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Sample records for adsorbed water molecules

  1. Quasielastic neutron scattering from adsorbed water molecules on pyrogenic silica surfaces

    NASA Astrophysics Data System (ADS)

    Tumanov, A. A.; Zarko, V. I.

    1994-04-01

    Quasielastic neutron scattering (QNS) from hydrated samples of high dispersion (Aerosil) and of porous dioxide silicon was investigated. The broadening of the QNS peak analysis permits one to obtain the effective diffusion coefficient D of adsorbed water molecules. It was obtained that the D-value increases with silica hydration. The mean square displacement of the water molecules from equilibrium < x2> equals approximately 0.1 Å 2 and does not depend on the quantity of adsorbed water.

  2. Relaxation dynamics of surface-adsorbed water molecules in nanoporous silica probed by terahertz spectroscopy

    NASA Astrophysics Data System (ADS)

    Huang, Yu-Ru; Liu, Kao-Hsiang; Mou, Chung-Yuan; Sun, Chi-Kuang

    2015-08-01

    Relaxation dynamics of an exclusively adsorbed water molecule in mesoporous silica MCM-41-S was studied by using terahertz spectroscopy. With the temperature controlled from 0 to 50 °C, we observed strongly frequency- and temperature-dependent dielectric relaxation responses, implying that, unlike ice, surface-adsorbed water molecules retained flourishing picosecond dynamics. Based on the Debye relaxation model, a relaxation time constant was found to increase from 1.77 to 4.83 ps when the water molecule was cooled from 50 to 0 °C. An activation energy of ˜15 kJ/mol, which was in close agreement with a hydrogen-bonding energy, was further extracted from the Arrhenius analysis. Combined with previous molecular dynamics simulations, our results indicate that the reorientation relaxation originated from the "flip-flop" rotation of a three hydrogen-bonded surface-adsorbed water molecule.

  3. Dynamics of water molecules adsorbed by silica and resin SGK-7

    NASA Astrophysics Data System (ADS)

    Lisichkin, Yu. V.; Sakharova, L. A.; Tumanov, A. A.

    2014-01-01

    This paper has presented neutron spectroscopy data on the dynamics of light water molecules adsorbed in the cation exchanger (ion-exchange resin) SGK-7 and on the surface of aerosils (highly dispersed pyrogenic silica) with different levels of hydration. The measurements have been performed on a DIN-2PI spectrometer (Frank Laboratory of Neutron Physics of the Joint Institute for Nuclear Research, Dubna, Russia). The characteristics of the diffusive and vibrational motions of adsorbed water molecules have been determined from the experimental neutron scattering spectra. The data obtained in the quasi-elastic neutron scattering region have been analyzed using a model accounting for the effects of restricted translational and rotational diffusion. The results have demonstrated a significant decrease in the diffusion mobility of adsorbed water molecules as compared to conventional (bulk) water. In particular, the self-diffusion coefficient decreases several times, and the diffusion rate is the lower, the smaller is the thickness of the hydration layer. The dependences of the intensity and half-width of the quasi-elastic scattering peak on the magnitude of the neutron momentum transfer q in the scattering process exhibit a nonmonotonic character. This indicates manifestation of the effects of restricted translational diffusion, rotational diffusion, and jump diffusion. The partial distributions of vibrational frequencies of hydrogen atoms of water molecules adsorbed by the cation exchanger and aerosils have been obtained from the inelastic neutron scattering data.

  4. Adsorbed Water Illustration

    NASA Technical Reports Server (NTRS)

    2008-01-01

    The Thermal and Electrical Conductivity Probe on NASA's Phoenix Mars Lander detected small and variable amounts of water in the Martian soil.

    In this schematic illustration, water molecules are represented in red and white; soil minerals are represented in green and blue. The water, neither liquid, vapor, nor solid, adheres in very thin films of molecules to the surfaces of soil minerals. The left half illustrates an interpretation of less water being adsorbed onto the soil-particle surface during a period when the tilt, or obliquity, of Mars' rotation axis is small, as it is in the present. The right half illustrates a thicker film of water during a time when the obliquity is greater, as it is during cycles on time scales of hundreds of thousands of years. As the humidity of the atmosphere increases, more water accumulates on mineral surfaces. Thicker films behave increasingly like liquid water.

    The Phoenix Mission is led by the University of Arizona, Tucson, on behalf of NASA. Project management of the mission is by NASA's Jet Propulsion Laboratory, Pasadena, Calif. Spacecraft development is by Lockheed Martin Space Systems, Denver.

  5. Infrared spectroscopy of water clusters co-adsorbed with hydrogen molecules on a sodium chloride film

    NASA Astrophysics Data System (ADS)

    Yamakawa, Koichiro; Fukutani, Katsuyuki

    2016-06-01

    Hydrogen gas containing a trace of water vapor was dosed on a vacuum-evaporated sodium chloride film at 13 K, and water clusters formed on the substrate were investigated by infrared absorption spectroscopy. Absorption bands due to (H2O)n clusters with n = 3-6 and an induced absorption band due to hydrogen were clearly observed. With increasing gas dosage, the intensities of the cluster bands increased linearly while the intensity of the hydrogen band was constant. This suggests that the water clusters were formed in two-dimensional matrices of hydrogen. We found that the water clusters did exist on the surface upon heating even after the hydrogen molecules had desorbed. A further rise of the substrate temperature up to 27 K yielded the formation of larger clusters, (H2O)n with n > 6 . We also discuss the origins of the two bands of the trimer in terms of pseudorotation and a metastable isomer.

  6. Hydrophobic Porous Material Adsorbs Small Organic Molecules

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K.; Hickey, Gregory S.

    1994-01-01

    Composite molecular-sieve material has pore structure designed specifically for preferential adsorption of organic molecules for sizes ranging from 3 to 6 angstrom. Design based on principle that contaminant molecules become strongly bound to surface of adsorbent when size of contaminant molecules is nearly same as that of pores in adsorbent. Material used to remove small organic contaminant molecules from vacuum systems or from enclosed gaseous environments like closed-loop life-support systems.

  7. Size selective hydrophobic adsorbent for organic molecules

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K. (Inventor); Hickey, Gregory S. (Inventor)

    1997-01-01

    The present invention relates to an adsorbent formed by the pyrolysis of a hydrophobic silica with a pore size greater than 5 .ANG., such as SILICALITE.TM., with a molecular sieving polymer precursor such as polyfurfuryl alcohol, polyacrylonitrile, polyvinylidene chloride, phenol-formaldehyde resin, polyvinylidene difluoride and mixtures thereof. Polyfurfuryl alcohol is the most preferred. The adsorbent produced by the pyrolysis has a silicon to carbon mole ratio of between about 10:1 and 1:3, and preferably about 2:1 to 1:2, most preferably 1:1. The pyrolysis is performed as a ramped temperature program between about 100.degree. and 800.degree. C., and preferably between about 100.degree. and 600.degree. C. The present invention also relates to a method for selectively adsorbing organic molecules having a molecular size (mean molecular diameter) of between about 3 and 6 .ANG. comprising contacting a vapor containing the small organic molecules to be adsorbed with the adsorbent composition of the present invention.

  8. Imaging the wave functions of adsorbed molecules

    PubMed Central

    Lüftner, Daniel; Ules, Thomas; Reinisch, Eva Maria; Koller, Georg; Soubatch, Serguei; Tautz, F. Stefan; Ramsey, Michael G.; Puschnig, Peter

    2014-01-01

    The basis for a quantum-mechanical description of matter is electron wave functions. For atoms and molecules, their spatial distributions and phases are known as orbitals. Although orbitals are very powerful concepts, experimentally only the electron densities and -energy levels are directly observable. Regardless whether orbitals are observed in real space with scanning probe experiments, or in reciprocal space by photoemission, the phase information of the orbital is lost. Here, we show that the experimental momentum maps of angle-resolved photoemission from molecular orbitals can be transformed to real-space orbitals via an iterative procedure which also retrieves the lost phase information. This is demonstrated with images obtained of a number of orbitals of the molecules pentacene (C22H14) and perylene-3,4,9,10-tetracarboxylic dianhydride (C24H8O6), adsorbed on silver, which are in excellent agreement with ab initio calculations. The procedure requires no a priori knowledge of the orbitals and is shown to be simple and robust. PMID:24344291

  9. Structure and properties of water film adsorbed on mica surfaces

    NASA Astrophysics Data System (ADS)

    Zhao, Gutian; Tan, Qiyan; Xiang, Li; Cai, Di; Zeng, Hongbo; Yi, Hong; Ni, Zhonghua; Chen, Yunfei

    2015-09-01

    The structure profiles and physical properties of the adsorbed water film on a mica surface under conditions with different degrees of relative humidity are investigated by a surface force apparatus. The first layer of the adsorbed water film shows ice-like properties, including a lattice constant similar with ice crystal, a high bearing capacity that can support normal pressure as high as 4 MPa, a creep behavior under the action of even a small normal load, and a character of hydrogen bond. Adjacent to the first layer of the adsorbed water film, the water molecules in the outer layer are liquid-like that can flow freely under the action of external loads. Experimental results demonstrate that the adsorbed water layer makes the mica surface change from hydrophilic to weak hydrophobic. The weak hydrophobic surface may induce the latter adsorbed water molecules to form water islands on a mica sheet.

  10. Adsorbed molecules in external fields: Effect of confining potential.

    PubMed

    Tyagi, Ashish; Silotia, Poonam; Maan, Anjali; Prasad, Vinod

    2016-12-01

    We study the rotational excitation of a molecule adsorbed on a surface. As is well known the interaction potential between the surface and the molecule can be modeled in number of ways, depending on the molecular structure and the geometry under which the molecule is being adsorbed by the surface. We explore the effect of change of confining potential on the excitation, which is largely controlled by the static electric fields and continuous wave laser fields. We focus on dipolar molecules and hence we restrict ourselves to the first order interaction in field-molecule interaction potential either through permanent dipole moment or/and the molecular polarizability parameter. It is shown that confining potential shapes, strength of the confinement, strongly affect the excitation. We compare our results for different confining potentials. PMID:27387127

  11. States of water adsorbed on perindopril crystals

    NASA Astrophysics Data System (ADS)

    Stepanov, V. A.; Khmelevskaya, V. S.; Bogdanov, N. Yu.; Gorchakov, K. A.

    2011-10-01

    The relationship between the structural state of adsorbed water, the crystal structure of the substances, and the solubility of the perindopril salt C19H32N2O5 · C4H11N in water was studied by IR spectroscopy and X-ray diffractometry. The high-frequency shift of the stretching vibrations of adsorbed water and the solubility depend on the crystal structure of the drug substance. A reversible chemical reaction occurred between the adsorbed water and the perindopril salt.

  12. Inhomogeneous distribution of organic molecules adsorbed in sol gel glasses

    NASA Astrophysics Data System (ADS)

    Meneses-Nava, M. A.; Chávez-Cerda, S.; Sánchez-Villicaña, V.; Sánchez-Mondragón, J. J.; King, T. A.

    1999-09-01

    The effects of the porous matrix upon the radiative characteristics of quinine sulphate doped sol-gel glasses are investigated. The broadenings of the absorption and fluorescence spectra are explained by the attachment of the molecules on distorted sites or in a non-planar fashion, creating an inhomogeneous distribution of adsorbed molecules. For this reason, each emitting center relaxes with its own characteristics. This inhomogeneous distribution is also supported by the non-exponential and the wavelength dependence of the fluorescence decay.

  13. Probing atomic positions of adsorbed ammonia molecules in zeolite.

    PubMed

    Ye, Lin; Lo, Benedict T W; Qu, Jin; Wilkinson, Ian; Hughes, Tim; Murray, Claire A; Tang, Chiu C; Tsang, Shik Chi Edman

    2016-02-25

    Atomic positions and interactions between adsorbed guest molecules, such as ammonia in H-ZSM-5 microporous solids, are for the first time revealed by making use of the change in the periodical scattering parameter using in situ synchrotron powder X-ray diffraction combined with refinement within experimental errors. PMID:26833032

  14. Adsorbed water and CO on Pt electrode modified with Ru

    NASA Astrophysics Data System (ADS)

    Futamata, Masayuki; Luo, Liqiang

    Highly sensitive ATR-SEIRA spectroscopy was exploited to elucidate water, CO and electrolyte anions adsorbed on the Ru modified Pt film electrode. CO on Ru domains was oxidized below ca. +0.3 V, followed by pronounced water adsorption. Since the oxidation potential of CO on Pt domain was significantly reduced compared to bare Pt, these water molecules on Ru obviously prompt CO oxidation on adjacent Pt surface as consistent with the bifunctional mechanism. Diffusion of adsorbate from Ru to Pt surfaces was indicated in dilute CH 3OH solution by spectral changes with potential.

  15. Hydrogen molecule on lithium adsorbed graphene: A DFT study

    NASA Astrophysics Data System (ADS)

    Kaur, Gagandeep; Gupta, Shuchi; Gaganpreet, Dharamvir, Keya

    2016-05-01

    Electronic structure calculations for the adsorption of molecular hydrogen on lithium (Li) decorated and pristine graphene have been studied systematically using SIESTA code [1] within the framework of the first-principle DFT under the Perdew-Burke-Ernzerhof (PBE) form of the generalized gradient approximation (GGA)[2], including spin polarization. The energy of adsorption of hydrogen molecule on graphene is always enhanced by the presence of co-adsorbed lithium. The most efficient adsorption configuration is when H2 is lying parallel to lithium adsorbed graphene which is in contrast to its adsorption on pristine graphene (PG) where it prefers perpendicular orientation.

  16. Candidate Source of Flux Noise in SQUIDs: Adsorbed Oxygen Molecules.

    PubMed

    Wang, Hui; Shi, Chuntai; Hu, Jun; Han, Sungho; Yu, Clare C; Wu, R Q

    2015-08-14

    A major obstacle to using superconducting quantum interference devices (SQUIDs) as qubits is flux noise. We propose that the heretofore mysterious spins producing flux noise could be O_{2} molecules adsorbed on the surface. Using density functional theory calculations, we find that an O_{2} molecule adsorbed on an α-alumina surface has a magnetic moment of ~1.8 μ_{B}. The spin is oriented perpendicular to the axis of the O-O bond, the barrier to spin rotations is about 10 mK. Monte Carlo simulations of ferromagnetically coupled, anisotropic XY spins on a square lattice find 1/f magnetization noise, consistent with flux noise in Al SQUIDs. PMID:26317742

  17. Theory of raman scattering from molecules adsorbed at semiconductor surfaces

    NASA Astrophysics Data System (ADS)

    Ueba, H.

    1983-09-01

    A theory is presented to calculate the Raman polarizability of an adsorbed molecule at a semiconductor surface, where the electronic excitation in the molecular site interacts with excitons (elementary excitations in the semiconductor) through non-radiative energy transfer between them, in an intermediate state in the Raman scattering process. The Raman polarizability thus calculated is found to exhibit a peak at the energy corresponding to a resonant excitation of excitons, thereby suggesting the possibility of surface enhanced Raman scattering on semiconductor surfaces. The mechanism studied here can also give an explanation of a recent observation of the Raman excitation profiles of p-NDMA and p-DMAAB adsorbed on ZnO or TiO 2, where those profiles were best described by assuming a resonant intermediate state of the exciton transition in the semiconductors. It is also demonstrated that in addition to vibrational Raman scattering, excitonic Raman scattering of adsorbed molecules will occur in the coupled molecule-semiconductor system, where the molecular returns to its ground electronic state by leaving an exciton in the semiconductor. A spectrum of the excitonic Raman scattering is expected to appear in the background of the vibrational Raman band and to be characterized by the electronic structure of excitons. A desirable experiment is suggested for an examination of the theory.

  18. A simple model for electronic properties of surface adsorbed molecules

    NASA Astrophysics Data System (ADS)

    Dhakal, Rajesh; Schwalm, William

    We adapt a minimal approximation to one electron quantum theory of molecules referred as Fast Accurate Kinetic Energy method. This in principle handles large complex molecular structures with less computational effort to compute electronic properties of adsorbed molecules. Kinetic energy integrals are calculated accurately but multi-electron potential energy integrals are approximated. The neighboring atom interactions are included also. For layers of isopthalic acids formed on pyrolytic graphite the configuration changes as a function of length of hydrocarbon tails. We study properties of this system as a function of tail length.

  19. SPR-MS: from identifying adsorbed molecules to image tissues

    NASA Astrophysics Data System (ADS)

    Masson, Jean-François; Breault-Turcot, Julien; Forest, Simon; Chaurand, Pierre

    2015-03-01

    Surface plasmon resonance (SPR) sensors have become valuable analytical sensors for biomolecule detection. While SPR is heralded with high sensitivity, label-free and real-time detection, nonspecific adsorption and detection of ultralow concentrations remain issues. Nonspecific adsorption can be minimized using adequate surface chemistry. For example, we have employed peptide monolayers to reduce nonspecific adsorption of crude serum or cell lysate. It is important to uncover the nature of molecules nonspecifically adsorbing to surfaces in these biofluids, to further improve understanding of the nonspecific adsorption processes. Mass spectrometry (MS) provides a complementary tool to SPR to identify biomolecule adsorbed to surface. Trypsic digestion of the proteins adsorbed to surfaces led to identification of characteristic peptides from the proteins involved in nonspecific adsorption. Nonspecific adsorption in crude cell lysate results mainly from lipids, as confirmed with SPR and MS but proteins were observed on some surfaces. In another application of SPR and MS, imaging SPR can be used in combination to imaging MS to image tissue sections. Thin sections of mouse liver were inserted in the fluidic chamber of a SPRi instrument and proteins were transferred to the SPRi chip. The SPR chip was then imaged using MALDI imaging MS to identify the biomolecules that were transferred to the SPRi chip.

  20. Controlling spins in adsorbed molecules by a chemical switch

    PubMed Central

    Wäckerlin, Christian; Chylarecka, Dorota; Kleibert, Armin; Müller, Kathrin; Iacovita, Cristian; Nolting, Frithjof; Jung, Thomas A.; Ballav, Nirmalya

    2010-01-01

    The development of chemical systems with switchable molecular spins could lead to the architecture of materials with controllable magnetic or spintronic properties. Here, we present conclusive evidence that the spin of an organometallic molecule coupled to a ferromagnetic substrate can be switched between magnetic off and on states by a chemical stimulus. This is achieved by nitric oxide (NO) functioning as an axial ligand of cobalt(II)tetraphenylporphyrin (CoTPP) ferromagnetically coupled to nickel thin-film (Ni(001)). On NO addition, the coordination sphere of Co2+ is modified and a NO–CoTPP nitrosyl complex is formed, which corresponds to an off state of the Co spin. Thermal dissociation of NO from the nitrosyl complex restores the on state of the Co spin. The NO-induced reversible off–on switching of surface-adsorbed molecular spins observed here is attributed to a spin trans effect. PMID:20975713

  1. Modeling the binding of fulvic acid by goethite: the speciation of adsorbed FA molecules

    NASA Astrophysics Data System (ADS)

    Filius, Jeroen D.; Meeussen, Johannes C. L.; Lumsdon, David G.; Hiemstra, Tjisse; van Riemsdijk, Willem H.

    2003-04-01

    Under natural conditions, the adsorption of ions at the solid-water interface may be strongly influenced by the adsorption of organic matter. In this paper, we describe the adsorption of fulvic acid (FA) by metal(hydr)oxide surfaces with a heterogeneous surface complexation model, the ligand and charge distribution (LCD) model. The model is a self-consistent combination of the nonideal competitive adsorption (NICA) equation and the CD-MUSIC model. The LCD model can describe simultaneously the concentration, pH, and salt dependency of the adsorption with a minimum of only three adjustable parameters. Furthermore, the model predicts the coadsorption of protons accurately for an extended range of conditions. Surface speciation calculations show that almost all hydroxyl groups of the adsorbed FA molecules are involved in outer sphere complexation reactions. The carboxylic groups of the adsorbed FA molecule form inner and outer sphere complexes. Furthermore, part of the carboxylate groups remain noncoordinated and deprotonated.

  2. Dynamics of photoinduced electron transfer from adsorbed molecules into solids

    NASA Astrophysics Data System (ADS)

    Gundlach, L.; Ernstorfer, R.; Willig, F.

    2007-08-01

    Ultrafast interfacial electron transfer from the donor orbital of organic chromophores into empty electronic acceptor states of a semiconductor and of a metal was investigated by two-photon photoemission spectroscopy (2PPE). Experimental tools and procedures have been developed for carrying out wet-chemistry preparation of the molecule/solid interface. The organic chromophore perylene was investigated with several different bridge/anchor groups on TiO2(110). One perylene compound was investigated for comparison on Ag(110). Angle and polarization dependent 2PPE measurements revealed the orientation of the perylene chromophore on the surface as controlled by the adsorption geometry of the respective anchor group on TiO2. UPS measurements gave the position of the HOMO level of the chromophore with respect to the Fermi level of the solid. The donor level of each molecule was found high enough to fulfill the “wide band limit” of heterogeneous electron transfer dynamics. Time constants for heterogeneous electron transfer were extracted from 2PPE transients. A difference by a factor of four was found, 13 fs against 47 fs, when a conjugated bond was exchanged for a saturated bond in the otherwise identical bridge group. The two different contributions to the 2PPE transients arising firstly from the excited state of the chromophore and secondly from the injected electrons were separated by measuring the latter contribution separately in the case of instantaneous interfacial electron transfer realized with catechol as adsorbate. The time scales measured for the electron transfer step and for the subsequent electron escape process from the surface into the bulk of TiO2 showed both good agreement with recent theoretical predictions of other groups for these systems.

  3. Thermodynamic formalism of water uptakes on solid porous adsorbents for adsorption cooling applications

    SciTech Connect

    Sun, Baichuan; Chakraborty, Anutosh

    2014-05-19

    This Letter presents a thermodynamic formulation to calculate the amount of water vapor uptakes on various adsorbents such as zeolites, metal organic frameworks, and silica gel for the development of an advanced adsorption chiller. This formalism is developed from the rigor of the partition distribution function of each water vapor adsorptive site on adsorbents and the condensation approximation of adsorptive water molecules and is validated with experimental data. An interesting and useful finding has been established that the proposed model is thermodynamically connected with the pore structures of adsorbent materials, and the water vapor uptake highly depends on the isosteric heat of adsorption at zero surface coverage and the adsorptive sites of the adsorbent materials. Employing the proposed model, the thermodynamic trends of water vapor uptakes on various adsorbents can be estimated.

  4. Polarizabilities of Adsorbed and Assembled Molecules: Measuring the Conductance through Buried Contacts

    PubMed Central

    2010-01-01

    We have measured the polarizabilities of four families of molecules adsorbed to Au{111} surfaces, with structures ranging from fully saturated to fully conjugated, including single-molecule switches. Measured polarizabilities increase with increasing length and conjugation in the adsorbed molecules and are consistent with theoretical calculations. For single-molecule switches, the polarizability reflects the difference in substrate−molecule electronic coupling in the ON and OFF conductance states. Calculations suggest that the switch between the two conductance states is correlated with an oxidation state change in a nitro functional group in the switch molecules. PMID:21077677

  5. Does Moisture Influence the Chemical Detection of Gas Molecules Adsorbed on Single-Wall Carbon Nanotubes?

    NASA Astrophysics Data System (ADS)

    Yu, Ming; Tian, W. Q.; Jayanthi, C. S.; Wu, S. Y.

    2009-03-01

    In this work, the role of water in the detection of hydrazine (N2H4) by a single-wall carbon nanotube (SWCNT) is investigated using first principles electronic structure calculations (DFT/GGA--USPP)[1]. This calculation is undertaken to interpret the experimental resistivity measurements for N2H4 adsorbed on SWCNT that reveal an n-type behavior [2]. Our preliminary theoretical studies of the adsorption of N2H4 on SWCNT revealed physisorption for N2H4 and an unaltered band structure for the SWCNT [3]. This prompted us to look into the role of water on the bonding of N2H4 to the SWCNT. We found that, by introducing a monolayer of water film on the (8,0) SWCNT, the adsorption of N2H4 can introduce occupied states near the Fermi level, exhibiting an n-type behavior. However, the introduction of just few water molecules was not sufficient to influence the electronic structure of N2H4/SWCNT. Presently, we are studying the influence of water films on the chemical detection of a variety of other gas molecules (N2, NH3, etc.) by SWCNTs, and the results from such studies will also be reported. [1]. G. Kresse et al. Phys. Rev. B 54, 11169 (1996). [2]. S. Desai, et al. (APS, March 2008). [3]. M. Yu, et al. (APS, March 2008).

  6. Laser electrospray mass spectrometry of adsorbed molecules at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Brady, John J.; Judge, Elizabeth J.; Simon, Kuriakose; Levis, Robert J.

    2010-02-01

    Atmospheric pressure mass analysis of solid phase biomolecules is performed using laser electrospray mass spectrometry (LEMS). A non-resonant femtosecond duration laser pulse vaporizes native samples at atmospheric pressure for subsequent electrospray ionization and transfer into a mass spectrometer. LEMS was used to detect a complex molecule (irinotecan HCl), a complex mixture (cold medicine formulation with active ingredients: acetaminophen, dextromethorphan HBr and doxylamine succinate), and a biological building block (deoxyguanosine) deposited on steel surfaces without a matrix molecule.

  7. Competition between Displacement and Dissociation of a Strong Acid Compared to a Weak Acid Adsorbed on Silica Particle Surfaces: The Role of Adsorbed Water.

    PubMed

    Fang, Yuan; Tang, Mingjin; Grassian, Vicki H

    2016-06-16

    The adsorption of nitric (HNO3) and formic (HCOOH) acids on silica particle surfaces and the effect of adsorbed water have been investigated at 296 K using transmission FTIR spectroscopy. Under dry conditions, both nitric and formic acids adsorb reversibly on silica. Additionally, the FTIR spectra show that both of these molecules remain in the protonated form. At elevated relative humidities (RH), adsorbed water competes both for surface adsorption sites with these acids as well as promotes their dissociation to hydronium ions and the corresponding anions. Compared to HNO3, the extent of dissociation is much smaller for HCOOH, very likely because it is a weaker acid. This study provides valuable insights into the interaction of HNO3 and HCOOH with silica surface on the molecular level and further reveals the complex roles of surface-adsorbed water in atmospheric heterogeneous chemistry of mineral dust particles-many of these containing silica. PMID:27220375

  8. Auger electron spectroscopy as a tool for measuring intramolecular charges of adsorbed molecules

    NASA Astrophysics Data System (ADS)

    Magkoev, T. T.

    A way for the determination of the values of intramolecular charges of adsorbed molecules of some binary dielectrics, based on Auger electron spectroscopy (AES), is proposed. These values can be obtained from the coverage dependences of the ratios of intensities of anion KL 23L 23 and KL 1L 1 Auger transitions, which are sensitive to the amount of charge at the 2p-orbitals. As an example, MgO adsorbed on Mo(110) is presented.

  9. Auger electron spectroscopy as a tool for measuring intramolecular charges of adsorbed molecules

    NASA Astrophysics Data System (ADS)

    Magkoev, T. T.

    1993-10-01

    A way for the determination of the values of intramolecular charges of adsorbed molecules of some binary dielectrics, based on Auger electron spectroscopy (AES), is proposed. These values can be obtained from the coverage dependences of the ratios of intensities of anion KL 23L 23 and KL 1L 1 Auger transitions, which are sensitive to the amount of charge at the 2p-orbitals. As an example, MgO adsorbed on Mo(110) is presented.

  10. Transient magnetization of core excited organic molecules adsorbed on graphene

    NASA Astrophysics Data System (ADS)

    Ravikumar, Abhilash; Baby, Anu; Lin, He; Brivio, Gian Paolo; Fratesi, Guido

    This work presents a density functional theory based computational investigation of electronic and magnetic properties of physisorbed and chemisorbed organic molecules on graphene in the ground state and core excited one at low molecular coverage. For physisorbed molecules, where the interaction with graphene is dominated by van der Waals forces and the system is non-magnetic in the ground state, it is found that the valence electrons relax towards a spin polarized configuration upon excitation of a core-level electron. The magnetism depends on efficient electron transfer from graphene on the femtosecond time scale. On the contrary, when graphene is covalently functionalized, the system is magnetic in the ground state presenting two spin dependent mid gap states localized around the adsorption site. At variance with the physisorbed case upon core-level excitation, the LUMO of the molecule and the mid gap states of graphene hybridize and the relaxed valence shell is not magnetic anymore. This project has received funding from the European Union Seventh Framework Programme under grant agreement n∘ 607232 [THINFACE].

  11. Rotational Spectromicroscopy: Imaging the Orbital Interaction between Molecular Hydrogen and an Adsorbed Molecule

    NASA Astrophysics Data System (ADS)

    Li, Shaowei; Yuan, Dingwang; Yu, Arthur; Czap, Gregory; Wu, Ruqian; Ho, W.

    2015-05-01

    A hydrogen molecule can diffuse freely on the surface and be trapped above an adsorbed molecule within the junction of a scanning tunneling microscope. The trapped dihydrogen exhibits the properties of a free rotor. Here we show that the intermolecular interaction between dihydrogen and Mg-porphyrin (MgP) can be visualized by imaging j =0 to 2 rotational excitation of dihydrogen. The interaction leads to a weakened H-H bond and modest electron donation from the dihydrogen to the lowest unoccupied molecular orbital of MgP, a process similarly observed for the interaction between dihydrogen and an adsorbed Au atom.

  12. Rotational Spectromicroscopy: Imaging the Orbital Interaction between Molecular Hydrogen and an Adsorbed Molecule.

    PubMed

    Li, Shaowei; Yuan, Dingwang; Yu, Arthur; Czap, Gregory; Wu, Ruqian; Ho, W

    2015-05-22

    A hydrogen molecule can diffuse freely on the surface and be trapped above an adsorbed molecule within the junction of a scanning tunneling microscope. The trapped dihydrogen exhibits the properties of a free rotor. Here we show that the intermolecular interaction between dihydrogen and Mg-porphyrin (MgP) can be visualized by imaging j=0 to 2 rotational excitation of dihydrogen. The interaction leads to a weakened H-H bond and modest electron donation from the dihydrogen to the lowest unoccupied molecular orbital of MgP, a process similarly observed for the interaction between dihydrogen and an adsorbed Au atom. PMID:26047242

  13. Dynamics of Molecules Adsorbed in Zeolitic Systems: Neutron Scattering and MD Simulation Studies

    SciTech Connect

    Mitra, S.; Sharma, V. K.; Mukhopadhyay, R.

    2011-07-15

    Zeolites represent a class of technologically important materials because of their characteristic properties of molecular sieving and catalysis, which makes them indispensable in the petroleum industries. While the catalytic properties depend upon many factors, a major role is played by the dynamics of hydrocarbon gases. In order to be able to tailor make these materials for use in industry for catalytic and sieving purposes, it is important to understand the dynamical properties of the guest molecules adsorbed in the zeolitic materials. It is of interest to study the effects of size and shape of guest molecules and also the host zeolitic structure, governing the diffusion mechanism of the adsorbed species. Here we report the results of Quasielastic Neutron Scattering (QENS) and classical molecular dynamics (MD) simulation studies of two hydrocarbons namely acetylene and propylene adsorbed in two structurally different zeolites Na-Y and ZSM-5.

  14. Giant Hysteresis of Single-Molecule Magnets Adsorbed on a Nonmagnetic Insulator.

    PubMed

    Wäckerlin, Christian; Donati, Fabio; Singha, Aparajita; Baltic, Romana; Rusponi, Stefano; Diller, Katharina; Patthey, François; Pivetta, Marina; Lan, Yanhua; Klyatskaya, Svetlana; Ruben, Mario; Brune, Harald; Dreiser, Jan

    2016-07-01

    TbPc2 single-molecule magnets adsorbed on a magnesium oxide tunnel barrier exhibit record magnetic remanence, record hysteresis opening, perfect out-of-plane alignment of the magnetic easy axes, and self-assembly into a well-ordered layer. PMID:27159732

  15. Vibrational dynamics of fullerene molecules adsorbed on metal surfaces studied with synchrotron infrared radiation

    SciTech Connect

    P. Rudolf; R. Raval; P. Dumas; Gwyn P. Williams

    2002-04-01

    Infrared (IR) spectroscopy of chemisorbed C{sub 60} on Ag (111), Au (110) and Cu (100) reveals that a non-IR-active mode becomes active upon adsorption, and that its frequency shifts proportionally with the charge transferred from the metal to the molecule by about 5 cm{sup -1} per electron. The temperature dependence of the frequency and the width of this IR feature have also been followed for C{sub 60>}/Cu (100) and were found to agree well with a weak anharmonic coupling (dephasing) to a low-frequency mode, which we suggest to be the frustrated translational mode of the adsorbed molecules.

    Additionally, the adsorption is accompanied by a broadband reflectance change, which is interpreted as due to the scattering of conduction electrons of the metal surface by the adsorbate. The reflectance change allows determination of the friction coefficient of the C{sub 60} molecules, which results in rather small values ({approx}2 x 10{sup 9}s{sup -1} for Ag and Au, and {approx}1.6 x 10{sup 9}s{sup -1} for Cu), consistent with a marked metallic character of the adsorbed molecules.

    Pre-dosing of alkali atoms onto the metal substrates drastically changes the IR spectra recorded during subsequent C{sub 60} deposition: anti-absorption bands, as well as an increase of the broadband reflectance, occur and are interpreted as due to strong electron-phonon coupling with induced surface states.

  16. Electron-Stimulated Oxidation of Thin Water Films Adsorbed on TiO2(110)

    SciTech Connect

    Lane, Christopher D.; Petrik, Nikolay G.; Orlando, Thomas M.; Kimmel, Greg A.

    2007-11-08

    Electron-stimulated reactions in thin (< 3 monolayer, ML) water films adsorbed on TiO2(110) are investigated. For electron fluences less than ~1×1016 e-/cm2, irradiation with 100 eV electrons results in electron-stimulated desorption (ESD) of atomic and molecular hydrogen, but no measurable O2. The ESD leaves adsorbed hydroxyls which oxidize the TiO2(110) surface and change the post-irradiation TPD spectra of the remaining water in characteristic ways. The species remaining on the TiO2(110) after irradiation of adsorbed water films are apparently similar to those produced without irradiation by co-dosing water and O2. Annealing above ~600 K reduces the oxidized surfaces, and water TPD spectra characteristic of ion sputtered and annealed TiO2(110) are recovered. The rate of electron-stimulated “oxidation” of the water films is proportional to the coverage of water in the first layer for coverages less than 1 ML. However, higher coverages suppress this reaction. When thin water films are irradiated, the rate of electron-stimulated oxidation is independent of the initial oxygen vacancy concentration, as is the final oxidized state achieved at high electron fluences. To explain the results, we propose that electron excitation of water molecules adsorbed on Ti4+ sites leads to desorption of hydrogen atoms and leaves an OH adsorbed at the site. If hydroxyls are present in the bridging oxygen rows, these react with the OH’s on the Ti4+ sites to reform water and heal the oxygen vacancy associated with the bridging OH. Once the bridge bonded hydroxyls have been eliminated, further irradiation increases the concentration of OH’s in the Ti4+ rows leading to the creation of species which block sites in the Ti4+ rows, perhaps H2O2 and/or HO2.

  17. Hydraulic properties of adsorbed water films in unsaturated porous media

    SciTech Connect

    Tokunaga, Tetsu K.

    2009-03-01

    Adsorbed water films strongly influence residual water saturations and hydraulic conductivities in porous media at low saturations. Hydraulic properties of adsorbed water films in unsaturated porous media were investigated through combining Langmuir's film model with scaling analysis, without use of any adjustable parameters. Diffuse double layer influences are predicted to be important through the strong dependence of adsorbed water film thickness (f) on matric potential ({Psi}) and ion charge (z). Film thickness, film velocity, and unsaturated hydraulic conductivity are predicted to vary with z{sup -1}, z{sup -2}, and z{sup -3}, respectively. In monodisperse granular media, the characteristic grain size ({lambda}) controls film hydraulics through {lambda}{sup -1} scaling of (1) the perimeter length per unit cross sectional area over which films occur, (2) the critical matric potential ({Psi}{sub c}) below which films control flow, and (3) the magnitude of the unsaturated hydraulic conductivity when {Psi} < {Psi}{sub c}. While it is recognized that finer textured sediments have higher unsaturated hydraulic conductivities than coarser sands at intermediate {Psi}, the {lambda}{sup -1} scaling of hydraulic conductivity predicted here extends this understanding to very low saturations where all pores are drained. Extremely low unsaturated hydraulic conductivities are predicted under adsorbed film-controlled conditions (generally < 0.1 mm y{sup -1}). On flat surfaces, the film hydraulic diffusivity is shown to be constant (invariant with respect to {Psi}).

  18. Rod-like cyanophenyl probe molecules nanoconfined to oxide particles: Density of adsorbed surface species

    NASA Astrophysics Data System (ADS)

    Frunza, Stefan; Frunza, Ligia; Ganea, Constantin Paul; Zgura, Irina; Brás, Ana Rita; Schönhals, Andreas

    2016-02-01

    Surface layers have already been observed by broadband dielectric spectroscopy for composite systems formed by adsorption of rod-like cyanophenyl derivates as probe molecules on the surface of oxide particles. In this work, features of the surface layer are reported; samples with different amounts of the probe molecules adsorbed onto oxide (nano) particles were prepared in order to study their interactions with the surface. Thermogravimetric analysis (TGA) was applied to analyze the amount of loaded probe molecules. The density of the surface species ns was introduced and its values were estimated from quantitative Fourier transform infrared spectroscopy (FTIR) coupled with TGA. This parameter allows discriminating the composites into several groups assuming a similar interaction of the probe molecules with the hosts of a given group. An influence factor H is further proposed as the ratio of the number of molecules in the surface layer showing a glassy dynamics and the number of molecules adsorbed tightly on the surface of the support: It was found for aerosil composites and used for calculating the maximum filling degree of partially filled silica MCM-41 composites showing only one dielectric process characteristic for glass-forming liquids and a bulk behavior for higher filling degrees.

  19. Adsorbed Oxygen Molecules as a Possible Source of Flux Noise in SQUIDs

    NASA Astrophysics Data System (ADS)

    Shi, Chuntai; Wang, Hui; Hu, Jun; Yu, Clare; Wu, Ruqian

    2015-03-01

    One of the dominant source of flux noise in SQUIDs is flux noise which has been attributed to mysterious fluctuating magnetic spins on the surface. We propose that the spins producing flux noise could be adsorbed O2 molecules that have a magnetic moment of about 2 μB. Using density functional calculations, we studied O2 molecules adsorbed on a sapphire surface. We find that the barrier for spin rotation is small enough to allow almost free spin reorientation due to thermal excitations at low temperatures. Monte Carlo simulations of a 2D XY spin model yields 1 / f noise where f is frequency. This work was supported by 1000 Talent Program of China through Fudan University. Work at UCI was supported by DOE-BES (Grant No. DE-FG02-05ER46237) and the Army Research Office (Grant No. W911NF-10-1-0494).

  20. Stability, structural and electronic properties of benzene molecule adsorbed on free standing Au layer

    NASA Astrophysics Data System (ADS)

    Katoch, Neha; Kapoor, Pooja; Sharma, Munish; Kumar, Ashok; Ahluwalia, P. K.

    2016-05-01

    We report stability and electronic properties of benzene molecule adsorbed on the Au atomic layer within the framework of density function theory (DFT). Horizontal configuration of benzene on the top site of Au monolayer prefers energetically over other studied configurations. On the adsorption of benzene, the ballistic conductance of Au monolayer is found to decrease from 4G0 to 2G0 suggesting its applications for the fabrications of organic sensor devices based on the Au atomic layers.

  1. Orientation and heat capacity of horizontally adsorbed molecules in electric fields

    NASA Astrophysics Data System (ADS)

    Liao, Ying-Yen

    2014-02-01

    The orientation and the heat capacity of horizontally adsorbed molecules are investigated in static electric fields. We evaluate the energy spectrum and the wave function to probe the rotational characteristics of the molecule. Numerical results indicate that the electric field and the effect of quantum confinement lead to anticrossing behaviors in the energy levels. The orientation reveals a stepped feature due to the anticrossing in the ground state. Moreover, the heat capacity displays two peaks near the anticrossing. By means of comparison, each peak of the heat capacity corresponds to a particular degree of orientation.

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

    PubMed

    Rubasinghege, Gayan; Grassian, Vicki H

    2013-04-18

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

  3. Detection of adsorbed water and hydroxyl on the moon

    USGS Publications Warehouse

    Clark, R.N.

    2009-01-01

    Data from the Visual and Infrared Mapping Spectrometer (VIAAS) on Cassini during its flyby of the AAoon in 1999 show a broad absorption at 3 micrometers due to adsorbed water and near 2.8 micrometers attributed to hydroxyl in the sunlit surface on the AAoon. The amounts of water indicated in the spectra depend on the type of mixing and the grain sizes in the rocks and soils but could be 10 to 1000 parts per million and locally higher. Water in the polar regions may be water that has migrated to the colder environments there. Trace hydroxyl is observed in the anorthositic highlands at lower latitudes.

  4. Adsorbent selection for endosulfan removal from water environment.

    PubMed

    Sudhakar, Y; Dikshit, A K

    1999-01-01

    In the present study, an attempt was made to select a low cost adsorbing material for the removal of endosulfan [C,C'-(1,4,5,6,7,7-hexachloro-8,9,10- trinorborn-5-en-2,3-ylene)(dimethylsulphite)] from water. Various low cost adsorbents like wood charcoal, kimberlite tailings, silica, macro fungi sojar caju were tried with activated charcoal as reference material. The above materials were selected from various sources encompassing organic, inorganic, clayey, and biological sources. For the selection of suitable adsorbent for endosulfan uptake, maximum adsorption capacity (Qmax) was chosen as the parameter. Kinetic profiles of removal were generated for all the materials to assess the equilibrium time. Equilibrium studies were carried out for all materials to assess the adsorption equilibrium model that they followed. The model that gave the best correlation coefficient by linear regression analysis, was adopted for the calculation of Qmax of the corresponding adsorbent material. Using linearised forms of equilibrium models like Langmuir, BET, and Freundlich, maximum adsorptive capacities were determined. Activated charcoal showed the best adsorptive capacity with Qmax of 2.145 mg/g followed by wood charcoal 1.773 mg/g, sojar caju 1.575 mg/g, kimberlite tailings 0.8821 mg/g, and silica 0.3231 mg/g. Albeit activated charcoal gave better performance, it was not considered as a candidate material because of its high cost. Wood charcoal was the next best adsorbent with Qmax 1.773 mg/g. Therefore, wood charcoal was chosen as the best material for endosulfan removal. The study of physical and chemical characteristics of wood charcoal revealed that it is a potential adsorbent and can even be improved further. PMID:10048207

  5. The low-temperature loss tangent of adsorbed water in alumina

    NASA Astrophysics Data System (ADS)

    Khasawneh, Mazin; Sarabi, Bahman; Khalil, M. S.; Stoutimore, M. J. A.; Gladchenko, Sergiy; Wellstood, F. C.; Lobb, C. J.; Osborn, Kevin

    2012-02-01

    Superconducting quantum information circuits use various amorphous dielectrics for capacitors, and alumina is the ubiquitous barrier material for Josephson junctions within these devices. The exposure of the devices to air allows water molecules to penetrate the dielectric films along grain boundaries, and become adsorbed onto internal surfaces. In this study we plan to use ALD-grown alumina and titanium oxide to study the penetration of water through films. Using blocking layers to selectively prevent water penetration, we then plan to measure the difference in the low-temperature loss tangent between an alumina film which is exposed to air and one which is not.

  6. Spectroscopic modeling of water molecule

    NASA Astrophysics Data System (ADS)

    Danylo, R. I.; Okhrimenko, B. A.

    2013-12-01

    This research is devoted to the vibrational spectroscopy inverse problem solution that gives a possibility to design a molecule and make conclusions about its geometry. The valence angle finding based on the usage of inverse spectral vibrational spectroscopy problem is a well-known task. 3N-matrix method was chosen to solve the proposed task. The usage of this method permits to make no assumptions about the molecule force field, besides it can be applied to molecules of matter in liquid state. Anharmonicity constants assessment is an important part of the valence angle finding. The reduction to zero vibrations is necessary because used matrix analytical expression were found in the harmonic approach. In order to find the single-valued inverse spectral problem of vibrational spectroscopy solution a shape parameter characterizing "mixing" of ω1 and ω2 vibrations forms must be found. The minimum of such a function Υ called a divergence parameter was found. This function characterizes method's accuracy. The valence angle assessment was reduced to the divergence parameter minimization. The β value concerning divergence parameter minimum was interpreted as the desired valence angle. The proposed method was applied for water molecule in liquid state: β = (88,8 ±1,7)° . The found angle fits the water molecule nearest surrounding tetrahedral model including hydrogen bond curvature in the first approximation.

  7. Turning things downside up: Adsorbate induced water flipping on Pt(111)

    SciTech Connect

    Kimmel, Greg A. E-mail: bruce.kay@pnnl.gov; Zubkov, Tykhon; Smith, R. Scott; Petrik, Nikolay G.; Kay, Bruce D. E-mail: bruce.kay@pnnl.gov

    2014-11-14

    We have examined the adsorption of the weakly bound species N{sub 2}, O{sub 2}, CO, and Kr on the (√(37)×√(37))R25.3{sup ∘} water monolayer on Pt(111) using a combination of molecular beam dosing, infrared reflection absorption spectroscopy, and temperature programmed desorption. In contrast to multilayer crystalline ice, the adsorbate-free water monolayer is characterized by a lack of dangling OH bonds protruding into the vacuum (H-up). Instead, the non-hydrogen-bonded OH groups are oriented downward (H-down) to maximize their interaction with the underlying Pt(111) substrate. Adsorption of Kr and O{sub 2} have little effect on the structure and vibrational spectrum of the “√(37)” water monolayer while adsorption of both N{sub 2}, and CO are effective in “flipping” H-down water molecules into an H-up configuration. This “flipping” occurs readily upon adsorption at temperatures as low as 20 K and the water monolayer transforms back to the H-down, “√(37)” structure upon adsorbate desorption above 35 K, indicating small energy differences and barriers between the H-down and H-up configurations. The results suggest that converting water in the first layer from H-down to H-up is mediated by the electrostatic interactions between the water and the adsorbates.

