (NIR) probes were designed and synthesized for HNO imaging in living cells. One of the probes was found to display high sensitivity towards HNO, with up to 67-fold of fluorescence increment after reaction with HNO. The detection limit was determined to be as low as 0.043 μM. The probe displayed high selectivity towards HNO over other biologically related species including metal ions, reactive oxygen species, reactive nitrogen species and reactive sulfur species. Furthermore, the probe was shown to be suitable for imaging of exogenous and endogenous HNO in living cells. Interestingly, the probe was found to be mainly localized in lysosomes. We envision that the new NIR probe described here will serve as a useful tool for further elucidation of the intricate roles of HNO in living cells. PMID:26584764

  8. Vacuum probe surface sampler

    NASA Technical Reports Server (NTRS)

    Zahlava, B. A. (Inventor)

    1973-01-01

    A vacuum probe surface sampler is described for rapidly sampling relatively large surface areas which possess relatively light loading densities of micro-organism, drug particles or the like. A vacuum head with a hollow handle connected to a suitable vacuum source is frictionally attached to a cone assembly terminating in a flared tip adapted to be passed over the surface to be sampled. A fine mesh screen carried by the vacuum head provides support for a membrane filter which collects the microorganisms or other particles. The head assembly is easily removed from the cone assembly without contacting the cone assembly with human hands.

  9. Controlled Scanning Probe Lithography

    NASA Astrophysics Data System (ADS)

    Ruskell, Todd G.; Sarid, Dror; Workman, Richard K.; Pyle, Jason L.

    1997-03-01

    A method for real-time monitoring of the quality and quantity of silicon oxide grown on silicon using conducting-tip scanning probe lithography has been developed. The sub-picoampere tip-sample currents measured during lithography in ambient conditions are shown to be proportional to the amount of silicon oxide being grown. In addition, we have demonstrated the ability to control the composition of the grown material by altering the lithographic environment. Silicon nitride growth is shown to result from lithography on silicon samples in an environment of annhydrous ammonia.

  10. Experimental probes of axions

    SciTech Connect

    Chou, Aaron S.; /Fermilab

    2009-10-01

    Experimental searches for axions or axion-like particles rely on semiclassical phenomena resulting from the postulated coupling of the axion to two photons. Sensitive probes of the extremely small coupling constant can be made by exploiting familiar, coherent electromagnetic laboratory techniques, including resonant enhancement of transitions using microwave and optical cavities, Bragg scattering, and coherent photon-axion oscillations. The axion beam may either be astrophysical in origin as in the case of dark matter axion searches and solar axion searches, or created in the laboratory from laser interactions with magnetic fields. This note is meant to be a sampling of recent experimental results.

  11. Temperature Swing Adsorption Compressor Development

    NASA Technical Reports Server (NTRS)

    Finn, John E.; Mulloth, Lila M.; Affleck, Dave L.

    2001-01-01

    Closing the oxygen loop in an air revitalization system based on four-bed molecular sieve and Sabatier reactor technology requires a vacuum pump-compressor that can take the low-pressure CO, from the 4BMS and compress and store for use by a Sabatier reactor. NASA Ames Research Center proposed a solid-state temperature-swing adsorption (TSA) compressor that appears to meet performance requirements, be quiet and reliable, and consume less power than a comparable mechanical compressor/accumulator combination. Under this task, TSA compressor technology is being advanced through development of a complete prototype system. A liquid-cooled TSA compressor has been partially tested, and the rest of the system is being fabricated. An air-cooled TSA compressor is also being designed.

  12. Integrated microcantilevers for high-resolution sensing and probing

    NASA Astrophysics Data System (ADS)