  8. Turning things downside up: Adsorbate induced water flipping on Pt(111)

    SciTech Connect

    Kimmel, Gregory A.; Zubkov, Tykhon; Smith, R. Scott; Petrik, Nikolay G.; Kay, Bruce D.

    2014-11-14

    We have examined the adsorption of the weakly bound species N2, O2, CO and Kr on the water monolayer on Pt(111) using a combination of molecular beam dosing, infrared reflection absorption spectroscopy (IRAS), and temperature programmed desorption (TPD). In contrast to multilayer crystalline ice, the adsorbate-free water monolayer is characterized by a lack of dangling OH bonds protruding into the vacuum (H-up). Instead, the non-hydrogen-bonded OH groups are oriented downward (H-down) to maximize their interaction with the underlying Pt(111) substrate. Adsorption of Kr and O2 have little effect on the structure and vibrational spectrum of the “ ” water monolayer while adsorption of both N2, and CO are effective in “flipping” H-down water molecules into an H-up configuration. This “flipping” occurs readily upon adsorption at temperatures as low as 20 K and the water monolayer transforms back to the H-down, “ ” structure upon adsorbate desorption above 35 K, indicating small energy differences and barriers between the H-down and H-up configurations. The results suggest that converting water in the first layer from H-down to H-up is mediated by the electrostatic interactions between the water and the adsorbates.

  9. Preparation and performance of chitosan encapsulated activated charcoal (ACCB) adsorbents for small molecules.

    PubMed

    Chandy, T; Sharma, C P

    1993-01-01

    A technique is described to encapsulate activated charcoal for haemoperfusion to be used in an artificial liver support. Activated charcoal was encapsulated within chitosan matrix (ACCB) in different concentrations, and was used as the supports for perfusion of a mixture of solutes, having molecular weight ranges from 60 to 69,000; under a flow rate of 8 ml/min. It seems the ACCB may be a good adsorbent system for the removal of toxic uric acid, creatinine, bilirubin, etc., from solutions; while larger molecules such as albumin are adsorbed less. The encapsulated charcoal did not leach out from the matrix during perfusion, and the system may be useful for detoxification of blood. The haemolytic potential of ACCB has been compatible with polystyrene control tubes. However, further studies are needed to determine their behaviour under clinical conditions. PMID:8263676

  10. Evidence for photo-induced charge separation between dye molecules adsorbed to aluminium oxide surfaces

    PubMed Central

    Cappel, Ute B.; Moia, Davide; Bruno, Annalisa; Vaissier, Valerie; Haque, Saif A.; Barnes, Piers R. F.

    2016-01-01

    Excited state dynamics and photo-induced charge transfer of dye molecules have been widely studied due to their relevance for organic and dye-sensitised solar cells. Herein, we present a femtosecond transient absorption spectroscopy study of the indolene dye D131 when adsorbed to inert Al2O3 substrates for different surface concentration of the dye. Surprisingly, we find that at high surface concentrations, the first singlet excited state of the dye is converted into a new state with an efficiency of about 80%. We assign the absorption features of this state to the oxidised dye and discuss the possibility of photo-induced charge separation between neighboring dye molecules. Our study is the first to show that this process can be highly efficient without the use of donor and acceptor molecules of different chemical structures. PMID:26891851

  11. Homeotropic orientation of a nematic liquid crystal by bent-core molecules adsorbed on its surface

    NASA Astrophysics Data System (ADS)

    Hwang, Jiyong; Yang, Seungbin; Lee, Hyojin; Kim, Jongyoon; Lee, Ji-Hoon; Kang, Shin-Woong; Choi, E.-Joon

    2015-06-01

    We reported the promotion of a homeotropic alignment of a nematic liquid crystal (NLC) by bent-core liquid-crystal (BLC) Molecules adsorbed its surface. The BLC was mixed at various concentrations with the NLC, and the mixtures were injected into an empty cell with a cell gap of 13 μm. Although the pure NLC showed a heterogeneous orientation, the BLC-NLC mixture was gradually transformed to a homeotropic alignment with increasing concentration of the BLC. We investigated the surface topography of the samples by using an atomic force microscopy (AFM) and found that the BLC molecules were segregated into a polyimide (PI) surface and formed protrusion domains with diameters of 50-100 nm. The BLC protrusions might promote the homeotropic orientation of the NLC molecules.

  12. Ultra-sensitive fluorescence spectroscopy of isolated surface-adsorbed molecules using an optical nanofiber.

    PubMed

    Stiebeiner, A; Rehband, O; Garcia-Fernandez, R; Rauschenbeutel, A

    2009-11-23

    The strong radial confinement and the pronounced evanescent field of the guided light in optical nanofibers yield favorable conditions for ultra-sensitive surface spectroscopy of molecules deposited on the fiber. Using the guided mode of the nanofiber for both excitation and fluorescence collection, we present spectroscopic measurements on 3,4,9,10-perylenetetracarboxylic dianhydride molecules (PTCDA) at ambient conditions. Surface coverages as small as 1 per thousand of a compact monolayer still give rise to fluorescence spectra with a good signal to noise ratio. Moreover, we analyze and quantify the self-absorption effects due to reabsorption of the emitted fluorescence light by circumjacent surface-adsorbed molecules distributed along the fiber waist. PMID:19997412

  13. Evidence for photo-induced charge separation between dye molecules adsorbed to aluminium oxide surfaces

    NASA Astrophysics Data System (ADS)

    Cappel, Ute B.; Moia, Davide; Bruno, Annalisa; Vaissier, Valerie; Haque, Saif A.; Barnes, Piers R. F.

    2016-02-01

    Excited state dynamics and photo-induced charge transfer of dye molecules have been widely studied due to their relevance for organic and dye-sensitised solar cells. Herein, we present a femtosecond transient absorption spectroscopy study of the indolene dye D131 when adsorbed to inert Al2O3 substrates for different surface concentration of the dye. Surprisingly, we find that at high surface concentrations, the first singlet excited state of the dye is converted into a new state with an efficiency of about 80%. We assign the absorption features of this state to the oxidised dye and discuss the possibility of photo-induced charge separation between neighboring dye molecules. Our study is the first to show that this process can be highly efficient without the use of donor and acceptor molecules of different chemical structures.

  14. Structure of water adsorbed on a mica surface

    SciTech Connect

    Park, Sung-Ho; Sposito, Garrison

    2002-01-29

    Monte Carlo simulations of hydration water on the mica (001) surface under ambient conditions revealed water molecules bound closely to the ditrigonal cavities in the surface, with a lateral distribution of approximately one per cavity, and water molecules interposed between K{sup +} counter ions in a layer situated about 2.5 {angstrom} from a surface O along a direction normal to the (001) plane. The calculated water O density profile was in quantitative agreement with recent X-ray reflectivity measurements indicating strong lateral ordering of the hydration water but liquid-like disorder otherwise.

  15. Structure formation in adsorbed overlayers comprising functional cross-shaped molecules: A Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Kasperski, Adam; Nieckarz, Damian; Szabelski, Paweł

    2015-11-01

    Surface confined self-assembly of functional star-shaped organic molecules is a promising method to create nanoporous networks with tailorable structure and functions. In this work we use the Monte Carlo simulation method to demonstrate how the morphology of these supramolecular assemblies can be tuned by manipulating intrinsic parameters of the building blocks and modified by the presence of co-adsorbed metal atoms. To that purpose we study the 2D self-assembly of planar cruciform molecules modeled as collections of interconnected segments, some of which were activated to represent discrete interaction centers. We consider a few exemplary adsorbed systems in which the molecules with different size, aspect ratio and intramolecular distribution of active centers form superstructures stabilized by short-range segment-segment interactions or by metal-segment interactions. These two situations correspond to supramolecular assemblies sustained by, for example, hydrogen bonding and metal-organic ligand coordination, respectively. The simulated results show that proper encoding of intramolecular interactions into the cruciform building bricks allows for directing the self-assembly towards largely diversified structures ranging from nanoclusters to porous grids. The obtained findings can facilitate designing and optimization of molecular networks comprising cross-shaped units including functionalized porphyrins and phthalocyanines and they can be helpful in preliminary selection of these building blocks.

  16. Adsorption of prototypical amino acids on silica: Influence of the pre-adsorbed water multilayer

    NASA Astrophysics Data System (ADS)

    Remesal, Elena R.; Amaya, Javier; Graciani, Jesús; Márquez, Antonio M.; Sanz, Javier Fdez.

    2016-04-01

    We explore the interaction between acetic acid, some typical α-amino acids (α-AAs), and a fully hydroxylated (0001) surface of α-quartz by means of theoretical calculations based on the density functional theory (DFT) under periodic boundary conditions. The influence of microsolvation, represented by a water multilayer, and dispersion forces is analyzed. All the considered molecules strongly adsorb on the hydroxylated surface and prefer to adsorb molecularly. The inclusion of dispersion forces increases the interaction energies by 15-30 kJ/mol, without significant changes in structure and mode of adsorption except for histidine where the interaction is improved through protonation of the α-amine group. When the water multilayer is included a decrease in the surface-adsorbate interaction energies is observed. Also, some α-AAs, glycine and alanine, change their adsorption mode and, now, the more stable structure is the zwitterion. Adsorption as zwitterions is always favored with respect to molecular interaction when dispersion forces are taken into account. Comparing the energies of adsorbed and solvated α-AA zwitterions, it turns out that inclusion of dispersion forces predicts that solvated zwitterions are the lower energy configurations.

  17. Aging of the nanosized photochromic WO3 films and the role of adsorbed water in the photochromism

    NASA Astrophysics Data System (ADS)

    Gavrilyuk, A. I.

    2016-02-01

    Here it has been reported on aging of the nanosized WO3 film, which is revealed is continuous reduction of the photochromic sensitivity over time. Water molecules physically adsorbed on the film surface from ambient air form donor-acceptor and hydrogen bonds, changing gradually the adsorption state to chemisorption which prevents an access of organic molecules that serve as hydrogen donors by the photochromism. The mechanism of the process has been investigated and discussed. The role of water in the photochromism has been highlighted. The difference in the efficiency for being of a hydrogen donor in the photochromic process between water and organic molecules is discussed.

  18. Thermal and Electronic Fluctuations of Flexible Adsorbed Molecules: Azobenzene on Ag(111)

    NASA Astrophysics Data System (ADS)

    Maurer, Reinhard J.; Liu, Wei; Poltavsky, Igor; Stecher, Thomas; Oberhofer, Harald; Reuter, Karsten; Tkatchenko, Alexandre

    2016-04-01

    We investigate the thermal and electronic collective fluctuations that contribute to the finite-temperature adsorption properties of flexible adsorbates on surfaces on the example of the molecular switch azobenzene C12 H10 N2 on the Ag(111) surface. Using first-principles molecular dynamics simulations, we obtain the free energy of adsorption that accurately accounts for entropic contributions, whereas the inclusion of many-body dispersion interactions accounts for the electronic correlations that govern the adsorbate binding. We find the adsorbate properties to be strongly entropy driven, as can be judged by a kinetic molecular desorption prefactor of 1024 s-1 that largely exceeds previously reported estimates. We relate this effect to sizable fluctuations across structural and electronic observables. A comparison of our calculations to temperature-programed desorption measurements demonstrates that finite-temperature effects play a dominant role for flexible molecules in contact with polarizable surfaces, and that recently developed first-principles methods offer an optimal tool to reveal novel collective behavior in such complex systems.

  19. Thermal and Electronic Fluctuations of Flexible Adsorbed Molecules: Azobenzene on Ag(111).

    PubMed

    Maurer, Reinhard J; Liu, Wei; Poltavsky, Igor; Stecher, Thomas; Oberhofer, Harald; Reuter, Karsten; Tkatchenko, Alexandre

    2016-04-01

    We investigate the thermal and electronic collective fluctuations that contribute to the finite-temperature adsorption properties of flexible adsorbates on surfaces on the example of the molecular switch azobenzene C_{12}H_{10}N_{2} on the Ag(111) surface. Using first-principles molecular dynamics simulations, we obtain the free energy of adsorption that accurately accounts for entropic contributions, whereas the inclusion of many-body dispersion interactions accounts for the electronic correlations that govern the adsorbate binding. We find the adsorbate properties to be strongly entropy driven, as can be judged by a kinetic molecular desorption prefactor of 10^{24}  s^{-1} that largely exceeds previously reported estimates. We relate this effect to sizable fluctuations across structural and electronic observables. A comparison of our calculations to temperature-programed desorption measurements demonstrates that finite-temperature effects play a dominant role for flexible molecules in contact with polarizable surfaces, and that recently developed first-principles methods offer an optimal tool to reveal novel collective behavior in such complex systems. PMID:27104719

  20. Alignment and assembly of adsorbed collagen molecules induced by anisotropic chemical nanopatterns.

    PubMed

    Denis, Frédéric A; Pallandre, Antoine; Nysten, Bernard; Jonas, Alain M; Dupont-Gillain, Christine C

    2005-10-01

    Collagen, a protein widely used to control cell-material interactions, is known to self-assemble in solution. Supramolecular structures also form on material surfaces following collagen adsorption. Herein, we report the use of anisotropic, flat, surface chemical nanopatterns, which consist of alkyl-terminated tracks drawn in an oligo(ethylene glycol)-terminated matrix, to direct collagen adsorption. As revealed by atomic force microscopy, the spontaneous collagen adsorption performed on such patterned substrates results in the accumulation of collagen on the hydrophobic tracks. Moreover, the width of the tracks (30-90 nm), which is much smaller than the length of the collagen molecule (approximately 300 nm), is the origin of preferential alignment of the molecules and of their assembly into continuous bundles of adsorbed collagen. This chemical guidance effect due to self-confinement of proteins upon adsorption may bring novel and valuable applications, specifically in biomaterials science and cell growth control. PMID:17193383

  1. Molecular resonant dissociation of surface-adsorbed molecules by plasmonic nanoscissors

    NASA Astrophysics Data System (ADS)

    Zhang, Zhenglong; Sheng, Shaoxiang; Zheng, Hairong; Xu, Hongxing; Sun, Mengtao

    2014-04-01

    The ability to break individual bonds or specific modes in chemical reactions is an ardently sought goal by chemists and physicists. While photochemistry based methodologies are very successful in controlling e.g. photocatalysis, photosynthesis and the degradation of plastic, it is hard to break individual molecular bonds for those molecules adsorbed on the surface because of the weak light-absorption in molecules and the redistribution of the resulting vibrational energy both inside the molecule and to its surrounding environment. Here we show how to overcome these obstacles with a plasmonic hot-electron mediated process and demonstrate a new method that allows the sensitive control of resonant dissociation of surface-adsorbed molecules by `plasmonic' scissors. To that end, we used a high-vacuum tip-enhanced Raman spectroscopy (HV-TERS) setup to dissociate resonantly excited NC2H6 fragments from Malachite green. The surface plasmons (SPs) excited at the sharp metal tip not only enhance the local electric field to harvest the light incident from the laser, but crucially supply `hot electrons' whose energy can be transferred to individual bonds. These processes are resonant Raman, which result in some active chemical bonds and then weaken these bonds, followed by dumping in lots of indiscriminant energy and breaking the weakest bond. The method allows for sensitive control of both the rate and probability of dissociation through their dependence on the density of hot electrons, which can be manipulated by tuning the laser intensity or tunneling current/bias voltage in the HV-TERS setup, respectively. The concepts of plasmonic scissors open up new versatile avenues for the deep understanding of in situ surface-catalyzed chemistry.The ability to break individual bonds or specific modes in chemical reactions is an ardently sought goal by chemists and physicists. While photochemistry based methodologies are very successful in controlling e.g. photocatalysis

  2. Water adsorbate influence on the Cu(110) surface optical response

    NASA Astrophysics Data System (ADS)

    Baghbanpourasl, Amirreza; Schmidt, Wolf Gero; Denk, Mariella; Cobet, Christoph; Hohage, Michael; Zeppenfeld, Peter; Hingerl, Kurt

    2015-11-01

    Surface reflectance anisotropy may be utilized for characterizing surfaces, interfaces, and adsorption structures. Here, the reflectance anisotropy and surface dielectric functions of the thermodynamically most favored water adsorbate structures on the Cu(110) surface (i.e. hexagonal bilayers, pentagonal chains, and partially dissociated water structures) are calculated from density-functional theory and compared with recent experimental data. It is shown that the water overlayer structures modify in a geometry-specific way the optical anisotropy of the bare surface which can be exploited for in situ determination of the adsorption structures. For hexagonal bilayer overlayer geometries, strong features in the vacuum ultraviolet region are predicted. The theoretical analysis shows a noticeable influence of intraband transitions also for higher photon energies and rather slight influences of the van der Waals interaction on the spectral signatures. Water induced strain effects on the surface optical response are found to be negligible.

  3. Utility of adsorbents in the purification of drinking water: a review of characterization, efficiency and safety evaluation of various adsorbents.

    PubMed

    Dubey, Shashi Prabha; Gopal, Krishna; Bersillon, J L

    2009-05-01

    Clean drinking water is one of the implicit requisites fora healthy human population. However the growing industrialization and extensive use of chemicals for various concerns, has increased the burden of unwanted pollutants in the drinking water of developing countries like India. The entry of potentially hazardous substances into the biota has been magnifying day by day. In the absence of a possible stoppage of these, otherwise, useful chemicals, the only way to maintain safer water bodies is to develop efficient purifying technologies. One such immensely beneficial procedure that has been in use is that of purification of water using 'adsorbents'. Indigenous minerals and natural plants products have potential for removing many pollutants viz. fluoride, arsenic, nitrate, heavy metals, pesticides as well as trihalomethanes. Adsorbents which are derived from carbon, alumina, zeolite, clay minerals, iron ores, industrial by products, and natural products viz. parts of the plants, herbs and algal biomass offer promising potential of removal. In the recent years attention has been paid to develop process involving screening/pretreatment/activation/impregnation using alkalies, acids, alum, lime, manganese dioxide, ferric chloride and other chemicals which are found to enhance their adsorbing efficiency. Chemical characterization of these adsorbents recapitulates the mechanism of the process. It is imperative to observe that capacities of the adsorbents may vary depending on the characteristics, chemical modifications and concentration of the individual adsorbent. Removal kinetics is found to be based on the experimental conditions viz. pH, concentration of the adsorbate, quantity of the adsorbent and temperature. It is suggested that isotherm model is suitable tool to assess the adsorption capacities in batch and column modes. Safety evaluation and risk assessment of the process/products may be useful to provide guidelines for its sustainable disposal. PMID:20120453

  4. Water molecules orientation in surface layer

    NASA Astrophysics Data System (ADS)

    Klingo, V. V.

    2000-08-01

    The water molecules orientation has been investigated theoretically in the water surface layer. The surface molecule orientation is determined by the direction of a molecule dipole moment in relation to outward normal to the water surface. Entropy expressions of the superficial molecules in statistical meaning and from thermodynamical approach to a liquid surface tension have been found. The molecules share directed opposite to the outward normal that is hydrogen protons inside is equal 51.6%. 48.4% water molecules are directed along to surface outward normal that is by oxygen inside. A potential jump at the water surface layer amounts about 0.2 volts.

  5. Titanate-based adsorbents for radioactive ions entrapment from water.

    PubMed

    Yang, Dongjiang; Liu, Hongwei; Zheng, Zhanfeng; Sarina, Sarina; Zhu, Huaiyong

    2013-03-21

    This feature article reviews some titanate-based adsorbents for the removal of radioactive wastes (cations and anions) from water. At the beginning, we discuss the development of the conventional ion-exchangeable titanate powders for the entrapment of radioactive cations, such as crystalline silicotitanate (CST), monosodium titanate (MST), peroxotitanate (PT). Then, we specially emphasize the recent progress in the uptake of radioactive ions by one-dimensional (1D) sodium titanate nanofibers and nanotubes, which includes the synthesis and phase transformation of the 1D nanomaterials, adsorption ability (capacity, selectivity, kinetics, etc.) of radioactive cations and anions, and the structural evolution during the adsorption process. PMID:23412572

  6. Mechanism of charge transfer and its impacts on Fermi-level pinning for gas molecules adsorbed on monolayer WS2.

    PubMed

    Zhou, Changjie; Yang, Weihuang; Zhu, Huili

    2015-06-01

    Density functional theory calculations were performed to assess changes in the geometric and electronic structures of monolayer WS2 upon adsorption of various gas molecules (H2, O2, H2O, NH3, NO, NO2, and CO). The most stable configuration of the adsorbed molecules, the adsorption energy, and the degree of charge transfer between adsorbate and substrate were determined. All evaluated molecules were physisorbed on monolayer WS2 with a low degree of charge transfer and accept charge from the monolayer, except for NH3, which is a charge donor. Band structure calculations showed that the valence and conduction bands of monolayer WS2 are not significantly altered upon adsorption of H2, H2O, NH3, and CO, whereas the lowest unoccupied molecular orbitals of O2, NO, and NO2 are pinned around the Fermi-level when these molecules are adsorbed on monolayer WS2. The phenomenon of Fermi-level pinning was discussed in light of the traditional and orbital mixing charge transfer theories. The impacts of the charge transfer mechanism on Fermi-level pinning were confirmed for the gas molecules adsorbed on monolayer WS2. The proposed mechanism governing Fermi-level pinning is applicable to the systems of adsorbates on recently developed two-dimensional materials, such as graphene and transition metal dichalcogenides. PMID:26049513

  7. Adsorbed water and thin liquid films on Mars

    NASA Astrophysics Data System (ADS)

    Boxe, C. S.; Hand, K. P.; Nealson, K. H.; Yung, Y. L.; Yen, A. S.; Saiz-Lopez, A.

    2012-07-01

    At present, bulk liquid water on the surface and near-subsurface of Mars does not exist due to the scarcity of condensed- and gas-phase water, pressure and temperature constraints. Given that the nuclei of soil and ice, that is, the soil solid and ice lattice, respectively, are coated with adsorbed and/or thin liquid films of water well below 273 K and the availability of water limits biological activity, we quantify lower and upper limits for the thickness of such adsorbed/water films on the surface of the Martian regolith and for subsurface ice. These limits were calculated based on experimental and theoretical data for pure water ice and water ice containing impurities, where water ice containing impurities exhibit thin liquid film enhancements, ranging from 3 to 90. Close to the cold limit of water stability (i.e. 273 K), thin liquid film thicknesses at the surface of the Martian regolith is 0.06 nm (pure water ice) and ranges from 0.2 to 5 nm (water ice with impurities). An adsorbed water layer of 0.06 nm implies a dessicated surface as the thickness of one monolayer of water is 0.3 nm but represents 0.001-0.02% of the Martian atmospheric water vapour inventory. Taking into account the specific surface area (SSA) of surface-soil (i.e. top 1 mm of regolith and 0.06 nm adsorbed water layer), shows Martian surface-soil may contain interfacial water that represents 6-66% of the upper- and lower-limit atmospheric water vapour inventory and almost four times and 33%, the lower- and upper-limit Martian atmospheric water vapour inventory. Similarly, taking the SSA of Martian soil, the top 1 mm or regolith at 5 nm thin liquid water thickness, yields 1.10×1013 and 6.50×1013 litres of waters, respectively, 55-325 times larger than Mars' atmospheric water vapour inventory. Film thicknesses of 0.2 and 5 nm represent 2.3×104-1.5×106 litres of water, which is 6.0×10-7-4.0×10-4%, respectively, of a 10 pr μm water vapour column, and 3.0×10-6-4.0×10-4% and 6.0×10

  8. Single-Molecule Magnets: Giant Hysteresis of Single-Molecule Magnets Adsorbed on a Nonmagnetic Insulator (Adv. Mater. 26/2016).

    PubMed

    Wäckerlin, Christian; Donati, Fabio; Singha, Aparajita; Baltic, Romana; Rusponi, Stefano; Diller, Katharina; Patthey, François; Pivetta, Marina; Lan, Yanhua; Klyatskaya, Svetlana; Ruben, Mario; Brune, Harald; Dreiser, Jan

    2016-07-01

    In Tb(Pc)2 single-molecule magnets, where Pc is phthalocyanine, adsorbed on magnesium oxide, the fluctuations of the terbium magnetic moment are strongly suppressed in contrast to the adsorption on silver. On page 5195, J. Dreiser and co-workers investigate that the molecules are perfectly organized by self-assembly, as seen in the scanning tunnelling microscopy image (top part of the design). The molecules are probed by circularly polarized X-rays depicted as green spirals. PMID:27383020

  9. Density-functional theory study of interactions between water and carbon monoxide adsorbed on platinum under electrochemical conditions

    NASA Astrophysics Data System (ADS)

    Santana, Juan A.; Ishikawa, Yasuyuki

    2009-08-01

    In the study of CO poisoning of the platinum-based hydrogen anode in the polymer electrolyte fuel cell, a key issue that has eluded our understanding is the interactions of CO adsorbed on Pt surfaces and solvent H 2O. Our density-functional theory calculations reveal a new interpretation of the adsorbed state of CO and its interaction with water under electrochemical conditions, which rationalizes the observed quantitative relationship between infrared intensities for adsorbed bridging CO (bridge) and water exhibiting a high-frequency O-H stretch (ca. 3650 cm -1). The theoretical modeling indicates that the observed feature is due to a water molecule firmly hydrogen-bonded to CO (bridge).

  10. Imaging the wave functions of adsorbed molecules using angle-resolved photoemmision data

    NASA Astrophysics Data System (ADS)

    Lüftner, Daniel; Ules, Thomas; Reinisch, Eva Maria; Koller, Georg; Soubatch, Serguei; Tautz, F. Stefan; Ramsey, Michael G.; Puschnig, Peter

    2014-03-01

    The frontier electronic orbitals of molecules are the prime determinants of the respective compounds' chemical, electronic, and optical properties. Although orbitals are very powerful concepts, experimentally only the electron densities and energy levels are directly observable. As has been shown in recent publications, angle-resolved photoemission (ARPES) intensity maps of organic molecular layers are related to the absolute value of the Fourier transform of the initial state molecular orbital. However, the lost phase information impedes the back-transformation of the orbital into real space. Here, we show how molecular orbital images as well as the absent phase information can be retrieved by applying an iterative procedure which takes experimental ARPES maps as input and only assumes spatial confinement of the orbital. The method is demonstrated for several molecular orbitals of two proto-typical pi-conjugated molecules: the LUMO, HOMO, and HOMO-1 of pentacene, and the LUMO and HOMO of PTCDA. The technique is simple and robust and further emphasizes the capabilities of ARPES looking at spatial distributions of wave functions of adsorbed molecules thereby complementing data obtained from scanning probe methods.

  11. Room temperature differential conductance measurements of triethylamine molecules adsorbed on Si(001).

    PubMed

    Naitabdi, Ahmed; Rochet, François; Carniato, Stéphane; Bournel, Fabrice; Gallet, Jean-Jacques

    2016-08-17

    We have measured the differential conductance of the triethylamine molecule (N(CH2CH3)3) adsorbed on Si(001)-2 × 1 at room temperature using scanning tunneling spectroscopy. Triethylamine can be engaged in a dative bonding with a silicon dimer, forming a Si-Si-N(CH2CH3)3 unit. We have examined the datively bonded adduct, either as an isolated molecule, or within an ordered molecular domain (reconstructed 4 × 2). The differential conductance curves, supported by DFT calculations, show that in the explored energy window (±2.5 near the Fermi level) the main features stem from the uncapped dangling bonds of the reacted dimer and of the adjacent unreacted ones that are electronically coupled The formation of a molecular domain, in which one dimer in two is left unreacted, is reflected in a shift of the up dimer atom occupied level away from the Fermi level, likely due to an increased π-bonding strength. In stark contrast with the preceding, pairs of dissociated molecule (a minority species) are electronically decoupled from the dimer dangling bond states. DFT calculation show that the lone-pair of the Si-N(CH2CH3)2 is a shallow level, that is clearly seen in the differential conductance curve. PMID:27499070

  12. Effect of resonance dipole-dipole interaction on spectra of adsorbed SF6 molecules.

    PubMed

    Dobrotvorskaia, Anna N; Kolomiitsova, Tatiana D; Petrov, Sergey N; Shchepkin, Dmitriy N; Smirnov, Konstantin S; Tsyganenko, Alexey A

    2015-09-01

    Adsorption of SF6 on zinc oxide and on silicalite-1 was investigated by a combination of IR spectroscopy with the calculations of spectra by means of a modernized model, developed previously for liquids. Comparison of the experimental spectra and the results of modeling shows that the complex band shapes in spectra of adsorbed molecules with extremely high absorbance are due to the strong resonance dipole-dipole interaction (RDDI) rather that the surface heterogeneity or the presence of specific surface sites. Perfect agreement between calculated and observed spectra was found for ZnO, while some dissimilarity in band intensities for silicalite-1 was attributed to complicated geometry of molecular arrangement in the channels. PMID:25897721

  13. Removal of acutely hazardous pharmaceuticals from water using multi-template imprinted polymer adsorbent.

    PubMed

    Venkatesh, Avinash; Chopra, Nikita; Krupadam, Reddithota J

    2014-05-01

    Molecularly imprinted polymer adsorbent has been prepared to remove a group of recalcitrant and acutely hazardous (p-type) chemicals from water and wastewaters. The polymer adsorbent exhibited twofold higher adsorption capacity than the commercially used polystyrene divinylbenzene resin (XAD) and powdered activated carbon adsorbents. Higher adsorption capacity of the polymer adsorbent was explained on the basis of high specific surface area formed during molecular imprinting process. Freundlich isotherms drawn showed that the adsorption of p-type chemicals onto polymer adsorbent was kinetically faster than the other reference adsorbents. Matrix effect on adsorption of p-type chemicals was minimal, and also polymer adsorbent was amenable to regeneration by washing with water/methanol (3:1, v/v) solution. The polymer adsorbent was unaltered in its adsorption capacity up to 10 cycles of adsorption and desorption, which will be more desirable in cost reduction of treatment compared with single-time-use activated carbon. PMID:24499987

  14. Poliovirus concentration from tap water with electropositive adsorbent filters.

    PubMed

    Sobsey, M D; Glass, J S

    1980-08-01

    Simple, reliable, and efficient concentration of poliovirus from tap water was obtained with two types of electropositive filter media, one of which is available in the form of a pleated cartridge filter (Virozorb 1MDS). Virus adsorption from tap water between pH 3.5 and 7.5 was more efficient with electropositive filters than with Filterite filters. Elution of adsorbed viruses was more efficient with beef extract in glycine, pH 9.5, than with glycine-NaOH, pH 11.0. In paired comparative studies, electropositive filters, with adsorption at pH 7.5 and no added polyvalent cation salts, gave less variable virus concentration efficiencies than did Filterite filters with adsorption at pH 3.5 plus added MgCl2. Recovery of poliovirus from 1,000-liter tap water volumes was approximately 30% efficient with both Virozorb 1MDS and Filterite pleated cartridge filters, but the former were much simpler to use. The virus adsorption behavior of these filters appears to be related to their surface charge properties, with more electropositive filters giving more efficient virus adsorption from tap water at higher pH levels. PMID:6258472

  15. Design of water molecule and its surrounding

    NASA Astrophysics Data System (ADS)

    Danylo, R. I.; Okhrimenko, B. A.; Yablochkova, K. S.

    2015-02-01

    Hydrogen bonds and their fluctuations are one of the factors that determine the unique properties of water [1]. Building models of formation and rupture of hydrogen bonds due to non-eigen vibrations of a molecule of water is to a large extent determined by the availability of accurate information on the geometric structure of the water molecule. Geometric parameters of the water molecule have been well studied for the gaseous state. This was aided by the possibility of an experimental study of the regularities in the rotational spectra of molecules. However, some questions about the geometry of the water molecule in the liquid state remain unanswered. For example, many sources state that the valence angle of the water molecule decreases during the transition into the liquid state [2]. Based on the experimental data of molecular vibration spectra in D2O and H2O molecules [3], the authors have estimated valence angle of water in the liquid state. Consequently, the value of the valence angle of water in liquid state was determined to be (89 +/-2)°. A question of determination of libration vibrations of water molecule, as well as the analysis of its consequent inversion doubling, based on the new information on the equilibrium angle of the water molecules in the liquid state, constitutes an interest and is discussed in the present paper.

  16. Electronic structure and binding geometry of tetraphenylporphyrin-derived molecules adsorbed on metal and metal oxide surfaces

    NASA Astrophysics Data System (ADS)

    Coh, Senia

    Tetraphenylporphyrin (TPP)-derived molecules have been studied extensively as efficient photosensitizers when chemisorbed on the metal oxide substrates in dye-sensitized solar cells. Still, many fundamental electronic properties of the dye/oxide interface are not understood and need careful consideration. In this thesis we present a comprehensive study of the electronic structure, energy level alignment and the adsorption geometry of the TPP-derived dye molecules adsorbed on TiO2(110), ZnO(1120) and Ag(100) single crystal surfaces using ultra-high vacuum (UHV) based surface sensitive techniques. The alignment of the molecular energy levels with respect to the TiO 2 and ZnO band edges for all TPP-derived molecules we studied was found to be insensitive to either the nature of the functional groups located on the phenyl rings, presence of zinc as a central metal ion and different binding geometry of the molecules. Binding geometry, molecule-molecule interaction and the aggregation effects in the adsorbed layer, that were observed in the UV-visible spectra of the molecules adsorbed on ZnO substrate were not observed in the ultraviolet photoemission (UPS) and inverse photoemission (IPS) spectra of the occupied and unoccupied molecular states. Using near edge X-ray absorption fine structure (NEXAFS) and scanning tunneling microscopy (STM), binding geometry of the two representative TPP-derivatives was directly determined to be upright, with the porphyrin ring under large angle with respect to the surface for the p-ZnTCPP molecules and with the porphyrin ring parallel to the surface for the m-ZnTCPP molecules. We observe that the energies and the energy level alignment of the ZnTPP molecular levels measured in UPS and IPS depend on the substrate on which the molecules are adsorbed (Ag(100) or TiO2(110) single crystal surfaces). The differences are attributed to different charge screening properties of these two materials. Image charges created in the substrates during

  17. The analysis of surface-adsorbed organic molecules by alkali-assisted MIES combined with UPS(He I)

    NASA Astrophysics Data System (ADS)

    Günster, J.; Ochs, D.; Dieckhoff, S.; Kempter, V.

    1996-12-01

    Metastable impact electron spectroscopy (MIES) in combination with UPS(He I) is applied to the study of s-triazine and triethoxytriazine molecules adsorbed on Si(100) either alone or in combination with cesium atoms. It is demonstrated that the presence of the Cs atoms facilitates the identification of the adsorbed species considerably. It is concluded that (i) non-dissociative adsorption of the studied organic molecules occurs whereby the basal rings of the molecules lie flat on the silicon surface, in accordance with previous studies by Bu and Lin, (ii) the binding of the molecules to the surface is mainly via the lone pair orbitals of the nitrogen in the ring, and (iii) s-triazine reacts strongly with oxygen which bonds to the carbon atoms of the triazine ring.

  18. Barriers to intramolecular rotation determined from the temperature dependence of the Henry constant in the region of adsorbed molecule rigidity failure

    NASA Astrophysics Data System (ADS)

    Dolgonosov, A. M.; Prudkovskii, A. G.

    2008-05-01

    A distribution for the rigid and nonrigid adsorbed molecule forms was found. Adsorbed molecule rigidity failure was shown to be accompanied by a weak nonlinear effect, which manifested itself as a temperature dependence of the Henry constant. A method for the determination of the barrier to intramolecular rotation from the temperature dependence of the molecule adsorption constant was suggested. Barriers to rotation about the C-C and C-O bonds were determined for several molecules.

  19. The effects of framework dynamics on the behavior of water adsorbed in the [Zn(l-L)(Cl)] and Co-MOF-74 metal-organic frameworks.

    PubMed

    Terranova, Zachary L; Paesani, Francesco

    2016-03-21

    The effects of framework flexibility on the structural and dynamical properties of water adsorbed in two prototypical metal-organic frameworks are investigated through molecular dynamics simulations. It is found that water molecules in the pores of a flexible model of [Zn(l-L)(Cl)] exhibit slower dynamics than when the framework is artificially held rigid in the simulations. In contrast, the water dynamics in Co-MOF-74 is predicted to be accelerated by the framework vibrations. The origin of this different behavior directly relates to how water interacts with the two frameworks, which, in turn, determines different hydrogen-bond patterns in the pores. While the first water molecules adsorbed in [Zn(l-L)(Cl)] donate a single hydrogen bond to the Zn-Cl groups and point the other hydrogen atom towards the center of the pore, water molecules adsorbed in Co-MOF-74 initially bind to the cobalt atoms of the framework via their oxygen atoms, thus leaving each molecule free to form two hydrogen bonds with additional molecules adsorbed at higher loading. The simulation results indicate that taking into account the framework flexibility in computer simulations is necessary for a quantitative modeling of adsorption and transport processes in metal-organic frameworks. PMID:26928975

  20. Direct comparison of the electronic coupling efficiency of sulfur and selenium alligator clips for molecules adsorbed onto gold electrodes

    NASA Astrophysics Data System (ADS)

    Patrone, L.; Palacin, S.; Bourgoin, J. P.

    2003-05-01

    Scanning tunneling microscopy experiments have been performed to compare the electronic coupling provided by S and by Se used as alligator clips for bisthiol- and biselenol-terthiophene molecules adsorbed onto gold. The molecules were inserted in a dodecanethiol (DT) self-assembled monolayer. Their apparent height above the dodecanethiol matrix was used as a measure of the electronic coupling strength corresponding to S and Se, respectively. We show that the insertion behaviors of the two molecules are qualitatively the same, and that Se provides systematically a better coupling link than S, whatever the tunneling conditions.

  1. Direct comparison of the electronic coupling efficiency of sulfur and selenium anchoring groups for molecules adsorbed onto gold electrodes

    NASA Astrophysics Data System (ADS)

    Patrone, L.; Palacin, S.; Bourgoin, J. P.; Lagoute, J.; Zambelli, T.; Gauthier, S.

    2002-08-01

    We performed air and ultra-high vacuum scanning tunneling microscopy experiments in order to compare the electronic coupling provided by S and by Se used as alligator clips for bisthiol- and biselenol-terthiophene molecules adsorbed onto gold. The molecules were inserted in a dodecanethiol self-assembled monolayer. Their apparent height above the dodecanethiol matrix was used as a measure of the electronic coupling strength corresponding to S and Se, respectively. We show that the insertion behaviors of the two molecules are qualitatively the same, and that Se provides systematically a better coupling link than S whatever the tunneling conditions.

  2. A slowing down of proton motion from HPTS to water adsorbed on the MCM-41 surface.

    PubMed

    Alarcos, Noemí; Cohen, Boiko; Douhal, Abderrazzak

    2016-01-28

    We report on the steady-state and femtosecond-nanosecond (fs-ns) behaviour of 8-hydroxypyrene-1,3,6-trisulfonate (pyranine, HPTS) and its interaction with mesoporous silica based materials (MCM-41) in both solid-state and dichloromethane (DCM) suspensions in the absence and presence of water. In the absence of water, HPTS forms aggregates which are characterized by a broad emission spectrum and multiexponential behavior (τsolid-state/DCM = 120 ps, 600 ps, 2.2 ns). Upon interaction with MCM41, the aggregate population is found to be lower, leading to the formation of adsorbed monomers. In the presence of water (1%), HPTS with and without MCM41 materials in DCM suspensions undergoes an excited-state intermolecular proton-transfer (ESPT) reaction in the protonated form (ROH*) producing a deprotonated species (RO(-)*). The long-time emission decays of the ROH* in different systems in the presence of water are multiexponential, and are analysed using the diffusion-assisted geminate recombination model. The obtained proton-transfer and recombination rate constants for HPTS and HPTS/MCM41 complexes in DCM suspensions in the presence of water are kPT = 13 ns(-1), krec = 7.5 Å ns(-1), and kPT = 5.4 ns(-1), krec = 2.2 Å ns(-1), respectively, The slowing down of both processes in the latter case is explained in terms of specific interactions of the dye and of the water molecules with the silica surface. The ultrafast dynamics (fs-regime) of the HPTS/MCM41 complexes in DCM suspensions, without and with water, shows two components which are assigned to intramolecular vibrational-energy relaxation (IVR) (∼120 fs vs. ∼0.8 ps), and vibrational relaxation/cooling (VC), and charge transfer (CT) processes (∼2 ps without water and ∼5 ps with water) of the adsorbed ROH*. Our results provide new knowledge on the interactions and the proton-transfer reaction dynamics of HPTS adsorbed on mesoporous materials. PMID:26705542

  3. Tunneling Spectroscopy Studies of Urea, Thiourea, and Selected Phosphonate Molecules Adsorbed on Aluminum Oxide

    NASA Astrophysics Data System (ADS)

    Crowder, Charles D.

    Experimental and calculated inelastic electron tunneling intensities were compared for several of the vibrational modes of thiourea adsorbed on aluminum oxide. The partial charge model of Kirtley, Scalapino, and Hansma was used to compute the theoretical intensities of each mode. The required partial charges were determined using a method developed by Momany. Essentially, the Coulomb potential resulting from point charges located at atom sites was fitted to the quantum mechanical electrostatic potential of a molecule calculated from Hartree-Fock theory. The effect of a vibrational mode pattern on the electrostatic potential of a molecule was investigated. This effect could not be acceptably modeled with a single point charge located on each atom, so one charge was used to represent the positive nucleus of each atom and a second charge was used to represent the valence cloud. The valence charge was allowed to move independently of the nuclear charge during a molecular vibration, and the motions of the two charges were found to be very different for hydrogen atoms. This model gave very reasonable agreement between the theoretical and observed relative intensities for the in plane vibrational modes of thiourea. An acceptable set of out of plane force constants could not be found. This caused problems in the interpretation of the out of plane relative intensities. Based on the in plane modes, it was concluded that thiourea bonded to aluminum oxide with the sulfur atom near the oxide and the sulfur-carbon bond perpendicular to the aluminum oxide surface. Quantum mechanical electrostatic potentials were also calculated for urea, phosphoric acid (PA), methylphosphonic acid (MPA), hydroxymethylphosphonic acid (HMP), and nitrotrismethylphosphonic acid (NTMP). Electron tunneling spectra were taken for PA, HMP and NTMP, and the observed frequencies were compared to values obtained from Fourier transform infrared, infrared and Raman spectroscopy. Upward shifts in the P=O and P

  4. Oil palm biomass-based adsorbents for the removal of water pollutants--a review.

    PubMed

    Ahmad, Tanweer; Rafatullah, Mohd; Ghazali, Arniza; Sulaiman, Othman; Hashim, Rokiah

    2011-07-01

    This article presents a review on the role of oil palm biomass (trunks, fronds, leaves, empty fruit bunches, shells, etc.) as adsorbents in the removal of water pollutants such as acid and basic dyes, heavy metals, phenolic compounds, various gaseous pollutants, and so on. Numerous studies on adsorption properties of various low-cost adsorbents, such as agricultural wastes and its based activated carbons, have been reported in recent years. Studies have shown that oil palm-based adsorbent, among the low-cost adsorbents mentioned, is the most promising adsorbent for removing water pollutants. Further, these bioadsorbents can be chemically modified for better efficiency and can undergo multiple reuses to enhance their applicability at an industrial scale. It is evident from a literature survey of more than 100 recent papers that low-cost adsorbents have demonstrated outstanding removal capabilities for various pollutants. The conclusion is been drawn from the reviewed literature, and suggestions for future research are proposed. PMID:21929380

  5. High physisorption affinity of water molecules to the hydroxylated aluminum oxide (001) surface.

    PubMed

    Kittaka, Shigeharu; Yamaguchi, Keisuke; Takahara, Shuichi

    2012-02-15

    The adsorption mechanism of water on the hydroxylated (001) plane of α-Al(2)O(3) was studied by measuring adsorption isotherms and GCMC simulations. The experimental adsorption isotherms for three α-Al(2)O(3) samples from different sources are typical type II, in which adsorption starts sharply at low pressures, suggesting a high affinity of water to the Al(2)O(3) surface. Water molecules are adsorbed in two registered forms (bilayer structure). In the first form, water is registered at the center of three surface hydroxyl groups by directing a proton of the water. In the second form, a water molecule is adsorbed by bridging two of the first-layer water molecules through hydrogen bonding, by which a hexagonal ring network is constructed over the hydroxylated surface. The network domains are spread over the surface, and their size decreases as the temperature increases. The simulated adsorption isotherms present a characteristic two-dimensional (2D) phase diagram including a 2D critical point at 365K, which is higher than that on the hydroxylated Cr(2)O(3) surface (319 K). This fact substantiates the high affinity of water molecules to the α-Al(2)O(3) surfaces, which enhances the adsorbability originating from higher heat of adsorption. The higher affinity of water molecules to the α-Al(2)O(3) (001) plane is ascribed to the high compatibility of the crystal plane to form a hexagonal ring network of (001) plane of ice Ih. PMID:22178567

  6. Effects of molecule-insulator interaction on geometric property of a single phthalocyanine molecule adsorbed on an ultrathin NaCl film

    NASA Astrophysics Data System (ADS)

    Miwa, Kuniyuki; Imada, Hiroshi; Kawahara, Shota; Kim, Yousoo

    2016-04-01

    The adsorption structure and orientation of a metal-free phthalocyanine (H2Pc ) and a magnesium phthalocyanine (MgPc) on a bilayer of NaCl films were investigated both theoretically and experimentally by means of first-principles calculations based on density functional theory and by scanning tunneling microscopy. H2Pc is adsorbed with its center over the sodium cation, and H-N bonds in the molecule are aligned with the [100] or [010] surface direction of a bilayer (001)-terminated NaCl film. The most stable structures of MgPc on the NaCl film show two kinds of orientations corresponding to the molecule rotated by ±7∘ relative to the [110] surface direction, with the Mg cation positioned over the chlorine anion in both cases. The energetic barrier for switching between these orientations is as low as 9.0 meV, and during an STM measurement, an orientational change of MgPc can be observed. The interaction between the adsorbed molecule and the NaCl film were analyzed in terms of dispersion interaction, Mg-Cl chemical bonding, and electrostatic interaction. It is found that the small electrostatic interaction between the molecule and the film gives a dominant contribution to determining the molecular orientation. Our detailed and comprehensive studies of the molecule-insulator interaction will provide knowledge to understand and control the properties of molecules on an insulating material.

  7. Modelling water molecules inside cyclic peptide nanotubes

    NASA Astrophysics Data System (ADS)

    Tiangtrong, Prangsai; Thamwattana, Ngamta; Baowan, Duangkamon

    2016-03-01

    Cyclic peptide nanotubes occur during the self-assembly process of cyclic peptides. Due to the ease of synthesis and ability to control the properties of outer surface and inner diameter by manipulating the functional side chains and the number of amino acids, cyclic peptide nanotubes have attracted much interest from many research areas. A potential application of peptide nanotubes is their use as artificial transmembrane channels for transporting ions, biomolecules and waters into cells. Here, we use the Lennard-Jones potential and a continuum approach to study the interaction of a water molecule in a cyclo[(- D-Ala- L-Ala)_4-] peptide nanotube. Assuming that each unit of a nanotube comprises an inner and an outer tube and that a water molecule is made up of a sphere of two hydrogen atoms uniformly distributed over its surface and a single oxygen atom at the centre, we determine analytically the interaction energy of the water molecule and the peptide nanotube. Using this energy, we find that, independent of the number of peptide units, the water molecule will be accepted inside the nanotube. Once inside the nanotube, we show that a water molecule prefers to be off-axis, closer to the surface of the inner nanotube. Furthermore, our study of two water molecules inside the peptide nanotube supports the finding that water molecules form an array of a 1-2-1-2 file inside peptide nanotubes. The theoretical study presented here can facilitate thorough understanding of the behaviour of water molecules inside peptide nanotubes for applications, such as artificial transmembrane channels.

  8. Removal of pesticides from water and wastewater by different adsorbents: a review.

    PubMed

    Ahmad, Tanweer; Rafatullah, Mohd; Ghazali, Arniza; Sulaiman, Othman; Hashim, Rokiah; Ahmad, Anees

    2010-10-01

    In this review article, the use of various low-cost adsorbents for the removal of pesticides from water and wastewater has been reviewed. Pesticides may appear as pollutants in water sources, having undesirable impacts to human health because of their toxicity, carcinogenicity, and mutagenicity or causing aesthetic problems such as taste and odors. These pesticides pollute the water stream and it can be removed very effectively using different low-cost adsorbents. It is evident from a literature survey of about 191 recently published papers that low-cost adsorbents have demonstrated outstanding removal capabilities for pesticides. PMID:21069614

  9. Characterization of Adsorbed Molecular Water on the Surface of a Stretched Polytetrafluoroethylene Tape Analyzed by (1)H NMR.

    PubMed

    Wakai, Chihiro; Shimoaka, Takafumi; Hasegawa, Takeshi

    2016-03-10

    A single molecule often exhibits a largely different material character from a bulk matter. Although a perfluoroalkyl (Rf) compound is a representative one, many interests have mostly been devoted to the bulk character only thus far, leaving the single molecular character unclear. Recently, a new theoretical framework, stratified dipole-arrays (SDA) theory, has appeared for comprehensive understanding of Rf compounds in terms of both single and bulk systems. On this theory, a mechanically stretched polytetrafluoroethylene (PTFE) is expected to exhibit a single-molecular character having dipole-driven properties, which should attract molecular water. In the present study, a stretched PTFE tape is revealed to attract molecular water (not water droplet) in fact, and the adsorbed water molecules are highly restricted in motion by the dipole-dipole interaction studied by using (1)H NMR, which agrees with the prediction by the SDA theory. PMID:26848611

  10. Charge transfer interactions of a Ru(II) dye complex and related ligand molecules adsorbed on Au(111)

    SciTech Connect

    Britton, Andrew J.; Weston, Matthew; O'Shea, James N.; Taylor, J. Ben; Rienzo, Anna; Mayor, Louise C.

    2011-10-28

    The interaction of the dye molecule, N3 (cis-bis(isothiocyanato)bis(2,2{sup '}-bipyridyl-4,4{sup '}-dicarboxylato) -ruthenium(II)), and related ligand molecules with a Au(111) surface has been studied using synchrotron radiation-based electron spectroscopy. Resonant photoemission spectroscopy (RPES) and autoionization of the adsorbed molecules have been used to probe the coupling between the molecules and the substrate. Evidence of charge transfer from the states near the Fermi level of the gold substrate into the lowest unoccupied molecular orbital (LUMO) of the molecules is found in the monolayer RPES spectra of both isonicotinic acid and bi-isonicotinic acid (a ligand of N3), but not for the N3 molecule itself. Calibrated x-ray absorption spectroscopy and valence band spectra of the monolayers reveals that the LUMO crosses the Fermi level of the surface in all cases, showing that charge transfer is energetically possible both from and to the molecule. A core-hole clock analysis of the resonant photoemission reveals a charge transfer time of around 4 fs from the LUMO of the N3 dye molecule to the surface. The lack of charge transfer in the opposite direction is understood in terms of the lack of spatial overlap between the {pi}*-orbitals in the aromatic rings of the bi-isonicotinic acid ligands of N3 and the gold surface.

  11. Thermodynamic properties of adsorbed water on silica gel - Exergy losses in adiabatic sorption processes

    NASA Astrophysics Data System (ADS)

    Worek, W. M.; Zengh, W.; San, J.-Y.

    1991-09-01

    In order to perform exergy analyses to optimize the transient heat and mass transfer processes involving sorption by solid adsorbents, the thermodynamic properties of adsorbed water must be determined. In this paper, the integral enthalpy and entropy are determined directly from isotherm data of water adsorbed on silica gel particles and silica gel manufactured in the form of a felt with 25 percent cotton as a support and Teflon as a binder. These results are then used to evaluate the exergy losses, due to the sorption and the convective heat and mass transfer processes, that occur in each portion of an adiabatic desiccant dehumidificaton cycle.

  12. The origin of the low efficiency of carbon removal from the Nickel/Yttrium-Stabilized Zirconia triple-phase boundary by adsorbed water

    NASA Astrophysics Data System (ADS)

    Zhang, Yanxing; Yang, Zongxian

    2015-04-01

    Carbon removal from the anode triple-phase boundary (TPB) of solid oxide fuel cells (SOFCs) by adsorbed water molecule was studied using the density functional calculations, and a detailed dynamic picture was presented. It is found that the adsorbed H2O molecule can dissociate easily at the Ni/YSZ interface and on the YSZ part compared with the Ni part and react with the interface carbon to form the CHO species. The dissociation process of CHO to CH and O is more favorable as compared with that of CHO to CO and H. The CH fragment can easily diffuse to the O vacancy formed in the dynamic reaction processes and dissociate into C and H, which regenerates carbon at the interface. This might be the main reasons for the low efficiency of carbon removal from the TPB of Ni/YSZ by adsorbed water.

  13. From single molecules to water networks: Dynamics of water adsorption on Pt(111).

    PubMed

    Naderian, Maryam; Groß, Axel

    2016-09-01

    The adsorption dynamics of water on Pt(111) was studied using ab initio molecular dynamics simulations based on density functional theory calculations including dispersion corrections. Sticking probabilities were derived as a function of initial kinetic energy and water coverage. In addition, the energy distribution upon adsorption was monitored in order to analyze the energy dissipation process. We find that on the water pre-covered surface the sticking probability is enhanced because of the attractive water-water interaction and the additional effective energy dissipation channels to the adsorbed water molecules. The water structures forming directly after the adsorption on the pre-covered surfaces do not necessarily correspond to energy minimum structures. PMID:27609006

  14. Water molecule conformation outside a metal surface

    NASA Astrophysics Data System (ADS)

    Flores, F.; Gabbay, I.; March, N. H.

    1981-05-01

    The effect of a metal surface on the conformation of a water molecule has been analyzed by discussing two independent effects: (i) the screening of the proton-proton repulsion, (ii) the interaction of the lone-pair orbitals with the surface. Both effects tend to increase the HOH angle. However, the interaction between the lone-pairs with the surface is the dominant effect for a water molecule approaching the surface. In particular, for a chemisorbed state this interaction is responsible for the major part of the molecule deformation. We have estimated that for H 2O chemisorbed on Ru, the HOH angle must increase from the free molecule value of 104.5° by 3.1 ± 0.5° in good agreement with the experimental evidence.

  15. Chemical reactions of water molecules on Ru(0001) induced by selective excitation of vibrational modes

    SciTech Connect

    Mugarza, Aitor; Shimizu, Tomoko K.; Ogletree, D. Frank; Salmeron, Miquel

    2009-05-07

    Tunneling electrons in a scanning tunneling microscope were used to excite specific vibrational quantum states of adsorbed water and hydroxyl molecules on a Ru(0 0 0 1) surface. The excited molecules relaxed by transfer of energy to lower energy modes, resulting in diffusion, dissociation, desorption, and surface-tip transfer processes. Diffusion of H{sub 2}O molecules could be induced by excitation of the O-H stretch vibration mode at 445 meV. Isolated molecules required excitation of one single quantum while molecules bonded to a C atom required at least two quanta. Dissociation of single H{sub 2}O molecules into H and OH required electron energies of 1 eV or higher while dissociation of OH required at least 2 eV electrons. In contrast, water molecules forming part of a cluster could be dissociated with electron energies of 0.5 eV.

  16. Heat capacity measurements of atoms and molecules adsorbed on evaporated metal films

    SciTech Connect

    Kenny, T.W.

    1989-05-01

    Investigations of the properties of absorbed monolayers have received great experimental and theoretical attention recently, both because of the importance of surface processes in practical applications such as catalysis, and the importance of such systems to the understanding of the fundamentals of thermodynamics in two dimensions. We have adapted the composite bolometer technology to the construction of microcalorimeters. For these calorimeters, the adsorption substrate is an evaporated film deposited on one surface of an optically polished sapphire wafer. This approach has allowed us to make the first measurements of the heat capacity of submonolayer films of /sup 4/He adsorbed on metallic films. In contrast to measurements of /sup 4/He adsorbed on all other insulating substrates, we have shown that /sup 4/He on silver films occupies a two-dimensional gas phase over a broad range of coverages and temperatures. Our apparatus has been used to study the heat capacity of Indium flakes. CO multilayers, /sup 4/He adsorbed on sapphire and on Ag films and H/sub 2/ adsorbed on Ag films. The results are compared with appropriate theories. 68 refs., 19 figs.

  17. Low-cost adsorbents for heavy metals uptake from contaminated water: a review.

    PubMed

    Babel, Sandhya; Kurniawan, Tonni Agustiono

    2003-02-28

    In this article, the technical feasibility of various low-cost adsorbents for heavy metal removal from contaminated water has been reviewed. Instead of using commercial activated carbon, researchers have worked on inexpensive materials, such as chitosan, zeolites, and other adsorbents, which have high adsorption capacity and are locally available. The results of their removal performance are compared to that of activated carbon and are presented in this study. It is evident from our literature survey of about 100 papers that low-cost adsorbents have demonstrated outstanding removal capabilities for certain metal ions as compared to activated carbon. Adsorbents that stand out for high adsorption capacities are chitosan (815, 273, 250 mg/g of Hg(2+), Cr(6+), and Cd(2+), respectively), zeolites (175 and 137 mg/g of Pb(2+) and Cd(2+), respectively), waste slurry (1030, 560, 540 mg/g of Pb(2+), Hg(2+), and Cr(6+), respectively), and lignin (1865 mg/g of Pb(2+)). These adsorbents are suitable for inorganic effluent treatment containing the metal ions mentioned previously. It is important to note that the adsorption capacities of the adsorbents presented in this paper vary, depending on the characteristics of the individual adsorbent, the extent of chemical modifications, and the concentration of adsorbate. PMID:12573840

  18. Thermodynamic and dynamic characteristics of hydroxypropylmethylcellulose adsorbed films at the air-water interface.

    PubMed

    Pérez, Oscar E; Sánchez, Cecilio Carrera; Rodríguez Patino, Juan M; Pilosof, Ana M R

    2006-01-01

    Surface pressure isotherms and structural and surface dilatational properties of three hydroxypropylmethycelluloses (HPMCs, called E4M, E50LV, and F4M) adsorbed films at the air-water interface were determined. In this work we present evidence that HPMC molecules are able to diffuse and saturate the air-water interface at very low concentrations in the bulk phase. As bulk concentration increased, structural changes at a molecular level occurred at the interface. These changes corresponded to transition from an expanded structure (structure I) to a condensed one (structure II). When the surface concentration of HPMC was high enough, the collapse of the monolayer was observed. The three HPMCs formed very elastic films at the air-water interface, even at low surface pressures. E4M showed features that make it unique. For instance it showed the highest surface activity, mainly at low bulk concentrations (<10(-4) wt %). The differences observed in surface activity may be attributed to differences in the hydroxypropyl molar substitution and molecular weight of HPMC. All three HPMCs formed films of similar viscoelasticity and elastic dilatational modulus, which can be accounted for by their similar degree of methyl substitution. PMID:16398540

  19. Anisotropic orientational motion of molecular adsorbates at the air-water interface

    SciTech Connect

    Zimdars, D.; Dadap, J.I.; Eisenthal, K.B.; Heinz, T.F.

    1999-04-29

    The ultrafast orientational motions of coumarin 314 (C314) adsorbed at the air/water interface were investigated by time-resolved surface second harmonic generation (TRSHG). The theory and method of using TRSHG to detect both out-of-plane and in-plane orientational motions are discussed. The interfacial solute motions were found to be anisotropic, with differing out-of-plane and in-plane reorientation time constants. This report presents the first direct observation of in-plane orientational motion of a molecule (C314) at the air/water interface using TRSHG. The in-plane reorientation time constant is 600 {+-} 40 ps. The out-of-plane reorientation time constant is 350 {+-} 20 ps. The out-of-plane orientational motion of C314 is similar to the previous results on rhodamine 6G at the air/water interface which indicated increased interfacial friction compared with bulk aqueous solution. The surface reorientation times are 2--3 times slower than the bulk isotropic orientational diffusion time.

  20. Sticking of Molecules on Nonporous Amorphous Water Ice

    NASA Astrophysics Data System (ADS)

    He, Jiao; Acharyya, Kinsuk; Vidali, Gianfranco

    2016-05-01

    Accurate modeling of physical and chemical processes in the interstellar medium (ISM) requires detailed knowledge of how atoms and molecules adsorb on dust grains. However, the sticking coefficient, a number between 0 and 1 that measures the first step in the interaction of a particle with a surface, is usually assumed in simulations of ISM environments to be either 0.5 or 1. Here we report on the determination of the sticking coefficient of H2, D2, N2, O2, CO, CH4, and CO2 on nonporous amorphous solid water. The sticking coefficient was measured over a wide range of surface temperatures using a highly collimated molecular beam. We showed that the standard way of measuring the sticking coefficient—the King–Wells method—leads to the underestimation of trapping events in which there is incomplete energy accommodation of the molecule on the surface. Surface scattering experiments with the use of a pulsed molecular beam are used instead to measure the sticking coefficient. Based on the values of the measured sticking coefficient, we suggest a useful general formula of the sticking coefficient as a function of grain temperature and molecule-surface binding energy. We use this formula in a simulation of ISM gas–grain chemistry to find the effect of sticking on the abundance of key molecules both on grains and in the gas phase.

  1. Low-cost magnetic adsorbent for As(III) removal from water: adsorption kinetics and isotherms.

    PubMed

    Kango, Sarita; Kumar, Rajesh

    2016-01-01

    Magnetite nanoparticles as adsorbent for arsenic (As) were coated on sand particles. The coated sand was used for the removal of highly toxic element 'As(III)' from drinking water. Here, batch experiments were performed with the variation of solution pH, adsorbent dose, contact time and initial arsenic concentration. The adsorbent showed significant removal efficiency around 99.6 % for As(III). Analysis of adsorption kinetics revealed that the adsorbent follows pseudo-second-order kinetics model showing R (2) = 0.999, whereas for pseudo-first-order kinetics model, the value of R (2) was 0.978. In the case of adsorption equilibrium, the data is well fitted with Langmuir adsorption isotherm model (R (2) > 0.99), indicating monolayer adsorption of As(III) on the surface of adsorbent. The existence of commonly present ions in water influences the removal efficiency of As(III) minutely in the following order PO4 (3-) > HCO3 (-) > Cl(-) > SO4 (2-). The obtained adsorbent can be used to overcome the problem of water filtration in rural areas. Moreover, as the nano-magnetite is coated on the sand, it avoids the problem of extraction of nanoparticles from treated water and can easily be removed by a simple filtration process. PMID:26711813

  2. Adsorption and Desorption of Carbon Dioxide and Water Mixtures on Synthetic Hydrophobic Carbonaceous Adsorbents

    NASA Technical Reports Server (NTRS)

    Finn, John E.; Harper, Lynn D. (Technical Monitor)

    1994-01-01

    Several synthetic carbonaceous adsorbents produced through pyrolysis of polymeric materials are available commercially. Some appear to have advantages over activated carbon for certain adsorption applications. In particular, they can have tailored hydrophobicities that are significantly greater than that of activated carbon, while moderately high surfaces areas are retained. These sorbents are being investigated for possible use in removing trace contaminants and excess carbon dioxide from air in closed habitats, plant growth chambers, and other applications involving purification of humid gas streams. We have analyzed the characteristics of a few of these adsorbents through adsorption and desorption experiments and standard characterization techniques. This paper presents pure and multicomponent adsorption data collected for carbon dioxide and water on two synthetic carbonaceous adsorbents having different hydrophobicities and capillary condensation characteristics. The observations are interpreted through consideration of the pore structure and surface chemistry of the solids and interactions between adsorbed carbon dioxide, water, and the solvent gas.

  3. Effect of alkane chain length and counterion on the freezing transition of cationic surfactant adsorbed film at alkane mixture - water interfaces.

    PubMed

    Tokiwa, Yuhei; Sakamoto, Hiroyasu; Takiue, Takanori; Aratono, Makoto; Matsubara, Hiroki

    2015-05-21

    Penetration of alkane molecules into the adsorbed film gives rise to a surface freezing transition of cationic surfactant at the alkane-water interface. To examine the effect of the alkane chain length and counterion on the surface freezing, we employed interfacial tensiometry and ellipsometry to study the interface of cetyltrimethylammonium bromide and cetyltrimethylammonium chloride aqueous solutions against dodecane, tetradecane, hexadecane, and their mixtures. Applying theoretical equations to the experimental results obtained, we found that the alkane molecules that have the same chain length as the surfactant adsorb preferentially into the surface freezing film. Furthermore, we demonstrated that the freezing transition temperature of cationic surfactant adsorbed film was independent of the kind of counterion. PMID:25932500

  4. Why can water cages adsorb aqueous methane? A potential of mean force calculation on hydrate nucleation mechanisms.

    PubMed

    Guo, Guang-Jun; Li, Meng; Zhang, Yi-Gang; Wu, Chang-Hua

    2009-11-28

    By performing constrained molecular dynamics simulations in the methane-water system, we successfully calculated the potential of mean force (PMF) between a dodecahedral water cage (DWC) and dissolved methane for the first time. As a function of the distance between DWC and methane, this is characterized by a deep well at approximately 6.2 A and a shallow well at approximately 10.2 A, separated by a potential barrier at approximately 8.8 A. We investigated how the guest molecule, cage rigidity and the cage orientation affected the PMF. The most important finding is that the DWC itself strongly adsorbs methane and the adsorption interaction is independent of the guests. Moreover, the activation energy of the DWC adsorbing methane is comparable to that of hydrogen bonds, despite differing by a factor of approximately 10% when considering different water-methane interaction potentials. We explain that the cage-methane adsorption interaction is a special case of the hydrophobic interaction between methane molecules. The strong net attraction in the DWC shell with radii between 6.2 and 8.8 A may act as the inherent driving force that controls hydrate formation. A cage adsorption hypothesis for hydrate nucleation is thus proposed and discussed. PMID:19890529

  5. Difference in Surface Properties between Insoluble Monolayer and Adsorbed Film from Kinetics of Water Evaporation and BAM Image.

    PubMed

    Moroi, Yoshikiyo; Rusdi, Muhammad; Kubo, Izumi

    2004-05-20

    The evaporation rate of water molecules across three kinds of interfaces (air/water interface (1), air/surfactant solution interface (2), and air/water interface covered by insoluble monolayer (3)) was examined using a remodeled thermogravimetric balance. There was no difference in both the evaporation rate and the activation energy for the first two interfaces for three types of surfactant solutions below and above the critical micelle concentration (cmc). This means that the molecular surface area from the Gibbs surface excess has nothing to do with the evaporation rate. In the third case, the insoluble monolayer of 1-heptadecanol decreased the evaporation rate and increased the activation energy, indicating a clear difference between an insoluble monolayer and an adsorbed film of soluble surfactant. This difference was substantiated by BAM images, too. The images of three surfactant solution interfaces were similar to that of just the water surface, while distinct structures of molecular assemblies were observed for the insoluble monolayer. The concentration profile of water molecules in an air/liquid interfacial region was derived by Fix's second law. The profile indicates that a definite layer just beneath the air/liquid interface of the surfactant solution is made mostly of water molecules and that the layer thickness is a few times the root-mean-square displacement %@mt;sys@%%@rl;;@%2%@ital@%Dt%@rsf@%%@rlx@%%@mx@% of the water molecules. The thickness was found to be more than a few nanometers, as estimated from several relaxation times derived from the other kinetics than evaporation of amphiphilic molecules in aqueous systems and a maximum evaporation rate of purified water. PMID:18950121

  6. The Dipole Polarizability of a Water Molecule in Liquid Water

    NASA Astrophysics Data System (ADS)

    Distasio, Robert; Maitra, Rahul

    The dipole polarizability, α, provides a measure of the tendency of a molecule or material to deform (or polarize) in the presence of an electric field. Within the framework of density functional theory (DFT), we present a hierarchy of first principles based approaches for computing α of a molecule located in the condensed phase. This hierarchy includes a successive treatment of both short-range (hybridization, Pauli exchange-repulsion, etc.) and long-range (Coulomb) electrodynamical response screening in the computation of α, while simultaneously accounting for the surrounding condensed-phase environment. Utilizing highly accurate liquid water configurations generated from van der Waals inclusive hybrid DFT based ab initio molecular dynamics, we computed α for a given water molecule in liquid water as a first application of this approach. Our findings will be compared and contrasted with α computed for an isolated gas-phase water molecule.

  7. Charge-transfer photodissociation of adsorbed molecules via electron image states

    SciTech Connect

    Jensen, E. T.

    2008-01-28

    The 248 and 193 nm photodissociations of submonolayer quantities of CH{sub 3}Br and CH{sub 3}I adsorbed on thin layers of n-hexane indicate that the dissociation is caused by dissociative electron attachment from subvacuum level photoelectrons created in the copper substrate. The characteristics of this photodissociation-translation energy distributions and coverage dependences show that the dissociation is mediated by an image potential state which temporarily traps the photoelectrons near the n-hexane-vacuum interface, and then the charge transfers from this image state to the affinity level of a coadsorbed halomethane which then dissociates.

  8. Adsorption/Desorption Behavior Of Water Vapor In An Adsorbent Desiccant Rotor

    NASA Astrophysics Data System (ADS)

    Tsujiguchi, Takuya; Kodama, Akio

    Desiccant cooling system can be driven with a low temperature heat such as around 80°C obtained from exhaust gas and so on. Among the configuration of the cooling cycle, honeycomb rotary adsorber is the most important part to achieve higher cooling performance. By means of computer simulation, angular and axial distributions of the amount of adsorbed water, air humidity, air temperature and adsorbent temperature inside the desiccant rotor at various operating conditions were investigated. In the mathematical model, lumped mass transfer coefficient was used and its value were derived from the fitting with experimental results to improve the reliability of discussion about the simultaneous heat/mass transfer in the desiccant rotor. It was found that the part of honeycomb rotary adsorber which is close to the regeneration air inlet cannot work well as an adsorbent at higher regeneration temperature regardless of outside air condition and regeneration air humidity. On the other hand, since the driving force was extremely low throughout all the axial positions, water vapor was adsorbed gradually at the whole axial position of rotor under a lower regeneration temperature. Consequently, this study could clarify the importance of the optimization of the rotor in terms of its length depending on the operating and air conditions.

  9. Removal of radioactive iodine from water using Ag2O grafted titanate nanolamina as efficient adsorbent.

    PubMed

    Bo, Arixin; Sarina, Sarina; Zheng, Zhanfeng; Yang, Dongjiang; Liu, Hongwei; Zhu, Huaiyong

    2013-02-15

    Emergency treatment of radioactive material leakage and safety disposal of nuclear waste is a constant concern all along with the development of radioactive materials applications. To provide a solution, titanate with large surface area (143 m(2)g(-1)) and a lamina morphology (the thickness of the lamina is in range of tens of nanometers) was prepared from inorganic titanium compounds by hydrothermal reactions at 433 K. Ag(2)O nanocrystals (5-30 nm) were deposited onto the titanate lamina. The surface of the titanate lamina has crystallographic similarity to that of Ag(2)O nanocrystals. Hence, the deposited Ag(2)O nanocrystals and titanate substrate join together at these surfaces, forming a well-matched phase coherent interface between them. Such coherence between the two phases reduces the overall energy by minimizing surface energy and anchors the Ag(2)O nanocrystals firmly on the external surface of the titanate structure. The composite thus obtained was applied as efficient adsorbent to remove radioactive iodine from water (one gram adsorbent can capture up to 3.4 mmol of I(-) anions). The composite adsorbent can be recovered easily for safe disposal. The structure changes of the titanate lamina and the composite adsorbent were monitored by various techniques. The isotherm and kinetics of iodine adsorption, competitive adsorption and column adsorption using the adsorbent were studied to assess its iodine removal abilities. The adsorbent exhibited a capacity as high as 3.4 mmol of iodine per gram of adsorbent in 1h. Therefore, Ag(2)O deposited titanate lamina is an effective adsorbent for removing radioactive iodine from water. PMID:23313892

  10. Removal and recycle of phosphate from treated water of sewage plants with zirconium ferrite adsorbent by high gradient magnetic separation

    NASA Astrophysics Data System (ADS)

    Ito, D.; Nishimura, K.; Miura, O.

    2009-03-01

    Zirconium ferrite particles are good adsorbent for phosphate ions. Magnetic separation characteristics for removal of phosphate from treated water of sewage plants with the adsorbent have been studied to prevent eutrophication of semi-enclosed bay, e.g. the bay of Tokyo. Based on the adsorption for the phosphate ions and ferromagnetic properties of the zirconium ferrite adsorbent, high gradient magnetic separation characteristics with using superconducting magnet was discussed. Very rapid magnetic filtration velocity, i.e. 1m/s, and regeneration properties of the adsorbent indicate that the zirconium ferrite is the excellent adsorbent for phosphorus removal and recycle from treated water of large scale sewage plants.

  11. Preliminary results on the immobilisation of radionuclides from waters with specific adsorbers based on phosphate salts.

    PubMed

    Valentini Ganzerli, Maria Teresa; Maggi, Luigino; Crespi Caramella, Vera; Berzero, Antonella

    2004-11-01

    The present paper is focused on the ability of aluminium phosphate (ALPC), magnesium ammonium phosphate (MGPC), magnesium hydrogen phosphate (MGHPC), and calcium hydrogenphosphate (CAHPC), adsorbed onto charcoal, to immobilise actinides by adsorption from natural waters. The objective of this process is to evaluate the environmental pollution due to the actinides. Europium, thorium, protactinium, neptunyl, and uranyl ions were chosen to simulate actinides in the +3, +4, +5 and +6 oxidation state. The adsorbers were tested using natural waters samples. The adsorption trends and capacities were analysed. ALPC and MGPC exhibited a similar behaviour and adsorbed demonstrating that the +5, +4 and +3 actinide ions can be easily immobilised from natural waters and may be successfully used at pH 7-8. MGHPC may be used at a higher pH, whereas CAHPC is effective in the whole pH range. In all cases, thorium, protactinium and europium were strongly PMID:15626242

  12. Adsorbed states of chlorophenol on Cu(110) and controlled switching of single-molecule junctions

    NASA Astrophysics Data System (ADS)

    Okuyama, H.; Kitaguchi, Y.; Hattori, T.; Ueda, Y.; Ferrer, N. G.; Hatta, S.; Aruga, T.

    2016-06-01

    A molecular junction of substituted benzene (chlorophenol) is fabricated and controlled by using a scanning tunneling microscope (STM). Prior to the junction formation, the bonding geometry of the molecule on the surface is characterized by STM and electron energy loss spectroscopy (EELS). EELS shows that the OH group of chlorophenol is dissociated on Cu(110) and that the molecule is bonded nearly flat to the surface via an O atom, with the Cl group intact. We demonstrate controlled contact of an STM tip to the "available" Cl group and lift-up of the molecule while it is anchored to the surface via an O atom. The asymmetric bonding motifs of the molecule to the electrodes allow for reversible control of the junction.

  13. Adsorbed states of chlorophenol on Cu(110) and controlled switching of single-molecule junctions.

    PubMed

    Okuyama, H; Kitaguchi, Y; Hattori, T; Ueda, Y; Ferrer, N G; Hatta, S; Aruga, T

    2016-06-28

    A molecular junction of substituted benzene (chlorophenol) is fabricated and controlled by using a scanning tunneling microscope (STM). Prior to the junction formation, the bonding geometry of the molecule on the surface is characterized by STM and electron energy loss spectroscopy (EELS). EELS shows that the OH group of chlorophenol is dissociated on Cu(110) and that the molecule is bonded nearly flat to the surface via an O atom, with the Cl group intact. We demonstrate controlled contact of an STM tip to the "available" Cl group and lift-up of the molecule while it is anchored to the surface via an O atom. The asymmetric bonding motifs of the molecule to the electrodes allow for reversible control of the junction. PMID:27369529

  14. How hottest geometries and adsorptive parameters influence the SER(R)S spectra of Methylene Blue molecules adsorbed on nanocolloidal gold particles of varied sizes?

    PubMed

    Roy, Sannak Dutta; Ghosh, Manash; Chowdhury, Joydeep

    2015-12-01

    The SER(R)S spectra of Methylene Blue (MB) molecule adsorbed on gold nanocolloidal particles (AuNCs) have been investigated. The adsorptive parameters of the molecule adsorbed on AuNCs have been evaluated with the aid of Fluorescence Spectroscopy study. Fluorescence spectroscopic studies have been further applied to understand the concentration of probe molecule actually adsorbed on AuNC surfaces. Gigantic enhancements ∼10(6)-10(16) orders of magnitude have been recorded for the enhanced Raman bands in the SER(R)S spectra. Three-dimensional Finite Difference Time Domain (3D-FDTD) simulations studies have been carried out to predict the distributions of electric fields around the possible nanoaggregated hot geometries considered to be responsible for the huge enhancements of SER(R)S bands of the MB molecule. PMID:26172467

  15. Clusters of mobile molecules in supercooled water

    NASA Astrophysics Data System (ADS)

    Giovambattista, Nicolas; Buldyrev, Sergey V.; Stanley, H. Eugene; Starr, Francis W.

    2005-07-01

    We study the spatially heterogeneous dynamics in water via molecular dynamics simulations using the extended simple point charge potential. We identify clusters formed by mobile molecules and study their properties. We find that these clusters grow in size and become more compact as temperature decreases. We analyze the probability density function of cluster size, and we study the cluster correlation length. We find that clusters appear to be characterized by a fractal dimension consistent with that of lattice animals. We relate the cluster size and correlation length to the configurational entropy, Sconf . We find that these quantities depend weakly on 1/Sconf . In particular, the linearity found between the cluster mass n* and 1/Sconf suggests that n* may be interpreted as the mass of the cooperatively rearranging regions that form the basis of the Adam-Gibbs approach to the dynamics of supercooled liquids. We study the motion of molecules within a cluster, and find that each molecule preferentially follows a neighboring molecule in the same cluster. Based on this finding we hypothesize that stringlike cooperative motion may be a general mechanism for molecular rearrangement of complex, as well as simple liquids. By mapping each equilibrium configuration onto its corresponding local potential energy minimum or inherent structure (IS), we are able to compare the mobile molecule clusters in the equilibrium system with the molecules forming the clusters identified in the transitions between IS. We find that (i) mobile molecule clusters obtained by comparing different system configurations and (ii) clusters obtained by comparing the corresponding IS are completely different for short time scales, but are the same on the longer time scales of diffusive motion.

  16. Enhanced removal of nitrate from water using surface modification of adsorbents--a review.

    PubMed

    Loganathan, Paripurnanda; Vigneswaran, Saravanamuthu; Kandasamy, Jaya

    2013-12-15

    Elevated concentration of nitrate results in eutrophication of natural water bodies affecting the aquatic environment and reduces the quality of drinking water. This in turn causes harm to people's health, especially that of infants and livestock. Adsorbents with the high capacity to selectively adsorb nitrate are required to effectively remove nitrate from water. Surface modifications of adsorbents have been reported to enhance their adsorption of nitrate. The major techniques of surface modification are: protonation, impregnation of metals and metal oxides, grafting of amine groups, organic compounds including surfactant coating of aluminosilicate minerals, and heat treatment. This paper reviews current information on these techniques, compares the enhanced nitrate adsorption capacities achieved by the modifications, and the mechanisms of adsorption, and presents advantages and drawbacks of the techniques. Most studies on this subject have been conducted in batch experiments. These studies need to include continuous mode column trials which have more relevance to real operating systems and pilot-plant trials. Reusability of adsorbents is important for economic reasons and practical treatment applications. However, only limited information is available on the regeneration of surface modified adsorbents. PMID:24211565

  17. Mechanism of charge transfer and its impacts on Fermi-level pinning for gas molecules adsorbed on monolayer WS{sub 2}

    SciTech Connect

    Zhou, Changjie; Zhu, Huili; Yang, Weihuang

    2015-06-07

    Density functional theory calculations were performed to assess changes in the geometric and electronic structures of monolayer WS{sub 2} upon adsorption of various gas molecules (H{sub 2}, O{sub 2}, H{sub 2}O, NH{sub 3}, NO, NO{sub 2}, and CO). The most stable configuration of the adsorbed molecules, the adsorption energy, and the degree of charge transfer between adsorbate and substrate were determined. All evaluated molecules were physisorbed on monolayer WS{sub 2} with a low degree of charge transfer and accept charge from the monolayer, except for NH{sub 3}, which is a charge donor. Band structure calculations showed that the valence and conduction bands of monolayer WS{sub 2} are not significantly altered upon adsorption of H{sub 2}, H{sub 2}O, NH{sub 3}, and CO, whereas the lowest unoccupied molecular orbitals of O{sub 2}, NO, and NO{sub 2} are pinned around the Fermi-level when these molecules are adsorbed on monolayer WS{sub 2}. The phenomenon of Fermi-level pinning was discussed in light of the traditional and orbital mixing charge transfer theories. The impacts of the charge transfer mechanism on Fermi-level pinning were confirmed for the gas molecules adsorbed on monolayer WS{sub 2}. The proposed mechanism governing Fermi-level pinning is applicable to the systems of adsorbates on recently developed two-dimensional materials, such as graphene and transition metal dichalcogenides.

  18. Dynamics of water molecules in glucose solutions.

    SciTech Connect

    Talon, C.; Smith, L. J.; Brady, J. W.; Copley, J. R. D.; Price, D. L.; Saboungi, M. L.; Materials Science Division; Centre de Recherche sur la Matiyre Divisye; Cornell Univ.; NIST; Centre de Recherche sur les Matyriaux y Haute Tempyrature

    2004-04-22

    The effects of the solution of glucose molecules on the dynamics of solvent water have been studied by quasielastic neutron scattering (QENS) measurements on solutions of selectively deuterated glucose in natural water. The data are fitted to two Lorentzians ascribed to pure translational and mixed translational and rotational character, respectively. The addition of the glucose to the water causes a substantial slowing down, by a factor 10 for the translational diffusion and 3-4 for the rotational motion at the highest concentration studied, 1:11 C{sub 6}H{sub 12}O{sub 6}:H{sub 2}O. The values obtained for water diffusion constants are consistent with previous QENS and NMR experiments on monosaccharide solutions but an order of magnitude higher than those derived from a recent molecular dynamics simulation.

  19. Interactions of adsorbed CO₂ on water ice at low temperatures.

    PubMed

    Karssemeijer, L J; de Wijs, G A; Cuppen, H M

    2014-08-01

    We present a computational study into the adsorption properties of CO2 on amorphous and crystalline water surfaces under astrophysically relevant conditions. Water and carbon dioxide are two of the most dominant species in the icy mantles of interstellar dust grains and a thorough understanding of their solid phase interactions at low temperatures is crucial for understanding the structural evolution of the ices due to thermal segregation. In this paper, a new H2O-CO2 interaction potential is proposed and used to model the ballistic deposition of CO2 layers on water ice surfaces, and to study the individual binding sites at low coverages. Contrary to recent experimental results, we do not observe CO2 island formation on any type of water substrate. Additionally, density functional theory calculations are performed to assess the importance of induced electrostatic interactions. PMID:24955794

  20. Effects of non-local exchange on core level shifts for gas-phase and adsorbed molecules

    SciTech Connect

    Van den Bossche, M.; Grönbeck, H.; Martin, N. M.; Gustafson, J.; Lundgren, E.; Hakanoglu, C.; Weaver, J. F.

    2014-07-21

    Density functional theory calculations are often used to interpret experimental shifts in core level binding energies. Calculations based on gradient-corrected (GC) exchange-correlation functionals are known to reproduce measured core level shifts (CLS) of isolated molecules and metal surfaces with reasonable accuracy. In the present study, we discuss a series of examples where the shifts calculated within a GC-functional significantly deviate from the experimental values, namely the CLS of C 1s in ethyl trifluoroacetate, Pd 3d in PdO and the O 1s shift for CO adsorbed on PdO(101). The deviations are traced to effects of the electronic self-interaction error with GC-functionals and substantially better agreements between calculated and measured CLS are obtained when a fraction of exact exchange is used in the exchange-correlation functional.

  1. Silica-based materials as drug adsorbents: first principle investigation on the role of water microsolvation on Ibuprofen adsorption.

    PubMed

    Delle Piane, Massimo; Vaccari, Stefano; Corno, Marta; Ugliengo, Piero

    2014-08-01

    Silica-based materials find applications as excipients and, particularly for those of mesoporous nature, as drug delivery agents for pharmaceutical formulations. Their performance can be crucially affected by water moisture, as it can modify the behavior of these formulations, by limiting their shelf life. Here we describe the role of water microsolvation on the features of ibuprofen adsorbed on a model of amorphous silica surface by means of density functional theory (DFT) simulations. Starting from the results of the simulation of ibuprofen in interaction with a dry hydrophobic amorphous silica surface, a limited number of water molecules has been added to study the configurational landscape of the microsolvated system. Structural and energetics properties, as well as the role of dispersive forces, have been investigated. Our simulations have revealed that the silica surface exhibits a higher affinity for water than for ibuprofen, even if several structures coexist at room temperature, with an active competition of ibuprofen and water for the exposed surface silanols. Dispersive interactions play a key role in this system, as pure DFT fails to correctly describe its potential energy surface. Indeed, van der Waals forces are the leading contribution to adsorption, independently of whether the drug is hydrogen-bonded directly to the surface or via water molecules. PMID:24467179

  2. Ion removal from waste water using immobilized adsorbents

    SciTech Connect

    Isaacson, A.E.; Jeffers, T.H.

    1995-12-31

    This paper summarizes experiments investigating the removal of various anions from dilute aqueous streams using mixtures of ferric hydroxide and peat moss immobilized in porous polymer beads. Cyclic load-strip tests were conducted at aqueous-to-bead radios of 20, 10, and 5 for loading, stripping, and conditioning, respectively. Beads were stripped with a sodium hydroxide solution and regenerated with a dilute acid. Waste waters containing arsenic, chromium, molybdenum, selenium, tungsten, and vanadium were tested. The maximum waste loading on the beads was determined for each waste water; experimental isotherms are presented.

  3. Hindered and modulated rotational states and spectra of adsorbed diatomic molecules

    SciTech Connect

    Shih, Y.T.; Chuu, D.S.; Mei, W.N.

    1996-10-01

    Both vertical and horizontal adsorption configurations of a diatomic molecule were modeled as the rigid rotor with which the spatial motion was confined by a finite conical well. In addition to the polar hindering potential, a sinusoidal azimuthal modulation, which bears the local symmetry of the adsorption site, was incorporated. Eigenfunctions for different models were expressed analytically in terms of the hypergeometric functions, and eigenvalues were solved numerically. We found that the rotational energy levels exhibit oscillatory behavior when plotted as functions of the hindrance angle. This particular phenomenon was interpreted as the occurrence of resonance transmission of the rotor wave function at certain hindrance condition. We also found that the rotational levels were grouped into bands when the azimuthal modulation strength was increased. The solutions were used to calculate the rotational-state distribution of desorbed molecules, and agreement with the previous experiment was obtained. {copyright} {ital 1996 The American Physical Society.}

  4. Electrocatalytic reduction of dioxygen to water by iridium porphyrins adsorbed on edge plane graphite electrodes

    SciTech Connect

    Collman, J.P.; Chng, Leng Leng; Tyvoll, D.A.

    1995-03-15

    Electrocatalytic effects of adsorbed iridium porphyrin complexes for the reduction of oxygen to water was studied. The Ir(II) metal center is proposed as the active catalytic center and catalytic effects can be attributed to transformation to Ir(II) centers.

  5. Formation of 1D adsorbed water structures on CaO(001)

    NASA Astrophysics Data System (ADS)

    Zhao, Xunhua; Bhattacharya, Saswata; Ghiringhelli, Luca M.; Levchenko, Sergey V.; Scheffler, Matthias

    2015-03-01

    Understanding the interaction of water with oxide surfaces is of fundamental importance for basic and engineering sciences. Recently, a spontaneous formation of one-dimensional (1D) adsorbed water structures have been observed on CaO(001). Interestingly, at other alkaline earth metal oxides, in particular MgO(001) and SrO(001), such structures have not been found experimentally. We calculate the relative stability of adsorbed water structures on the three oxides using density-functional theory combined with the ab initio atomistic thermodynamics. Low-energy structures at different coverages are obtained with a first-principles genetic algorithm. Finite-temperature vibrational spectra are calculated using ab initio molecular dynamics. We find a range of (T, p) conditions where 1D structures are thermodynamically stable on CaO(001). The orientation and vibrational spectra of the 1D structures are in agreement with the experiments. The formation of the 1D structures is found to be actuated by a symmetry breaking in the adsorbed water tetramer, as well as by a balance between water-water and water-substrate interactions, determined by the lattice constant of the oxide.

  6. Water-soluble adsorbent β-cyclodextrin-grafted polyethyleneimine for removing bilirubin from plasma.

    PubMed

    Wang, Zhi; Wei, Houliang; Jia, Lingyun; Xu, Li; Zou, Chunyi; Xie, Jian

    2012-10-01

    A water-soluble adsorbent was developed for removing bilirubin from the plasma of hyperbilirubinemia patient. The adsorbent was synthesized by grafting β-cyclodextrin (β-CD) to branched polyethyleneimine (PEI) matrix. The resulting β-CD-PEI polymer had an average molecular weight of 163.7 kD, and it contained 56.3 β-CD functional groups. In β-CD-PEI-spiked dialysis, 35.8% of plasma bilirubin was removed, which was higher than that removed by the same concentration of bovine serum albumin. β-CD-PEI also removed aromatic amino acids and bile acids. The results indicated that β-CD-PEI could be an effective adsorbent for blood purification application aiming at the removal of toxins. PMID:22836125

  7. Hard coal as a potential low-cost adsorbent for removal of 4-chlorophenol from water.

    PubMed

    Kuśmierek, Krzysztof; Zarębska, Katarzyna; Świątkowski, Andrzej

    2016-01-01

    The potential use of raw hard coals as low-cost adsorbents for the removal of 4-chlorophenol (4-CP) from aqueous solutions was examined. The effect of experimental parameters such as the pH and salt presence was evaluated. The kinetic studies showed the equilibrium time was found to be 2 h for all of the adsorbents and that the adsorption process followed the pseudo-second order kinetic model. The adsorption isotherms of the 4-CP on the hard coals were fitted to the Langmuir, Freundlich, Langmuir-Freundlich, Sips and Redlich-Peterson equations. Based on the results obtained, hard coals appear to be a promising adsorbent for the removal of some hazardous water pollutants, like 4-CP and related compounds. PMID:27120657

  8. Adsorption/Desorption Behavior of Water Vapor in an Adsorbent Desiccant Rotor

    NASA Astrophysics Data System (ADS)

    Tsujiguchi, Takuya; Kodama, Akio

    To clarify the operating and design concept of desiccant rotor, which is a most important component of an adsorptive desiccant cooling process, adsorption / desorption behavior of water vapor in a desiccant rotor has been investigated by means of computer simulation. Mass transfer coefficient in the mathematical model could be related to cycle time by applying the penetration theory. Considering this relationship, influences of the rotation speed of the desiccant rotor, process / regeneration air velocity and their velocity ratio were investigated. It was found that the optimum rotation speed tended to disappear when the regeneration air temperature was low and its humidity was considerably small compared to the process inlet air, since the product air condition approached to regeneration air condition as the rotation speed increased. Decrease of the dehumidifying performance was observed at higher air velocity and the corresponding higher rotation speed since the adsorbent rotor was not fully regenerated due to shorter regeneration time and shorter residence time of process / regeneration air in the adsorbent rotor prevented the mass transfer between air and adsorbent. It was also found that the dehumidifying performance was not improved even though the adsorbent was fully regenerated by higher regeneration air velocity as the sensible heat transferred from the regeneration zone via adsorbent itself increased and disturbed adsorption.