    Li, Xinxin; Lee, Dong-Weon

    2012-02-01

    This topical review is focused on microcantilever-based sensing and probing functions that are realized by integrating a mechanically compliant cantilever with self-sensing and self-actuating elements, specific sensing materials as well as functionalized nano-tips. Such integrated cantilever devices have shown great promise in ultra-sensitive applications such as on-the-spot portable bio/chemical detection and in situ micro/nanoscale surface analysis and manipulation. The technical details of this review will be given in a sequence of cantilever sensors and, then, cantilever-tip probes. For the integrated cantilever sensors, the frequency-output style dynamic cantilevers are described first, with the contents including optimized resonance modes, sensing-group-modified nanostructures for specific bio/chemical mass adsorption and nanoscale sensing effects, etc. Thereafter, the static cantilever sensors for surface-stress detection are described in the sequence of the sensing mechanism, surface modification of the sensitive molecule layer and the model of specific reaction-induced surface-energy variation. After technical description of the cantilever sensors, the emphasis of the review moves to functionalized nano-tip equipped cantilever-tip probing devices. The probing functions are not only integrated on the cantilever but also integrated at the sharp apex of the tip. After description of single integrated cantilever probes and their applications in surface scanning and imaging, arrayed cantilever-tip devices and their simultaneous parallel operation for high throughput imaging and nanomechanical data storage are also addressed. With cantilever-tip probes as key elements, micro-analysis instruments are introduced that can be widely used for macro/nanoscale characterizations.

  13. On the Henry constant and isosteric heat at zero loading in gas phase adsorption.

    PubMed

    Do, D D; Nicholson, D; Do, H D

    2008-08-01

    The Henry constant and the isosteric heat of adsorption at zero loading are commonly used as indicators of the strength of the affinity of an adsorbate for a solid adsorbent. It is assumed that (i) they are observable in practice, (ii) the Van Hoff's plot of the logarithm of the Henry constant versus the inverse of temperature is always linear and the slope is equal to the heat of adsorption, and (iii) the isosteric heat of adsorption at zero loading is either constant or weakly dependent on temperature. We show in this paper that none of these three points is necessarily correct, first because these variables might not be observable since they are outside the range of measurability; second that the linearity of the Van Hoff plot breaks down at very high temperature, and third that the isosteric heat versus loading is a strong function of temperature. We demonstrate these points using Monte Carlo integration and Monte Carlo simulation of adsorption of various gases on a graphite surface. Another issue concerning the Henry constant is related to the way the adsorption excess is defined. The most commonly used equation is the one that assumes that the void volume is the volume extended all the way to a boundary passing through the centres of the outermost solid atoms. With this definition the Henry constant can become negative at high temperatures. Although adsorption at these temperatures may not be practical because of the very low value of the Henry constant, it is more useful to define the Henry constant in such a way that it is always positive at all temperatures. Here we propose the use of the accessible volume; the volume probed by the adsorbate when it is in nonpositive regions of the potential, to calculate the Henry constant.

  14. Adsorption of dissolved organics in lake water by aluminum oxide. Effect of molecular weight

    USGS Publications Warehouse

    Davis, J.A.; Gloor, R.

    1981-01-01

    Dissolved organic compounds in a Swiss lake were fractionated into three molecular size classes by gel exclusion chromatography, and adsorption of each fraction on colloidal alumina was studied as a function of pH. Organic compounds with molecular weight (Mr) greater than 1000 formed strong complexes with the alumina surface, but low molecular weight compounds were weakly adsorbed. Electrophoretic mobility measurements indicated that alumina particles suspended in the original lake water were highly negatively charged because of adsorbed organic matter. Most of the adsorbed organic compounds were in the Mr range 1000 < Mr < 3000. Adsorption of these compounds during the treatment of drinking water by alum coagulation may be responsible for the preferential removal of trihalomethane precursors. Adsorption may also influence the molecular-weight distribution of dissolved organic material in lakes. surface, the present work will focus on the influence of molecular size and pH on the adsorption behavior of dissolved organic material of a Swiss lake. From a geochemical point of view, it is important to know the molecular-weight distribution of adsorbed organic matter so that we may better assess its reactivity with trace elements. The study also serves as a first step in quantifying the role of adsorption in the geochemical cycle of organic carbon in lacustrine environments. For water-treatment practice, we need to determine whether molecular weight fractionation occurs during adsorption by aluminum oxide. Such a fractionation could be significant in the light of recent reports that chloroform and other organochlorine compounds are preferentially produced by particular molecular-weight fractions (25-27). ?? 1981 American Chemical Society.

  15. Fluorescent Probe Encapsulated in SNAP-Tag Protein Cavity To Eliminate Nonspecific Fluorescence and Increase Detection Sensitivity.

    PubMed

    Zeng, Yan-Syun; Gao, Ruo-Cing; Wu, Ting-Wei; Cho, Chien; Tan, Kui-Thong

    2016-08-17

    Despite the promising improvements made recently on fluorescence probes for the detection of enzymes and reactive small molecules, two fundamental problems remain: weaker fluorescence of many dyes in aqueous buffers and strong nonspecific signals in samples containing high protein levels. In this paper, we introduce a novel fluorescent probe encapsulated in protein cavity (FPEPC) concept as demonstrated by SNAP-tag protein and three environment-sensitive fluorescence probes to overcome these two problems. The probes were constructed by following the current probe design for enzymes and reactive small molecules but with an additional benzylguanine moiety for selective SNAP-tag conjugation. The SNAP-tag conjugated probes achieved quantitative nitroreductase and hydrogen sulfide detection in blood plasma, whereas analyte concentrations were overestimated up to 700-fold when bare fluorescent probes were employed for detection. Furthermore, detection sensitivity was increased dramatically, as our probes displayed 390-fold fluorescence enhancement upon SNAP-tag conjugation, in stark contrast to the weak fluorescence of the free probes in aqueous solutions. Compared with the conventional approaches where fluorescent probes are encapsulated into polymers and nanoparticles, our simple and general approach successfully overcame many key issues such as dye leakage, long preparation steps, inconsistent dye-host ratios, difficulty in constructing in situ in a complex medium, and limited application to detect only small metabolites.

  16. a Hreels Characterization of Adsorption on Oxide - Platinum Model Catalysts

    NASA Astrophysics Data System (ADS)

    Hensley, David A.

    1990-01-01

    The techniques of Auger Electron Spectroscopy (AES) and High Resolution Electron Energy Loss Spectroscopy (HREELS) are reviewed. These techniques are used to examine oxide supported Pt model catalysts. The model catalysts are prepared in situ by vapor deposition techniques, in which submonolayer amounts of Pt are deposited onto the oxide supports. HREELS was used to examine adsorption on three models. For the first model, Pt deposited onto an oxidized Al foil, it is shown that CO adsorbs primarily in terminal sites on the Pt, and that the HREELS peaks are dominated by the impact mechanism. Ethylene adsorption on the model catalyst is compared to previously published spectra of ethylene on Pt(111) and a model catalyst prepared by standard chemical techniques. From these comparisons two stable ethylene species are found to be present on the model catalyst at 165 K. It is further shown that on warming, the decomposition of the ethylene species is dissimilar to that which has been observed on the other models. The second model is made by Pt deposition onto a single crystal of TiO_2. For the case of the sample at 165 K, HREELS is used to identify the two adsorbed species which were seen on the first model. On warming, it is shown that the ethylene decomposes in a way similar to that which has been observed on Pt(111). The ethylidyne species is identified on this model catalyst at 300 K. For the third model, a new way of making a Pt/Al _2O_3 catalyst is used. Reactive aluminum evaporation is used to deposit a thin alumina film onto a Pd substrate. The Pt is vapor then deposited onto this surface. CO adsorption is used to examine the thermal stability of this model, and ethylene adsorption is examined, to compare to the results obtained from the first model. It is seen that for this model, ethylene decomposition follows the standard pattern, thus showing that this preparation technique produces a good model of a Pt/Al_2O_3 catalyst.

  17. Asphaltene multilayer growth in porous medium probed by SANS

    NASA Astrophysics Data System (ADS)

    Gummel, J.; Corvis, Y.; Jestin, J.; M'hamdi, J.; Barré, L.

    2009-02-01

    Presence of suspended particles such as asphaltene in crude oils could significantly affect the production by means of deposition in porous media especially near the well bore. We investigate this phenomenon using the ability of Small Angle Neutron Scattering technique to probe directly the asphaltene adsorption process in a porous medium at the nanometer length scale under flow conditions. A device based on a quartz tube filled with SiC particles constitute the porous medium in which an asphaltene solution in a mixture of good (toluene)/bad (heptane) solvent is injected under controlled flow. The contrast matching technique enables to match the porous medium scattering contributions and to measure the signal of the deposit. Such a device can be used for curves surface measurements on a setup originally designed for bulk studies and permit thus the direct comparison with measurements on flat surfaces (neutron reflectivity) and indirect adsorption measurements (adsorption isotherm). We show here that asphaltene in good solvent leads to a monolayer whereas addition of bad solvent results in a multilayer growth which is consistent with the deposition behaviour described in the literature.