  9. Optimization of the preparation process of biological sludge adsorbents for application in water treatment.

    PubMed

    Gómez-Pacheco, C V; Rivera-Utrilla, J; Sánchez-Polo, M; López-Peñalver, J J

    2012-05-30

    The objective of this study was to optimize the preparation of treatment plant wastewater sludge adsorbents for application in water treatment. The optimal adsorption capacity was obtained with adsorbents prepared by pyrolysis at 700°C for 3h. We studied the effect of binder type on the adsorbents, finding that their textural properties were not substantially affected by the addition of phenolic resins but their surface area was reduced by the presence of clayey soil. Analysis of the composition of surface groups in these materials revealed: (i) a high concentration of basic surface groups in non-activated pyrolyzed sludge, (ii) an increase in the concentration of basic surface groups after chemical activation, (iii) no modification in the concentration of carboxyl or basic groups with the addition of binding agent before the activation, and (iv) total disappearance of carbonyl groups from sample surfaces with the addition of humic acid or clayey soil as binder. All these adsorbents had a low C content. The capacity of these sludge-derived materials to adsorb methylene blue, 2,4-dichlorophenol, tetracycline, and (Cd(II)) was studied. Their adsorption capacity was considerably increased by the chemical activation but reduced by the pre-activation addition of a binding agent (humic acid, phenolic resin, and clayey soil). PMID:22472426

  10. Removal of lead and zinc ions from water by low cost adsorbents.

    PubMed

    Mishra, P C; Patel, R K

    2009-08-30

    In this study, activated carbon, kaolin, bentonite, blast furnace slag and fly ash were used as adsorbent with a particle size between 100 mesh and 200 mesh to remove the lead and zinc ions from water. The concentration of the solutions prepared was in the range of 50-100 mg/L for lead and zinc for single and binary systems which are diluted as required for batch experiments. The effect of contact time, pH and adsorbent dosage on removal of lead and zinc by adsorption was investigated. The equilibrium time was found to be 30 min for activated carbon and 3h for kaolin, bentonite, blast furnace slag and fly ash. The most effective pH value for lead and zinc removal was 6 for activated carbon. pH value did not effect lead and zinc removal significantly for other adsorbents. Adsorbent doses were varied from 5 g/L to 20 g/L for both lead and zinc solutions. An increase in adsorbent doses increases the percent removal of lead and zinc. A series of isotherm studies was undertaken and the data evaluated for compliance was found to match with the Langmuir and Freundlich isotherm models. To investigate the adsorption mechanism, the kinetic models were tested, and it follows second order kinetics. Kinetic studies reveals that blast furnace slag was not effective for lead and zinc removal. The bentonite and fly ash were effective for lead and zinc removal. PMID:19299083

  11. Alteration of an annealed and irradiated lunar fines sample by adsorbed water

    NASA Technical Reports Server (NTRS)

    Holmes, H. F.; Agron, P. A.; Eichler, E.; Fuller, E. L., Jr.; Okelley, G. D.; Gammage, R. B.

    1975-01-01

    Apollo 12 lunar fines sample 12070,403 was annealed at 1000 C and subsequently irradiated with a beam of 130 MeV Fe(9+) ions. Adsorptions of nitrogen and water were measured before and after the irradiation. Prior to the irradiation, the fines were nonporous and water had no effect on the physical characteristics of the lunar fines. In contrast, after the irradiation, the interaction with water caused an increase in the specific surface area and created a pore system. These results are definitive evidence that the interaction of water with damage tracks is the prime factor involved in the alteration of lunar fines by adsorbed water.

  12. Copper ions removal from water using functionalized carbon nanotubes–mullite composite as adsorbent

    SciTech Connect

    Tofighy, Maryam Ahmadzadeh; Mohammadi, Toraj

    2015-08-15

    Highlights: • CNTs–mullite composite was prepared via chemical vapor deposition (CVD) method. • The prepared composite was modified with concentrated nitric acid and chitosan. • The modified CNTs–mullite composites were used as novel adsorbents. • Copper ion removal from water by the prepared adsorbents was performed. • Langmuir and Freundlich isotherms and two kinetic models were applied to fit the experimental data. - Abstract: Carbon nanotubes–mullite composite was synthesized by direct growth of carbon nanotubes on mullite particles via chemical vapor deposition method using cyclohexanol and ferrocene as carbon precursor and catalyst, respectively. The carbon nanotubes–mullite composite was oxidized with concentrated nitric acid and functionalized with chitosan and then used as a novel adsorbent for copper ions removal from water. The results demonstrated that modification with concentrated nitric acid and chitosan improves copper ions adsorption capacity of the prepared composite, significantly. Langmuir and Freundlich isotherms and two kinetic models were applied to fit the experimental data. The carbon nanotubes growth on mullite particles to form the carbon nanotubes–mullite composite with further modification is an inherently safe approach for many promising environmental applications to avoid some concerns regarding environment, health and safety. It was found that the modified carbon nanotubes–mullite composite can be considered as an excellent adsorbent for copper ions removal from water.

  13. Comparative study on adsorption of perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) by different adsorbents in water.

    PubMed

    Yao, Yuan; Volchek, Konstantin; Brown, Carl E; Robinson, Adam; Obal, Terry

    2014-01-01

    Perfluorinated compounds (PFCs) are emerging environmental pollutants. Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are the two primary PFC contaminants that are widely found in water, particularly in groundwater. This study compared the adsorption behaviors of PFOS and PFOA on several commercially available adsorbents in water. The tested adsorbents include granular activated carbon (GAC: Filtrasorb 400), powdered activated carbon, multi-walled carbon nanotube (MCN), double-walled carbon nanotube, anion-exchange resin (AER: IRA67), non-ion-exchange polymer, alumina, and silica. The study demonstrated that adsorption is an effective technique for the removal of PFOS/PFOA from aqueous solutions. The kinetic tests showed that the adsorption onto AER reaches equilibrium rapidly (2 h), while it takes approximately 4 and 24 h to reach equilibrium for MCN and GAC, respectively. In terms of adsorption capacity, AER and GAC were identified as the most effective adsorbents to remove PFOS/PFOA from water. Furthermore, MCN, AER, and GAC proved to have high PFOS/PFOA removal efficiencies (≥98%). AER (IRA67) and GAC (Filtrasorb 400) were thus identified as the most promising adsorbents for treating PFOS/PFOA-contaminated groundwater at mg L(-1) level based on their equilibrium times, adsorption capacities, removal efficiencies, and associated costs. PMID:25521134

  14. Switching orientation of adsorbed molecules: Reverse domino on a metal surface

    NASA Astrophysics Data System (ADS)

    Braatz, C. R.; Esat, T.; Wagner, C.; Temirov, R.; Tautz, F. S.; Jakob, P.

    2016-01-01

    A thus far unknown phase of 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA) on Ag(111), characterized by an all perpendicular orientation of the planar molecules and bound to the Ag substrate through the carboxyl oxygen atoms has been identified using infrared absorption spectroscopy and scanning tunneling microscopy. Its formation process requires second layer NTCDA to squeeze into empty spaces between relaxed monolayer NTCDA molecules. Remarkably, this process causes initially parallel oriented NTCDA to likewise adopt the new, highly inclined adsorption geometry. According to our SPA-LEED and STM findings, the new phase displays a distinct long range order and shows a pronounced tendency to form 1D rows or narrow islands. We suggest that extra NTCDA preferentially transforms into the upright configuration close to existing islands and attaches to them, i.e. the transformation process proceeds in a directed and recurrent manner (reverse domino scenario). Identical processing starting with a compressed NTCDA/Ag(111) monolayer leads to a purely parallel oriented bilayer, that is, the NTCDA monolayer phase is retained and merely acts as a passive template for bilayer NTCDA. The new vertical NTCDA phase represents an unusual molecular system with π-orbitals oriented parallel to a metal surface. A substantially reduced coupling of these orbitals to Ag(111) electronic levels is conjectured, which will have a major impact on intermolecular couplings and electronically excited state lifetimes.

  15. Tribochemical synthesis of nano-lubricant films from adsorbed molecules at sliding solid interface: Tribo-polymers from α-pinene, pinane, and n-decane

    NASA Astrophysics Data System (ADS)

    He, Xin; Barthel, Anthony J.; Kim, Seong H.

    2016-06-01

    The mechanochemical reactions of adsorbed molecules at sliding interfaces were studied for α-pinene (C10H16), pinane (C10H18), and n-decane (C10H22) on a stainless steel substrate surface. During vapor phase lubrication, molecules adsorbed at the sliding interface could be activated by mechanical shear. Under the equilibrium adsorption condition of these molecules, the friction coefficient of sliding steel surfaces was about 0.2 and a polymeric film was tribochemically produced. The synthesis yield of α-pinene tribo-polymers was about twice as much as pinane tribo-polymers. In contrast to these strained bicyclic hydrocarbons, n-decane showed much weaker activity for tribo-polymerization at the same mechanical shear condition. These results suggested that the mechanical shear at tribological interfaces could induce the opening of the strained ring structure of α-pinene and pinane, which leads to polymerization of adsorbed molecules at the sliding track. On a stainless steel surface, such polymerization reactions of adsorbed molecules do not occur under typical surface reaction conditions. The mechanical properties and boundary lubrication efficiency of the produced tribo-polymer films are discussed.

  16. Development of a Household Water Defluoridation Process Using Aluminium Hydroxide Based Adsorbent.

    PubMed

    Mulugeta, Eyobel; Zewge, Feleke; Chandravanshi, Bhagwan Singh

    2015-06-01

    In this study, the removal of fluoride from water using aluminium hydroxide based adsorbent has been investigated in continuous operation. The effect of fluoride influent concentration, feed flowrate, and adsorbent bed height onto the breakthrough characteristics of the adsorption system were examined. The fixed-bed adsorption system was found to perform better with lower influent fluoride concentration, lower flowrate, and higher bed depth. Thermodynamic evaluation using the bed depth service time model indicated that the fluoride adsorption capacity was 25.8 mg F-/g of adsorbent, which is high compared to commercially available activated alumina (1.8 to 1.9 mg/g). Kinetic studies showed that the rate of adsorption in continuous studies was in the range of 6.12×10(-3) to 39.3×10(-3) L/mg.h under different operating conditions. The household defluoridation unit (HDU) was tested at an up-flow mode and it was determined that the HDU packed with 0.9 kg of adsorbent with 28.3 cm of bed depth resulted in a specific safe water yield of 823.79 L. Regeneration of the exhaust media using 1% NaOH and 0.1 M HCl showed that the adsorbent could be reused. The estimated running cost of the unit was 2.0 U.S. dollar/m3 of treated water, with the potential to minimize further. Hence, it was concluded that the proposed method is simple and exhibits superior performance for the treatment of fluoride-contaminated water with the potential for household application. PMID:26459821

  17. Rotational motion of a single water molecule in a buckyball.

    PubMed

    Farimani, A Barati; Wu, Yanbin; Aluru, N R

    2013-11-01

    Encapsulation of a single water molecule in a buckyball (C60) can provide fundamental insights into the properties of water. Investigation of a single water molecule is feasible through its solitary confinement in C60. In this paper, we performed a detailed study of the properties and dynamics of a single water molecule in a buckyball using DFT and MD simulations. We report on the enhancement of rotational diffusion and entropy of a water molecule in C60, compared to a bulk water molecule. H2O@C60 has zero translational diffusion and terahertz revolution frequency. The harmonic, high amplitude rotation of a single water molecule in C60 is compared to stochastic behavior of bulk water molecules. The combination of large rotational and negligible translational motion of water in C60 creates new opportunities in nanotechnology applications. PMID:24061613

  18. The Impact of Adsorbed Triethylene Glycol on Water Wettability of the {1014} Calcium Carbonate Surface

    NASA Astrophysics Data System (ADS)

    Olsen, R.

    2015-12-01

    Water flooding is increasingly being used as a method of enhanced oil recovery and frequently involves calcium carbonate reservoirs. Very often, thermodynamic conditions in the upper few hundred meters allow for hydrate formation. One possible method of preventing hydrates is to inject hydrate inhibitors such as triethylene glycol (TEG) into the reservoir. Thus, it is of importance to know how such glycols affect water wettability, which is an important factor defining the oil behavior in such reservoirs. Wettability of a surface is defined by the contact angle of a liquid drop on the surface. The stronger the liquid is attracted to the surface, the smaller the wetting angle becomes, implying an increased degree of wetting. Therefore, it is possible to gain qualitative knowledge of the change in wetting properties with respect to external influences by studying corresponding changes in free energy of adsorption of the liquid. In our work [1], we used molecular dynamics (MD) and Born-Oppenheimer molecular dynamics (BOMD) to study how adsorbed TEG on the {1014} calcium carbonate surface affected adsorbed water. We used the changes in density profiles of water to estimate changes in adsorption free energy of water. The adaptive biasing force (ABF) method was applied to TEG to calculate the adsorption free energy of TEG on the calcium carbonate surface. We found that water wetting of the calcium carbonate surface decreased in the presence of adsorbed TEG. [1] - Olsen, R.; Leirvik, K.; Kvamme, B.; Kuznetsova, T. Adsorption Properties of Triethylene Glycol on a Hydrated {1014} Calcite Surface and Its Effect on Adsorbed Water, Langmuir 2015, DOI: 10.1021/acs.langmuir.5b02228

  19. A comparison of didodecyldimethylammonium bromide adsorbed at mica/water and silica/water interfaces using neutron reflection.

    PubMed

    Griffin, Lucy R; Browning, Kathryn L; Truscott, Chris L; Clifton, Luke A; Webster, John; Clarke, Stuart M

    2016-09-15

    The layer structure of the dichain alkyl ammonium surfactant, didodecyldimethylammonium bromide (DDAB), adsorbed from water on to silica and mica surfaces has been determined using neutron reflection. Although sometimes considered interchangeable surfaces for study, we present evidence of significant differences in the adsorbed layer structure below the critical micelle concentration. A complete DDAB bilayer was assembled at the water/mica interface at concentrations below the critical micelle concentration (CMC). In contrast it is not until the CMC was reached that the complete bilayer structure formed on the oxidised silicon crystal. Removal of the complete bilayer on both surfaces was attempted by both washing and ion exchange yet the adsorbed structure proved tenacious. PMID:27318715

  20. Magnetic graphene-carbon nanotube iron nanocomposites as adsorbents and antibacterial agents for water purification.

    PubMed

    Sharma, Virender K; McDonald, Thomas J; Kim, Hyunook; Garg, Vijayendra K

    2015-11-01

    One of the biggest challenges of the 21st century is to provide clean and affordable water through protecting source and purifying polluted waters. This review presents advances made in the synthesis of carbon- and iron-based nanomaterials, graphene-carbon nanotubes-iron oxides, which can remove pollutants and inactivate virus and bacteria efficiently in water. The three-dimensional graphene and graphene oxide based nanostructures exhibit large surface area and sorption sites that provide higher adsorption capacity to remove pollutants than two-dimensional graphene-based adsorbents and other conventional adsorbents. Examples are presented to demonstrate removal of metals (e.g., Cu, Pb, Cr(VI), and As) and organics (e.g., dyes and oil) by grapheme-based nanostructures. Inactivation of Gram-positive and Gram-negative bacterial species (e.g., Escherichia coli and Staphylococcus aureus) is also shown. A mechanism involving the interaction of adsorbents and pollutants is briefly discussed. Magnetic graphene-based nanomaterials can easily be separated from the treated water using an external magnet; however, there are challenges in implementing the graphene-based nanotechnology in treating real water. PMID:26498500

  1. Thermodynamic investigation of trichloroethylene adsorption in water-saturated microporous adsorbents

    SciTech Connect

    Farrell, J.; Hauck, B.; Jones, M.

    1999-08-01

    Adsorption of trichloroethylene (TCE) in adsorbents containing hydrophilic and hydrophobic micropores was investigated in order to determine the mechanisms responsible for TCE adsorption on mineral solids. A high-pressure liquid chromatography method was used to measure TCE adsorption isotherms on three microporous adsorbents. Silica gel and zeolite type NaX were used as hydrophilic model adsorbents, and hexamethyldisilazane (HMDS)-treated silica gel was used as a model hydrophobic adsorbent. Batch uptake and desorption isotherms were also measured on the hydrophilic silica gel. Uptake of TCE by all three adsorbents was linear over the concentration range investigated. However, the silica gel desorption isotherm was highly nonlinear, as indicated by its Freundlich isotherm exponent of 0.58. Capillary phase separation into hydrophobic micropores was postulated as being responsible for the isotherm hysteresis. Supporting this hypothesis was the conformance of the TCE adsorption isotherm to Dubinin-Radushkevitch volume filling of micropores theory. The enthalpies for TCE adsorption on all three solids were determined by van't Hoff analysis of distribution coefficients measured over a temperature range from 5 to 90 C. The TCE adsorption enthalpies on the silica gel and HMDS silica gel were exothermic, but on the zeolite adsorption was endothermic. High exothermic adsorption enthalpies on the silica gel adsorbents indicated that TCE adsorption was occurring in hydrophobic micropores, and that adsorption on surfaces with large radii of curvature contributed only minimally to the total uptake. This indicates that the predominant mechanism for TCE adsorption on these mineral solids is not partitioning into the vicinal water layer.

  2. Interaction between water molecules and zinc sulfide nanoparticles studied by temperature-programmed desorption and molecular dynamics simulations.

    PubMed

    Zhang, Hengzhong; Rustad, James R; Banfield, Jillian F

    2007-06-14

    We have investigated the bonding of water molecules to the surfaces of ZnS nanoparticles (approximately 2-3 nm sphalerite) using temperature-programmed desorption (TPD). The activation energy for water desorption was derived as a function of the surface coverage through kinetic modeling of the experimental TPD curves. The binding energy of water equals the activation energy of desorption if it is assumed that the activation energy for adsorption is nearly zero. Molecular dynamics (MD) simulations of water adsorption on 3 and 5 nm sphalerite nanoparticles provided insights into the adsorption process and water binding at the atomic level. Water binds with the ZnS nanoparticle surface mainly via formation of Zn-O bonds. As compared with bulk ZnS crystals, ZnS nanoparticles can adsorb more water molecules per unit surface area due to the greatly increased curvature, which increases the distance between adjacent adsorbed molecules. Results from both TPD and MD show that the water binding energy increases with decreasing the water surface coverage. We attribute the increase in binding energy with decreasing surface water coverage to the increasing degree of surface under-coordination as removal of water molecules proceeds. MD also suggests that the water binding energy increases with decreasing particle size due to the further distance and hence lower interaction between adsorbed water molecules on highly curved smaller particle surfaces. Results also show that the binding energy, and thus the strength of interaction of water, is highest in isolated nanoparticles, lower in nanoparticle aggregates, and lowest in bulk crystals. Given that water binding is driven by surface energy reduction, we attribute the decreased binding energy for aggregated as compared to isolated particles to the decrease in surface energy that occurs as the result of inter-particle interactions. PMID:17518448

  3. Photon-exposure-dependent photon-stimulated desorption for obtaining photolysis cross section of molecules adsorbed on surface by monochromatic soft x-ray photons.

    PubMed

    Chou, L-C; Jang, C-Y; Wu, Y-H; Tsai, W-C; Wang, S-K; Chen, J; Chang, S-C; Liu, C-C; Shai, Y; Wen, C-R

    2008-12-01

    Photon-exposure-dependent positive- and negative-ion photon-stimulated desorption (PSD) was proposed to study the photoreactions and obtain the photolysis cross sections of molecules adsorbed on a single-crystal surface by monochromatic soft x-ray photons with energy near the core level of adsorbate. The changes in the F(+) and F(-) PSD ion yields were measured from CF(3)Cl molecules adsorbed on Si(111)-7x7 at 30 K (CF(3)Cl dose=0.3x10(15) molecules/cm(2), approximately 0.75 monolayer) during irradiation of monochromatic soft x-ray photons near the F(1s) edge. The PSD ion yield data show the following characteristics: (a) The dissociation of adsorbed CF(3)Cl molecules is due to a combination of direct photodissociation via excitation of F(1s) core level and substrate-mediated dissociation [dissociative attachment and dipolar dissociation induced by the photoelectrons emitting from the silicon substrate]. (b) the F(+) ion desorption is associated with the bond breaking of the surface CF(3)Cl, CF(2)Cl, CFCl, and SiF species. (c) the F(-) yield is mainly due to DA and DD of the adsorbed CF(3)Cl molecules. (d) The surface SiF is formed by reaction of the surface Si atom with the neutral fluorine atom, F(+), or F(-) ion produced by scission of C-F bond of CF(3)Cl, CF(2)Cl, or CFCl species. A kinetic model was proposed for the explanation of the photolysis of this submonolayer CF(3)Cl-covered surface. Based on this model and the variation rates of the F(+)F(-) signals during fixed-energy monochromatic photon bombardment at 690.2 and 692.6 eV [near the F(1s) edge], the photolysis cross section was deduced as a function of energy. PMID:19063541

  4. Removal of arsenic from water using the adsorbent: New Zealand iron-sand.

    PubMed

    Panthi, Sudan Raj; Wareham, David Geraint

    2011-01-01

    Adsorption is a technology used to remove arsenic from water contaminated at levels above drinking water standards. In this study, New Zealand Iron-Sand (NZIS), a naturally-available adsorbent was investigated for its efficiency in removing both As (III) and As (V). Several batch tests were conducted with different concentrations of arsenic at different pH conditions. During the batch tests, the maximum adsorption of As (III) occurred at a pH of 7.5, while As (V) adsorption reached its maximum value at a pH of 3. Both Langmuir and Freundlich adsorption models were found to fit with R(2) values greater than 0.92. From the Langmuir adsorption model, the maximum adsorption capacity of NZIS for As (III) and As (V) were estimated to be 1,250 and 500 μg/g, respectively. These values were substantial enough to consider NZIS a promising new adsorbent for arsenic removal. PMID:21991930

  5. A multifunctional azobenzene-based polymeric adsorbent for effective water remediation

    NASA Astrophysics Data System (ADS)

    Wan, Decheng; Chen, Feng; Geng, Qingrui; Lu, Hang; Willcock, Helen; Liu, Qiuming; Wang, Fangyingkai; Zou, Kaidian; Jin, Ming; Pu, Hongting; Du, Jianzhong

    2014-12-01

    The efficient removal of trace carcinogenic organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs) and ionic dyes, from water is an important technical challenge. We report a highly effective recyclable multifunctional azobenzene (AZ)-based silica-supported polymeric adsorbent which can simultaneously remove both PAHs and anionic dyes from water to below parts per billion (ppb) level based on multiple interactions such as the hydrophobic effect, π-π stacking and electrostatic interactions, thus providing a new strategy for designer water remediation materials.

  6. A multifunctional azobenzene-based polymeric adsorbent for effective water remediation

    PubMed Central

    Wan, Decheng; Chen, Feng; Geng, Qingrui; Lu, Hang; Willcock, Helen; Liu, Qiuming; Wang, Fangyingkai; Zou, Kaidian; Jin, Ming; Pu, Hongting; Du, Jianzhong

    2014-01-01

    The efficient removal of trace carcinogenic organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs) and ionic dyes, from water is an important technical challenge. We report a highly effective recyclable multifunctional azobenzene (AZ)-based silica-supported polymeric adsorbent which can simultaneously remove both PAHs and anionic dyes from water to below parts per billion (ppb) level based on multiple interactions such as the hydrophobic effect, π–π stacking and electrostatic interactions, thus providing a new strategy for designer water remediation materials. PMID:25465671

  7. Nanotribological properties of water films adsorbing atop, and absorbing below, graphene layers supported by metal substrates

    NASA Astrophysics Data System (ADS)

    Liu, Zijian; Curtis, C. K.; Stine, R.; Sheehan, P.; Krim, J.

    The tribological properties of graphite, a common lubricant with known sensitivity to the presence of water, have been studied extensively at the macroscopic and microscopic scales. Although far less attention has been devoted to the tribological properties of graphene, it has been established that the tribological response to the presence of water is dissimilar from that of graphite. We report here a quartz crystal microbalance study of the nanotribological properties of water films adsorbed/absorbed on graphene layers prepared by either chemical decomposition on nickel(111) substrates or transfer of freestanding graphene layers to aluminum substrates. Sliding friction levels of the water films were also measured for metal surfaces in the absence of a graphene layer. We observe very high friction levels for water adsorbed atop graphene on Ni(111) and very low levels for water on aluminum. For the case of graphene/aluminum, the data indicate that the water is absorbing between the graphene layer and the aluminum. Dissipation levels moreover indicate the presence of an interstitial water increases sliding friction between the graphene and the aluminum substrate Work supported by NSF and NRL.

  8. Adsorption and removal kinetics of phosphonate from water using natural adsorbents.

    PubMed

    Kumar, R Anil; Velayudhan, K T; Ramachandran, V; Bhai, R Susheela; Unnikrishnan, G; Vasu, K

    2010-01-01

    The removal of phosphonate from water was studied using some natural adsorbents. Potassium phosphonate is a fungicide used for the control of Phytophthora capsici, which is prevalent in black pepper (Piper nigrum L.). Batch adsorption kinetic experiments were conducted on the adsorption of phosphonate onto the adsorbents. The concentration of phosphonate was measured on a high-performance liquid chromatograph fitted with a conductivity detector. The percentage removal of phosphonate by powdered laterite stone (PLS) from water was 40.4%, within a residence time of 15 minutes. The mechanisms of the rate of adsorption were analyzed and compared using the pseudo-second-order, Elovich, and intraparticle diffusion models. The experimental data was found to correlate well with the pseudo-second-order kinetic model, indicating adsorption as a chemisorption process. A possible reaction in the phosphonate-PLS system also has been proposed. The PLS can be used as a low-cost natural adsorbent for phosphonate removal from water. PMID:20112539

  9. Modification of commercial NaY zeolite to give high water diffusivity and adsorb a large amount of water.

    PubMed

    Katoh, Masahiro; Kimura, Michisato; Sugino, Mao; Horikawa, Toshihide; Nakagawa, Keizo; Sugiyama, Shigeru

    2015-10-01

    By using NaY zeolites as desiccant materials, commercial NaY zeolite was alkali treated with 1 M NaOH aqueous solution and then Mg(2+) ion-exchanged by 0.5 M Mg(NO3)2 aqueous solution. Alkali treatment (AT) of NaY zeolite removed silicon atoms selectivity from the framework of Y-type zeolite and enhanced water diffusivity of Y-type zeolite. On the other hand, Mg(2+) ion-exchange of NaY zeolite increased the amount of water adsorbed. Prepared Y-AT-Mg zeolite had both water adsorption velocity and a large difference of water adsorbed amount between adsorption at 30 °C and desorption at 100 °C. PMID:26072446

  10. Adsorption / Desorption Behavior of Water Vapor in an Adsorbent Desiccant Rotor

    NASA Astrophysics Data System (ADS)

    Tsujiguchi, Takuya; Kodama, Akio

    Adsorption / desorption behavior of water vapor onto desiccant rotor has been investigated to improve the desiccant cooling system by means of computer simulation. In this paper, we paid attention to the relationship between the equilibrium amount of water adsorbed onto the desiccant material and the relative humidity, that is adsorption isotherm as a principal characteristic feature of adsorbent. Considering actual adsorbents, five types of adsorption isotherms were assumed to clarify the influence of adsorption isotherm on the dehumidifying performance. After the investigation on the influences of some operating conditions on the dehumidifying performance at each selected adsorption isotherm, it was found that higher dehumidifying performance and reduction of length of desiccant rotor could be achieved by selecting appropriate adsorption isotherm. It was also predicted that S-shaped adsorption isotherm which is raised sharply at relative humidity around 15 % could produce the lowest air humidity at regeneration air temperature 80 °C. Moreover influence of the intraparticle diffusion coefficient which significantly influence on the adsorption / desorption rate was discussed choosing two adsorption isotherm from the above five isotherms. It seems that effective range of the intraparticle diffusion coefficient for the significant improvement of the dehumidifying performance was strongly influenced by the shape of adsorption isotherm.

  11. Arsenic removal from water/wastewater using adsorbents--A critical review.

    PubMed

    Mohan, Dinesh; Pittman, Charles U

    2007-04-01

    Arsenic's history in science, medicine and technology has been overshadowed by its notoriety as a poison in homicides. Arsenic is viewed as being synonymous with toxicity. Dangerous arsenic concentrations in natural waters is now a worldwide problem and often referred to as a 20th-21st century calamity. High arsenic concentrations have been reported recently from the USA, China, Chile, Bangladesh, Taiwan, Mexico, Argentina, Poland, Canada, Hungary, Japan and India. Among 21 countries in different parts of the world affected by groundwater arsenic contamination, the largest population at risk is in Bangladesh followed by West Bengal in India. Existing overviews of arsenic removal include technologies that have traditionally been used (oxidation, precipitation/coagulation/membrane separation) with far less attention paid to adsorption. No previous review is available where readers can get an overview of the sorption capacities of both available and developed sorbents used for arsenic remediation together with the traditional remediation methods. We have incorporated most of the valuable available literature on arsenic remediation by adsorption ( approximately 600 references). Existing purification methods for drinking water; wastewater; industrial effluents, and technological solutions for arsenic have been listed. Arsenic sorption by commercially available carbons and other low-cost adsorbents are surveyed and critically reviewed and their sorption efficiencies are compared. Arsenic adsorption behavior in presence of other impurities has been discussed. Some commercially available adsorbents are also surveyed. An extensive table summarizes the sorption capacities of various adsorbents. Some low-cost adsorbents are superior including treated slags, carbons developed from agricultural waste (char carbons and coconut husk carbons), biosorbents (immobilized biomass, orange juice residue), goethite and some commercial adsorbents, which include resins, gels, silica

  12. The large quadrupole of water molecules.

    PubMed

    Niu, Shuqiang; Tan, Ming-Liang; Ichiye, Toshiko

    2011-04-01

    Many quantum mechanical calculations indicate water molecules in the gas and liquid phase have much larger quadrupole moments than any of the common site models of water for computer simulations. Here, comparisons of multipoles from quantum mechanical∕molecular mechanical (QM∕MM) calculations at the MP2∕aug-cc-pVQZ level on a B3LYP∕aug-cc-pVQZ level geometry of a waterlike cluster and from various site models show that the increased square planar quadrupole can be attributed to the p-orbital character perpendicular to the molecular plane of the highest occupied molecular orbital as well as a slight shift of negative charge toward the hydrogens. The common site models do not account for the p-orbital type electron density and fitting partial charges of TIP4P- or TIP5P-type models to the QM∕MM dipole and quadrupole give unreasonable higher moments. Furthermore, six partial charge sites are necessary to account reasonably for the large quadrupole, and polarizable site models will not remedy the problem unless they account for the p-orbital in the gas phase since the QM calculations show it is present there too. On the other hand, multipole models by definition can use the correct multipoles and the electrostatic potential from the QM∕MM multipoles is much closer than that from the site models to the potential from the QM∕MM electron density. Finally, Monte Carlo simulations show that increasing the quadrupole in the soft-sticky dipole-quadrupole-octupole multipole model gives radial distribution functions that are in good agreement with experiment. PMID:21476758

  13. The Large Quadrupole of Water Molecules

    SciTech Connect

    Niu, Shuqiang; Tan, Ming-Liang; Ichiye, Toshhiko

    2011-04-07

    Many quantum mechanical calculations indicate water molecules in the gas and liquid phase have much larger quadrupole moments than any of the common site models of water for computer simulations. Here, comparisons of multipoles from quantum mechanical/molecular mechanical (QM/MM) calculations at the MP2/aug-cc-pVQZ level on a B3LYP/aug-cc-pVQZ level geometry of a waterlike cluster and from various site models show that the increased square planar quadrupole can be attributed to the p-orbital character perpendicular to the molecular plane of the highest occupied molecular orbital as well as a slight shift of negative charge toward the hydrogens. The common site models do not account for the p-orbital type electron density and fitting partial charges of TIP4P- or TIP5P-type models to the QM/MM dipole and quadrupole give unreasonable higher moments. Furthermore, six partial charge sites are necessary to account reasonably for the large quadrupole, and polarizable site models will not remedy the problem unless they account for the p-orbital in the gas phase since the QM calculations show it is present there too. On the other hand, multipole models by definition can use the correct multipoles and the electrostatic potential from the QM/MM multipoles is much closer than that from the site models to the potential from the QM/MM electron density. Finally, Monte Carlo simulations show that increasing the quadrupole in the soft-sticky dipole-quadrupole-octupole multipole model gives radial distribution functions that are in good agreement with experiment

  14. The large quadrupole of water molecules

    NASA Astrophysics Data System (ADS)

    Niu, Shuqiang; Tan, Ming-Liang; Ichiye, Toshiko

    2011-04-01

    Many quantum mechanical calculations indicate water molecules in the gas and liquid phase have much larger quadrupole moments than any of the common site models of water for computer simulations. Here, comparisons of multipoles from quantum mechanical/molecular mechanical (QM/MM) calculations at the MP2/aug-cc-pVQZ level on a B3LYP/aug-cc-pVQZ level geometry of a waterlike cluster and from various site models show that the increased square planar quadrupole can be attributed to the p-orbital character perpendicular to the molecular plane of the highest occupied molecular orbital as well as a slight shift of negative charge toward the hydrogens. The common site models do not account for the p-orbital type electron density and fitting partial charges of TIP4P- or TIP5P-type models to the QM/MM dipole and quadrupole give unreasonable higher moments. Furthermore, six partial charge sites are necessary to account reasonably for the large quadrupole, and polarizable site models will not remedy the problem unless they account for the p-orbital in the gas phase since the QM calculations show it is present there too. On the other hand, multipole models by definition can use the correct multipoles and the electrostatic potential from the QM/MM multipoles is much closer than that from the site models to the potential from the QM/MM electron density. Finally, Monte Carlo simulations show that increasing the quadrupole in the soft-sticky dipole-quadrupole-octupole multipole model gives radial distribution functions that are in good agreement with experiment.

  15. Fluorescence dynamics of microsphere-adsorbed sunscreens

    NASA Astrophysics Data System (ADS)

    Krishnan, R.

    2005-03-01

    Sunscreens are generally oily substances which are prepared in organic solvents, emulsions or dispersions with micro- or nanoparticles. These molecules adsorb to and integrate into skin cells. In order to understand the photophysical properties of the sunscreen, we compare steady-state and time-resolved fluorescence in organic solvent of varying dielectric constant ɛ and adsorbed to polystyrene microspheres and dispersed in water. Steady-state fluorescence is highest and average fluorescence lifetime longest in toluene, the solvent of lowest ɛ. However, there is no uniform dependence on ɛ. Sunscreens PABA and padimate-O show complex emission spectra. Microsphere-adsorbed sunscreens exhibit highly non-exponential decay, illustrative of multiple environments of the adsorbed molecule. The heterogeneous fluorescence dynamics likely characterizes sunscreen adsorbed to cells.

  16. Orientation Difference of Chemically Immobilized and Physically Adsorbed Biological Molecules on Polymers Detected at the Solid/Liquid Interfaces in Situ

    PubMed Central

    Ye, Shuji; Nguyen, Khoi Tan; Boughton, Andrew P.; Mello, Charlene M.; Chen, Zhan

    2009-01-01

    A surface sensitive second order nonlinear optical technique, sum frequency generation (SFG) vibrational spectroscopy, was applied to study peptide orientation on polymer surfaces, supplemented by a linear vibrational spectroscopy, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). Using the antimicrobial peptide Cecropin P1 as a model system, we have quantitatively demonstrated that chemically immobilized peptides on polymers adopt a more ordered orientation than less tightly bound physically adsorbed peptides. These differences were also observed in different chemical environments, e.g., air versus water. Although numerous studies have reported a direct correlation between the choice of immobilization method and the performance of an attached biological molecule, the lack of direct biomolecular structure and orientation data has made it difficult to elucidate the relationship between structure, orientation and function at a surface. In this work, we directly studied the effect of chemical immobilization method on biomolecular orientation/ordering, an important step for future studies of biomolecular activity. The methods for orientation analysis described within are also of relevance to understanding biosensors, biocompatibility, marine-antifouling, membrane protein functions, and antimicrobial peptide activities. PMID:19961170

  17. Adsorption structure of water molecules on the Be(0001) surface

    SciTech Connect

    Yang, Yu; Li, Yanfang; Wang, Shuangxi; Zhang, Ping

    2014-06-07

    By using density functional theory calculations, we systematically investigate the adsorption of water molecules at different coverages on the Be(0001) surface. The coverage dependence of the prototype water structures and energetics for water adlayer growth are systematically studied. The structures, energetics, and electronic properties are calculated and compared with other available studies. Through our systematic investigations, we find that water molecules form clusters or chains on the Be(0001) surface at low coverages. When increasing the water coverage, water molecules tend to form a 2 × 2 hexagonal network on the Be(0001) surface.

  18. The role of adsorbed water on the friction of a layer of submicron particles

    USGS Publications Warehouse

    Sammis, Charles G.; Lockner, David A.; Reches, Ze’ev

    2011-01-01

    Anomalously low values of friction observed in layers of submicron particles deformed in simple shear at high slip velocities are explained as the consequence of a one nanometer thick layer of water adsorbed on the particles. The observed transition from normal friction with an apparent coefficient near μ = 0.6 at low slip speeds to a coefficient near μ = 0.3 at higher slip speeds is attributed to competition between the time required to extrude the water layer from between neighboring particles in a force chain and the average lifetime of the chain. At low slip speeds the time required for extrusion is less than the average lifetime of a chain so the particles make contact and lock. As slip speed increases, the average lifetime of a chain decreases until it is less than the extrusion time and the particles in a force chain never come into direct contact. If the adsorbed water layer enables the otherwise rough particles to rotate, the coefficient of friction will drop to μ = 0.3, appropriate for rotating spheres. At the highest slip speeds particle temperatures rise above 100°C, the water layer vaporizes, the particles contact and lock, and the coefficient of friction rises to μ = 0.6. The observed onset of weakening at slip speeds near 0.001 m/s is consistent with the measured viscosity of a 1 nm thick layer of adsorbed water, with a minimum particle radius of approximately 20 nm, and with reasonable assumptions about the distribution of force chains guided by experimental observation. The reduction of friction and the range of velocities over which it occurs decrease with increasing normal stress, as predicted by the model. Moreover, the analysis predicts that this high-speed weakening mechanism should operate only for particles with radii smaller than approximately 1 μm. For larger particles the slip speed required for weakening is so large that frictional heating will evaporate the adsorbed water and weakening will not occur.

  19. Electrophoretic deposition of adsorbed arsenic on fine iron oxide particles in tap water

    NASA Astrophysics Data System (ADS)

    Sharif, Syahira Mohd; Bakar, Noor Fitrah Abu; Naim, M. Nazli; Rahman, Norazah Abd; Talib, Suhaimi Abdul

    2016-02-01

    Electrophoretic deposition (EPD) technique has been demonstrated to remove arsenic with natural adsorbent (fine iron oxide particles) in tap water samples. Characterizations of metal element particularly arsenic and fine iron oxide particles in tap water from two different locations, i.e. commercial and residential areas, were conducted. Results showed that the concentration of arsenic in tap water from residential area was higher than commercial area samples i.e. 0.022 ± 0.004 and 0.016 ± 0.008 ppm, respectively. The same finding was observed in zeta potential value where it was higher in the residential area than commercial area, i.e. -42.27 ± 0.12 and -34.83 ± 0.23 mV, respectively. During the removal of arsenic using the EPD technique, direct current (DC) voltage was varied from 5 to 25V at a constant electrode distance of 30 mm. Effect of zeta potential, voltage and electrode type were intensively investigated. High percentage removal of arsenic was obtained from carbon plate than carbon fibre electrode. The percentage removal of arsenic from all samples slightly decreased with increasing of the applied voltage. EDX analysis confirmed that arsenic has adsorbed onto deposited iron oxide particles on the anode electrode. Overall, EPD technique was found to be successful in removing arsenic onto fine iron oxide particles in tap water with 26% ± 1.05 of removal.

  20. Conductivity Measurements of Pyrrole Molecules Incorporated into Chemically Adsorbed Monolayer by Conducting Probe Technique in Atomic Force Microscope

    NASA Astrophysics Data System (ADS)

    Yamamoto, Shin‑ichi; Ogawa, Kazufumi

    2006-03-01

    A monomolecular layer containing pyrrolyl groups at the surface was prepared between two parallel Pt electrodes on a glass substrate by a chemical adsorption technique using N-[11-(trichlorosilyl)undecyl] pyrrole (PNN). Then, the pyrrolyl was polymerized with pure water by applying a DC voltage of 10 V between the two Pt electrodes. It was confirmed using an optical microscope that many electric paths were formed between the two Pt electrodes by a decoration technique using electrochemical polymerization in an aqueous medium containing pyrrole after the polymerization. Next, a conductive probe of an atomic force microscope (AFM) was used to examine an electrical polymerized path through the surface of the polypyrrolyl group in a chemically adsorbed monomolecular layer. The resistance of one electric path in the monomolecular layer was measured using an AFM with an attached Au-covered tip at room temperature. With a measurement volume of about 0.2 nm (the thickness of the electric path in the monomolecular layer) × 200 μm (the average width of the electric path) × 100 μm (the distance between the Pt electrode and the Au-covered AFM tip), the resistance at room temperature of one electric path was 4 k Ω under ambient conditions. From the results in the atmosphere, the conductivity of a super long conjugated polypyrrolyl group without any dopant in a lateral direction was ohmically estimated to be at least 6.0 × 105 S/m.

  1. Surface photochemistry of adsorbed nitrate: the role of adsorbed water in the formation of reduced nitrogen species on α-Fe2O3 particle surfaces.

    PubMed

    Nanayakkara, Charith E; Jayaweera, Pradeep M; Rubasinghege, Gayan; Baltrusaitis, Jonas; Grassian, Vicki H

    2014-01-01

    The surface photochemistry of nitrate, formed from nitric acid adsorption, on hematite (α-Fe2O3) particle surfaces under different environmental conditions is investigated using X-ray photoelectron spectroscopy (XPS). Following exposure of α-Fe2O3 particle surfaces to gas-phase nitric acid, a peak in the N1s region is seen at 407.4 eV; this binding energy is indicative of adsorbed nitrate. Upon broadband irradiation with light (λ > 300 nm), the nitrate peak decreases in intensity as a result of a decrease in adsorbed nitrate on the surface. Concomitant with this decrease in the nitrate coverage, there is the appearance of two lower binding energy peaks in the N1s region at 401.7 and 400.3 eV, due to reduced nitrogen species. The formation as well as the stability of these reduced nitrogen species, identified as NO(-) and N(-), are further investigated as a function of water vapor pressure. Additionally, irradiation of adsorbed nitrate on α-Fe2O3 generates three nitrogen gas-phase products including NO2, NO, and N2O. As shown here, different environmental conditions of water vapor pressure and the presence of molecular oxygen greatly influence the relative photoproduct distribution from nitrate surface photochemistry. The atmospheric implications of these results are discussed. PMID:24299394

  2. Adsorption characteristics of water vapor on gear-pellet and honeycomb-pellet types of adsorbents containing A-type zeolite

    SciTech Connect

    Nakamura, A.; Munakata, K.; Hara, K.; Narita, S.; Sugiyama, T.; Kotoh, K.; Tanaka, M.; Uda, T.

    2015-03-15

    It is necessary to recover or process tritiated species that are extensively coexistent in nuclear fusion installations. A conventional way to recover tritium release to atmosphere is catalytic oxidation of tritiated species and adsorption of tritiated water vapor on adsorbents with high surface areas. Therefore, new adsorbents with low pressure loss and high surface areas need to be developed and utilized for such large-scale adsorption systems. In this study, attention was focused on new adsorbents, which are gear-type pellet MS5A adsorbent, gear-type pellet MS4A adsorbent and honeycomb-type pellet MS5A adsorbent. The adsorption characteristics of the new adsorbent were comparatively studied with conventional type of adsorbents (pellet-type MS5A adsorbent and pebble-type MS5A adsorbent), in terms of adsorption capacity, pressure loss and adsorption rate. It was found that the adsorption capacity of water vapor on the gear-type adsorbents is higher than that on a honeycomb-type adsorbent. The experimental breakthrough curves indicate that the adsorption rates of water vapor on gear-type and honeycomb-type adsorbents are smaller than that on conventional type adsorbents. Various adsorption models were also tested to correlate the experimental isotherms. It was found that the Langmuir-Freundlich model could properly correlate the experimental adsorption isotherms.

  3. Grand canonical Monte Carlo simulation of the adsorption isotherms of water molecules on model soot particles

    NASA Astrophysics Data System (ADS)

    Moulin, F.; Picaud, S.; Hoang, P. N. M.; Jedlovszky, P.

    2007-10-01

    The grand canonical Monte Carlo method is used to simulate the adsorption isotherms of water molecules on different types of model soot particles. The soot particles are modeled by graphite-type layers arranged in an onionlike structure that contains randomly distributed hydrophilic sites, such as OH and COOH groups. The calculated water adsorption isotherm at 298K exhibits different characteristic shapes depending both on the type and the location of the hydrophilic sites and also on the size of the pores inside the soot particle. The different shapes of the adsorption isotherms result from different ways of water aggregation in or/and around the soot particle. The present results show the very weak influence of the OH sites on the water adsorption process when compared to the COOH sites. The results of these simulations can help in interpreting the experimental isotherms of water adsorbed on aircraft soot.

  4. Fluoride removal in water by a hybrid adsorbent lanthanum-carbon.

    PubMed

    Vences-Alvarez, Esmeralda; Velazquez-Jimenez, Litza Halla; Chazaro-Ruiz, Luis Felipe; Diaz-Flores, Paola E; Rangel-Mendez, Jose Rene

    2015-10-01

    Various health problems associated with drinking water containing high fluoride levels, have motivated researchers to develop more efficient adsorbents to remove fluoride from water for beneficial concentrations to human health. The objective of this research was to anchor lanthanum oxyhydroxides on a commercial granular activated carbon (GAC) to remove fluoride from water considering the effect of the solution pH, and the presence of co-existing anions and organic matter. The activated carbon was modified with lanthanum oxyhydroxides by impregnation. SEM and XRD were performed in order to determine the crystal structure and morphology of the La(III) particles anchored on the GAC surface. FT-IR and pK(a)'s distribution were determined in order to elucidate both the possible mechanism of the lanthanum anchorage on the activated carbon surface and the fluoride adsorption mechanism on the modified material. The results showed that lanthanum ions prefer binding to carboxyl and phenolic groups on the activated carbon surface. Potentiometric titrations revealed that the modified carbon (GAC-La) possesses positive charge at a pH lower than 9. The adsorption capacity of the modified GAC increased five times in contrast to an unmodified GAC adsorption capacity at an initial F(-) concentration of 20 mg L(-1). Moreover, the presence of co-existing anions had no effect on the fluoride adsorption capacity at concentrations below 30 mg L(-1), that indicated high F(-) affinity by the modified adsorbent material (GAG-La). PMID:26070190

  5. Forsterite Carbonation in Wet-scCO2: Dependence on Adsorbed Water Concentration

    NASA Astrophysics Data System (ADS)

    Loring, J.; Benezeth, P.; Qafoku, O.; Thompson, C.; Schaef, T.; Bonneville, A.; McGrail, P.; Felmy, A.; Rosso, K.

    2013-12-01

    Capturing and storing CO2 in basaltic formations is one of the most promising options for mitigating atmospheric CO2 emissions resulting from the burning of fossil fuels. These geologic reservoirs have high reactive potential for CO2-mineral trapping due to an abundance of divalent-cation containing silicates, such as forsterite (Mg2SiO4). Recent studies have shown that carbonation of these silicates under wet scCO2 conditions, e. g. encountered near a CO2 injection well, proceeds along a different pathway and is more effective than in CO2-saturated aqueous fluids. The presence of an adsorbed water film on the forsterite surface seems to be key to reactivity towards carbonation. In this study, we employed in situ high pressure IR spectroscopy to investigate the dependence of adsorbed water film thickness on forsterite carbonation chemistry. Post reaction ex situ SEM, TEM, TGA, XRD, and NMR measurements will also be discussed. Several IR titrations were performed of forsterite with water at 50 °C and 90 bar scCO2. Aliquots of water were titrated at 4-hour reaction-time increments. Once a desired total water concentration was reached, data were collected for about another 30 hours. One titration involved 10 additions, which corresponds to 6.8 monolayers of adsorbed water. Clearly, a carbonate was precipitating, and its spectral signature matched magnesite. Another titration involved 8 aliquots, or up to 4.4 monolayers of water. The integrated absorbance under the CO stretching bands of carbonate as a function of time after reaching 4.4 monolayers showed an increase and then a plateau. We are currently unsure of the identity of the carbonate that precipitated, but it could be an amorphous anhydrous phase or magnesite crystals with dimensions of only several nanometers. A third titration only involved 3 additions, or up to 1.6 monolayers of water. The integrated absorbance under the CO stretching bands of carbonate as a function of time after reaching 1.6 monolayers

  6. Mechanical properties of hexadecane-water interfaces with adsorbed hydrophobic bacteria

    NASA Astrophysics Data System (ADS)

    Kang, Zhewen

    Certain strains of hydrophobic bacteria are known to play critical roles in petroleum-related applications. The aim of this study was to investigate how hydrophobic bacteria in their stationary phase could adsorb onto the hexadecane-water interface and alter its mechanical properties. The two strains of bacteria used in forming the interfacial films were Acinetobacter venetianus RAG-1 (a Gram-negative bacterium) and Rhodococcus erythropolis 20S-E1-c (Gram-positive). Experiments at two different length scales (millimetre and micrometre) were conducted and the results were compared. In addition, a simple flow experiment was designed in a constricted channel and the results were related to the intrinsic mechanical properties of bacteria-adsorbed films. On the millimetre scale, using the pendant drop technique, the film interfacial tension was monitored as the surface area was made to undergo changes. Under static conditions, both types of bacteria showed no significant effect on the interfacial tension. When subjected to transient excitations, the two bacterial films exhibited qualitatively similar, yet quantitative distinct rheological properties (including film elasticities and relaxation times). Under continuous reduction of surface area, the RAG-1 system showed a "paper-like" interface, while the interface of the 20S-E1-c system was "soap film-like." These macroscopic observations could be explained by the surface ultrastructures of the two cell strains. On the micrometre scale, using the micropipette technique, colloidal stability of the bacteria-coated oil droplets was examined through direct-contact experiments. Both types of bacteria were seen to function as effective stabilizers. In addition, the adsorbed bacteria also interacted with one another at the interface, giving rise to higher order 2-D rheological properties. A technique of directly probing the mechanical properties of the emulsion drop surfaces revealed that (a) the films behaved as purely elastic

  7. Ceria modified activated carbon: an efficient arsenic removal adsorbent for drinking water purification

    NASA Astrophysics Data System (ADS)

    Sawana, Radha; Somasundar, Yogesh; Iyer, Venkatesh Shankar; Baruwati, Babita

    2016-03-01

    Ceria (CeO2) coated powdered activated carbon was synthesized by a single step chemical process and demonstrated to be a highly efficient adsorbent for the removal of both As(III) and As(V) from water without any pre-oxidation process. The formation of CeO2 on the surface of powdered activated carbon was confirmed by X-ray diffraction, Raman spectroscopy and X-ray photoelectron spectroscopy. The percentage of Ce in the adsorbent was confirmed to be 3.5 % by ICP-OES. The maximum removal capacity for As(III) and As(V) was found to be 10.3 and 12.2 mg/g, respectively. These values are comparable to most of the commercially available adsorbents. 80 % of the removal process was completed within 15 min of contact time in a batch process. More than 95 % removal of both As(III) and As(V) was achieved within an hour. The efficiency of removal was not affected by change in pH (5-9), salinity, hardness, organic (1-4 ppm of humic acid) and inorganic anions (sulphate, nitrate, chloride, bicarbonate and fluoride) excluding phosphate. Presence of 100 ppm phosphate reduced the removal significantly from 90 to 18 %. The equilibrium adsorption pattern of both As(III) and As(V) fitted well with the Freundlich model with R 2 values 0.99 and 0.97, respectively. The material shows reusability greater than three times in a batch process (arsenic concentration reduced below 10 ppb from 330 ppb) and a life of at least 100 L in a column study with 80 g material when tested under natural hard water (TDS 1000 ppm, pH 7.8, hardness 600 ppm as CaCO3) spiked with 330 ppb of arsenic.

  8. Photon-exposure-dependent photon-stimulated desorption for obtaining photolysis cross section of molecules adsorbed on surface by monochromatic soft x-ray photons

    SciTech Connect

    Chou, L.-C.; Jang, C.-Y.; Wu, Y.-H.; Tsai, W.-C.; Wang, S.-K.; Chen, J.; Chang, S.-C.; Liu, C.-C.; Shai, Y.; Wen, C.-R.

    2008-12-07

    Photon-exposure-dependent positive- and negative-ion photon-stimulated desorption (PSD) was proposed to study the photoreactions and obtain the photolysis cross sections of molecules adsorbed on a single-crystal surface by monochromatic soft x-ray photons with energy near the core level of adsorbate. The changes in the F{sup +} and F{sup -} PSD ion yields were measured from CF{sub 3}Cl molecules adsorbed on Si(111)-7x7 at 30 K (CF{sub 3}Cl dose=0.3x10{sup 15} molecules/cm{sup 2}, {approx}0.75 monolayer) during irradiation of monochromatic soft x-ray photons near the F(1s) edge. The PSD ion yield data show the following characteristics: (a) The dissociation of adsorbed CF{sub 3}Cl molecules is due to a combination of direct photodissociation via excitation of F(1s) core level and substrate-mediated dissociation [dissociative attachment and dipolar dissociation induced by the photoelectrons emitting from the silicon substrate]. (b) the F{sup +} ion desorption is associated with the bond breaking of the surface CF{sub 3}Cl, CF{sub 2}Cl, CFCl, and SiF species. (c) the F{sup -} yield is mainly due to DA and DD of the adsorbed CF{sub 3}Cl molecules. (d) The surface SiF is formed by reaction of the surface Si atom with the neutral fluorine atom, F{sup +}, or F{sup -} ion produced by scission of C-F bond of CF{sub 3}Cl, CF{sub 2}Cl, or CFCl species. A kinetic model was proposed for the explanation of the photolysis of this submonolayer CF{sub 3}Cl-covered surface. Based on this model and the variation rates of the F{sup +}/F{sup -} signals during fixed-energy monochromatic photon bombardment at 690.2 and 692.6 eV[near the F(1s) edge], the photolysis cross section was deduced as a function of energy.

  9. Continuous-time core-level photon-stimulated desorption spectroscopy for monitoring soft x-ray-induced reactions of molecules adsorbed on a single-crystal surface

    SciTech Connect

    Chou, L.-C.; Wen, C.-R.

    2006-05-15

    Continuous-time core-level photon-stimulated desorption (PSD) spectroscopy was proposed for monitoring the soft x-ray-induced reactions of molecules adsorbed on a single-crystal surface. Monochromatic synchrotron radiation was used as a soft x-ray light source in the photon-induced reactions of CF{sub 3}Cl adsorbed on a Si(111)-7x7 surface at 30 K and also as a probe for studying the produced fluorination states of the bonding surface Si atom in the positive-ion PSD spectroscopy. The F{sup +} PSD spectrum was obtained by monitoring the F{sup +} signal as a function of incident photon energy near the Si(2p) edge (98-110 eV). Sequential F{sup +} PSD spectra were measured as a function of photon exposure at four adsorbate coverages (the first dose=0.3x10{sup 15} molecules/cm{sup 2}, the second dose=0.8x10{sup 15} molecules/cm{sup 2}, the third dose=2.2x10{sup 15} molecules/cm{sup 2}, and the fourth dose=3.2x10{sup 15} molecules/cm{sup 2}). For the first and second CF{sub 3}Cl-dosed surfaces, the sequential F{sup +} PSD spectra show the variation of their shapes with photon exposure and indicate the formation of surface SiF species. The sequential F{sup +} PSD spectra for the third and fourth CF{sub 3}Cl-dosed surfaces also show the variation of their shapes with photon exposure and depict the production of surface SiF and SiF{sub 3} species.

  10. Hollow Co@C prepared from a Co-ZIF@microporous organic network: magnetic adsorbents for aromatic pollutants in water.

    PubMed

    Hong, Seokjo; Yoo, Jin; Park, Nojin; Lee, Sang Moon; Park, Je-Geun; Park, Ji Hoon; Son, Seung Uk

    2015-12-28

    This work shows the new engineering strategy of magnetic adsorbents by the combination of zeolitic imidazolate framework (ZIF) and microporous organic network (MON) chemistry. ZIF-67 nanoparticles containing Co(2+) ions were coated with MON. The thermolysis of ZIF-67@MON under argon resulted in hollow carbon materials bearing cobalt nanoparticles which showed promising performance as magnetic adsorbents for aromatic pollutants in water. PMID:26490193

  11. Seasonally-Active Water on Mars: Vapour, Ice, Adsorbate, and the Possibility of Liquid

    NASA Astrophysics Data System (ADS)

    Richardson, M. I.

    2002-12-01

    Seasonally-active water can be defined to include any water reservoir that communicates with other reservoirs on time scales of a year or shorter. It is the interaction of these water reservoirs, under the influence of varying solar radiation and in conjunction with surface and atmospheric temperatures, that determines the phase-stability field for water at the surface, and the distribution of water in various forms below, on, and above the surface. The atmosphere is the critical, dynamical link in this cycling system, and also (fortunately) one of the easiest to observe. Viking and Mars Global Surveyor observations paint a strongly asymmetric picture of the global seasonal water cycle, tied proximately to planetary eccentricity, and the existence of residual ice caps of different composition at the two poles. The northern summer experiences the largest water vapour columns, and is associated with sublimation from the northern residual water ice cap. The southern summer residual carbon dioxide ice cap is cold trap for water. Asymmetry in the water cycle is an unsolved problem. Possible solutions may involve the current timing of perihelion (the water cap resides at the pole experiencing the longer but cooler summer), the trapping of water ice in the northern hemisphere by tropical water ice clouds, and the bias in the annual-average, zonal-mean atmospheric circulation resulting from the zonal-mean difference in the elevation of the northern and southern hemispheres. Adsorbed and frozen water have proven harder to constrain. Recent Odyssey Gamma Ray Spectrometer results suggest substantial ground ice in the mid- and high-latitudes, but this water is likely below the seasonal skin depth for two reasons: the GRS results are best fit with such a model, and GCM models of the water cycle produce dramatically unrealistic atmospheric vapour distributions when such a very near surface, GRS-like distribution is initialized - ultimately removing the water to the northern and

  12. Hybrid materials: Magnetite-Polyethylenimine-Montmorillonite, as magnetic adsorbents for Cr(VI) water treatment.

    PubMed

    Larraza, Iñigo; López-Gónzalez, Mar; Corrales, Teresa; Marcelo, Gema

    2012-11-01

    Hybrid materials formed by the combination of a sodium rich Montmorillonite (MMT), with magnetite nanoparticles (40 nm, Fe(3)O(4) NPs) coated with Polyethylenimine polymer (PEI 800 g/mol or PEI 25000 g/mol) were prepared. The intercalation of the magnetite nanoparticles coated with PEI among MMT platelets was achieved by cationic exchange. The resulting materials presented a high degree of exfoliation of the MMT sheets and a good dispersion of Fe(3)O(4) NPs on both the surface and among the layers of MMT. The presence of amine groups in the PEI structure not only aids the exfoliation of the MMT layers, but also gives to the hybrid material the necessary functionality to interact with heavy metals. These hybrid materials were used as magnetic sorbent for the removal of hexavalent chromium from water. The effect that pH, Cr(VI) concentration, and adsorbent material composition have on the Cr(VI) removal efficiency was studied. A complete characterization of the materials was performed. The hybrid materials showed a slight dependence of the removal efficiency with the pH in a wide range (1-9). A maximum amount of adsorption capacity of 8.8 mg/g was determined by the Langmuir isotherm. Results show that these hybrid materials can be considered as potential magnetic adsorbent for the Cr(VI) removal from water in a wide range of pH. PMID:22841705

  13. Water and ion transport in ultra-adsorbing porous magnesium carbonate studied by dielectric spectroscopy

    NASA Astrophysics Data System (ADS)

    Pochard, Isabelle; Frykstrand, Sara; Ahlström, Olle; Forsgren, Johan; Strømme, Maria

    2014-01-01

    Porous materials are used in application areas ranging from drug and vaccine delivery, medical implants, molecular sieves and cosmetics to catalysis and humidity control. In the present work, we employed an alternative approach to gain in-depth understanding about water interaction properties in such materials by the use of dielectric spectroscopy and thereby show that it is possible to obtain information that is not accessible from the more commonly employed water interaction analysis techniques. Specifically, the complex dielectric response of Upsalite, a novel, super-hydroscopic, high-surface area, porous magnesium carbonate material was measured in isothermal frequency scans between 10-3 and 106 Hz at controlled relative humidity (RH). We found the dielectric constant of the dry material to be 1.82. The ratio of bound to free water present in Upsalite after adsorption at room temperature was found to be high irrespective of the surrounding humidity with values ranging from ˜67% to ˜90%. We further found that OH- ions are the charge carriers responsible for the electrode polarization observed in the dielectric response and that the amount of these ions that are free to move in the material corresponds to a concentration of the order of 1-10 μmol l-1 independent of RH. Finally, the OH- diffusion coefficient displayed a drastic decrease with decreasing RH, typical of transport in unsaturated conditions. The presented results provide detailed insight about water interactions in the novel water adsorbing material under study and it is foreseen that the employed analysis methods can be used to evaluate other types of moisture adsorbing materials as well as the movement of functional species in the pores of inorganic drug delivery materials and materials tailored for adsorption of harmful charged species.

  14. Novel Anionic Clay Adsorbents for Boiler-Blow-Down Waters Reclaim and Reuse

    SciTech Connect

    Muhammad Sahimi; Theodore Tsotsis

    2010-01-08

    Arsenic (As) and Selenium (Se) are found in water in the form of oxyanions. Relatively high concentrations of As and Se have been reported both in power plant discharges, as well as, in fresh water supplies. The International Agency for Research on Cancer currently classifies As as a group 1 chemical, that is considered to be carcinogenic to humans. In Phase I of this project we studied the adsorption of As and Se by uncalcined and calcined layered double hydroxide (LDH). The focus of the present work is a systematic study of the adsorption of As and Se by conditioned LDH adsorbents. Conditioning the adsorbent significantly reduced the Mg and Al dissolution observed with uncalcined and calcined LDH. The adsorption rates and isotherms have been investigated in batch experiments using particles of four different particle size ranges. As(V) adsorption is shown to follow a Sips-type adsorption isotherm. The As(V) adsorption rate on conditioned LDH increases with decreasing adsorbent particle size; the adsorption capacity, on the other hand, is independent of the particle size. A homogeneous surface diffusion model (HSDM) and a bi-disperse pore model (BPM) - the latter viewing the LDH particles as assemblages of microparticles and taking into account bulk diffusion in the intraparticle pore space, and surface diffusion within the microparticles themselves - were used to fit the experimental kinetic data. The HSDM estimated diffusivity values dependent on the particle size, whereas the BPM predicted an intracrystalline diffusivity, which is fairly invariant with particle size. The removal of As(V) on conditioned LDH adsorbents was also investigated in flow columns, where the impact of important solution and operational parameters such as influent As concentration, pH, sorbent particle size and flow rate were studied. An early breakthrough and saturation was observed at higher flow rates and at higher influent concentrations, whereas a decrease in the sorbent particle

  15. Removal of atrazine from water by low cost adsorbents derived from agricultural and industrial wastes.

    PubMed

    Sharma, Rajendra Kumar; Kumar, Anoop; Joseph, P E

    2008-05-01

    In the present study six adsorbents viz. wood charcoal, fly ash, coconut charcoal, saw dust, coconut fiber and baggasse charcoal were studied for their capacity to remove atrazine from water. The removal efficiency of different adsorbents varied from 76.5% to 97.7% at 0.05 ppm concentration and 78.5% to 95.5% at 0.1 ppm concentration of atrazine solution, which was less than removal efficiency of activated charcoal reported as 98% for atrazine (Adams and Watson, J Environ Eng ASCE 39:327-330, 1996). Wood charcoal was a cheap (Rs 15 kg(-1)) and easily available material in house holds. Since wood charcoal was granular in nature, it could be used for the removal of atrazine from water to the extent of 95.5%-97.7%. Fly ash is a waste product of thermal plant containing 40%-50% silica, 20%-35% alumina, 12%-30% carbon and unburnt minerals having a high pH of 9-10. It is very cheap and abundant material and has comparatively good adsorption capacity. It was found that fly ash effectively removed about 84.1%-88.5% atrazine from water at 0.05 and 0.1 ppm levels. Coconut shell is also waste product. Therefore, both are inexpensive. The removal efficiency of atrazine from water was 92.4%-95.2% by coconut shell charcoal and 85.9%-86.3% by coconut fiber. Sawdust is generally used as domestic fuel and found everywhere. It is also very cheap (Re. 1 kg(-1)). Baggasse charcoal is a waste product of sugar mill and abundant material. Its cost is due to transport expense, which depends upon distance from the sugar mill. The removal efficiency of sawdust and baggasse charcoal was found 78.5-80.5 and 76.5-84.6, respectively. The efficacy of chemically treated adsorbents for the removal of atrazine from water is in the order: wood charcoal > coconut shell charcoal > fly ash > coconut fiber charcoal > baggasse charcoal > sawdust. PMID:18357400

  16. Oxygen Isotope Fractionation Effects in Soil Water via Cations Adsorbed to High-CEC Clays

    NASA Astrophysics Data System (ADS)

    Oerter, E.; Finstad, K.; Schaefer, J.; Goldsmith, G. R.; Dawson, T. E.; Amundson, R.

    2012-12-01

    In isotope-based approaches to hydrology, soil and sediment are implicitly considered to be an inert matrix in which water resides or moves. Yet, this assumption is inconsistent with the fact that soils contain a wide range of solutes, and highly variable concentrations of chemically reactive clay particles, all of which may react with bulk water and create pools of energetically differing water with varying isotope compositions. The empirical basis of this hypothesis is the work of Sofer and Gat (1972, EPSL, 15(3)), who showed that the formation of hydration spheres around cations in aqueous solutions fractionate oxygen isotopes of water in ways that appear to be dependent on the cation's ionic potential and concentration. Because soil solutions commonly have high solid to fluid ratios, the potential for solids to create substantial pools of low free energy water, with corresponding isotope fractionation of the free and low energy waters, may be a common process. The potential for this to create measurable isotopic effects would be most evident in soils with high Cation Exchange Capacity (CEC). In order to test this hypothesis, montmorillonite (CEC ≈ 100 meq/100g), kaolinite (CEC≈10) and quartz (CEC≈0) mineral powders were saturated with 3M MgCl2 and KCl solutions (separately), rinsed with methanol and dried to saturate all available CEC sites with either Mg or K cations. Triplicate sets of monominerallic-deionized water mixtures were created at 5, 25, 50, 75 and 95% gravimetric water content. Each set of samples was then subjected to one of three water extraction techniques designed to access specific "pools" of soil water: (1) direct equilibration with CO2 to sample the soil's "free water", i.e. water not adsorbed to cations via hydration spheres; (2) centrifugation to simulate permanent wilting point conditions, thereby yielding most micro-pore, macro-pore, and free water; and (3) cryogenic vacuum distillation to recover all the soil water (free, pore and

  17. Biotransformation of pink water TNT on the surface of a low-cost adsorbent pine bark.

    PubMed

    Chusova, O; Nõlvak, H; Odlare, M; Truu, J; Truu, M; Oopkaup, K; Nehrenheim, E

    2015-09-01

    This two-week anaerobic batch study evaluated 2,4,6-trinitrotoluene (TNT) removal efficiency from industrial pink water by (1) adsorption on low-cost adsorbent pine bark, and (2) adsorption coupled with TNT biotransformation by specialised microbial communities. Samples of the supernatant and acetonitrile extracts of pine bark were analysed by HPLC, while the composition of the bacterial community of the experimental batches, inocula and pine bark were profiled by high-throughput sequencing the V6 region of the bacterial 16S rRNA gene. Integrated adsorption and biotransformation proved to be the most efficient method for TNT removal from pink water. The type of applied inoculum had a profound effect on TNT removal efficiencies and microbial community structures, which were dominated by phylotypes belonging to the Enterobacteriaceae family. The analysis of acetonitrile extracts of pine bark supported the hypothesis that the microbial community indigenous to pine bark has the ability to degrade TNT. PMID:26142875

  18. A method for preparing ferric activated carbon composites adsorbents to remove arsenic from drinking water.

    PubMed

    Zhang, Qiao Li; Lin, Y C; Chen, X; Gao, Nai Yun

    2007-09-30

    Iron oxide/activated carbon (FeO/AC) composite adsorbent material, which was used to modify the coal-based activated carbon (AC) 12 x 40, was prepared by the special ferric oxide microcrystal in this study. This composite can be used as the adsorbent to remove arsenic from drinking water, and Langmuir isotherm adsorption equation well describes the experimental adsorption isotherms. Then, the arsenic desorption can subsequently be separated from the medium by using a 1% aqueous NaOH solution. The apparent characters and physical chemistry performances of FeO/AC composite were investigated by X-ray diffraction (XRD), nitrogen adsorption, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Batch and column adsorption experiments were carried out to investigate and compare the arsenic removal capability of the prepared FeO/AC composite material and virgin activated carbon. It can be concluded that: (1) the main phase present in this composite are magnetite (Fe(3)O(4)), maghemite (gamma-Fe(2)O(3)), hematite (alpha-Fe(2)O(3)) and goethite (alpha-FeO(OH)); (2) the presence of iron oxides did not significantly affect the surface area or the pore structure of the activated carbon; (3) the comparisons between the adsorption isotherms of arsenic from aqueous solution onto the composite and virgin activated carbon showed that the FeO/AC composite behave an excellent capacity of adsorption arsenic than the virgin activated carbon; (4) column adsorption experiments with FeO/AC composite adsorbent showed that the arsenic could be removed to below 0.01 mg/L within 1250 mL empty bed volume when influent concentration was 0.5mg/L. PMID:17434260

  19. Fabrication of a novel hydrophobic/ion-exchange mixed-mode adsorbent for the dispersive solid-phase extraction of chlorophenols from environmental water samples.

    PubMed

    Gao, Li; Wei, Yinmao

    2016-08-01

    A novel mixed-mode adsorbent was prepared by functionalizing silica with tris(2-aminoethyl)amine and 3-phenoxybenzaldehyde as the main mixed-mode scaffold due to the presence of the plentiful amino groups and benzene rings in their molecules. The adsorption mechanism was probed with acidic, natural and basic compounds, and the mixed hydrophobic and ion-exchange interactions were found to be responsible for the adsorption of analytes. The suitability of dispersive solid-phase extraction was demonstrated in the determination of chlorophenols in environmental water. Several parameters, including sample pH, desorption solvent, ionic strength, adsorbent dose, and extraction time were optimized. Under the optimal extraction conditions, the proposed dispersive solid-phase extraction coupled with high-performance liquid chromatography showed good linearity range and acceptable limits of detection (0.22∽0.54 ng/mL) for five chlorophenols. Notably, the higher extraction recoveries (88.7∽109.7%) for five chlorophenols were obtained with smaller adsorbent dose (10 mg) and shorter extraction time (15 min) compared with the reported methods. The proposed method might be potentially applied in the determination of trace chlorophenols in real water samples. PMID:27420911

  20. Activated carbons and low cost adsorbents for remediation of tri- and hexavalent chromium from water.

    PubMed

    Mohan, Dinesh; Pittman, Charles U

    2006-09-21

    Hexavalent chromium is a well-known highly toxic metal, considered a priority pollutant. Industrial sources of Cr(VI) include leather tanning, cooling tower blowdown, plating, electroplating, anodizing baths, rinse waters, etc. The most common method applied for chromate control is reduction of Cr(VI) to its trivalent form in acid (pH approximately 2.0) and subsequent hydroxide precipitation of Cr(III) by increasing the pH to approximately 9.0-10.0 using lime. Existing overviews of chromium removal only cover selected technologies that have traditionally been used in chromium removal. Far less attention has been paid to adsorption. Herein, we provide the first review article that provides readers an overview of the sorption capacities of commercial developed carbons and other low cost sorbents for chromium remediation. After an overview of chromium contamination is provided, more than 300 papers on chromium remediation using adsorption are discussed to provide recent information about the most widely used adsorbents applied for chromium remediation. Efforts to establish the adsorption mechanisms of Cr(III) and Cr(VI) on various adsorbents are reviewed. Chromium's impact environmental quality, sources of chromium pollution and toxicological/health effects is also briefly introduced. Interpretations of the surface interactions are offered. Particular attention is paid to comparing the sorption efficiency and capacities of commercially available activated carbons to other low cost alternatives, including an extensive table. PMID:16904258

  1. Development of a nanosphere adsorbent for the removal of fluoride from water.

    PubMed

    Zhang, Kaisheng; Wu, Shibiao; He, Junyong; Chen, Liang; Cai, Xingguo; Chen, Kai; Li, Yulian; Sun, Bai; Lin, Dongyue; Liu, Guqing; Kong, Lingtao; Liu, Jinhuai

    2016-08-01

    A new uniform-sized CeCO3OH nanosphere adsorbent was developed, and tested to establish its efficiency, using kinetic and thermodynamic studies, for fluoride removal. The results demonstrated that the CeCO3OH nanospheres exhibited much high adsorption capacities for fluoride anions due to electrostatic interactions and exchange of the carbonate and hydroxyl groups on the adsorbent surface with fluoride anions. Adsorption kinetics was fitted well by the pseudo-second-order model as compared to a pseudo-first-order rate expression, and adsorption isotherm data were well described by Langmuir model with max adsorption capacity of 45mg/g at pH 7.0. Thermodynamic examination demonstrated that fluoride adsorption on the CeCO3OH nanospheres was reasonably endothermic and spontaneous. Moreover, the CeCO3OH nanospheres have less influence on adsorption of F(-) by pH and co-exiting ions, such as SO4(2-), Cl(-), HCO3(-), CO3(2-), NO3(-) and PO4(3-), and the adsorption efficiency is very high at the low initial fluoride concentrations in the basis of the equilibrium adsorption capacities. This study indicated that the CeCO3OH nanospheres could be developed into a very viable technology for highly effective removal of fluoride from drinking water. PMID:27138842

  2. Magnetic zeolites: a new adsorbent for removal of metallic contaminants from water.

    PubMed

    Oliveira, Luiz C A; Petkowicz, Diego I; Smaniotto, Alessandra; Pergher, Sibele B C

    2004-10-01

    In this work the adsorption features of Na Y zeolite with the magnetic properties of iron oxides have been combined in a composite to produce a magnetic adsorbent. These magnetic composites can be used as an adsorbent for metallic contaminants in water and subsequently removed from the medium by a simple magnetic process. The zeolites:iron oxide magnetic composites, were prepared by using Na Y with weight ratio of 3:1 and were characterized by powder X-ray diffraction (XRD), magnetization measurements, chemical analyses, N(2) adsorption isotherms and Mössbauer spectroscopy. Nitrogen adsorption isotherms showed that the surface area decreased from 505 m(2)g(-1) for the pure Na Y to 353 m(2)g(-1) for the Na Y:Fe oxide 3:1 composite. The adsorption isotherms of metal ions Cr(3+), Cu(2+) and Zn(2+) from aqueous solution onto the composites also showed that the presence of iron oxide does not affect the adsorption capacity. PMID:15350421

  3. Trapping and desorption of complex organic molecules in water at 20 K

    NASA Astrophysics Data System (ADS)

    Burke, Daren J.; Puletti, Fabrizio; Woods, Paul M.; Viti, Serena; Slater, Ben; Brown, Wendy A.

    2015-10-01

    The formation, chemical, and thermal processing of complex organic molecules (COMs) is currently a topic of much interest in interstellar chemistry. The isomers glycolaldehyde, methyl formate, and acetic acid are particularly important because of their role as pre-biotic species. It is becoming increasingly clear that many COMs are formed within interstellar ices which are dominated by water. Hence, the interaction of these species with water ice is crucially important in dictating their behaviour. Here, we present the first detailed comparative study of the adsorption and thermal processing of glycolaldehyde, methyl formate, and acetic acid adsorbed on and in water ices at astrophysically relevant temperatures (20 K). We show that the functional group of the isomer dictates the strength of interaction with water ice, and hence the resulting desorption and trapping behaviour. Furthermore, the strength of this interaction directly affects the crystallization of water, which in turn affects the desorption behaviour. Our detailed coverage and composition dependent data allow us to categorize the desorption behaviour of the three isomers on the basis of the strength of intermolecular and intramolecular interactions, as well as the natural sublimation temperature of the molecule. This categorization is extended to other C, H, and O containing molecules in order to predict and describe the desorption behaviour of COMs from interstellar ices.

  4. Infrared Spectroscopy and Catalysis Research: Infrared spectra of adsorbed molecules provide important information in the study of catalysis.

    PubMed

    Eischens, R P

    1964-10-23

    The examples discussed here represent only a small part of the published work relating to infrared spectra of adsorbed molecules. The publications in this field indicate that infrared spectroscopy is being used for surface chemistry research in about 50 laboratories throughout the world. This effort is mainly devoted to problems related to catalysis, and in this field infrared spectroscopy is the most widely used physical tool for surface chemistry studies. The general acceptance of infrared spectroscopy is primarily due to the fact that it provides information which is pertinent to the understanding of surface reactions on an atomic scale. During the last decade significant progress has also been made in the classical chemical techniques of catalysis study and in utilization of physical tools which depend on phenomena of magnetism, conductivity, low-energy electron diffraction, and electron emission. Probably the most important progress has been in the field of inorganic chemistry, where dramatic advances have been made in knowledge of metal coordination compounds. Such knowledge is vital to the understanding of catalysis on metal surfaces. I believe this progress has produced an attitude of sophisticated optimism among catalysis researchers with regard to eventual understanding of heterogeneous catalysis. This attitude is closely related to the realization that there is no "secret of catalysis" which places catalytic action beyond the limits of ordinary chemical knowledge (22). This view implies that the chemical aspects of heterogeneous catalysis are not unique and that the use of solid catalysts merely provides a highly effective exposure of catalytic atoms and facilitates separation of the products from the catalyst. Many capable catalysis researchers believe that studies of homogeneous catalysis provide the most direct route for the study of heterogeneous catalysis. Obviously homogeneous reactions catalyzed by compounds containing only one or two metal atoms

  5. Interactions of water, methanol and diethyl ether molecules with the surface of oxidized activated carbon

    NASA Astrophysics Data System (ADS)

    Salame, Issa I.; Bandosz, Teresa J.

    Two samples of oxidized activated carbon of wood origin were used as adsorbents of water, methanol, and diethyl ether. Structural and chemical characteristics of the samples' surfaces were obtained using adsorption of nitrogen and Boehm titration. The adsorption isotherms of water and methanol were measured using a volumetric apparatus whereas the adsorption of diethyl ether was studied by means of inverse gas chromatography at finite concentration. Then the isotherms at three different temperatures were used to calculate the isosteric heats of adsorption. The results showed that the strength of interaction depends on the porosity of the sample and its surface chemistry. The effect of surface chemistry and the presence of oxygenated groups are predominant in the case of water and the least important in the case of diethyl ether. This is the result of the chemical nature of the molecules, their sizes, and the relative strengths of the dispersive interactions in small pores in comparison with hydrogen bonding to surface functional groups.

  6. Shape-selective adsorption of aromatic molecules from water by tetramethylammonium-smectite

    USGS Publications Warehouse

    Lee, J.; Mortland, M.M.; Boyd, S.A.; Chiou, C.T.

    1989-01-01

    The adsorption of aromatic compounds by smectite exchanged with tetramethylammonium (TMA) has been studied. Aromatic compounds adsorbed by TMA-smectite are assumed to adopt a tilted orientation in a face-to-face arrangment with the TMA tetrahedra. The sorptive characteristics of TMA-smectite were influenced strongly by the presence of water. The dry TMA-smectite showed little selectivity in the uptake of benzen, toluene and xylene. In the presence of water, TMA-smectite showed a high degree of selectivity based on molecular size/shape, resulting in high uptake of benzene and progressively lower uptake of larger aromatic molecules. This selectivity appeared to result from the shrinkage of interlamellar cavities by water.

  7. Photoinduced conversion of carbon dioxide and water molecules to methanol on the surface of molybdenum oxide MoO x ( x < 2)

    NASA Astrophysics Data System (ADS)

    Silaev, I. V.; Khubezhov, S. A.; Ramonova, A. G.; Grigorkina, G. S.; Kaloeva, A. G.; Demeev, Z. S.; Bliev, A. P.; Sekiba, D.; Ogura, S.; Fukutani, K.; Magkoev, T. T.

    2016-03-01

    X-ray and UV photoelectron spectroscopic data are used to demonstrate that, when pulsed laser light with a photon energy of 6.4 eV acts on the surface of nonstoichiometric molybdenum oxide MoO x ( x < 2), methanol is effectively formed from adsorbed molecules of carbon dioxide and water. The processes in which CO2 and H2O molecules are adsorbed on substrate surface defects and their bonds are activated, enhanced under the effect of photons, should be regarded as the key factors.

  8. Clusterization of water molecules as deduced from statistical mechanical approach

    NASA Astrophysics Data System (ADS)

    Krasnoholovets, Volodymyr

    2004-12-01

    Using the methods of statistical mechanics we have shown that a homogeneous water network is unstable and spontaneously disintegrates to the nonhomogeneous state (i.e. peculiar clusters), which can be treated as an ordinary state of liquid water. The major peculiarity of the concept is that it separates the paired potential into two independent components—the attractive potential and the repulsive one, which in turn should feature a very different dependence on the distance from the particle (a water molecule in the present case). We choose the interaction potential as a combination of the ionic crystal potential and the vibratory potential associated with the elastic properties of the water system as a whole. The number ℵ of water molecules that enters a cluster is calculated as a function of several parameters, such as the dielectric constant, the mass of a water molecule, the distance between nearest molecules, and the vibrations of nearest molecules in their nodes. The number of H2O molecules that comprise a cluster is estimated as about ℵ ≈ 900, which agrees with the available experimental data.

  9. Observation and analysis of Fano-like lineshapes in the Raman spectra of molecules adsorbed at metal interfaces

    NASA Astrophysics Data System (ADS)

    Dey, S.; Banik, M.; Hulkko, E.; Rodriguez, K.; Apkarian, V. A.; Galperin, M.; Nitzan, A.

    2016-01-01

    Surface-enhanced Raman scattering (SERS) from bipyridyl ethylene adsorbed on gold dumbbells shows Fano-like spectra at high incident light intensity. This is accompanied by an increased electronic temperature, while no vibrational anti-Stokes scattering is observed. Theory indicates that interference between vibrational and electronic Raman scattering can yield such asymmetric scattering lineshapes. The best fit to observations is however obtained by disregarding this coupling and accounting for the detailed lineshape of the continuous electronic component of the SERS.

  10. On the Several Molecules and Nanostructures of Water

    PubMed Central

    Whitney, Cynthia Kolb

    2012-01-01

    This paper investigates the water molecule from a variety of viewpoints. Water can involve different isotopes of Hydrogen and Oxygen, it can form differently shaped isomer molecules, and, when frozen, it occupies space differently than most other substances do. The tool for conducting the investigation of all this is called ‘Algebraic Chemistry’. This tool is a quantitative model for predicting the energy budget for all sorts of changes between different ionization states of atoms that are involved in chemical reactions and in changes of physical state. The model is based on consistent patterns seen in empirical data about ionization potentials, together with rational scaling laws that can interpolate and extrapolate for situations where no data are available. The results of the investigation of the water molecule include comments, both positive and negative, about technologies involving heavy water, poly water, Brown’s gas, and cold fusion. PMID:22312305

  11. On the several molecules and nanostructures of water.

    PubMed

    Whitney, Cynthia Kolb

    2012-01-01

    This paper investigates the water molecule from a variety of viewpoints. Water can involve different isotopes of Hydrogen and Oxygen, it can form differently shaped isomer molecules, and, when frozen, it occupies space differently than most other substances do. The tool for conducting the investigation of all this is called 'Algebraic Chemistry'. This tool is a quantitative model for predicting the energy budget for all sorts of changes between different ionization states of atoms that are involved in chemical reactions and in changes of physical state. The model is based on consistent patterns seen in empirical data about ionization potentials, together with rational scaling laws that can interpolate and extrapolate for situations where no data are available. The results of the investigation of the water molecule include comments, both positive and negative, about technologies involving heavy water, poly water, Brown's gas, and cold fusion. PMID:22312305

  12. Quantum Behavior of Water Molecules Confined to Nanocavities in Gemstones.

    PubMed

    Gorshunov, Boris P; Zhukova, Elena S; Torgashev, Victor I; Lebedev, Vladimir V; Shakurov, Gil'man S; Kremer, Reinhard K; Pestrjakov, Efim V; Thomas, Victor G; Fursenko, Dimitry A; Dressel, Martin

    2013-06-20

    When water is confined to nanocavities, its quantum mechanical behavior can be revealed by terahertz spectroscopy. We place H2O molecules in the nanopores of a beryl crystal lattice and observe a rich and highly anisotropic set of absorption lines in the terahertz spectral range. Two bands can be identified, which originate from translational and librational motions of the water molecule isolated within the cage; they correspond to the analogous broad bands in liquid water and ice. In the present case of well-defined and highly symmetric nanocavities, the observed fine structure can be explained by macroscopic tunneling of the H2O molecules within a six-fold potential caused by the interaction of the molecule with the cavity walls. PMID:26283245

  13. Removal efficiency of water purifier and adsorbent for iodine, cesium, strontium, barium and zirconium in drinking water.

    PubMed

    Sato, Itaru; Kudo, Hiroaki; Tsuda, Shuji

    2011-01-01

    The severe incident of Fukushima Daiichi Nuclear Power Station has caused radioactive contamination of environment including drinking water. Radioactive iodine, cesium, strontium, barium and zirconium are hazardous fission products because of the high yield and/or relatively long half-life. In the present study, 4 pot-type water purifiers and several adsorbents were examined for the removal effects on these elements from drinking water. Iodide, iodate, cesium and barium were removed by all water purifiers with efficiencies about 85%, 40%, 75-90% and higher than 85%, respectively. These efficiencies lasted for 200 l, which is near the recommended limits for use of filter cartridges, without decay. Strontium was removed with initial efficiencies from 70% to 100%, but the efficiencies were slightly decreased by use. Zirconium was removed by two models, but hardly removed by the other models. Synthetic zeolite A4 efficiently removed cesium, strontium and barium, but had no effect on iodine and zirconium. Natural zeolite, mordenite, removed cesium with an efficiency as high as zeolite A4, but the removal efficiencies for strontium and barium were far less than those of zeolite A4. Activated carbon had little removal effects on these elements. In case of radioactive contamination of tap water, water purifiers may be available for convenient decontamination of drinking water in the home. PMID:22129747

  14. Sulfonated graphene nanosheets as a superb adsorbent for various environmental pollutants in water.

    PubMed

    Shen, Yi; Chen, Baoliang

    2015-06-16

    Graphene nanosheets, as a novel nanoadsorbent, can be further modified to optimize the adsorption capability for various pollutants. To overcome the structural limits of graphene (aggregation) and graphene oxide (hydrophilic surface) in water, sulfonated graphene (GS) was prepared by diazotization reaction using sulfanilic acid. It was demonstrated that GS not only recovered a relatively complete sp(2)-hybridized plane with high affinity for aromatic pollutants but also had sulfonic acid groups and partial original oxygen-containing groups that powerfully attracted positively charged pollutants. The saturated adsorption capacities of GS were 400 mg/g for phenanthrene, 906 mg/g for methylene blue and 58 mg/g for Cd(2+), which were much higher than the corresponding values for reduced graphene oxide and graphene oxide. GS as a graphene-based adsorbent exhibits fast adsorption kinetic rate and superior adsorption capacity toward various pollutants, which mainly thanks to the multiple adsorption sites in GS including the conjugate π region sites and the functional group sites. Moreover, the sulfonic acid groups endow GS with the good dispersibility and single or few nanosheets which guarantee the adsorption processes. It is great potential to expose the adsorption sites of graphene nanosheets for pollutants in water by regulating their microstructures, surface properties and water dispersion. PMID:26008607

  15. Effects of water molecules on photoluminescence from hierarchical peptide nanotubes and water probing capability.

    PubMed

    Wang, Minjie; Xiong, Shijie; Wu, Xinglong; Chu, Paul K

    2011-10-01

    Photoluminescence (PL) spectra reveal that deficiency of water molecules in the channel cores of bioinspired hierarchical diphenylalanine ( L -Phe- L -Phe, FF) peptide nanotubes (PNTs) not only modifies the bandgap of the subnanometer crystalline structure formed by the self-assembly process, but also induces a characteristic ultraviolet PL peak the position of which is linearly proportional to the number of water molecules in the PNTs. Addition or loss of water molecules gives rise to the UV PL redshift or blueshift. Density functional theory calculation also confirms that addition of water molecules to the PNTs causes splitting of the valence-band peak, which corresponds to the shift and splitting of the observed UV PL peak. Water molecules play an important role in the biological properties of FF PNTs and the results demonstrate that the PL spectra can be used to probe the number of water molecules bonded to the FF molecules. PMID:22049551

  16. State of Water Molecules and Silanol Groups in Opal Minerals: a Near Infrared Spectroscopic Study of Opals from Slovakia

    NASA Astrophysics Data System (ADS)

    Bobon, Miroslav; Christy, Alfred A.; Kluvanec, Daniel; Illasova, L'udmila

    2011-06-01

    Recently near infrared spectroscopy in combination with double derivative technique has been effectively used by Christy [1] to differentiate between free silanol groups and hydrogen bonded silanol groups on silica gel. The method has given some insight into the type of functionalities and their location in silica gel samples. The inportant information in this respect comes from the overtones of the OH groups of water molecules hydrogen bonded to free silanol groups, and hydrogen bonded silanol groups absorbing in the region 5500- 5100 Cm-1 region. The approach was adapted to study the state of water and silanol functionalities and their locations in opals from Slovakia. Twenty opal samples classified into CT and A classes and one quartz sample were used in this work. The samples were crushed using a hydrolic press and powderised. Each sample was then subjected to evacuation process to remove surface adsorbed water at 200°C and the near infrared spectrum of the sample was measured using a Perkin Elmer NTS near infrared spectrometer equipped with a transflectance accessory. The detailed analysis of the sample was carried out using the second derivative profile of the spectrum. The samples were also heated to 750°C to study the state of water molecules in Opal minerals. The results indicate that the opal samples contain 1) surface adsorbed water 2) free and hydrogen bonded silanol groups on the surface 3) Trapped water in the bulk 4) free and hydrogen bonded silanol groups in the cavity surfaces in the bulk. A part of the water molecules found in the bulk of opal minerals are free molecules and the rest are found in hydrogen bonded state to free and hydrogen bonded silanol groups. [1] A. A. Christy, New insights into the surface functionalities and adsorption evolution of water molecules on silica gel surface: A study by second derivative Near Infrared Spectroscopy, Vib. Spectrosc. 54 (2010) 42-49.

  17. Investigation of interparticle forces in natural waters: effects of adsorbed humic acids on iron oxide and alumina surface properties.