  18. Decoration of gold nanoparticles with cysteine in solution: reactive molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Monti, Susanna; Carravetta, Vincenzo; Ågren, Hans

    2016-06-01

    The dynamics of gold nanoparticle functionalization by means of adsorption of cysteine molecules in water solution is simulated through classical reactive molecular dynamics simulations based on an accurately parametrized force field. The adsorption modes of the molecules are characterized in detail disclosing the nature of the cysteine-gold interactions and the stability of the final material. The simulation results agree satisfactorily with recent experimental and theoretical data and confirm previous findings for a similar system. The covalent attachments of the molecules to the gold support are all slow physisorptions followed by fast chemisorptions. However, a great variety of binding arrangements can be observed. Interactions with the adsorbate caused surface modulations in terms of adatoms and dislocations which contributed to strengthen the cysteine adsorption.The dynamics of gold nanoparticle functionalization by means of adsorption of cysteine molecules in water solution is simulated through classical reactive molecular dynamics simulations based on an accurately parametrized force field. The adsorption modes of the molecules are characterized in detail disclosing the nature of the cysteine-gold interactions and the stability of the final material. The simulation results agree satisfactorily with recent experimental and theoretical data and confirm previous findings for a similar system. The covalent attachments of the molecules to the gold support are all slow physisorptions followed by fast chemisorptions. However, a great variety of binding arrangements can be observed. Interactions with the adsorbate caused surface modulations in terms of adatoms and dislocations which contributed to strengthen the cysteine adsorption. Electronic supplementary information (ESI) available: Different views of the AuNP surface coverage. Distance map describing the position of each molecule in relation to the others on the AuNP (alpha carbon distances). See DOI: 10.1039/C

  19. Adsorption of water vapor by poly(styrenesulfonic acid), sodium salt: isothermal and isobaric adsorption equilibria.

    PubMed

    Toribio, F; Bellat, J P; Nguyen, P H; Dupont, M

    2004-12-15

    Air conditioning and dehumidifying systems based on sorption on solids are of great interest, especially in humid climates, because they allow reduction of thermal loads and use of chlorofluorocarbons. Previous studies have shown that hydrophilic polymers such as sulfonic polymers can have very high performance in water adsorption from air. The aim of this study was to characterize the water vapor adsorption properties of fully sulfonated and monosulfonated poly(styrenesulfonic acid), sodium salt, and to elucidate the mechanism of adsorption on these materials. Adsorption isotherms have been determined by TGA between 298 and 317 K for pressures ranging from 0.1 to 45 hPa. They have type II of the IUPAC classification and a small hysteresis loop between adsorption and desorption processes was observed only for the monosulfonated sample. Water content is up to 80% weight at 80% relative humidity. Adsorption isotherms have been well fitted with the FHH model. Adsorption-desorption isobars have been determined by TGA under 37 hPa in the temperature range 298-373 K. They show that these polymers can be completely regenerated by heating at 313 K under humidified air. No degradation of the adsorption properties has been observed after several regenerations. Adsorption enthalpies and entropies have been deduced from the Clapeyron equation and from DSC measurements. A good agreement was found. A mechanism of adsorption is proposed considering two kinds of adsorbate: bounded water in electrostatic interaction with functional groups and free water resulting from condensation.

  20. Modeling the adsorption of mixed gases based on pure gas adsorption properties

    NASA Astrophysics Data System (ADS)

    Tzabar, N.; Holland, H. J.; Vermeer, C. H.; ter Brake, H. J. M.

    2015-12-01

    Sorption-based Joule-Thomson (JT) cryocoolers usually operate with pure gases. A sorption-based compressor has many benefits; however, it is limited by the pressure ratios it can provide. Using a mixed-refrigerant (MR) instead of a pure refrigerant in JT cryocoolers allows working at much lower pressure ratios. Therefore, it is attractive using MRs in sorption- based cryocoolers in order to reduce one of its main limitations. The adsorption of mixed gases is usually investigated under steady-state conditions, mainly for storage and separation processes. However, the process in a sorption compressor goes through various temperatures, pressures and adsorption concentrations; therefore, it differs from the common mixed gases adsorption applications. In order to simulate the sorption process in a compressor a numerical analysis for mixed gases is developed, based on pure gas adsorption characteristics. The pure gas adsorption properties have been measured for four gases (nitrogen, methane, ethane, and propane) with Norit-RB2 activated carbon. A single adsorption model is desired to describe the adsorption of all four gases. This model is further developed to a mixed-gas adsorption model. In future work more adsorbents will be tested using these four gases and the adsorption model will be verified against experimental results of mixed-gas adsorption measurements.