    PubMed

    Sander, Sylvia; Mosley, Luke M; Hunter, Keith A

    2004-09-15

    The nature of interparticle forces acting on colloid particle surfaces with adsorbed surface films of the internationally used humic acid standard material, Suwannee River Humic Acid (SHA), has been investigated using an atomic force microscope (AFM). Two particle surfaces were used, alumina and a hydrous iron oxide film coated onto silica particles. Adsorbed SHA dominated the interactive forces for both surface types when present. At low ionic strength and pH > 4, the force curves were dominated by electrostatic repulsion of the electrical double layers, with the extent of repulsion decreasing as electrolyte (NaCl) concentration increased, scaling with the Debye length (kappa(-1)) of the electrolyte according to classical theory. At pH approximately 4, electrostatic forces were largely absent, indicating almost complete protonation of carboxylic acid (-COOH) functional groups on the adsorbed SHA. Under these conditions and also at high electrolyte concentration ([NaCl] > 0.1 M), the absence of electrostatic forces allowed observation of repulsion forces arising from steric interaction of adsorbed SHA as the oxide surfaces approached closely to each other (separation < 10 nm). This steric barrier shrank as electrolyte concentration increased, implying tighter coiling of the adsorbed SHA molecules. In addition, adhesive bridging between surfaces was observed only in the presence of SHA films, implying a strong energy barrier to spontaneous detachment of the surfaces from each other once joined. This adhesion was especially strong in the presence of Ca2+ which appears to bridge SHA layers on each surface. Overall, our results show that SHA is a good model for the NOM adsorbed on colloids. PMID:15487789

  18. Adsorption Properties of Triethylene Glycol on a Hydrated {101̅4} Calcite Surface and Its Effect on Adsorbed Water.

    PubMed

    Olsen, Richard; Leirvik, Kim N; Kvamme, Bjørn; Kuznetsova, Tatiana

    2015-08-11

    Molecular dynamics (MD) and Born-Oppenheimer MD (BOMD) simulations were employed to investigate adsorption of aqueous triethylene glycol (TEG) on a hydrated {101̅4} calcite surface at 298 K. We analyzed the orientation of TEG adsorbed on calcite, as well as the impact of TEG on the water density and adsorption free energy. The adsorption energies of TEG, free energy profiles for TEG, details of hydrogen bonding between water and adsorbed TEG, and dihedral angle distribution of adsorbed TEG were estimated. We found that while the first layer of water was mostly unaffected by the presence of adsorbed TEG, the density of the second water layer was decreased by 71% at 75% surface coverage of TEG. TEG primarily attached to the calcite surface via two adjacent adsorption sites. Hydrogen bonds between water and adsorbed TEG in the second layer almost exclusively involved the hydroxyl oxygen of TEG. The adsorption energy of TEG on calcite in a vacuum environment calculated by classical MD amounted to 217 kJ/mol, which agreed very well with estimates found by using BOMD. Adsorption on hydrated calcite yielded a drastically lower value of 33 kJ/mol, with the corresponding adsorption free energy of 55.3 kJ/mol, giving an entropy increase of 22.3 kJ/mol due to adsorption. We found that the presence of TEG resulted in a decreased magnitude of the adsorption free energy of water, thus decreasing the calcite wettability. This effect can have a profound effect on oil and gas reservoir properties and must be carefully considered when evaluating the risk of hydrate nucleation. PMID:26161580

  19. Tuning of surface wettability of RGO-based aerogels for various adsorbates in water using different amino acids.

    PubMed

    Liu, Wenjun; Wang, Yongke; Li, Zhaohui

    2014-09-14

    RGO-based aerogels with varied and controllable surface wettability were fabricated using different amino acids. Hydrophobic cys-RGO aerogels prepared by L-cysteine exhibited an outstanding adsorption toward oils and organic solvents, while hydrophilic lys-RGO aerogels obtained from L-lysine can be used as adsorbents for heavy metal ions in water. PMID:25057754

  20. Polymer composite adsorbents using particles of molecularly imprinted polymers or aluminium oxide nanoparticles for treatment of arsenic contaminated waters.

    PubMed

    Önnby, L; Pakade, V; Mattiasson, B; Kirsebom, H

    2012-09-01

    Removal of As(V) by adsorption from water solutions was studied using three different synthetic adsorbents. The adsorbents, (a) aluminium nanoparticles (Alu-NPs, <50 nm) incorporated in amine rich cryogels (Alu-cryo), (b) molecular imprinted polymers (<38 μm) in polyacrylamide cryogels (MIP-cryo) and (c) thiol functionalised cryogels (SH-cryo) were evaluated regarding material characteristics and arsenic removal in batch test and continuous mode. Results revealed that a composite design with particles incorporated in cryogels was a successful means for applying small particles (nano- and micro- scale) in water solutions with maintained adsorption capacity and kinetics. Low capacity was obtained from SH-cryo and this adsorbent was hence excluded from the study. The adsorption capacities for the composites were 20.3 ± 0.8 mg/g adsorbent (Alu-cryo) and 7.9 ± 0.7 mg/g adsorbent (MIP-cryo) respectively. From SEM images it was seen that particles were homogeneously distributed in Alu-cryo and heterogeneously distributed in MIP-cryo. The particle incorporation increased the mechanical stability and the polymer backbones of pure polyacrylamide (MIP-cryo) were of better stability than the amine containing polymer backbone (Alu-cryo). Both composites worked well in the studied pH range of pH 2-8. Adsorption tested in real wastewater spiked with arsenic showed that co-ions (nitrate, sulphate and phosphate) affected arsenic removal for Alu-cryo more than for MIP-cryo. Both composites still adsorbed well in the presence of counter-ions (copper and zinc) present at low concentrations (μg/l). The unchanged and selective adsorption in realistic water observed for MIP-cryo was concluded to be due to a successful imprinting, here controlled using a non-imprinted polymer (NIP). A development of MIP-cryo is needed, considering its low adsorption capacity. PMID:22687522

  1. Molecules to Materials for PEC Water Splitting

    SciTech Connect

    Neale, N. R.; Ruddy, D. A.; Lee, K.; Seabold, J. A.; Deutsch, T. G.; Dukovic, G.

    2013-01-01

    Advances in heterogeneous catalysis are driven by the formation of structure-property relationships at solid-liquid and solid-gaseous interfaces. The establishment of these relationships relies on cooperative research efforts on several fronts: prediction and analysis using high-level theoretical models, the development of new synthetic methods to prepare specific solid-state compositions and structures, new analytical methods to identify the active site and define interfacial properties, and mechanistic analysis of functioning catalysts. However, customized materials that allow for fine control of the interfacial properties at solid-liquid boundaries represent difficult synthetic targets. We have been investigating molecular synthons as precursors to advanced materials to address this challenge. In this presentation, we will discuss (1) the chemistry of molecular inorganic complexes, (2) their conversion to mixed-metal oxides, and (3) structure-property relationships of the resulting oxides relevant to PEC water splitting.

  2. Dynamics of Confined Water Molecules in Aqueous Salt Hydrates

    SciTech Connect

    Werhahn, Jasper C.; Pandelov, S.; Yoo, Soohaeng; Xantheas, Sotiris S.; Iglev, H.

    2011-04-01

    The unusual properties of water are largely dictated by the dynamics of the H bond network. A single water molecule has more H bonding sites than atoms, hence new experimental and theoretical investigations about this peculiar liquid have not ceased to appear. Confinement of water to nanodroplets or small molecular clusters drastically changes many of the liquid’s properties. Such confined water plays a major role in the solvation of macro molecules such as proteins and can even be essential to their properties. Despite the vast results available on bulk and confined water, discussions about the correlation between spectral and structural properties continue to this day. The fast relaxation of the OH stretching vibration in bulk water, and the variance of sample geometries in the experiments on confined water obfuscate definite interpretation of the spectroscopic results in terms of structural parameters. We present first time-resolved investigations on a new model system that is ideally suited to overcome many of the problems faced in spectroscopical investigation of the H bond network of water. Aqueous hydrates of inorganic salts provide water molecules in a crystal grid, that enables unambiguous correlations of spectroscopic and structural features. Furthermore, the confined water clusters are well isolated from each other in the crystal matrix, so different degrees of confinement can be achieved by selection of the appropriate salt.

  3. Can the state of platinum species be unambiguously determined by the stretching frequency of an adsorbed CO probe molecule?

    PubMed

    Aleksandrov, Hristiyan A; Neyman, Konstantin M; Hadjiivanov, Konstantin I; Vayssilov, Georgi N

    2016-08-10

    The paper addresses possible ambiguities in the determination of the state of platinum species by the stretching frequency of a CO probe, which is a common technique for characterization of platinum-containing catalytic systems. We present a comprehensive comparison of the available experimental data with our theoretical modeling (density functional) results of pertinent systems - platinum surfaces, nanoparticles and clusters as well as reduced or oxidized platinum moieties on a ceria support. Our results for CO adsorbed on-top on metallic Pt(0), with C-O vibrational frequencies in the region 2018-2077 cm(-1), suggest that a decrease of the coordination number of the platinum atom, to which CO is bound, by one lowers the CO frequency by about 7 cm(-1). This trend corroborates the Kappers-van der Maas correlation derived from the analysis of the experimental stretching frequency of CO adsorbed on platinum-containing samples on different supports. We also analyzed the effect of the charge of platinum species on the CO frequency. Based on the calculated vibrational frequencies of CO in various model systems, we concluded that the actual state of the platinum species may be mistaken based only on the measured value of the C-O vibrational frequency due to overlapping regions of frequencies corresponding to different types of species. In order to identify the actual state of platinum species one has to combine this powerful technique with other approaches. PMID:27444400

  4. Theoretical study of impulsive orientation of asymmetric top water molecules

    NASA Astrophysics Data System (ADS)

    Rangan, Chitra; Senchuk, Andrew

    2008-05-01

    We theoretically study the orientation of a polar, asymmetric top molecule by a terahertz half-cycle pulse. This study is motivated by recent experimental results by C. Herne and P.H. Bucksbaum on the orientation of water molecule using terahertz half-cycle pulses. The half-cycle pulse is modelled as an impulse. The degree of orientation is calculated. Our aim is to characterize the calculated orientation curves in terms of rotational spectroscopy constants.

  5. Soluble hydrocarbons uptake by porous carbonaceous adsorbents at different water ionic strength and temperature: something to consider in oil spills.

    PubMed

    Flores-Chaparro, Carlos E; Ruiz, Luis Felipe Chazaro; Alfaro-De la Torre, Ma Catalina; Rangel-Mendez, Jose Rene

    2016-06-01

    Nowadays, petrochemical operations involve risks to the environment and one of the biggest is oil spills. Low molecular aromatics like benzene, toluene, and naphthalene dissolve in water, and because of their toxicological characteristics, these produce severe consequences to the environment. The oil spill cleanup strategies are mainly designed to deal with the heavy fractions accumulated on the water surface. Unfortunately, very limited information is available regarding the treatment of dissolved fractions.A commercial (Filtrasorb 400) and modified activated carbons were evaluated to remove benzene, toluene, and naphthalene from water, which are the most soluble aromatic hydrocarbons, at different ionic strengths (I) and temperatures (0-0.76 M and 4-25 °C, respectively). This allowed simulating the conditions of fresh and saline waters when assessing the performance of these adsorbents. It was found that the hydrocarbons adsorption affinity increased 12 % at a I of 0.5 M, due to the less negative charge of the adsorbent, while at a high I (≃0.76 M) in a synthetic seawater, the adsorption capacity decreased 21 % that was attributed to the adsorbent's pores occlusion by water clusters. Approximately, 40 h were needed to reach equilibrium; however, the maximum adsorption rate occurred within the first hour in all the cases. Moreover, the hydrocarbons adsorption and desorption capacities increased when the temperature augmented from 4 to 25 °C. On the other hand, thermally and chemically modified materials showed that the interactions between adsorbent-contaminant increased with the basification degree of the adsorbent surface. PMID:26903130

  6. Adsorption of apolar molecules at the water liquid-vapor interface: A Monte Carlo simulations study of the water-n-octane system

    NASA Astrophysics Data System (ADS)

    Jedlovszky, Pál; Varga, Imre; Gilányi, Tibor

    2003-07-01

    The adsorption of n-octane at the water liquid-vapor interface has been investigated by Monte Carlo computer simulation. For this purpose, simulation of five different water-apolar interfacial systems have been performed, in which the number of n-octane molecules has been varied. The results clearly show that the apolar n-octane molecules are adsorbed from the vapor phase at the interface. The adsorption is driven by the weak attraction due to the dispersion forces acting between the water molecules and the methyl and methylene groups of the octanes. This weak attraction is, however, amplified by the fact that it is added up for the CH2 and CH3 groups belonging to the same molecule. Consistently, the n-octane molecules located closest to the aqueous phase are found to prefer all-trans conformation and parallel alignment with the plane of the interface. On the other hand, entropic effects become more important among the molecules of the outer part of the adsorption layer. Hence, the preferred orientation of these molecules is perpendicular to the interface, as they can be extended toward the less dense region of the apolar phase; and gauche dihedrals appear more frequently here than among the molecules located next to the aqueous phase.

  7. Valorization of solid waste products from olive oil industry as potential adsorbents for water pollution control--a review.

    PubMed

    Bhatnagar, Amit; Kaczala, Fabio; Hogland, William; Marques, Marcia; Paraskeva, Christakis A; Papadakis, Vagelis G; Sillanpää, Mika

    2014-01-01

    The global olive oil production for 2010 is estimated to be 2,881,500 metric tons. The European Union countries produce 78.5% of the total olive oil, which stands for an average production of 2,136,000 tons. The worldwide consumption of olive oil increased of 78% between 1990 and 2010. The increase in olive oil production implies a proportional increase in olive mill wastes. As a consequence of such increasing trend, olive mills are facing severe environmental problems due to lack of feasible and/or cost-effective solutions to olive-mill waste management. Therefore, immediate attention is required to find a proper way of management to deal with olive mill waste materials in order to minimize environmental pollution and associated health risks. One of the interesting uses of solid wastes generated from olive mills is to convert them as inexpensive adsorbents for water pollution control. In this review paper, an extensive list of adsorbents (prepared by utilizing different types of olive mill solid waste materials) from vast literature has been compiled, and their adsorption capacities for various aquatic pollutants removal are presented. Different physicochemical methods that have been used to convert olive mill solid wastes into efficient adsorbents have also been discussed. Characterization of olive-based adsorbents and adsorption mechanisms of various aquatic pollutants on these developed olive-based adsorbents have also been discussed in detail. Conclusions have been drawn from the literature reviewed, and suggestions for future research are proposed. PMID:24068561

  8. Measuring sub-nm adsorbed water layer thickness and desorption rate using a fused-silica whispering-gallery microresonator

    NASA Astrophysics Data System (ADS)

    Ganta, D.; Dale, E. B.; Rosenberger, A. T.

    2014-05-01

    We report an optical method for measuring the thickness of the water layer adsorbed onto the surface of a high-Q fused-silica microresonator. Light from a tunable diode laser operating near 1550 nm is coupled into the microresonator to excite whispering-gallery modes (WGMs). By observing thermal distortion or even bistability of the WGM resonances caused by absorption in the water layer, the contribution of that absorption to the total loss is determined. Thereby, the thickness of the water layer is found to be ˜0.1 nm (approximately one monolayer). This method is further extended to measure the desorption rate of the adsorbed water, which is roughly exponential with a decay time of ˜40 h when the fused-silica microresonator is held in a vacuum chamber at low pressure.

  9. A comprehensive study of methyl and ethylmercury determination in natural water by adsorbent preconcentration an GC/AFS analysis

    SciTech Connect

    Cai, Y.; Jaffe, R.; Jones, R.

    1996-10-01

    This paper presents a sample preparation method for the determination of MeHg and ethylmercury (EtHg) in water samples by adsorbent preconcentration and capillary gas chromatography/atomic fluorescence detection (GC/AFS). MeHg and EtHg were preconcentrated from water on to a screening column packed with sulfhydryl cotton fiber (SCF) adsorbent. The MeHg and EtHg were elated by a mixture of acidic potassium bromide and copper sulfate solution, and then extracted using dichloromethane. Breakthrough volume of the SCF column used was tested using high organic matter-containing water from the Florida Everglades and seawater from Florida Bay. Good recoveries were achieved for both MeHg (85%) and EtHg (70%), and no breakthrough was found up to 2 L of sample. The detection limit was 0.01 ng/L in a 2 L water sample for both MeHg and EtHg.

  10. Unprecedentedly rapid transport of single-file rolling water molecules

    NASA Astrophysics Data System (ADS)

    Qiu, Tong; Huang, Ji-Ping

    2015-10-01

    The realization of rapid and unidirectional single-file water-molecule flow in nanochannels has posed a challenge to date. Here, we report unprecedentedly rapid unidirectional single-file water-molecule flow under a translational terahertz electric field, which is obtained by developing a Debye doublerelaxation theory. In addition, we demonstrate that all the single-file molecules undergo both stable translation and rotation, behaving like high-speed train wheels moving along a railway track. Independent molecular dynamics simulations help to confirm these theoretical results. The mechanism involves the resonant relaxation dynamics of H and O atoms. Further, an experimental demonstration is suggested and discussed. This work has implications for the design of high-efficiency nanochannels or smaller nanomachines in the field of nanotechnology, and the findings also aid in the understanding and control of water flow across biological nanochannels in biology-related research.

  11. How Many Water Molecules Does it Take to Dissociate HCl?

    PubMed

    Vargas-Caamal, Alba; Cabellos, Jose Luis; Ortiz-Chi, Filiberto; Rzepa, Henry S; Restrepo, Albeiro; Merino, Gabriel

    2016-02-18

    The potential energy surfaces of the HCl(H2O)n (n is the number of water molecules) clusters are systematically explored using density functional theory and high-level ab initio computations. On the basis of electronic energies, the number of water molecules needed for HCl dissociation is four as reported by some experimental groups. However, this number is five owing to the inclusion of entropic factors. Wiberg bond indices are calculated and analyzed, and the results provide a quadratic correlation and classification of clusters according to the nondissociated, partially dissociated, and fully dissociated character of the H-Cl bond. Our computations show that if temperature is not controlled during the experiment, the values obtained for the dipole moment (or for any measurable property) are susceptible to change, providing a different picture of the number of water molecules needed for HCl dissociation in a nanoscopic droplet. PMID:26774026

  12. Transport behavior of water molecules through two-dimensional nanopores

    SciTech Connect

    Zhu, Chongqin; Li, Hui; Meng, Sheng

    2014-11-14

    Water transport through a two-dimensional nanoporous membrane has attracted increasing attention in recent years thanks to great demands in water purification and desalination applications. However, few studies have been reported on the microscopic mechanisms of water transport through structured nanopores, especially at the atomistic scale. Here we investigate the microstructure of water flow through two-dimensional model graphene membrane containing a variety of nanopores of different size by using molecular dynamics simulations. Our results clearly indicate that the continuum flow transits to discrete molecular flow patterns with decreasing pore sizes. While for pores with a diameter ≥15 Å water flux exhibits a linear dependence on the pore area, a nonlinear relationship between water flux and pore area has been identified for smaller pores. We attribute this deviation from linear behavior to the presence of discrete water flow, which is strongly influenced by the water-membrane interaction and hydrogen bonding between water molecules.

  13. SPAM: A Simple Approach for Profiling Bound Water Molecules.

    PubMed

    Cui, Guanglei; Swails, Jason M; Manas, Eric S

    2013-12-10

    A method that identifies the hydration shell structure of proteins and estimates the relative free energies of water molecules within that hydration shell is described. The method, which we call "SPAM" (maps spelled in reverse), utilizes explicit solvent molecular dynamics (MD) simulations to capture discrete hydration sites at the water-protein interface and computes a local free energy measure from the distribution of interaction energies between water and the environment at a specific site. SPAM is able to provide a qualitative estimate of the thermodynamic profile of bound water molecules that correlates nicely with well-studied structure-activity relationships and observed binding "hot spots". This is demonstrated in retrospective analyses of HIV1 protease and hen egg white lysozyme, where the effects of water displacement and solvent binding have been studied extensively. The simplicity and effectiveness of SPAM allow for prospective application during the drug discovery process. PMID:26592287

  14. Structures of water molecules in carbon nanotubes under electric fields

    SciTech Connect

    Winarto,; Takaiwa, Daisuke; Yamamoto, Eiji; Yasuoka, Kenji

    2015-03-28

    Carbon nanotubes (CNTs) are promising for water transport through membranes and for use as nano-pumps. The development of CNT-based nanofluidic devices, however, requires a better understanding of the properties of water molecules in CNTs because they can be very different from those in the bulk. Using all-atom molecular dynamics simulations, we investigate the effect of axial electric fields on the structure of water molecules in CNTs having diameters ranging from (7,7) to (10,10). The water dipole moments were aligned parallel to the electric field, which increases the density of water inside the CNTs and forms ordered ice-like structures. The electric field induces the transition from liquid to ice nanotubes in a wide range of CNT diameters. Moreover, we found an increase in the lifetime of hydrogen bonds for water structures in the CNTs. Fast librational motion breaks some hydrogen bonds, but the molecular pairs do not separate and the hydrogen bonds reform. Thus, hydrogen bonds maintain the water structure in the CNTs, and the water molecules move collectively, decreasing the axial diffusion coefficient and permeation rate.

  15. Structures of water molecules in carbon nanotubes under electric fields

    NASA Astrophysics Data System (ADS)

    Winarto, Takaiwa, Daisuke; Yamamoto, Eiji; Yasuoka, Kenji

    2015-03-01

    Carbon nanotubes (CNTs) are promising for water transport through membranes and for use as nano-pumps. The development of CNT-based nanofluidic devices, however, requires a better understanding of the properties of water molecules in CNTs because they can be very different from those in the bulk. Using all-atom molecular dynamics simulations, we investigate the effect of axial electric fields on the structure of water molecules in CNTs having diameters ranging from (7,7) to (10,10). The water dipole moments were aligned parallel to the electric field, which increases the density of water inside the CNTs and forms ordered ice-like structures. The electric field induces the transition from liquid to ice nanotubes in a wide range of CNT diameters. Moreover, we found an increase in the lifetime of hydrogen bonds for water structures in the CNTs. Fast librational motion breaks some hydrogen bonds, but the molecular pairs do not separate and the hydrogen bonds reform. Thus, hydrogen bonds maintain the water structure in the CNTs, and the water molecules move collectively, decreasing the axial diffusion coefficient and permeation rate.

  16. [Investigation of membrane permeability of carp spermatozoa for water molecules].

    PubMed

    Pugovkin, A Iu; Kopeĭka, E F; Nardid, O A; Cherkashina, Ia O

    2014-01-01

    The fundamentals of a photometry method for determination of membrane permeability of some fish spermatozoa for water molecules are presented. Osmotic tolerance of carp spermatozoa membranes was studied using EPR-spectroscopy and photometric analysis methods. It was shown that carp spermatozoa look like the ideal osmometers in their reaction on media of different osmolarity. The value of membrane permeability of carp spermatozoa for water molecules was determined. Data obtained can be used in cryobiology for creating cryoprotective media and regimes of fish sperm cryopreservation. PMID:25715589

  17. Cellulose based cationic adsorbent fabricated via radiation grafting process for treatment of dyes waste water.

    PubMed

    Goel, Narender Kumar; Kumar, Virendra; Misra, Nilanjal; Varshney, Lalit

    2015-11-01

    A cationized adsorbent was prepared from cellulosic cotton fabric waste via a single step-green-radiation grafting process using gamma radiation source, wherein poly[2-(methacryloyloxy) ethyl]trimethylammonium chloride (PMAETC) was covalently attached to cotton cellulose substrate. Radiation grafted (PMAETC-g-cellulose) adsorbent was investigated for removal of acid dyes from aqueous solutions using two model dyes: Acid Blue 25 (AB25) and Acid Blue 74 (AB74). The equilibrium adsorption data was analyzed by Langmuir and Freundlich isotherms, whereas kinetic data was analyzed by pseudo first order, pseudo second order, intra particle diffusion and Boyd's models. The PMAETC-g-cellulose adsorbent with 25% grafting yield exhibited equilibrium adsorption capacities of ∼ 540.0mg/g and ∼ 340.0mg/g for AB25 and AB74, respectively. Linear and nonlinear fitting of adsorption data suggested that the equilibrium adsorption process followed Langmuir adsorption isotherm model, whereas, the kinetic adsorption process followed pseudo-second order model. The multi-linearities observed in the intra-particle kinetic plots suggested that the intraparticle diffusion was not the only rate-controlling process in the adsorption of acid dyes on the adsorbent, which was further supported by Boyd's model. The adsorbent could be regenerated by eluting the adsorbed dye from the adsorbent and could be repeatedly used. PMID:26256369

  18. Coordination structure of adsorbed Zn(II) at Water-TiO2 interfaces

    SciTech Connect

    He, G.; Pan, G.; Zhang, M.; Waychunas, G.A.

    2011-01-15

    The local structure of aqueous metal ions on solid surfaces is central to understanding many chemical and biological processes in soil and aquatic environments. Here, the local coordination structure of hydrated Zn(II) at water-TiO{sub 2} interfaces was identified by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) spectroscopy combined with density functional theory (DFT) calculations. A nonintegral coordination number of average {approx}4.5 O atoms around a central Zn atom was obtained by EXAFS analysis. DFT calculations indicated that this coordination structure was consistent with the mixture of 4-coordinated bidentate binuclear (BB) and 5-coordinated bidentate mononuclear (BM) metastable equilibrium adsorption (MEA) states. The BB complex has 4-coordinated Zn, while the monodentate mononuclear (MM) complex has 6-coordinated Zn, and a 5-coordinated adsorbed Zn was found in the BM adsorption mode. DFT calculated energies showed that the lower-coordinated BB and BM modes were thermodynamically more favorable than the higher-coordinated MM MEA state. The experimentally observed XANES fingerprinting provided additional direct spectral evidence of 4- and 5-coordinated Zn-O modes. The overall spectral and computational evidence indicated that Zn(II) can occur in 4-, 5-, and 6-oxygen coordinated sites in different MEA states due to steric hindrance effects, and the coexistence of different MEA states formed the multiple coordination environments.

  19. Conformations of polyaniline molecules adsorbed on Au(111) probed by in situ STM and ex situ XPS and NEXAFS.

    PubMed

    Lee, YiHui; Chang, ChinZen; Yau, ShuehLin; Fan, LiangJen; Yang, YawWen; Yang, LiangYueh Ou; Itaya, Kingo

    2009-05-13

    In situ scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and near edge X-ray absorption fine structure (NEXAFS) have been used to examine the conformation of a monolayer of polyaniline (PAN) molecules produced on a Au(111) single-crystal electrode by anodization at 1.0 V [vs reversible hydrogen electrode (RHE)] in 0.10 M H(2)SO(4) containing 0.030 M aniline. The as-produced PAN molecules took on a well-defined linear conformation stretching for 500 A or more, as shown by in situ and ex situ STM. The XPS and NEXAFS results indicated that the linear PAN seen at 1.0 V assumed the form of an emeraldine salt made of PAN chains and (bi)sulfate anions. Shifting the potential from 1.0 to 0.7 V altered the shape of the PAN molecules from straight to crooked, which was ascribed to restructuring of the Au(111) electrified interface on the basis of voltammetric and XPS results. In situ STM showed that further decreasing the potential to 0.5 V transformed the crooked PAN threads into a mostly linear form again, with preferential alignment and formation of some locally ordered structures. PAN molecules could be reduced from emeraldine to leucoemeraldine as the potential was decreased to 0.2 V or less. In situ STM showed that the fully reduced PAN molecules were straight but mysteriously shortened to approximately 50 A in length. The conformation of PAN did not recuperate when the potential was shifted positively to 1.0 V. PMID:19361217

  20. Non-targeted evaluation of selectivity of water-compatible class selective adsorbents for the analysis of steroids in wastewater.

    PubMed

    Kopperi, Matias; Riekkola, Marja-Liisa

    2016-05-12

    Selective adsorbents for solid-phase extraction are needed to meet the low concentration requirements of new environmental quality standard directives, especially for the analysis of estrogens in wastewater. In this work, bulk polymerization procedures were first optimized for the synthesis of non-imprinted polymers (NIP) with low non-specific adsorption of nonpolar compounds in aqueous environments. Water-compatible molecularly imprinted polymers (MIP) were then synthetized by increasing the selectivity of the polymer towards steroids with a testosterone template (average imprinting factor > 10). In addition, the affinity of synthetized entrapped β-cyclodextrin-epichlorohydrin polymers (ECD) towards steroids was clarified. The polymers were applied to the extraction of spiked wastewater effluent samples and their performance compared to commercially available adsorbents. The selectivity of the studied adsorbents was evaluated utilizing liquid chromatography ‒ mass spectrometry as well as comprehensive two-dimensional gas chromatography ‒ time-of-flight mass spectrometry. Affinity between adsorbents and steroids as well as matrix removal potential were measured with targeted methodologies, and two novel non-targeted methodologies were proposed to quantitatively measure adsorbent selectivity by utilizing chemometrics. Semi-quantitative selectivity was measured from the ratio of peak areas between steroidal and other compounds. Semi-qualitative selectivity was calculated from the ratio between the number of tentatively identified steroidal and other compounds. The synthetized polymers provided good matrix removal potential (ion suppression 15-30%) and semi-qualitative selectivity (∼4 units) compared to the commercial adsorbents (ion suppression 45-80%, selectivity < 3 units). Simple non-targeted approaches provided a novel method of quantifying the selectivity of extraction. PMID:27114222

  1. Application of ultradisperse magnetic adsorbents for removal of small concentrations of pollutants from large volumes of water

    NASA Astrophysics Data System (ADS)

    Nechitailo, Galina S.; Kuznetsov, Anatoli; Kuznetsov, Oleg

    2016-07-01

    Pollution of natural bodies of water (rivers, lakes, ground water, etc) is unfortunately very common, both from natural sources like volcanic activity; and, even more importantly, from human activity, including disposal of industrial and municipal waste, mining, etc. Many toxic substances are harmful for humans and other organisms even in very low concentrations (e.g., less than 1 µg/L of cadmium is harmful, for Hg it is 0.5 µg/L, for phenol - 1 µg/L), and can remain in water for decades or longer. Cleaning large volumes of water even from low concentrations of pollutants is a challenging technological task and is very expensive. We propose to use suspension of ultradisperse magnetic adsorbents, for example, nanostructured ferro-carbon particles, produced by plasmachemical technique, for removing small concentrations of pollutants from large volumes of water. The suspension is introduced into the water. Due to their small sizes and densities similar to water (we measured the density of FC-4 ferro-carbon to be about 1 g/cm3; presumably due to porosity) the particles do not sediment for a long time (hours, days or longer), move due to Brownian motion and adsorb a variety of substances from the water. The particle surface can be modified to provide selectivity of the adsorption. Sorption capacities of ferro-carbon adsorbents is in dozens of percent. Therefore, to collect 1 kg of a pollutant, 2 to 20 kg of the adsorbents is required. Then the particles with the adsorbed contaminant can be collected (e.g., downstream of the river) using a variety of magnetic traps. The traps can consist of ferromagnetic wires and permanent magnets, a variety of simple and inexpensive designs are available. As a model system, the kinetics of adsorption of a highly diluted (0.002 mg/ml) aqueous solution of a low molecular weight compound (toluidine blue) by a small concentration of a ferro-carbon powder (FC-4) was studied by spectrophotometry. Before each measurement, the particles

  2. Targeted adsorption of molecules in the colon with the novel adsorbent-based medicinal product, DAV132: A proof of concept study in healthy subjects.

    PubMed

    de Gunzburg, Jean; Ducher, Annie; Modess, Christiane; Wegner, Danilo; Oswald, Stefan; Dressman, Jennifer; Augustin, Violaine; Feger, Céline; Andremont, Antoine; Weitschies, Werner; Siegmund, Werner

    2015-01-01

    During antibiotic treatments, active residuals reaching the colon profoundly affect the bacterial flora resulting in the emergence of resistance. To prevent these effects, we developed an enteric-coated formulated activated-charcoal based product, DAV132, meant to deliver its adsorbent to the ileum and neutralize antibiotic residues in the proximal colon. In a randomized, control, crossover study, the plasma pharmacokinetics of the probe drugs amoxicillin (500 mg) absorbed in the proximal intestine, and sulfapyridine (25 mg) metabolized from sulfasalazine in the cecum and rapidly absorbed, were compared after a single administration in 18 healthy subjects who had received DAV132, uncoated formulated activated charcoal (FAC) or water 16 and 8 hours before, concomitantly with the probe drugs, and 8 hours thereafter. The AUC0-96 h of amoxicillin was reduced by more than 70% when it was taken with FAC, but bioequivalent when it was taken with water or DAV132. By contrast, the AUC0-96 h of sulfapyridine was reduced by more than 90% when administered with either FAC or DAV132 in comparison with water. The results show that DAV132 can selectively adsorb drug compounds in the proximal colon, without interfering with drug absorption in the proximal small intestine, thereby constituting a proof of concept that DAV132 actually functions in humans. PMID:25042595

  3. Visualizing Water Molecules in Transmembrane Proteins Using Radiolytic Labeling Methods

    SciTech Connect

    Orban, T.; Gupta, S; Palczewski, K; Chance, M

    2010-01-01

    Essential to cells and their organelles, water is both shuttled to where it is needed and trapped within cellular compartments and structures. Moreover, ordered waters within protein structures often colocalize with strategically placed polar or charged groups critical for protein function, yet it is unclear if these ordered water molecules provide structural stabilization, mediate conformational changes in signaling, neutralize charged residues, or carry out a combination of all these functions. Structures of many integral membrane proteins, including G protein-coupled receptors (GPCRs), reveal the presence of ordered water molecules that may act like prosthetic groups in a manner quite unlike bulk water. Identification of 'ordered' waters within a crystalline protein structure requires sufficient occupancy of water to enable its detection in the protein's X-ray diffraction pattern, and thus, the observed waters likely represent a subset of tightly bound functional waters. In this review, we highlight recent studies that suggest the structures of ordered waters within GPCRs are as conserved (and thus as important) as conserved side chains. In addition, methods of radiolysis, coupled to structural mass spectrometry (protein footprinting), reveal dynamic changes in water structure that mediate transmembrane signaling. The idea of water as a prosthetic group mediating chemical reaction dynamics is not new in fields such as catalysis. However, the concept of water as a mediator of conformational dynamics in signaling is just emerging, because of advances in both crystallographic structure determination and new methods of protein footprinting. Although oil and water do not mix, understanding the roles of water is essential to understanding the function of membrane proteins.

  4. Measurement of Emissivity of Water Vapor Adsorbents with Infrared Radiation Thermometer

    NASA Astrophysics Data System (ADS)

    Hamamoto, Yoshinori; Mori, Hideo; Akai, Takafumi; Mitani, Tadafumi

    One of the aims in this study is a development of a numerical analysis model to evaluate a desiccant dehumidifier which regenerates with concentration of solar ray. Inside of a desiccant rotor, in addition to convective heat transfer between airflow and adsorbent surface, radiative heat transfers from one adsorbent surface to another. As a matter of course, absorption and transmission of solar ray on the adsorbent surface occur. It is necessary to measure the emissivity, reflectivity, absorptivity and transmissivity. This paper presents the measurement of emissivity of vapor adsorbents. The measuring apparatus consists of an infrared radiation thermometer. Emissivity was measured in some temperature and humidity conditions. It was clarified that the emissivity decreased with the increase of relative humidity of adsorbent. The emissivity of silica gel particle was less than about 25% in high relative humidity condition compared with dry condition. An empirical formula was presented to predict an influence of the equilibrium adsorption on the emissivity. Moreover, it was clarified that the influence of the equilibrium adsorption on the emissivity of a sheet of adsorbent rotor was negligible.

  5. David Adler Lectureship Award Talk: Friction and energy dissipation mechanisms in adsorbed molecules and molecularly thin films

    NASA Astrophysics Data System (ADS)

    Krim, Jacqueline

    2015-03-01

    Studies of the fundamental origins of friction have undergone rapid progress in recent years, with the development of new experimental and computational techniques for measuring and simulating friction at atomic length and time scales. The increased interest has sparked a variety of discussions and debates concerning the nature of the atomic-scale and quantum mechanisms that dominate the dissipative process by which mechanical energy is transformed into heat. Measurements of the sliding friction of physisorbed monolayers and bilayers can provide information on the relative contributions of these various dissipative mechanisms. Adsorbed films, whether intentionally applied or present as trace levels of physisorbed contaminants, moreover are ubiquitous at virtually all surfaces. As such, they impact a wide range of applications whose progress depends on precise control and/or knowledge of surface diffusion processes. Examples include nanoscale assembly, directed transport of Brownian particles, material flow through restricted geometries such as graphene membranes and molecular sieves, passivation and edge effects in carbon-based lubricants, and the stability of granular materials associated with frictional and frictionless contacts. Work supported by NSFDMR1310456.

  6. On the widths of Stokes lines in Raman scattering from molecules adsorbed at metal surfaces and in molecular conduction junctions

    NASA Astrophysics Data System (ADS)

    Gao, Yi; Galperin, Michael; Nitzan, Abraham

    2016-06-01

    Within a generic model we analyze the Stokes linewidth in surface enhanced Raman scattering (SERS) from molecules embedded as bridges in molecular junctions. We identify four main contributions to the off-resonant Stokes signal and show that under zero voltage bias (a situation pertaining also to standard SERS experiments) and at low bias junctions only one of these contributions is pronounced. The linewidth of this component is determined by the molecular vibrational relaxation rate, which is dominated by interactions with the essentially bosonic thermal environment when the relevant molecular electronic energy is far from the metal(s) Fermi energy(ies). It increases when the molecular electronic level is close to the metal Fermi level so that an additional vibrational relaxation channel due to electron-hole (eh) exciton in the molecule opens. Other contributions to the Raman signal, of considerably broader linewidths, can become important at larger junction bias.

  7. Development of high efficiency silica coated β-cyclodextrin polymeric adsorbent for the removal of emerging contaminants of concern from water.

    PubMed

    Bhattarai, Bikash; Muruganandham, M; Suri, Rominder P S

    2014-05-30

    This article reports the removal of several emerging contaminants (ECs) from water using novel adsorbent comprising of β-cyclodextrin (β-CD) coated on silica. Fourteen different adsorbents were synthesized under different experimental conditions using two different crosslinking agents (hexamethylene diisocyanate (HMDI) and epichlorohydrin (EPI)) and co-polymers (glycidoxypropyl trimethoxysilane (GPTS) and aminopropyl triethoxysilane (APTES). The adsorption capacities of the synthesized adsorbents were initially evaluated using 17β-estradiol, perfluorooctanoic acid (PFOA), and bisphenol-A (BPA) as adsorbates. The adsorbent prepared by using HMDI as crosslinking agent with DMSO as solvent was observed to perform the best, and removed more than 90% of 17β-estradiol, PFOA, and BPA. Furthermore, the β-CD loading on the ECs removal was studied which showed that the adsorbate removal increases with increase in loading of β-CD on the substrate. The best adsorbent was resynthesized in seven batches and its performance was reproducible for the removal of ten steroid hormones. The adsorbent showed very good regeneration potential for four successive adsorption-regeneration cycles to remove steroid hormones and PFOA. A plausible mechanism of adsorption is proposed. The synthesized best adsorbent is characterized using FTIR, HR-TEM, TGA and nitrogen adsorption analysis. The TGA results showed that the adsorbent has thermal stability of upto 300°C. PMID:24727017

  8. Novel Anionic Clay Adsorbents for Boiler-Blow Down Waters Reclaim and Reuse

    SciTech Connect

    Muhammad Sahimi; Theodore T. Tsotsis

    2005-12-01

    Our goal in this study is to utilize novel anionic clay sorbents for treating and reclaiming/reusing power-plant effluents, in particular, boiler blow-down waters containing heavy metals, such as As and Se. Developing and using novel materials for such application is dictated by the challenge posed by reclaiming and recycling these too-clean-to-clean effluent streams, generated during electricity production, whose contaminant levels are in the ppm/ppb (or even less) trace levels. During the study model blow-down streams have been treated in batch experiments. Adsorption isotherms as a function of pH/temperature have been established for both As and Se. Adsorption rates have also measured as a function of concentration, temperature, pH, and space time. For both the equilibrium and rate measurements, we have studied the As/Se interaction, and competition from background anions. A homogeneous surface diffusion model is used to describe the experimental kinetic data. The estimated diffusivity values are shown to depend on the particle size. On the other hand, a model taking into account the polycrystalline nature of these adsorbent particles, and the presence of an intercrystallite porous region predicts correctly that the surface diffusivity is particle size independent. A mathematical model to describe flow experiments in packed-beds has also been developed during phase I of this project. The goal is to validate this model with flow experiments in packed-beds during the phase II of this project, to determine the adsorption capacity under flow conditions, and to compare it with the capacity estimated from the adsorption isotherms determined from the batch studies.

  9. Orbital tomography: Molecular band maps, momentum maps and the imaging of real space orbitals of adsorbed molecules

    PubMed Central

    Offenbacher, Hannes; Lüftner, Daniel; Ules, Thomas; Reinisch, Eva Maria; Koller, Georg; Puschnig, Peter; Ramsey, Michael G.

    2015-01-01

    The frontier orbitals of molecules are the prime determinants of their chemical, optical and electronic properties. Arguably, the most direct method of addressing the (filled) frontier orbitals is ultra-violet photoemission spectroscopy (UPS). Although UPS is a mature technique from the early 1970s on, the angular distribution of the photoemitted electrons was thought to be too complex to be analysed quantitatively. Recently angle resolved UPS (ARUPS) work on conjugated molecules both, in ordered thick films and chemisorbed monolayers, has shown that the angular (momentum) distribution of the photocurrent from orbital emissions can be simply understood. The approach, based on the assumption of a plane wave final state is becoming known as orbital tomography. Here we will demonstrate, with selected examples of pentacene (5A) and sexiphenyl (6P), the potential of orbital tomography. First it will be shown how the full angular distribution of the photocurrent (momentum map) from a specific orbital is related to the real space orbital by a Fourier transform. Examples of the reconstruction of 5A orbitals will be given and the procedure for recovering the lost phase information will be outlined. We then move to examples of sexiphenyl where we interrogate the original band maps of thick sexiphenyl in the light of our understanding of orbital tomography that has developed since then. With comparison to theoretical simulations of the molecular band maps, the molecular conformation and orientation will be concluded. New results for the sexiphenyl monolayer on Al(1 1 0) will then be presented. From the band maps it will be concluded that the molecule is planarised and adopts a tilted geometry. Finally the momentum maps down to HOMO-11 will be analysed and real space orbitals reconstructed. PMID:26752804

  10. Optical and electronic properties of SO2 molecule adsorbed on Si-doped (8, 0) boron nitride nanotube

    NASA Astrophysics Data System (ADS)

    Guo, Shuang-Shuang; Wei, Xiu-Mei; Zhang, Jian-Min; Zhu, Gang-Qiang; Guo, Wan-Jin

    2016-09-01

    The study of the optical properties of pristine BNNT, Si-doped BNNTs and SO2 molecule adsorption on Si-doped BNNTs is that, to our knowledge, few relevant research have ever been found. In this paper, the adsorption behaviors of Sulfur dioxide (SO2) molecule on Si-doped Boron nitride nanotubes (BNNTs) are investigated applying the first-principles calculations. The main contribution of this paper is that the foremost investigation for the optical properties of the pristine BNNT, Si-doped BNNTs and SO2 adsorption on Si-doped BNNTs. Additionally, the electronic properties and the structural properties are also presented. In our calculations of optical properties, the dielectric constant, the refractive index and the absorption coefficient are obtained. Comparing the pristine BNNT, our results indicate that, the blue-shifts (in the main peaks of the dielectric constant of SiB -BNNT and SO2-SiB -BNNT), and the red-shifts (in the main peaks of the refractive index of SiN -BNNT and SO2-SiN -BNNT) are appeared. Under these conditions, Si-doped BNNT and Si-doped BNNT with SO2 adsorption, the gaps are reduced both for the speculated optical band gaps and the electronic structure band gaps.

  11. State of water molecules and silanol groups in opal minerals: a near infrared spectroscopic study of opals from Slovakia

    NASA Astrophysics Data System (ADS)

    Boboň, Miroslav; Christy, Alfred A.; Kluvanec, Daniel; Illášová, L'udmila

    2011-12-01

    Recently, near infrared spectroscopy in combination with double derivative technique has been effectively used by Christy (Vib Spectrosc 54:42-49, 2010) to study and differentiate between free and hydrogen bonded silanol groups on silica gel surface. The method has given some insight into the type of functionalities, their location in silica gel samples, and the way the water molecules bind onto the silanol groups. The important information in this respect comes from the overtones of the OH groups of water molecules hydrogen-bonded to free silanol groups, and hydrogen-bonded silanol groups absorbing in the region 5,500-5,100 cm-1. Chemically, opal minerals are hydrated silica and the same approach was adapted to study the state of water molecules, silanol functionalities, and their locations in opal samples from Slovakia. Twenty opal samples classified into CT and A classes and one quartz sample were used in this work. The samples were crushed using a hydraulic press and powderized. Each sample was then subjected to evacuation process to remove surface-adsorbed water at 200°C, and the near infrared spectrum of each sample was measured using a Perkin Elmer NTS FT-NIR spectrometer equipped with a transflectance accessory and a DTGS detector. The samples were also heated to 750°C to remove the hydrogen-bonded silanol groups on the surface to reveal their locality. Second derivative profiles of the near infrared reflectance spectra were obtained using the instrument's software and used in the detailed analysis of the samples. The analysis of the near infrared spectra and their second derivative profiles had the aim in finding relationships between the surface chemical structure and the classification of opal samples. The dry opal samples were also tested for their surface adsorption effectivity toward water molecules. The results indicate that the opal samples contain (1) surface-adsorbed water, (2) free and hydrogen-bonded silanol groups on the surface, (3) trapped

  12. Tuning dissociation using isoelectronically doped graphene and hexagonal boron nitride: Water and other small molecules

    NASA Astrophysics Data System (ADS)

    Al-Hamdani, Yasmine S.; Alfè, Dario; von Lilienfeld, O. Anatole; Michaelides, Angelos

    2016-04-01

    Novel uses for 2-dimensional materials like graphene and hexagonal boron nitride (h-BN) are being frequently discovered especially for membrane and catalysis applications. Still however, a great deal remains to be understood about the interaction of environmentally and industrially relevant molecules such as water with these materials. Taking inspiration from advances in hybridising graphene and h-BN, we explore using density functional theory, the dissociation of water, hydrogen, methane, and methanol on graphene, h-BN, and their isoelectronic doped counterparts: BN doped graphene and C doped h-BN. We find that doped surfaces are considerably more reactive than their pristine counterparts and by comparing the reactivity of several small molecules, we develop a general framework for dissociative adsorption. From this a particularly attractive consequence of isoelectronic doping emerges: substrates can be doped to enhance their reactivity specifically towards either polar or non-polar adsorbates. As such, these substrates are potentially viable candidates for selective catalysts and membranes, with the implication that a range of tuneable materials can be designed.

  13. Tuning dissociation using isoelectronically doped graphene and hexagonal boron nitride: Water and other small molecules.

    PubMed

    Al-Hamdani, Yasmine S; Alfè, Dario; von Lilienfeld, O Anatole; Michaelides, Angelos

    2016-04-21

    Novel uses for 2-dimensional materials like graphene and hexagonal boron nitride (h-BN) are being frequently discovered especially for membrane and catalysis applications. Still however, a great deal remains to be understood about the interaction of environmentally and industrially relevant molecules such as water with these materials. Taking inspiration from advances in hybridising graphene and h-BN, we explore using density functional theory, the dissociation of water, hydrogen, methane, and methanol on graphene, h-BN, and their isoelectronic doped counterparts: BN dopedgraphene and C doped h-BN. We find that dopedsurfaces are considerably more reactive than their pristine counterparts and by comparing the reactivity of several small molecules, we develop a general framework for dissociative adsorption. From this a particularly attractive consequence of isoelectronic doping emerges: substrates can be doped to enhance their reactivity specifically towards either polar or non-polar adsorbates. As such, these substrates are potentially viable candidates for selective catalysts and membranes, with the implication that a range of tuneable materials can be designed. PMID:27389233

  14. THE APPLICATION OF HIGH RESOLUTION ELECTRON ENERGY LOSS SPECTROSCOPY TO THE CHARACTERIZATION OF ADSORBED MOLECULES ON RHODIUM SINGLE CRYSTAL SURFACES

    SciTech Connect

    Dubois, L.H.; Somorjai, G.A.

    1980-01-01

    The scattering of low energy electrons by metal surfaces has been studied for many years now. The electron's ease of generation and detection and high surface sensitivity (low penetration depth) make it an ideal probe for surface scientists. The impinging electron can interact with the surface in basically two ways: it can either elastically reflect (or diffract) from the surface without losing energy or lose a portion of it's incident energy and inelastically scatter. In this paper we will be concerned with only one of many possible inelastic scattering processes: the loss of the electron's energy to the vibrational modes of atoms and molecules chemisorbed on the surface. This technique is known as high resolution electron energy loss spectroscopy (or ELS, EELS, HRELS, HREELS, etc.).

  15. Hadronic chemistry applied to hydrogen and water molecules

    NASA Astrophysics Data System (ADS)

    Tangde, Vijay M.

    2012-09-01

    The decades of research of R M Santilli resulted into the formulation of iso-, geno- and hyper- mathematics [1, 2] that helped in understanding numerous diversified problems and removing inadequacies in most of the established and celebrated theories of 20th century physics and chemistry, for example, the theories of relativity, quantum mechanics (chemistry), astrophysics, particle physics, and so on. This involves the isotopic, genotopic, etc. lifting of Lie algebra that generated Lie admissible mathematics to properly describe irreversible processes. The studies on Hadronic m Mechanics based on Santilli's mathematics for the first time has removed the very fundamental limitations of quantum chemistry [3, 4] [2, 3, 4]. Herein, we review a Santilli-Shillady model[3, 4, 5] of hydrogen and water molecules characterized by a bond at short distances of the two valance electrons into a singlet quasi-particle state called isoelectronium for hydrogen molecule and two isoelctronia (one per H-O dimer) in case of water molecule. We especially emphasis on: the numerically exact representation of binding energies from unadulterated first axiomatic principle, the reduction of the hydrogen molecule to a restricted three body problem that admits exact analytic solutions and the reduction of computer time by at least a factor of 1000 folds due to a much faster convergent series.

  16. Optimal Electromagnetic (EM) Geophysical Techniques to Map the Concentration of Subsurface Ice and Adsorbed Water on Mars and the Moon

    NASA Astrophysics Data System (ADS)

    Stillman, D. E.; Grimm, R. E.

    2013-12-01

    Water ice is ubiquitous in our Solar System and is a probable target for planetary exploration. Mapping the lateral and vertical concentration of subsurface ice from or near the surface could determine the origin of lunar and martian ice and quantify a much-needed resource for human exploration. Determining subsurface ice concentration on Earth is not trivial and has been attempted previously with electrical resistivity tomography (ERT), ground penetrating radar (GPR), airborne EM (AEM), and nuclear magnetic resonance (NMR). These EM geophysical techniques do not actually detect ice, but rather the absence of unfrozen water. This causes a non-unique interpretation of frozen and dry subsurface sediments. This works well in the arctic because most locations are not dry. However, for planetary exploration, liquid water is exceedingly rare and subsurface mapping must discriminate between an ice-rich and a dry subsurface. Luckily, nature has provided a unique electrical signature of ice: its dielectric relaxation. The dielectric relaxation of ice creates a temperature and frequency dependence of the electrical properties and varies the relative dielectric permittivity from ~3.1 at radar frequencies to >100 at low frequencies. On Mars, sediments smaller than silt size can hold enough adsorbed unfrozen water to complicate the measurement. This is because the presence of absorbed water also creates frequency-dependent electrical properties. The dielectric relaxation of adsorbed water and ice can be separated as they have different shapes and frequency ranges as long as a spectrum spanning the two relaxations is measured. The volume concentration of ice and adsorbed water is a function of the strength of their relaxations. Therefore, we suggest that capacitively-coupled dielectric spectroscopy (a.k.a. spectral induced polarization or complex resistivity) can detect the concentration of both ice and adsorbed water in the subsurface. To prove this concept we have collected

  17. Halloysite Nanotubes as a New Adsorbent for Solid Phase Extraction and Spectrophotometric Determination of Iron in Water and Food Samples

    NASA Astrophysics Data System (ADS)

    Samadi, A.; Amjadi, M.

    2016-07-01

    Halloysite nanotubes (HNTs) have been introduced as a new solid phase extraction adsorbent for preconcentration of iron(II) as a complex with 2,2-bipyridine. The cationic complex is effectively adsorbed on the sorbent in the pH range of 3.5-6.0 and efficiently desorbed by trichloroacetic acid. The eluted complex has a strong absorption around 520 nm, which was used for determination of Fe(II). After optimizing extraction conditions, the linear range of the calibration graph was 5.0-500 μg/L with a detection limit of 1.3 μg/L. The proposed method was successfully applied for the determination of trace iron in various water and food samples, and the accuracy was assessed through the recovery experiments and analysis of a certified reference material (NIST 1643e).

  18. Scrutinizing individual CoTPP molecule adsorbed on coinage metal surfaces from the interplay of STM experiment and theory

    NASA Astrophysics Data System (ADS)

    Houwaart, Torsten; Le Bahers, Tangui; Sautet, Philippe; Auwärter, Willi; Seufert, Knud; Barth, Johannes V.; Bocquet, Marie-Laure

    2015-05-01

    The cobalt tetraphenyl porphyrin (CoTPP) molecule and its adsorption on clean Cu and Ag surfaces are comparatively analyzed within the Density Functional Theory (DFT) framework. Different sets of exchange-correlation functionals - the Local Density Approximation (LDA) and the Gradient Generalized Approximation (along with the PBE functional and the semi-empirical Grimme's corrections of dispersion) - are compared. Two prominent structural adsorption properties are disclosed in all sets of calculations: an asymmetric saddle deformation of CoTPP with an enhanced tilting of the upwards bent pyrroles and a single adsorption site where the Co center occupies a bridge position and one molecular axis (along the direction of the lowered pair of opposite pyrroles) is aligned with the dense-packed < 1 1 bar 0 > substrate direction. The similarities between Cu(111) and Ag(111) surfaces extend to the interfacial electronic structure with similar electronic redistribution and molecular charging. However subtle differences between the two substrates are revealed with bias-dependent STM simulations, especially in the low-bias imaging range. The STM calculations underline the difficulty for the commonly used GGA + D2 DFT framework to quantitatively predict the energy positions of the frontier molecular orbitals (MOs).

  19. Dynamic mechanical properties of a polyelectrolyte adsorbed insoluble lipid monolayer at the air-water interface.

    PubMed

    Park, Chang Young; Kim, Mahn Won

    2015-04-23

    Polymers have been used to stabilize interfaces or to tune the mechanical properties of interfaces in various contexts, such as in oil emulsions or biological membranes. Although the structural properties of these systems are relatively well-studied, instrumental limitations continue to make it difficult to understand how the addition of polymer affects the dynamic mechanical properties of thin and soft films. We have solved this challenge by developing a new instrument, an optical-tweezer-based interface shear microrheometer (ISMR). With this technique, we observed that the interface shear modulus, G*, of a dioctadecyldimethylammonium chloride (DODAC) monolayer at the air-water interface significantly increased with adsorption of polystyrenesulfonate (PSS). In addition, the viscous film (DODAC monolayer) became a viscoelastic film with PSS adsorption. At a low salt concentration, 10 mM of NaCl in the subphase, the viscoelasticity of the DODAC/PSS composite was predominantly determined by a particular property of PSS, that is, it behaves as a Gaussian chain in a θ-solvent. At a high salt concentration, 316 mM of NaCl, the thin film behaved as a polymer melt excluding water molecules. PMID:25826703

  20. Quantum behaviour of water molecule in gemstone: terahertz fingerprints

    NASA Astrophysics Data System (ADS)

    Zhukova, Elena S.; Gorshunov, Boris P.; Torgashev, Victor I.; Lebedev, Vladimir V.; Shakurov, Gil'man S.; Kremer, Reinhard K.; Pestrjakov, Efim V.; Thomas, Victor G.; Fursenko, Dimitry A.; Dressel, Martin

    2014-03-01

    We have shown that a weak interaction of a lone H2O molecule with the ''walls'' of nano-sized crystalline cage of gemstone (beryl) results in emergence of a rich set of molecular vibrational states. By analogy with translational and librational bands in liquid water and ice corresponding absorption bands are explained as due to translational (T) and librational (L) movements of the H2O molecule which is hydrogen bonded to the cage walls. In beryl crystal lattice, however, the six-fold symmetry of the cage brings about additional effect of splitting of the T and L bands into fine structure due to tunnelling within the six-well potential relief. The presented results will be of use for analysis of more complicated systems with confined water molecules like H2O chains in carbon nano-tubes, molecular clusters in e.g. zeolites, clays, silica gels and other natural or synthetic frameworks, as well as for interfacial water in biological systems.

  1. Insight into water molecules bonding on 4d metal surfaces

    NASA Astrophysics Data System (ADS)

    Carrasco, Javier; Michaelides, Angelos; Scheffler, Matthias

    2008-03-01

    Water-metal interactions are of capital importance to a wide variety of phenomena in materials science, catalysis, corrosion, electrochemistry, etc. Here we address the nature of the bond between water molecules and metal surfaces through a careful systematic study. Specifically, the bonding of isolated water molecules to a series of close-packed transition metal surfaces - Ru(0001), Rh(111), Pd(111) and Ag(111) - has been examined in detail with density functional theory (DFT). Aiming to understand the origin behind energetic and structural trends along the 4d series we employ a range of analysis tools, such as decomposition of the density of states, electron density differences, electronic reactivity function and inspection of individual Kohn-Sham orbitals. The results obtained allow us to rationalize the bonding between water and transition metal surfaces as a balance of covalent and electrostatic interactions. A frontier orbital scheme based on so-called two-center four-electron interactions between molecular orbitals of water and d band states of the surface proves incisive in understanding these systems.

  2. Interaction Of Water Molecules With SiC(001) Surfaces

    SciTech Connect

    Cicero, G; Catellani, A; Galli, G

    2004-08-10

    We have investigated the interaction of water molecules with the polar Si- and C- terminated surfaces of cubic Silicon Carbide by means of ab initio molecular dynamics simulations at finite temperature. Different water coverages were considered, from {1/4} to a complete monolayer. Irrespective of coverage, we find that water dissociates on the silicon terminated surfaces, leading to important changes in both its structural and electronic properties. On the contrary, the carbon terminated surface remains inert when exposed to water. We propose experiments to reveal the ionic and electronic structure of wet Si-terminated surfaces predicted by our calculations, which at full coverage are notably different from those of hydrated Si(001) substrates. Finally, we discuss the implications of our results for SiC surface functionalization.

  3. Anomalous water molecules and mechanistic effects of water nanotube clusters confined to molecular porous crystals.

    PubMed

    Tadokoro, Makoto; Ohhara, Takashi; Ohhata, Yuhki; Suda, Takaaki; Miyasato, Yuji; Yamada, Takeshi; Kikuchi, Tatsuya; Tanaka, Ichiro; Kurihara, Kazuo; Oguni, Masaharu; Nakasuji, Kazuhiro; Yamamuro, Osamu; Ryota, Kuroki

    2010-02-18

    The movement of water molecules in the limited space present within nanoscale regions, which is different from the molecular motion of bulk water, is significantly affected by strong interfacial interactions with the surrounding outer walls. Hence, most of the water molecules that are confined to nanochannel spaces having widths less than ca. 2 nm can generally be classified together as "structural water". Since the motions of such water molecules are limited by interfacial interactions with the outer wall, the nature of structural water, which is strongly influenced by the interactions, will have different characteristics from normal water. For our investigations on the characteristics of structural water, we have developed a nanoporous crystal with a diameter of ca. 1.6 nm; it was constructed from 1-D hydrophilic channels by self-organization of the designed molecules. A tubelike three-layered water cluster, called a water nanotube (WNT), is formed in each internal channel space and is regulated by H-bonds with the outer wall. The WNT undergoes a glass transition (T(g) = 107 K) and behaves as a liquid; it freezes at 234 K and changes into an icelike nanotube cluster. In this study, the structure of the WNT is investigated through neutron structure analysis, and it is observed to stabilize by a mechanistic anchor effect of structural water. Furthermore, from neutron-scattering experiments, it is seen that a few water molecules around the center of the WNT move approximately with the same diffusion constant as those in bulk water; however, the residence time and average jump length are longer, despite the restrictions imposed by the H-bonding with structural water. The behavior of mobile water within a WNT is investigated; this can be used to elucidate the mechanism for the effect of structural water on vital functions on the cell surface. PMID:20102158

  4. The spontaneous synchronized dance of pairs of water molecules

    SciTech Connect

    Roncaratti, Luiz F.; Cappelletti, David Pirani, Fernando

    2014-03-28

    Molecular beam scattering experiments have been performed to study the effect of long-range anisotropic forces on the collision dynamics of two small polar molecules. The main focus of this paper is on water, but also ammonia and hydrogen sulphide molecules have been investigated, and some results will be anticipated. The intermolecular distances mainly probed are of the order of 1 nm and therefore much larger than the molecular dimensions. In particular, we have found that the natural electric field gradient, generated by different spatial orientations of the permanent electric dipoles, is able to promote the transformation of free rotations into coupled pendular states, letting the molecular partners involved in the collision complex swinging to and fro around the field direction. This long-ranged concerted motion manifested itself as large increases of the magnitude of the total integral cross section. The experimental findings and the theoretical treatment developed to shed light on the details of the process suggest that the transformation from free rotations to pendular states depends on the rotational level of both molecules, on the impact parameter, on the relative collision velocity, on the dipole moment product and occurs in the time scale of picoseconds. The consequences of this intriguing phenomenon may be important for the interpretation and, in perspective, for the control of elementary chemical and biological processes, given by polar molecules, ions, and free radicals, occurring in several environments under various conditions.

  5. Potassium Niobate Nanolamina: A Promising Adsorbent for Entrapment of Radioactive Cations from Water

    PubMed Central

    Sun, Jin; Yang, Dongjiang; Sun, Cuihua; Liu, Long; Yang, Shuanglei; (Alec) Jia, Yi; Cai, Rongsheng; Yao, Xiangdong

    2014-01-01

    Processing and managing radioactive waste is a great challenge worldwide as it is extremely difficult and costly; the radioactive species, cations or anions, leaked into the environment are a serious threat to the health of present and future generations. We report layered potassium niobate (K4Nb6O17) nanolamina as adsorbent to remove toxic Sr2+, Ba2+ and Cs+ cations from wastewater. The results show that K4Nb6O17 nanolamina can permanently confine the toxic cations within the interlayer spacing via a considerable deformation of the metastable layered structure during the ion exchange process. At the same time, the nanolaminar adsorbent exhibits prompt adsorption kinetics, high adsorption capacity and selectivity, and superior acid resistance. These merits make it be a promising material as ion exchanger for the removal of radioactive cations from wastewater. PMID:25472721

  6. Water-insoluble sericin/β-cyclodextrin/PVA composite electrospun nanofibers as effective adsorbents towards methylene blue.

    PubMed

    Zhao, Rui; Wang, Yong; Li, Xiang; Sun, Bolun; Jiang, Ziqiao; Wang, Ce

    2015-12-01

    A novel water-insoluble sericin/β-cyclodextrin/poly (vinyl alcohol) composite nanofiber adsorbent was prepared by electrospinning and followed by thermal crosslinking for removal of cationic dye methylene blue from aqueous solution. Fourier transform infrared spectroscopy and solubility experiments confirmed that sericin and β-cyclodextrin were incorporated into the nanofibers and the crosslinking reaction occurred successfully. Kinetics, isotherms and thermodynamics analysis were studied for adsorption of methylene blue. The adsorption process is better fitted with the pseudo-second-order model and Langmuir isotherm model. The maximum adsorption capacities are 187.97, 229.89, and 261.10mg/g at the temperatures 293, 313 and 333 K, respectively. Thermodynamic parameters showed that methylene blue adsorption was endothermic and spontaneous. In addition, the fiber membrane adsorbent could be easily separated from dye solution and showed high recyclable removal efficiency. All these results suggest that crosslinked sericin/β-cyclodextrin/poly(vinyl alcohol) composite nanofibers could be potential recyclable adsorbents in dye wastewater treatment. PMID:26433644

  7. Expansion Hamiltonian model for a diatomic molecule adsorbed on a surface: Vibrational states of the CO/Cu(100) system including surface vibrations

    NASA Astrophysics Data System (ADS)

    Meng, Qingyong; Meyer, Hans-Dieter

    2015-10-01

    Molecular-surface studies are often done by assuming a corrugated, static (i.e., rigid) surface. To be able to investigate the effects that vibrations of surface atoms may have on spectra and cross sections, an expansion Hamiltonian model is proposed on the basis of the recently reported [R. Marquardt et al., J. Chem. Phys. 132, 074108 (2010)] SAP potential energy surface (PES), which was built for the CO/Cu(100) system with a rigid surface. In contrast to other molecule-surface coupling models, such as the modified surface oscillator model, the coupling between the adsorbed molecule and the surface atoms is already included in the present expansion SAP-PES model, in which a Taylor expansion around the equilibrium positions of the surface atoms is performed. To test the quality of the Taylor expansion, a direct model, that is avoiding the expansion, is also studied. The latter, however, requests that there is only one movable surface atom included. On the basis of the present expansion and direct models, the effects of a moving top copper atom (the one to which CO is bound) on the energy levels of a bound CO/Cu(100) system are studied. For this purpose, the multiconfiguration time-dependent Hartree calculations are carried out to obtain the vibrational fundamentals and overtones of the CO/Cu(100) system including a movable top copper atom. In order to interpret the results, a simple model consisting of two coupled harmonic oscillators is introduced. From these calculations, the vibrational levels of the CO/Cu(100) system as function of the frequency of the top copper atom are discussed.

  8. Expansion Hamiltonian model for a diatomic molecule adsorbed on a surface: Vibrational states of the CO/Cu(100) system including surface vibrations

    SciTech Connect

    Meng, Qingyong; Meyer, Hans-Dieter

    2015-10-28

    Molecular-surface studies are often done by assuming a corrugated, static (i.e., rigid) surface. To be able to investigate the effects that vibrations of surface atoms may have on spectra and cross sections, an expansion Hamiltonian model is proposed on the basis of the recently reported [R. Marquardt et al., J. Chem. Phys. 132, 074108 (2010)] SAP potential energy surface (PES), which was built for the CO/Cu(100) system with a rigid surface. In contrast to other molecule-surface coupling models, such as the modified surface oscillator model, the coupling between the adsorbed molecule and the surface atoms is already included in the present expansion SAP-PES model, in which a Taylor expansion around the equilibrium positions of the surface atoms is performed. To test the quality of the Taylor expansion, a direct model, that is avoiding the expansion, is also studied. The latter, however, requests that there is only one movable surface atom included. On the basis of the present expansion and direct models, the effects of a moving top copper atom (the one to which CO is bound) on the energy levels of a bound CO/Cu(100) system are studied. For this purpose, the multiconfiguration time-dependent Hartree calculations are carried out to obtain the vibrational fundamentals and overtones of the CO/Cu(100) system including a movable top copper atom. In order to interpret the results, a simple model consisting of two coupled harmonic oscillators is introduced. From these calculations, the vibrational levels of the CO/Cu(100) system as function of the frequency of the top copper atom are discussed.

  9. Functionalized paper--A readily accessible adsorbent for removal of dissolved heavy metal salts and nanoparticles from water.

    PubMed

    Setyono, Daisy; Valiyaveettil, Suresh

    2016-01-25

    Paper, a readily available renewable resource, comprises of interwoven cellulosic fibers, which can be functionalized to develop interesting low-cost adsorbent material for water purification. In this study, polyethyleneimine (PEI)-functionalized paper was used for the removal of hazardous pollutants such as Au and Ag nanoparticles, Cr(VI) anions, Ni(2+), Cd(2+), and Cu(2+) cations from spiked water samples. Compared to untreated paper, the PEI-coated paper showed significant improvement in adsorption capacities toward the pollutants investigated in this study. Kinetics, isotherm models, pH, and desorption studies were carried out to study the adsorption mechanism of pollutants on the adsorbent surface. Adsorption of pollutants was better described by pseudo-second order kinetics and Langmuir isotherm model. Maximum adsorption of anionic pollutants was achieved at pH 5 while that of cations was at pH>6. Overall, the PEI-functionalized paper showed interesting Langmuir adsorption capacities for heavy metal ions such as Cr(VI) (68 mg/g), Ni(2+) (208 mg/g), Cd(2+) (370 mg/g), and Cu(2+) (435 mg/g) ions at neutral pH. In addition, the modified paper was also used to remove Ag-citrate (79 mg/g), Ag-PVP (46 mg/g), Au-citrate (30 mg/g), Au-PVP (17 mg/g) nanoparticles from water. Desorption of NPs from the adsorbent was done by washing with 2 M HCl or thiourea solution, while heavy metal ions were desorbed using 1 M NaOH or HNO3 solution. The modified paper retained its extraction efficiencies upon desorption of pollutants. PMID:26452090

  10. Analyte induced water adsorbability in gas phase biosensors: the influence of ethinylestradiol on the water binding protein capacity.

    PubMed

    Snopok, Borys; Kruglenko, Ivanna

    2015-05-01

    An ultra-sensitive gas phase biosensor/tracer/bio-sniffer is an emerging technology platform designed to provide real-time information on air-borne analytes, or those in liquids, through classical headspace analysis. The desired bio-sniffer measures gaseous 17α- ethinylestradiol (ETED) as frequency changes on a quartz crystal microbalance (QCM), which is a result of the interactions of liquid sample components in the headspace (ETED and water) with a biorecognition layer. The latter was constructed by immobilization of polyclonal antiserum against a phenolic A-ring of estrogenic receptors through protein A. The QCM response exhibited stretched exponential kinetics of negative frequency shifts with reversible and "irreversible" components of mass uptake onto the sensor surface in static headspace conditions when exposed to water solutions of ETED over the sensor working range, from 10(-10) to 10(-17) g L(-1). It was shown that the variations in the QCM response characteristics are due to the change of the water-binding capacity of the sensing layer induced by protein transformations initiated by the binding of ETED molecules. This result is well correlated with the natural physiological function of estrogens in controlling the homeostasis of body fluids in living beings. PMID:25763411

  11. High-harmonic generation in aligned water molecules

    NASA Astrophysics Data System (ADS)

    Wang, Song; Devin, Julien; Hoffmann, Matthias; Cryan, James; Kaldun, Andreas; Bucksbaum, Philip

    2016-05-01

    In recent years, the use of high harmonic generation (HHG) in aligned molecular vapors has become a powerful tool to study ultrafast dynamics of electronic and nuclear wave packets. In our new experimental setup, we are able to orient H2 O and D2 O molecules using a single cycle terahertz (THz) pulse. Aligning water is especially interesting as the highest occupied molecular orbital (HOMO) of water contains a node in the xz plane of the molecular frame, allowing us to perform HHG from second highest occupied molecular orbital (HOMO-1) only, by setting the polarization of the fundamental laser along the z-axis of the aligned water molecules. We are particularly interested in the HOMO-1 state, as there is fast motion of the H-O-H angle leading to sub-wavelength dynamics. On this poster we present our all-optical alignment setup where HHG and single-cycle THz generation take place in high-vacuum, where measurements with arbitrary polarization angles between the two are possible. In addition, we discuss the effects of the molecular orientation on HHG, including symmetry breaking that could produce even harmonics and isotope effects between H2 O and D2 O due to different vibrational energies. This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division.

  12. Single ionization of water molecules in collisions with bare ions

    NASA Astrophysics Data System (ADS)

    Mondal, A.; Mandal, C. R.; Purkait, M.

    2016-04-01

    We present the double differential cross sections (DDCSs) for the direct ionization of water molecules by impact of fully stripped helium, carbon and oxygen atoms, respectively. In the present formalism, we have represented the wavefunction in the entrance channel as the product of a plane wave for the projectile and an accurate one-center-molecular wavefunction of the water molecule by Moccia (1964 J. Chem. Phys. 40 2186). In the exit channel, we have expressed the total wavefunction as the product of pair-wise Coulomb wavefunctions among the ejected electron, projectile ion and the residual target ion, respectively. The contributions of DDCSs for five different molecular orbitals of water to the spectrum of angular distributions have been analyzed for several electron emission energies. The present results for DDCSs are compared with existing experimental and theoretical findings. We find an overall good agreement between our calculated results and the experimental findings for electron emission cross sections. In addition, DDCS results for ionization from different orbitals at a few electron emission energies are given in tabular form.

  13. Electric Dipole Moments of Nanosolvated Acid Molecules in Water Clusters

    NASA Astrophysics Data System (ADS)

    Guggemos, Nicholas; Slavíček, Petr; Kresin, Vitaly V.

    2015-01-01

    The electric dipole moments of (H2O)nDCl (n =3 - 9 ) clusters have been measured by the beam-deflection method. Reflecting the (dynamical) charge distribution within the system, the dipole moment contributes information about the microscopic structure of nanoscale solvation. The addition of a DCl molecule to a water cluster results in a strongly enhanced susceptibility. There is evidence for a noticeable rise in the dipole moment occurring at n ≈5 - 6 . This size is consistent with predictions for the onset of ionic dissociation. Additionally, a molecular-dynamics model suggests that even with a nominally bound impurity an enhanced dipole moment can arise due to the thermal and zero-point motion of the proton and the water molecules. The experimental measurements and the calculations draw attention to the importance of fluctuations in defining the polarity of water-based nanoclusters and generally to the essential role played by motional effects in determining the response of fluxional nanoscale systems under realistic conditions.

  14. Probing the effects of 2D confinement on hydrogen dynamics in water and ice adsorbed in graphene oxide sponges.

    PubMed

    Romanelli, Giovanni; Senesi, Roberto; Zhang, Xuan; Loh, Kian Ping; Andreani, Carla

    2015-12-21

    We studied the single particle dynamics of water and ice adsorbed in graphene oxide (GO) sponges at T = 293 K and T = 20 K. We used Deep Inelastic Neutron Scattering (DINS) at the ISIS neutron and muon spallation source to derive the hydrogen mean kinetic energy, 〈EK〉, and momentum distribution, n(p). The goal of this work was to study the hydrogen dynamics under 2D confinement and the potential energy surface, fingerprinting the hydrogen interaction with the layered structure of the GO sponge. The observed scattering is interpreted within the framework of the impulse approximation. Samples of both water and ice adsorbed in GO show n(p) functions with almost harmonic and anisotropic line shapes and 〈EK〉 values in excess of the values found at the corresponding temperatures in the bulk. The hydrogen dynamics are discussed in the context of the interaction between the interfacial water and ice and the confining hydrophilic surface of the GO sponge. PMID:26556604

  15. Ionization of water molecules by fast charged projectiles

    SciTech Connect

    Dubois, A.; Carniato, S.; Fainstein, P. D.; Hansen, J. P.

    2011-07-15

    Single-ionization cross sections of water molecules colliding with fast protons are calculated from lowest-order perturbation theory by taking all electrons and molecular orientations consistently into account. Explicit analytical formulas based on the peaking approximation are obtained for differential ionization cross sections with the partial contribution from the various electron orbitals accounted for. The results, which are in very good agreement with total and partial cross sections at high electron and projectile energies, display a strong variation on molecular orientation and molecular orbitals.

  16. Adsorption and trace detection of pharmacologically significant 5-methylthio-1, 3, 4-thiadiazole-2-thiol molecule adsorbed on silver nanocolloids and understanding the role of Albrecht's “A” and Herzberg-Teller contributions in the SERS spectra

    NASA Astrophysics Data System (ADS)

    Chowdhury, Joydeep; Chandra, Subhendu; Ghosh, Manash

    2015-01-01

    The surface enhanced Raman scattering (SERS) spectra of biologically and industrially significant 5-methylthio-1, 3, 4-thiadiazole 2-thiol molecule have been investigated. The SERS spectra at various concentrations of the adsorbate are compared with the Fourier transform Infrared (FTIR) and normal Raman spectra (NRS) of the probe molecule recorded in different environmental conditions. The optimized molecular structures of the most probable thione and the thiol forms of the molecule have been estimated from the density functional theory (DFT) calculations. The vibrational signatures of the molecule have been assigned from the potential energy distributions (PEDs). The detail vibrational analyses reveal that ∼54% of the thione form of the molecule is prevalent in the solid state and its population increases to ∼65% in ACN solvent medium. Concentration dependent SERS, together with the 2-dimensional correlation spectra (2D-COS), corroborate the presence of both the thione and the thiol forms of the molecule even in the surface adsorbed state. The orientations of the thione and the thiol forms of the molecule on the nanocolloidal silver surface have been predicted from the surface selection rule. The selective enhancement of Raman bands in the SERS spectra have been explored from the view of the Albrecht's "A" and Herzberg-Teller (HT) charge transfer (CT) contribution.

  17. Adsorption and trace detection of pharmacologically significant 5-methylthio-1, 3, 4-thiadiazole-2-thiol molecule adsorbed on silver nanocolloids and understanding the role of Albrecht's "A" and Herzberg-Teller contributions in the SERS spectra.

    PubMed

    Chowdhury, Joydeep; Chandra, Subhendu; Ghosh, Manash

    2015-01-25

    The surface enhanced Raman scattering (SERS) spectra of biologically and industrially significant 5-methylthio-1, 3, 4-thiadiazole 2-thiol molecule have been investigated. The SERS spectra at various concentrations of the adsorbate are compared with the Fourier transform Infrared (FTIR) and normal Raman spectra (NRS) of the probe molecule recorded in different environmental conditions. The optimized molecular structures of the most probable thione and the thiol forms of the molecule have been estimated from the density functional theory (DFT) calculations. The vibrational signatures of the molecule have been assigned from the potential energy distributions (PEDs). The detail vibrational analyses reveal that ∼54% of the thione form of the molecule is prevalent in the solid state and its population increases to ∼65% in ACN solvent medium. Concentration dependent SERS, together with the 2-dimensional correlation spectra (2D-COS), corroborate the presence of both the thione and the thiol forms of the molecule even in the surface adsorbed state. The orientations of the thione and the thiol forms of the molecule on the nanocolloidal silver surface have been predicted from the surface selection rule. The selective enhancement of Raman bands in the SERS spectra have been explored from the view of the Albrecht's "A" and Herzberg-Teller (HT) charge transfer (CT) contribution. PMID:25168230

  18. Inhibition of Lipid Oxidation in Oil-in-Water Emulsions by Interface-Adsorbed Myofibrillar Protein.

    PubMed

    Yang, Jiayi; Xiong, Youling L

    2015-10-14

    This study investigated the role of interfacial myofibrillar protein (MFP) in the oxidative stabilization of meat emulsions. Emulsions with 10% oil were prepared using either 2% (w/v) Tween 20 or 0.25, 0.5, and 1% (w/v) MFP and then subjected to hydroxyl radical oxidation at 4 °C for 0, 2, and 24 h. MFP was more readily oxidized (intrinsic fluorescence quenching, sulfur losses, and carbonyl formation) than oil [conjugated dienes and 2-thiobarbituric acid-reactive substances (TBARS)]. However, oxidized MFP in the continuous phase stimulated lipid oxidation after 24 h, sharply contrasting with interface-adsorbed MFP that inhibited TBARS formation nearly 90% (p < 0.05). Interfacial MFP from 2 h oxidized samples exhibited greater losses of fluorescence and more extensive polymerization of myosin (detected by sodium dodecyl sulfate-polyacrylamide gel electrophoresis) than MFP present in the continuous phase. Results indicated that, due to the physical localization, interface-adsorbed MFP in general and myosin in particular provided accentuated protection of emulsions against oxidation. PMID:26414649

  19. Water-molecule dissociation by proton and hydrogen impact

    NASA Astrophysics Data System (ADS)

    Luna, H.; de Barros, A. L. F.; Wyer, J. A.; Scully, S. W. J.; Lecointre, J.; Garcia, P. M. Y.; Sigaud, G. M.; Santos, A. C. F.; Senthil, V.; Shah, M. B.; Latimer, C. J.; Montenegro, E. C.

    2007-04-01

    Time-of-flight-based mass analysis of charged water fragments have been used to measure the dissociative and the nondissociative reaction pathways of water formed during collisions with 15to100keV and 500to3500keV H+ projectiles and with 8to100keV H0 projectiles. The fragmentation pathways resulting from the ionization and the electron capture collisions with the incident H+ and H0 projectiles, as well as collisions involving projectile electron loss by the incident H0 projectiles, were separately recorded by detecting the target product ions in coincidence with either the ejected target electrons or the charge-analyzed projectiles. The fragmentation profile shows that at high collision energies the ionization of water arises mainly through outer shell processes. At lower energies valence electron capture and ionization dominate and transfer ionization leads to substantially different fragmentation patterns. H0 and H+ projectiles are found to be equally efficient at ionizing the water molecule. These results are of particular interest to workers in astrophysics and those involved in cancer therapy with heavy particle ion beams.

  20. Quantum Tunneling of Water in Beryl: A New State of the Water Molecule

    NASA Astrophysics Data System (ADS)

    Kolesnikov, Alexander I.; Reiter, George F.; Choudhury, Narayani; Prisk, Timothy R.; Mamontov, Eugene; Podlesnyak, Andrey; Ehlers, George; Seel, Andrew G.; Wesolowski, David J.; Anovitz, Lawrence M.

    2016-04-01

    Using neutron scattering and ab initio simulations, we document the discovery of a new "quantum tunneling state" of the water molecule confined in 5 Å channels in the mineral beryl, characterized by extended proton and electron delocalization. We observed a number of peaks in the inelastic neutron scattering spectra that were uniquely assigned to water quantum tunneling. In addition, the water proton momentum distribution was measured with deep inelastic neutron scattering, which directly revealed coherent delocalization of the protons in the ground state.

  1. Ion condensation behavior and dynamics of water molecules surrounding the sodium poly(methacrylic acid) chain in water: a molecular dynamics study.

    PubMed

    Chung, Yung-Ting; Huang, Ching-I

    2012-03-28

    All-atom molecular dynamics simulations are used to study the condensation behavior of monovalent (Na(+)) and multivalent (Ca(2+)) salt counterions associated with the co-ions (Cl(-)) surrounding the charged poly(methacrylic acid) (PMAA) chain in water. The study is extended to the influences on chain conformation, local arrangement, and dynamics of water in the highly diluted aqueous solutions. We find that even when the salt ions are monovalent, they attract more than one charged monomer and act as a bridging agent within the chain, as the multivalent salt ions. In principle, the salt ions bridge between not only the "non-adjacent" but also the "adjacent" charged monomers, leading to a more coil-like and a locally stretched conformation, respectively. With an increase in the salt concentration, the amount of coiled-type condensed ions increase and reach a maximum when the chain conformation becomes the most collapsed; whereas, the stretched-type shows an opposite trend. Our results show that the attractive interactions through the condensed salt ions between the non-adjacent monomers are responsible for the conformational collapse. When the salt concentration increases high enough, a significant increase for the stretched-type condensed ions makes an expansion effect on the chain. These stretched-type salt ions, followed by the adsorption of the co-ions and water molecules, tend to form a multilayer organization outside surrounding the PMAA chain. Thus, the expansion degree of the chain conformation is greatly limited. When only the monovalent Na(+) ions are present in the solutions, water molecules are primarily adsorbed into either the condensed Na(+) ions or the COO(-) groups. These adsorbed water molecules form hydrogen bonds with each other and enhance the local bridging behavior associated with the Na(+) condensation on the resultant chain conformation. With an increase in the amount of multivalent Ca(2+) salt ions, more water molecules are bonded directly

  2. Searching for Water and Other Molecules with JWST

    NASA Astrophysics Data System (ADS)

    Valenti, Jeff

    2015-08-01

    The James Webb Space Telescope (JWST) will be a powerful tool for measuring water and other molecules in transiting exoplanets, warm circumstellar disks, brown dwarfs, and cool stars. In early 2019 the observatory is scheduled to begin science operations near the Sun-Earth L2 Lagrange point. The sunshield will allow the telescope and science instrument module to cool passively to approximately 40 K. The segmented primary mirror has 25 square meters of collecting area, giving the observatory unprecedented sensitivity in the infrared. JWST has four science instruments that cover wavelengths from 0.6 to 28 microns at spectral resolutions up to about R=3000. I will summarize relevant observatory constraints, instrument capabilities, and observing templates. I will illustrate practical issues with examples from the Science Operations Design Reference Mission. Finally, I will discuss the Cycle 1 proposal process, which begins in 2017.

  3. Contact Forces between TiO2 Nanoparticles Governed by an Interplay of Adsorbed Water Layers and Roughness.

    PubMed

    Laube, Jens; Salameh, Samir; Kappl, Michael; Mädler, Lutz; Colombi Ciacchi, Lucio

    2015-10-20

    Interparticle forces govern the mechanical behavior of granular matter and direct the hierarchical assembling of nanoparticles into supramolecular structures. Understanding how these forces change under different ambient conditions would directly benefit industrial-scale nanoparticle processing units such as filtering and fluidization. Here we rationalize and quantify the contributions of dispersion, capillary, and solvation forces between hydrophilic TiO2 nanoparticles with sub-10 nm diameter and show that the humidity dependence of the interparticle forces is governed by a delicate interplay between the structure of adsorbed water layers and the surface roughness. All-atom molecular dynamics modeling supported by force-spectroscopy experiments reveals an unexpected decrease in the contact forces at increasing humidity for nearly spherical particles, while the forces between rough particles are insensitive to strong humidity changes. Our results also frame the limits of applicability of discrete solvation and continuum capillary theories in a regime where interparticle forces are dominated by the molecular nature of surface adsorbates. PMID:26414448

  4. The use of graphene-based magnetic nanoparticles as adsorbent for the extraction of triazole fungicides from environmental water.

    PubMed

    Wang, Weina; Ma, Xiaoxing; Wu, Qiuhua; Wang, Chun; Zang, Xiaohuan; Wang, Zhi

    2012-09-01

    A graphene-based magnetic nanocomposite (graphene-ferriferrous oxide; G-Fe(3)O(4)) was synthesized and used as an effective adsorbent for the preconcentration of some triazole fungicides (myclobutanil, tebuconazole, and hexaconazole) in environmental water samples prior to high-performance liquid chromatography-ultraviolet detection. The method, which takes the advantages of both nanoparticle adsorption and magnetic phase separation from the sample solution, could avoid the time-consuming experimental procedures commonly involved in the traditional solid phase extraction such as centrifugation and filtrations. Various experimental parameters affecting the extraction efficiencies such as the amount of the magnetic nanocomposite, extraction time, the pH values of the sample solution, salt concentration, and desorption conditions were investigated. Under the optimum conditions, the enrichment factors of the method for the three analytes were 5824, 3600, and 4761, respectively. A good linearity was observed in the range of 0.1-50 ng/mL for tebuconazole and 0.05-50 ng/mL for myclobutanil and hexaconazole, respectively, with the correlation coefficients ranging from 0.9992 to 0.9996. The limits of detection (S/N = 3) of the method were between 0.005 and 0.01 ng/mL. The results indicated that as a magnetic solid-phase extraction adsorbent, the graphene-ferriferrous oxide (G-Fe(3)O(4)) has a great potential for the preconcentration of some compounds from liquid samples. PMID:22715113

  5. Adsorption of drinking water fluoride on a micron-sized magnetic Fe3O4@Fe-Ti composite adsorbent

    NASA Astrophysics Data System (ADS)

    Zhang, Chang; Li, Yingzhen; Wang, Ting-Jie; Jiang, Yanping; Wang, Haifeng

    2016-02-01

    A micron-sized magnetic adsorbent (MMA) for fluoride removal from drinking water was prepared by spray drying and subsequent calcination of a magnetic Fe3O4@Fe-Ti core-shell nanoparticle slurry. The MMA granules had high mechanical strength and stability against water scouring, can be easily separated from the water by a magnet, and had a high selectivity for fluoride versus common co-existing ions and high fluoride removal efficiency in a wide range of initial pH of 3-11. Abundant hydroxyl groups on the MMA surface acted as the active sites for fluoride adsorption, which resulted in a high affinity of the MMA for fluoride. The pH in the adsorption process affected the adsorption significantly. At neutral initial pH, the adsorption isotherm was well fitted with the Langmuir model, and the maximum adsorption capacity reached a high value of 41.8 mg/g. At a constant pH of 3, multilayer adsorption of fluoride occurred due to the abundant positive surface charges on the MMA, and the adsorption isotherm was well fitted with the Freundlich model. The MMA had a fast adsorption rate, and adsorption equilibrium was achieved within 2 min. The adsorption kinetics followed a quasi-second order model. The regeneration of the MMA was easy and fast, and can be completed within 2 min. After 10 recycles, the fluoride removal efficiency of the MMA still remained high. These properties showed that the MMA is a promising adsorbent for fluoride removal.

  6. Effects of water hardness and existence of adsorbent on toxic surface tension of surfactants for aquatic species.

    PubMed

    Oya, Masaru; Orito, Shintaro; Ishikawa, Yusuke; Iizuka, Tomoko

    2007-01-01

    We have studied the effectiveness of surface tension on surfactants risk assessment. gamma(tox) was defined as surface tension at a point where acute aquatic toxicity of a surfactant emerges. Oryzias latipes, Daphnia magna, and Podocopida were used for acute aquatic toxicity test of 7 surfactants and 3 detergents. Gamma(tox)values were plotted on surface tension curves, and the effect of water hardness on toxicity and surface tension were examined. Results showed that gamma(tox) varies greatly by kind of surfactant or detergent. Therefore, aquatic toxicity cannot only be explained by surface tension. The change of aquatic toxicity with varying water hardness, however, could be explained by the change of surface tension. Aquatic toxicity of LAS (Linear Alkylbenzene Sulphonate) increased and aquatic toxicity of SOAP decreased with an increase of water hardness, but both gamma(tox), values were constant. Aquatic toxicity was decreased by an addition of mud soil as adsorbent into surfactant solution. The toxicity change can be explained by the surface tension since gamma(tox) value of solution with and without mud soil were equal. These results showed that the change of aquatic toxicity of a surfactant caused by water property, such as water hardness, could be explained by the change of surface tension. PMID:17898487

  7. Adsorbent phosphates

    NASA Technical Reports Server (NTRS)

    Watanabe, S.

    1983-01-01

    An adsorbent which uses as its primary ingredient phosphoric acid salts of zirconium or titanium is presented. Production methods are discussed and several examples are detailed. Measurements of separating characteristics of some gases using the salts are given.

  8. Conformational changes of α-lactalbumin adsorbed at oil-water interfaces: interplay between protein structure and emulsion stability.

    PubMed

    Zhai, Jiali; Hoffmann, Søren V; Day, Li; Lee, Tzong-Hsien; Augustin, Mary Ann; Aguilar, Marie-Isabel; Wooster, Tim J

    2012-02-01

    The conformation and structural dimensions of α-lactalbumin (α-La) both in solution and adsorbed at oil-water interfaces of emulsions were investigated using synchrotron radiation circular dichroism (SRCD) spectroscopy, front-face tryptophan fluorescence (FFTF) spectroscopy, and dual polarization interferometry (DPI). The near-UV SRCD and the FFTF results demonstrated that the hydrophobic environment of the aromatic residues located in the hydrophobic core of native α-La was significantly altered upon adsorption, indicating the unfolding of the hydrophobic core of α-La upon adsorption. The far-UV SRCD results showed that adsorption of α-La at oil-water interfaces created a new non-native secondary structure that was more stable to thermally induced conformational changes. Specifically, the α-helical conformation increased from 29.9% in solution to 45.8% at the tricaprylin-water interface and to 58.5% at the hexadecane-water interface. However, the β-sheet structure decreased from 18.0% in solution to less than 10% at both oil-water interfaces. The DPI study showed that adsorption of α-La to a hydrophobic C18-water surface caused a change in the dimensions of α-La from the native globule-like shape (2.5-3.7 nm) to a compact/dense layer approximately 1.1 nm thick. Analysis of the colloidal stability of α-La stabilized emulsions showed that these emulsions were physically stable against droplet flocculation at elevated temperatures both in the absence and in the presence of 120 mM NaCl. In the absence of salt, the thermal stability of emulsions was due to the strong electrostatic repulsion provided by the adsorbed α-La layer, which was formed after the adsorption and structural rearrangement. In the presence of salt, although the electrostatic repulsion was reduced via electrostatic screening, heating did not induce strong and permanent droplet flocculation. The thermal stability of α-La stabilized emulsions in the presence of salt is a combined effect of

  9. The effect of surface modification on heavy metal ion removal from water by carbon nanoporous adsorbent

    NASA Astrophysics Data System (ADS)

    Baniamerian, M. J.; Moradi, S. E.; Noori, A.; Salahi, H.

    2009-12-01

    In this work, chemically oxidized mesoporous carbon (COMC) with excellent lead adsorption performance was prepared by an acid surface modification method from mesoporous carbon (MC) by wet impregnation method. The structural order and textural properties of the mesoporous materials were studied by XRD, SEM, and nitrogen adsorption. The presence of carboxylic functional groups on the carbon surface was confirmed by FT-IR analysis. Batch adsorption experiments were conducted to study the effect of adsorbent dose, initial concentration and temperature for the removal of Pb(II) from aqueous systems. The adsorption was maximum for the initial pH in the range of 6.5-8.0. The kinetic data were best fitted to the pseudo-second order model. The adsorption of chemically oxidized mesoporous carbon to Pb(II) fits to the Langmuir model. The larger adsorption capacity of chemically oxidized mesoporous carbon for Pb(II) is mainly due to the oxygenous functional groups formed on the surface of COMC which can react with Pb(II) to form salt or complex deposited on the surface of MC.

  10. Oxygen isotope fractionation effects in soil water via interaction with cations (Mg, Ca, K, Na) adsorbed to phyllosilicate clay minerals

    NASA Astrophysics Data System (ADS)

    Oerter, Erik; Finstad, Kari; Schaefer, Justin; Goldsmith, Gregory R.; Dawson, Todd; Amundson, Ronald

    2014-07-01

    In isotope-enabled hydrology, soil and vadose zone sediments have been generally considered to be isotopically inert with respect to the water they host. This is inconsistent with knowledge that clay particles possessing an electronegative surface charge and resulting cation exchange capacity (CEC) interact with a wide range of solutes which, in the absence of clays, have been shown to exhibit δ18O isotope effects that vary in relation to the ionic strength of the solutions. To investigate the isotope effects caused by high CEC clays in mineral-water systems, we created a series of monominerallic-water mixtures at gravimetric water contents ranging from 5% to 32%, consisting of pure deionized water of known isotopic composition with homoionic (Mg, Ca, Na, K) montmorillonite. Similar mixtures were also created with quartz to determine the isotope effect of non-, or very minimally-, charged mineral surfaces. The δ18O value of the water in these monominerallic soil analogs was then measured by isotope ratio mass spectrometry (IRMS) after direct headspace CO2 equilibration. Mg- and Ca-exchanged homoionic montmorillonite depleted measured δ18O values up to 1.55‰ relative to pure water at 5% water content, declining to 0.49‰ depletion at 30% water content. K-montmorillonite enriched measured δ18O values up to 0.86‰ at 5% water content, declining to 0.11‰ enrichment at 30% water. Na-montmorillonite produces no measureable isotope effect. The isotope effects observed in these experiments may be present in natural, high-clay soils and sediments. These findings have relevance to the interpretation of results of direct CO2-water equilibration approaches to the measurement of the δ18O value of soil water. The adsorbed cation isotope effect may bear consideration in studies of pedogenic carbonate, plant-soil water use and soil-atmosphere interaction. Finally, the observed isotope effects may prove useful as molecular scale probes of the nature of mineral-water

  11. Distribution of binding energies of a water molecule in the water liquid-vapor interface

    SciTech Connect

    Chempath, Shaji; Pratt, Lawrence R

    2008-01-01

    Distributions of binding energies of a water molecule in the water liquid-vapor interface are obtained on the basis of molecular simulation with the SPC/E model of water. These binding energies together with the observed interfacial density profile are used to test a minimally conditioned Gaussian quasi-chemical statistical thermodynamic theory. Binding energy distributions for water molecules in that interfacial region clearly exhibit a composite structure. A minimally conditioned Gaussian quasi-chemical model that is accurate for the free energy of bulk liquid water breaks down for water molecules in the liquid-vapor interfacial region. This breakdown is associated with the fact that this minimally conditioned Gaussian model would be inaccurate for the statistical thermodynamics of a dilute gas. Aggressive conditioning greatly improves the performance of that Gaussian quasi-chemical model. The analogy between the Gaussian quasi-chemical model and dielectric models of hydration free energies suggests that naive dielectric models without the conditioning features of quasi-chemical theory will be unreliable for these interfacial problems. Multi-Gaussian models that address the composite nature of the binding energy distributions observed in the interfacial region might provide a mechanism for correcting dielectric models for practical applications.

  12. Magnetic nanoporous carbon as an adsorbent for the extraction of phthalate esters in environmental water and aloe juice samples.

    PubMed

    Liu, Li; Hao, Yunhui; Ren, Yiqian; Wang, Chun; Wu, Qiuhua; Wang, Zhi

    2015-05-01

    In this work, magnetic nanoporous carbon with high surface area and ordered structure was synthesized using cheap commercial silica gel as template and sucrose as the carbon source. The prepared magnetic nanoporous carbon was firstly used as an adsorbent for the extraction of phthalate esters, including diethyl phthalate, diallyl phthalate, and di-n-propyl-phthalate, from lake water and aloe juice samples. Several parameters that could affect the extraction efficiency were optimized. Under the optimum conditions, the limit of detection of the method (S/N = 3) was 0.10 ng/mL for water sample and 0.20 ng/mL for aloe juice sample. The linearity was observed over the concentration range of 0.50-150.0 and 1.0-200.0 ng/mL for water and aloe juice samples, respectively. The results showed that the magnetic nanoporous carbon has a high adsorptive capability toward the target phthalate esters in water and aloe juice samples. PMID:25677269

  13. Use of industrial by-products and natural media to adsorb nutrients, metals and organic carbon from drinking water.

    PubMed

    Grace, Maebh A; Healy, Mark G; Clifford, Eoghan

    2015-06-15

    Filtration technology is well established in the water sector but is limited by inability to remove targeted contaminants, found in surface and groundwater, which can be damaging to human health. This study optimises the design of filters by examining the efficacy of seven media (fly ash, bottom ash, Bayer residue, granular blast furnace slag (GBS), pyritic fill, granular activated carbon (GAC) and zeolite), to adsorb nitrate, ammonium, total organic carbon (TOC), aluminium, copper (Cu) and phosphorus. Each medium and contaminant was modelled to a Langmuir, Freundlich or Temkin adsorption isotherm, and the impact of pH and temperature (ranging from 10 °C to 29 °C) on their performance was quantified. As retention time within water filters is important in contaminant removal, kinetic studies were carried out to observe the adsorption behaviour over a 24h period. Fly ash and Bayer residue had good TOC, nutrient and Cu adsorption capacity. Granular blast furnace slag and pyritic fill, previously un-investigated in water treatment, showed adsorption potential for all contaminants. In general, pH or temperature adjustment was not necessary to achieve effective adsorption. Kinetic studies showed that at least 60% of adsorption had occurred after 8h for all media. These media show potential for use in a multifunctional water treatment unit for the targeted treatment of specific contaminants. PMID:25777954

  14. NMR Study of Phase Transitions in Pure Water and Binary H(2)O/HNO(3) Films Adsorbed on Surface of Pyrogenic Silica.

    PubMed

    Bogdan; Kulmala; Gorbunov; Kruppa

    1996-01-15

    Pyrogenic silica (aerosil) was employed as host within which the phase transitions in the adsorbed pure water and binary H(2)O/HNO(3) films have been studied with NMR spectroscopy. The median freezing temperature and freezing temperature region were shown to be highly sensitive both to the average thickness of the adsorbed films and to the amount of adsorbed nitric acid. The molar concentration of nitric acid in the adsorbed films was found to be very small, on the order of 10(-3)-10(-2) (M/liter). The concentration was found to be greater in the layers adjacent to the surface of silica and sharply decreases with distance from the surface. The difference between the median freezing temperatures for adsorbed pure water and for the binary system was found to be about 9 K for films of equal thickness. This is about 150 times greater than the difference between the freezing temperatures of bulk pure water and a solution with the same concentration of nitric acid. PMID:10479419

  15. Extending the range of low energy electron diffraction (LEED) surface structure determination: Co-adsorbed molecules, incommensurate overlayers and alloy surface order studied by new video and electron counting LEED techniques

    SciTech Connect

    Ogletree, D.F.

    1986-11-01

    LEED multiple scattering theory is briefly summarized, and aspects of electron scattering with particular significance to experimental measurements such as electron beam coherence, instrument response and phonon scattering are analyzed. Diffuse LEED experiments are discussed. New techniques that enhance the power of LEED are described, including a real-time video image digitizer applied to LEED intensity measurements, along with computer programs to generate I-V curves. The first electron counting LEED detector using a ''wedge and strip'' position sensitive anode and digital electronics is described. This instrument uses picoampere incident beam currents, and its sensitivity is limited only by statistics and counting times. Structural results on new classes of surface systems are presented. The structure of the c(4 x 2) phase of carbon monoxide adsorbed on Pt(111) has been determined, showing that carbon monoxide molecules adsorb in both top and bridge sites, 1.85 +- 0.10 A and 1.55 +- 0.10 A above the metal surface, respectively. The structure of an incommensurate graphite overlayer on Pt(111) is analyzed. The graphite layer is 3.70 +- 0.05 A above the metal surface, with intercalated carbon atoms located 1.25 +- 0.10 A above hollow sites supporting it. The (2..sqrt..3 x 4)-rectangular phase of benzene and carbon monoxide coadsorbed on Pt(111) is analyzed. Benzene molecules adsorb in bridge sites parallel to and 2.10 +- 0.10 A above the surface. The carbon ring is expanded, with an average C-C bond length of 1.72 +- 0.15 A. The carbon monoxide molecules also adsorb in bridge sites. The structure of the (..sqrt..3 x ..sqrt..3) reconstruction on the (111) face of the ..cap alpha..-CuAl alloy has been determined.

  16. Cleaning Water Contaminated with Heavy Metal Ions Using Pyrolyzed Biochar Adsorbents

    EPA Science Inventory

    The extraction of pollutants from water using activated biochar materials is a low cost, sustainable approach for providing safe water in developing countries. The adsorption of copper ions, Cu (II), onto banana peels that were dried, pyrolyzed and activated was studied and compa...

  17. Momentum resolved electron stimulated desorption ion angular distribution, a new technique, probing the low frequency motion of adsorbed molecules on single crystal surfaces

    SciTech Connect

    Ahner, J.; Mocuta, D.; Yates, J.T. Jr.

    1999-07-01

    A new technique, momentum resolved electron stimulated desorption ion angular distribution (ESDIAD), provides a method for taking snapshots of the zero-point position and lateral momentum of particles adsorbed on crystalline surfaces. By employing state-of-the-art electronics and computer technology it is possible to record for each desorbing particle the desorption direction together with the flight time. High momentum and directional resolved images are obtained, with time-of-flight resolution in the picosecond range and data acquisition rates up to 100 kHz. This enables us to deconvolute spatial and momentum contributions to the ESDIAD pattern and to map the low frequency motion of the adsorbed particles. These maps reflect the adsorbate interactions with the substrate and with neighboring species on the substrate. For selected examples it is demonstrated that by measuring the three dimensional momentum vector for each desorbing particle it is possible to probe the lowest energy states of adsorbed species, as well as to measure the momentum distribution when the adsorbed species gains thermal energy. Such information can be used as a basis for thinking about anisotropies in lateral motion of particles on surfaces. One major opportunity involves the study of dissimilar chemisorbed species which, when imaged together in momentum and real space, give new insights into the first stages of interaction between the species, leading ultimately to a chemical reaction. {copyright} {ital 1999 American Vacuum Society.}

  18. Quantum Tunneling of Water in Beryl. A New State of the Water Molecule

    DOE PAGESBeta

    Kolesnikov, Alexander I.; Reiter, George F.; Choudhury, Narayani; Prisk, Timothy R.; Mamontov, Eugene; Podlesnyak, Andrey; Ehlers, George; Seel, Andrew G.; Wesolowski, David J.; Anovitz, Lawrence M.

    2016-04-22

    When using neutron scattering and ab initio simulations, we document the discovery of a new “quantum tunneling state” of the water molecule confined in 5 Å channels in the mineral beryl, characterized by extended proton and electron delocalization. We observed a number of peaks in the inelastic neutron scattering spectra that were uniquely assigned to water quantum tunneling. Additionally, the water proton momentum distribution was measured with deep inelastic neutron scattering, which directly revealed coherent delocalization of the protons in the ground state.

  19. Quantum Tunneling of Water in Beryl: A New State of the Water Molecule.

    PubMed

    Kolesnikov, Alexander I; Reiter, George F; Choudhury, Narayani; Prisk, Timothy R; Mamontov, Eugene; Podlesnyak, Andrey; Ehlers, George; Seel, Andrew G; Wesolowski, David J; Anovitz, Lawrence M

    2016-04-22

    Using neutron scattering and ab initio simulations, we document the discovery of a new "quantum tunneling state" of the water molecule confined in 5 Å channels in the mineral beryl, characterized by extended proton and electron delocalization. We observed a number of peaks in the inelastic neutron scattering spectra that were uniquely assigned to water quantum tunneling. In addition, the water proton momentum distribution was measured with deep inelastic neutron scattering, which directly revealed coherent delocalization of the protons in the ground state. PMID:27152824

  20. Disorder of Hydrofluorocarbon Molecules Entrapped in the Water Cages of Structure I Clathrate Hydrate.

    PubMed

    Takeya, Satoshi; Udachin, Konstantin A; Moudrakovski, Igor L; Ohmura, Ryo; Ripmeester, John A

    2016-05-23

    Water versus fluorine: Clathrate hydrates encaging hydrofluorocarbons as guests show both isotropic and anisotropic distributions within host water cages, depending on the number of fluorine atoms in the guest molecule; this is caused by changes in intermolecular interactions to host water molecules in the hydrates. PMID:27105807

  1. Influence of Chemical Composition on the Reaction Products Observed During Electron Stimulated Decomposition of Organohalides Adsorbed in Water (Ice) Films

    NASA Astrophysics Data System (ADS)

    Fairbrother, Howard; Perry, Christopher; Faradzhev, Nadir; Madey, Theodore

    2004-03-01

    We report on the reactions of CF_2Cl2 and other organohalides codeposited_ in water (ice) films (≈100 nm thick on Au) at ˜ 100K during X-ray or electron beam irradiation. X-ray irradiation produces a distribution of low energy secondary electrons that in CF_2Cl_2/H_2O(ice) films produce H_3O^+, CO2 and COF2 (carbonyl fluoride). Chloride and fluoride anions are also produced and solvated (trapped) within the ice film during X-ray or electron irradiation. Product partitioning is dependent on the film's chemical composition; in water rich films, CO2 and COF2 production is favored, while a thermally stable partially halogenated CF_xCly film is detected in CF_2Cl2 rich films. During the early stages of irradiation, the dominance of Cl^- anions indicates that DEA of CF_2Cl2 via C-Cl cleavage (CF_2Cl2 + e^- → ot CF_2Cl + Cl^-) is the primary initial process. These results obtained for CF_2Cl2 are compared with electron stimulated reactions of other organohalides (CCl_4, CDCl_3, CD_2Cl2 and CH_3I) adsorbed in water(ice)films.

  2. Electron capture by bare ions on water molecules

    NASA Astrophysics Data System (ADS)

    Rivarola, Roberto; Montenegro, Pablo; Monti, Juan; Fojón, Omar

    2016-05-01

    Single electron capture from water molecules by impact of bare ions is theoretically investigated at intermediate and high collision energies. This reaction is of fundamental importance to determine the deposition of energy in biological matter irradiated with ion beams (hadrontherapy), dominating other ionizing processes of the target at low-intermediate impact velocities and giving principal contributions to the energetic region where electronic stopping power maximizes. The dynamics of the interaction between the aggregates is described within the one active-electron continuum distorted wave-eikonal initial state theory. The orbitals of the target in the ground state are represented using the approximate self-consistent complete neglect of differential orbitals (SC-CNDO) model. The contribution of different molecular orbitals on the partial cross sections to selected n-principal quantum number projectile states is discriminated as well as the collaboration of these n-states on total cross sections. The latter ones are dominated by capture to n=1 states at high enough energies decreasing their contribution as n increases.

  3. Phosphate Remediation and Recovery from Lake Water using Modified Iron Oxide-based Adsorbents

    EPA Science Inventory

    Adsorption behavior of Bayoxide ® E33 (E33) and three E33-modified sorbents for the removal of phosphate from lake water was investigated in this study. E33-modified sorbents were synthesized by coating with manganese and nanoparticles. Characterization was done by X-ray diffract...

  4. Phosphate Remediation and Recovery from Lake Water using Modified Iron Oxide-based Adsorbents

    EPA Science Inventory

    Adsorption behavior of Bayoxide ® E33 (E33) and three E33-modified sorbents for the removal of phosphate from lake water was investigated in this study. E33-modified sorbents were synthesized by coating with manganese and nanoparticles. Characterization was done by X-ray diff...

  5. EXPERIENCE WITH GAC ADSORBERS AND FLUIDIZED BED REACTIVATION AT MANCHESTER WATER WORKS

    EPA Science Inventory

    Manchester, New Hampshire is a moderate-sized community approximately 60 miles north of Boston. ater supply to this population of roughly 100,000 residents is comprised of various sources. he major community supply is Manchester Water Works (MWW) with a distribution network of so...

  6. Quasiparticle excitations of adsorbates on doped graphene

    NASA Astrophysics Data System (ADS)

    Lischner, Johannes; Wickenburg, Sebastian; Wong, Dillon; Karrasch, Christoph; Wang, Yang; Lu, Jiong; Omrani, Arash A.; Brar, Victor; Tsai, Hsin-Zon; Wu, Qiong; Corsetti, Fabiano; Mostofi, Arash; Kawakami, Roland K.; Moore, Joel; Zettl, Alex; Louie, Steven G.; Crommie, Mike

    Adsorbed atoms and molecules can modify the electronic structure of graphene, but in turn it is also possible to control the properties of adsorbates via the graphene substrate. In my talk, I will discuss the electronic structure of F4-TCNQ molecules on doped graphene and present a first-principles based theory of quasiparticle excitations that captures the interplay of doping-dependent image charge interactions between substrate and adsorbate and electron-electron interaction effects on the molecule. The resulting doping-dependent quasiparticle energies will be compared to experimental scanning tunnelling spectra. Finally, I will also discuss the effects of charged adsorbates on the electronic structure of doped graphene.

  7. Nanogold-Decorated Silica Monoliths as Highly Efficient Solid-Phase Adsorbent for Ultratrace Mercury Analysis in Natural Waters.

    PubMed

    Huber, Jessica; Heimbürger, Lars-Eric; Sonke, Jeroen E; Ziller, Sebastian; Lindén, Mika; Leopold, Kerstin

    2015-11-01

    We propose a novel analytical method for mercury (Hg) trace determination based on direct Hg preconcentration from aqueous solution onto a gold nanoparticle-decorated silica monolith (AuNP@SiO2). Detection of Hg is performed after thermal desorption by means of atomic fluorescence spectrometry. This new methodology benefits from reagent-free, time- and cost-saving procedure, due to most efficient solid-phase adsorbent and results in high sensitive quantification. The excellent analytical performance of the whole procedure is demonstrated by a limit of detection as low as 1.31 ng L(-1) for only one-min accumulation duration. A good reproducibility with standard deviations ≤5.4% is given. The feasibility of the approach in natural waters was confirmed by a recovery experiment in spiked seawater with a recovery rate of 101%. Moreover, the presented method was validated through reference analysis of a submarine groundwater discharge sample by cold vapor-atomic fluorescence spectrometry resulting in a very good agreement of the found values. Hence the novel method is a very promising new tool for low-level Hg monitoring in natural waters providing easy-handling on-site preconcentration, reagent-free stabilization as well as reagent-free, highly sensitive detection. PMID:26460188

  8. Nano-silica fabricated with silver nanoparticles: antifouling adsorbent for efficient dye removal, effective water disinfection and biofouling control

    NASA Astrophysics Data System (ADS)

    Das, Sujoy K.; Khan, Md. Motiar R.; Parandhaman, T.; Laffir, Fathima; Guha, Arun K.; Sekaran, G.; Mandal, Asit Baran

    2013-05-01

    A nano-silica-AgNPs composite material is proposed as a novel antifouling adsorbent for cost-effective and ecofriendly water purification. Fabrication of well-dispersed AgNPs on the nano-silica surface, designated as NSAgNP, has been achieved through protein mediated reduction of silver ions at ambient temperature for development of sustainable nanotechnology. The coated proteins on AgNPs led to the formation of stable NSAgNP and protected the AgNPs from oxidation and other ions commonly present in water. The NSAgNP exhibited excellent dye adsorption capacity both in single and multicomponent systems, and demonstrated satisfactory tolerance against variations in pH and dye concentration. The adsorption mainly occurred through electrostatic interaction, though π-π interaction and pore diffusion also contributed to the process. Moreover, the NSAgNP showed long-term antibacterial activity against both planktonic cells and biofilms of Gram-negative Escherichia coli and Pseudomonas aeruginosa. The antibacterial activity of AgNPs retarded the initial attachment of bacteria on NSAgNP and thus significantly improved the antifouling properties of the nanomaterial, which further inhibited biofilm formation. Scanning electron and fluorescence microscopic studies revealed that cell death occurred due to irreversible damage of the cell membrane upon electrostatic interaction of positively charged NSAgNP with the negatively charged bacterial cell membrane. The high adsorption capacity, reusability, good tolerance, removal of multicomponent dyes and E. coli from the simulated contaminated water and antifouling properties of NSAgNP will provide new opportunities to develop cost-effective and ecofriendly water purification processes.A nano-silica-AgNPs composite material is proposed as a novel antifouling adsorbent for cost-effective and ecofriendly water purification. Fabrication of well-dispersed AgNPs on the nano-silica surface, designated as NSAgNP, has been achieved through

  9. Stabilization of Oil-in-Water Emulsions with Noninterfacially Adsorbed Particles.

    PubMed

    Pilapil, Brandy K; Jahandideh, Heidi; Bryant, Steven L; Trifkovic, Milana

    2016-07-19

    Classical (surfactant stabilized) and Pickering (particle stabilized) type emulsions have been widely studied to elucidate the mechanisms by which emulsion stabilization is achieved. In Pickering emulsions, a key defining factor is that the stabilizing particles reside at the liquid-liquid interface providing a mechanical barrier to droplet coalescence. This interfacial adsorption is achieved through the use of nanoparticles that are partially wet by both liquid phases, often through covalent surface modification of or surfactant adsorption to the nanoparticle surfaces. Herein, we demonstrate particle-induced stabilization of an oil-in-water emulsion with fully water wet nanoparticles (no interfacial adsorption) via synergistic interaction with low concentrations of surfactants. Laser scanning confocal microscopy analysis allows for unique and vital insights into the properties of these emulsions via both three-dimensional imaging and real-time monitoring of particle dynamics at the oil-water interface. Investigation of these "non-Pickering" particle stabilized emulsions suggests that the nonadsorbed particles impart stability to the emulsion primarily via entropic forces imparted by the accumulation of silica nanoparticles in the coherent phase between dispersed oil droplets. PMID:27351486

  10. Banana peel as an adsorbent for removing atrazine and ametryne from waters.

    PubMed

    Silva, Claudineia R; Gomes, Taciana F; Andrade, Graziela C R M; Monteiro, Sergio H; Dias, Ana C R; Zagatto, Elias A G; Tornisielo, Valdemar L

    2013-03-13

    The feasibility of using banana peel for removal of the pesticides atrazine and ametryne from river and treated waters has been demonstrated, allowing the design of an efficient, fast, and low-cost strategy for remediation of polluted waters. The conditions for removal of these pesticides in a laboratory scale were optimized as sample volume = 50 mL, banana mass = 3.0 g, stirring time = 40 min, and no pH adjustment necessary. KF(sor) values for atrazine and ametryne were evaluated as 35.8 and 54.1 μg g(-1) (μL mL(-1)) by using liquid scintillation spectrometry. Adsorption was also evaluated by LC-ESI-MS/MS. As quantification limits were 0.10 and 0.14 μg L(-1) for both pesticides, sample preconcentration was not needed. Linear analytical curves (up to 10 μg L(-1)), precise results (RSD < 4.5%), good recoveries (82.9-106.6%), and a > 90% removal efficiency were attained for both pesticides. Water samples collected near an intensively cultivated area were adequately remedied. PMID:23305150

  11. Nano-silica fabricated with silver nanoparticles: antifouling adsorbent for efficient dye removal, effective water disinfection and biofouling control.

    PubMed

    Das, Sujoy K; Khan, Md Motiar R; Parandhaman, T; Laffir, Fathima; Guha, Arun K; Sekaran, G; Mandal, Asit Baran

    2013-06-21

    A nano-silica-AgNPs composite material is proposed as a novel antifouling adsorbent for cost-effective and ecofriendly water purification. Fabrication of well-dispersed AgNPs on the nano-silica surface, designated as NSAgNP, has been achieved through protein mediated reduction of silver ions at ambient temperature for development of sustainable nanotechnology. The coated proteins on AgNPs led to the formation of stable NSAgNP and protected the AgNPs from oxidation and other ions commonly present in water. The NSAgNP exhibited excellent dye adsorption capacity both in single and multicomponent systems, and demonstrated satisfactory tolerance against variations in pH and dye concentration. The adsorption mainly occurred through electrostatic interaction, though π-π interaction and pore diffusion also contributed to the process. Moreover, the NSAgNP showed long-term antibacterial activity against both planktonic cells and biofilms of Gram-negative Escherichia coli and Pseudomonas aeruginosa. The antibacterial activity of AgNPs retarded the initial attachment of bacteria on NSAgNP and thus significantly improved the antifouling properties of the nanomaterial, which further inhibited biofilm formation. Scanning electron and fluorescence microscopic studies revealed that cell death occurred due to irreversible damage of the cell membrane upon electrostatic interaction of positively charged NSAgNP with the negatively charged bacterial cell membrane. The high adsorption capacity, reusability, good tolerance, removal of multicomponent dyes and E. coli from the simulated contaminated water and antifouling properties of NSAgNP will provide new opportunities to develop cost-effective and ecofriendly water purification processes. PMID:23680871

  12. Contaminants in drinking water and its mitigation using suitable adsorbents: an overview.

    PubMed

    Gopal, Krishna; Srivastava, Sachin Behari; Shukla, Satish; Bersillon, J L

    2004-10-01

    Various options are applicable for the removal of water pollutants included reverse osmosis, ion exchange, coagulation, co-precipitation, catalytic reduction, herbal filtration, electrodialysis and adsorption. This paper deals with the sorption phenomena for the removal of pollutants from drinking water. Attempts have been made to use low cost sorbents developed by pretreatment/activation/impregnation with alkalis, acids, iron oxide, manganese dioxide, ferric chloride, alum, lime, aluminum salts with natural products/indigenous minerals viz. activated alumina, activated carbon, groundnut husk, saw dust, chemically coated sand, fly ash, zeolites, clay minerals and other plant products. Application of Freundich and Langmuir isotherms were used to assess the adsorption capacity. Equilibrium isotherms were determined at optimum temperature and pH to characterize the sorption process. Statistical parameters such as mass transfer coefficients, multiple regression analysis were applied to establish the mechanism. It is suggested that the characterization of suitable, and exhausted sorbent through the application of fourier transformed infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray fluorescence (XRF) is essential to establish its surface bonding. Scope for safety evaluation and risk assessment to human and biosphere may provide the guideline and predication to the regulatory agencies for its sustainable use and safe disposal The ecotoxicological assessment of the leachates and low cost removal technology are discussed in this paper. PMID:15907077

  13. Modelling and experimental investigation on the application of water super adsorbents in waste air biofilters.

    PubMed

    Danaee, Soroosh; Fazaelipoor, Mohammad Hassan; Gholami, Abdollah; Ataei, Seyed Ahmad; Afzali, Daryoush

    2015-01-01

    In this research work, a synthetic water super absorbent polymer was included in the bed of a perlite-based biofilter for the removal of ethanol from air. The performance of this biofilter was compared with the performance of a control perlite-based biofilter lacking the water super absorbent. With the empty bed residence time of 2 min, both biofilters were able to remove more than 90% of the entering pollutant with the concentration of 1 g /m3, when regular moistening was applied. After last irrigation on day 23, the performance of the control biofilter was unchanged until day 35. From day 36 onwards, the control biofilter lost its activity gradually and became totally inactive on day 45. The performance of the super absorbent containing biofilter, however, was unchanged until day 58 before starting to lose its activity. A mechanistic model was developed to describe the performance of a biofilter under drying effects. The model could predict the trends of experimental results reasonably well. The model was also applied to predict the trends of experimental data from a published paper on the removal of hexane in a perlite/super absorbent containing biofilter. PMID:25347218

  14. Elastic response of a protein monolayer adsorbed at decorated water surface

    NASA Astrophysics Data System (ADS)

    Singh, Amarjeet; Konovalov, Oleg

    2015-05-01

    Under the in-plane isothermal compression the self-assembled protein monolayer expand in the direction perpendicular to the applied force as a function of applied compression. The structure finally buckle beyond a critical compression, which finally returns to the initial structure when the compression force was removed, behaving like an elastic body. We modelled the layer as homogeneous elastic medium and calculated elastic constants. Young's modulus of the protein layer is 2 orders of magnitude smaller than the bulk lysozyme crystals. It is of fundamental significance to be able to predict the elastic properties of the proteins at air-water interface since protein remains in their natural environment unlike protein crystals.

  15. A Water-Stable Cationic Metal-Organic Framework as a Dual Adsorbent of Oxoanion Pollutants.

    PubMed

    Desai, Aamod V; Manna, Biplab; Karmakar, Avishek; Sahu, Amit; Ghosh, Sujit K

    2016-06-27

    A three-dimensional water-stable cationic metal-organic framework (MOF) pillared by a neutral ligand and with Ni(II)  metal nodes has been synthesized employing a rational design approach. Owing to the ordered arrangement of the uncoordinated tetrahedral sulfate (SO4 (2-) ) ions in the channels, the compound has been employed for aqueous-phase ion-exchange applications. The compound exhibits rapid and colorimetric aqueous-phase capture of environmentally toxic oxoanions (with similar geometries) in a selective manner. This system is the first example of a MOF-based system which absorbs both dichromate (Cr2 O7 (2-) ) and permanganate (MnO4 (-) ) ions, with the latter acting as a model for the radioactive contaminant pertechnetate (TcO4 (-) ). PMID:26855323

  16. Emulsification efficiency of adsorbed chitosan for bacterial cells accumulation at the oil-water interface.

    PubMed

    Archakunakorn, Somwit; Charoenrat, Nattapat; Khamsakhon, Somruethai; Pongtharangkul, Thunyarat; Wongkongkatep, Pravit; Suphantharika, Manop; Wongkongkatep, Jirarut

    2015-04-01

    The use of bacterial cell or biocatalyst for industrial synthetic chemistry is on the way of significant growth since the biocatalyst requires low energy input compared to the chemical synthesis and can be considered as a green technology. However, majority of natural bacterial cell surface is hydrophilic which allows poor access to the hydrophobic substrate or product. In this study, Escherichia coli (E. coli) as a representative of hydrophilic bacterial cells were accumulated at the oil-water interface after association with chitosan at a concentration range of 0.75-750 mg/L. After association with negatively charged E coli having a ζ potential of -19.9 mV, a neutralization of positively charged chitosan occurred as evidenced by an increase in the ζ potential value of the mixtures with increasing chitosan concentration up to +3.5 mV at 750 mg/L chitosan. Both emulsification index and droplet size analysis revealed that chitosan-E. coli system is an excellent emulsion stabilizer to date because the threshold concentration was as low as 7.5 mg/L or 0.00075% w/v. A dramatic increase in the surface hydrophobicity of the E. coli as evidenced by an increase in contact angle from 19 to 88° with increasing chitosan concentration from 0 to 750 mg/L, respectively, resulted in an increase in the stability of oil-in-water emulsions stabilized by chitosan-E. coli system. The emulsion was highly stable even the emulsification was performed under 20% salt condition, or temperature ranged between 20 and 50 °C. Emulsification was failed when the oil volume fraction was higher than 0.5, indicating that no phase inversion occurred. The basic investigation presented in this study is a crucial platform for its application in biocatalyst industry and bioremediation of oil spill. PMID:25341365

  17. Effect of acidification and heating on the rheological properties of oil-water interfaces with adsorbed milk proteins.

    PubMed

    Mellema, M; Isenbart, J G

    2004-09-01

    The behavior of casein and whey proteins at the oil-water interface was studied using a dynamic drop tensiometer (DDT). The dilational modulus of the interface was measured for aqueous solutions of skim milk powder (SMP) and whey protein concentrate (WPC) with various additions (salt, calcium, lactose) and (order of) various processing steps. Acidification or heating was performed before or after creation of the interface. The elastic properties of oil-water interfaces with adsorbed milk proteins could partly determine the rate of partial coalescence and resulting product instability. For WPC, preacidification slows down the adsorption, but the modulus is not affected. This is probably because, although the whey proteins change conformation more slowly at the interface, still a homogeneous film is formed. If postacidification is applied, coarsening of the protein film leads to loss of interfacial rigidity. Preheating of the aqueous phase with WPC leads to denaturation and aggregation, but the aggregates formed are still surface active and give high moduli. If preheating of a WPC solution is followed by postacidification, the resulting modulus is high (approximately 60 mN/m). The oil-water interfacial properties of SMP are only minimally affected by preheating or by choice of powder (low, medium, or high heat). At low pH, however, aggregates are formed that are less surface active, and interfacial moduli are lower. If measurements are performed at high temperature (i.e., if postheating is applied), for both SMP and WPC systems, moduli became much lower (approximately 10 mN/m). This is probably because of accelerated rearrangements, leading to the formation of inhomogeneous film structures. PMID:15375034

  18. Solid-phase microextraction of phthalate esters in water sample using different activated carbon-polymer monoliths as adsorbents.

    PubMed

    Lirio, Stephen; Fu, Chung-Wei; Lin, Jhih-Yun; Hsu, Meng-Ju; Huang, Hsi-Ya

    2016-07-13

    In this study, the application of different activated carbon-polymer (AC-polymer) monoliths as adsorbents for the solid-phase microextraction (SPME) of phthalate esters (PAEs) in water sample were investigated. The activated carbon (AC) was embedded in organic polymers, poly(butyl methacrylate-co-ethylene dimethacrylate) (poly(BMA-EDMA)) or poly(styrene-co-divinylbenzene) (poly(STY-DVB)), via a 5-min microwave-assisted or a 15-min water bath heating polymerization. Preliminary investigation on the performance of the native poly(BMA-EDMA) and poly(STY-DVB) demonstrated remarkable adsorption efficiencies for PAEs. However, due to the strong hydrophobic, π-π, and hydrogen bonding interactions between the analytes and polymers, low extraction recoveries were achieved. In contrast, the presence of AC in native polymers not only enhanced the adsorption efficiencies but also assisted the PAE desorption, especially for AC-poly(STY-DVB) with extraction recovery ranged of 76.2-99.3%. Under the optimized conditions, the extraction recoveries for intra-, inter-day and column-to-column were in the range of 76.5-100.8% (<3.7% RSDs), 77.2-97.6% (<5.6% RSDs) and 75.5-99.7% (<6.2% RSDs), respectively. The developed AC-poly(STY-DVB) monolithic column showed good mechanical stability, which can be reused for more than 30 extraction times without any significant loss in the extraction recoveries of PAEs. The AC-poly(STY-DVB) monolithic column was successfully applied in SPME of PAEs in water sample with extraction recovery ranged of 78.8%-104.6% (<5.5% RSDs). PMID:27237837

  19. Study of water molecule decomposition in plasma by diode laser spectroscopy and optical actinometry methods

    NASA Astrophysics Data System (ADS)

    Bernatskiy, A. V.; Lagunov, V. V.; Ochkin, V. N.; Tskhai, S. N.

    2016-07-01

    The methods of diode laser radiation absorption at vibrational–rotational molecule transitions and optical actinometry with measurements of its electron emission spectra are used independently to study water molecule dissociation in glow discharge plasma in a mixture of water vapor and inert gases at reduced pressure. The methods yield close results. The dissociation reaches 98%.

  20. Key Role of Active-Site Water Molecules in Bacteriorhodopsin Proton-Transfer Reactions

    SciTech Connect

    Bondar, A.N.; Baudry, Jerome Y; Suhai, Sandor; Fischer, S.; Smith, Jeremy C

    2008-10-01

    The functional mechanism of the light-driven proton pump protein bacteriorhodopsin depends on the location of water molecules in the active site at various stages of the photocycle and on their roles in the proton-transfer steps. Here, free energy computations indicate that electrostatic interactions favor the presence of a cytoplasmic-side water molecule hydrogen bonding to the retinal Schiff base in the state preceding proton transfer from the retinal Schiff base to Asp85. However, the nonequilibrium nature of the pumping process means that the probability of occupancy of a water molecule in a given site depends both on the free energies of insertion of the water molecule in this and other sites during the preceding photocycle steps and on the kinetic accessibility of these sites on the time scale of the reaction steps. The presence of the cytoplasmic-side water molecule has a dramatic effect on the mechanism of proton transfer: the proton is channeled on the Thr89 side of the retinal, whereas the transfer on the Asp212 side is hindered. Reaction-path simulations and molecular dynamics simulations indicate that the presence of the cytoplasmic-side water molecule permits a low-energy bacteriorhodopsin conformer in which the water molecule bridges the twisted retinal Schiff base and the proton acceptor Asp85. From this low-energy conformer, proton transfer occurs via a concerted mechanism in which the water molecule participates as an intermediate proton carrier.

  1. Effect of anodizing voltage on the sorption of water molecules on porous alumina

    NASA Astrophysics Data System (ADS)

    Vrublevsky, I.; Chernyakova, K.; Bund, A.; Ispas, A.; Schmidt, U.

    2012-05-01

    The amount of water adsorbed on different centers on the surface of oxalic acid alumina films is a function of the anodizing voltage. It is decreased with increasing the anodizing voltage from 20 up to 50 V, came up to maximum value at 20-30 V and slightly increased at voltages above 50 V. Water adsorption by oxide films formed at voltages below 50 V can be due to the negative surface charge that is present on the alumina surface. The negative surface charge disappears in the films formed at voltages higher than 50 V, and thus, the water is adsorbed on aluminum ions in a tetrahedral and octahedral environment. The correlation between anodizing conditions of aluminum in oxalic acid and the structure and composition of anodic alumina was established by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), thermogravimetric and differential thermal analyses (TG/DTA).

  2. Adsorption of Small Molecules at Water--Hexane and Water--Membrane Interfaces

    NASA Astrophysics Data System (ADS)

    Wilson, Michael A.

    1996-03-01

    The interaction of solutes with aqueous interfaces plays a significant role in a variety of physical processes, including general anesthesia and atmospheric chemistry. We present molecular dynamics results for the transfer of several small solutes across water liquid--vapor, water--hexane and water--GMO bilayer membrane interfaces. (A. Pohorille and M. A. Wilson, J. Chem. Phys. (in press, 1995).)^, (A. Pohorille, P. CIeplak, and M. A. Wilson, Chem. Phys. (in press, 1995).) The free energies of transferring small polar molecules across the interface exhibit fairly deep minima while those of nonpolar molecules do not. This is due to a balance between nonelectrostatic contributions --- primarily the work required to create a cavity large enough to accommodate the solute --- and the solute--solvent electrostatic interactions.^1 The surface excess of solute is calculated and compared with experimental results from the Gibbs adsorption isotherm. The interfacial solubilities correlate with measured anesthetic potencies of these compounds, implying that the binding sites for anesthetics are located near the water--membrane interface.

  3. Regenerative adsorbent heat pump

    NASA Technical Reports Server (NTRS)

    Jones, Jack A. (Inventor)

    1991-01-01

    A regenerative adsorbent heat pump process and system is provided which can regenerate a high percentage of the sensible heat of the system and at least a portion of the heat of adsorption. A series of at least four compressors containing an adsorbent is provided. A large amount of heat is transferred from compressor to compressor so that heat is regenerated. The process and system are useful for air conditioning rooms, providing room heat in the winter or for hot water heating throughout the year, and, in general, for pumping heat from a lower temperature to a higher temperature.

  4. Efficient removal of arsenic from water using a granular adsorbent: Fe-Mn binary oxide impregnated chitosan bead.

    PubMed

    Qi, Jianying; Zhang, Gaosheng; Li, Haining

    2015-10-01

    A novel sorbent of Fe-Mn binary oxide impregnated chitosan bead (FMCB) was fabricated through impregnating Fe-Mn binary oxide into chitosan matrix. The FMCB is sphere-like with a diameter of 1.6-1.8 mm, which is effective for both As(V) and As(III) sorption. The maximal sorption capacities are 39.1 and 54.2 mg/g, respectively, outperforming most of reported granular sorbents. The arsenic was mainly removed by adsorbing onto the Fe-Mn oxide component. The coexisting SO4(2-), HCO3(-) and SiO3(2-) have no great influence on arsenic sorption, whereas, the HPO4(2-) shows negative effects. The arsenic-loaded FMCB could be effectively regenerated using NaOH solution and repeatedly used. In column tests, about 1500 and 3200 bed volumes of simulated groundwater containing 233 μg/L As(V) and As(III) were respectively treated before breakthrough. These results demonstrate the superiority of the FMCB in removing As(V) and As(III), indicating that it is a promising candidate for arsenic removal from real drinking water. PMID:26141284

  5. Sodium niobate adsorbents doped with tantalum (TaV) for the removal of bivalent radioactive ions in waste waters.

    PubMed

    Paul, Blain; Yang, Dongjiang; Martens, Wayde N; Frost, Ray L

    2011-04-01

    Sodium niobates doped with different amounts of tantalum (Ta(V)) were prepared via a thermal reaction process. It was found that pure nanofibrils and bar like solids can be obtained when tantalum is introduced into the reaction system. For the well crystallized fibril solids, the Na(+) ions are difficult to exchange, and the radioactive ions such as Sr(2+) and Ra(2+) just deposit on the surface of the fibers during the sorption process, resulting in lower sorption capacity and distribution coefficients (K(d)). However, the bar like solids are poorly crystallized and have many exchangeable Na(+) ions. They are able to remove highly hazardous bivalent radioactive isotopes such as Sr(2+) and Ra(2+) ions. Even in the presence of many Na(+) ions, they also have higher K(d). More importantly, such sorption finally intelligently triggers considerable collapse of the structure, resulting in permanent entrapment of the toxic bivalent cations in the solids, so that they can be safely disposed of. This study highlights new opportunities for the preparation of Nb-based adsorbents to efficiently remove toxic radioactive ions from contaminated water. PMID:21266294

  6. Preparation and characterization of γ-AlOOH @CS magnetic nanoparticle as a novel adsorbent for removing fluoride from drinking water.

    PubMed

    Wan, Zhen; Chen, Wei; Liu, Cheng; Liu, Yu; Dong, Changlong

    2015-04-01

    For this study, a novel adsorbent of γ-AlOOH @CS (pseudoboehmite and chitosan shell) magnetic nanoparticles (ACMN) with magnetic separation capabilities was developed to remove fluoride from drinking water. The adsorbent was first characterized, and then its performance in removing fluoride was evaluated. Kinetic data demonstrated rapid fluoride adsorption with more than 80% fluoride adsorption within the initial 20 min and equilibrium reached in 60 min. Based on the results of kinetic and isotherm models, the fluoride adsorption process on the ACMN's surface was a monolayer adsorption on a homogeneous surface. Thermodynamic parameters presented that the adsorption process is spontaneous and endothermic in nature. The mechanism for the adsorption involved electrostatic interaction and hydrogen bonding. Moreover, the calculated adsorption capacity of the ACMN for fluoride using the Langmuir model was 67.5 mg/g (20°C, pH=7.0±0.1), higher than other fluoride removal adsorbents. This nanoadsorbent performed well over a pH range of 4-10. The study found that PO4(3-) was the co-existing anion most able to hinder the nanoparticle's fluoride adsorption, followed by NO3(-) then Cl(-). Experimental results suggest that ACMN is a promising adsorbent for treating fluoride-contaminated water. PMID:25540828

  7. Hexagonal boron nitride nanosheets as adsorbents for solid-phase extraction of polychlorinated biphenyls from water samples.

    PubMed

    Jia, Shiliang; Wang, Zhenhua; Ding, Ning; Elaine Wong, Y-L; Chen, Xiangfeng; Qiu, Guangyu; Dominic Chan, T-W

    2016-09-14

    The adsorptive potential of hexagonal boron nitride nanosheets (h-BNNSs) for solid-phase extraction (SPE) of pollutants was investigated for the first time. Seven indicators of polychlorinated biphenyls (PCBs) were selected as target analytes. The adsorption of PCBs on the surface of the h-BNNSs in water was simulated by the density functional theory and molecular dynamics. The simulation results indicated that the PCBs are adsorbed on the surface by π-π, hydrophobic, and electrostatic interactions. The PCBs were extracted with an h-BNNS-packed SPE cartridge, and eluted by dichloromethane. Gas chromatography-tandem mass spectrometry working in the multiple reaction monitor mode was used for the sample quantification. The effect of extraction parameters, including the flow rate, pH value, breakthrough volume, and the ionic strength, were investigated. Under the optimal working conditions, the developed method showed low limits of detection (0.24-0.50 ng L(-1); signal-to-noise ratio = 3:1), low limits of quantification (0.79-1.56 ng L(-1); signal-to-noise ratio = 10:1), satisfactory linearity (r > 0.99) within the concentration range of 2-1000 ng L(-1), and good precision (relative standard deviation < 12%). The PCBs concentration in environmental water samples was determined by the developed method. This results demonstrate that h-BNNSs have high analytical potential in the enrichment of pollutants. PMID:27566347

  8. Infrared Spectra of Water Bending Bands of Propylene Oxide-Water Complexes: Sequential Solvation of a Chiral Molecule in Water

    NASA Astrophysics Data System (ADS)

    Liu, Xunchen; Xu, Yunjie

    2011-06-01

    Sequential solvation of propylene oxide (C3H6O), an prototypical chiral molecule, with water has been investigated using high resolution infrared spectroscopy and ab initio methods. In a number of low resolution studies, the vibrational and vibrational circular dichroism spectral features at the water bending vibration region had been shown to be highly sensitive to the water solvation structures around propylene oxide in aqueous solution. The current study aims to provide quantitative information about solvation of a chiral molecule with water molecules at the molecular level and to provide the experimental benchmarks for calculations of vibrational frequencies in these larger molecular complexes. The high resolution infrared spectra of the propylene oxide-water complexes have been measured using a pulsed jet infrared spectrometer equipped with a room temperature external cavity quantum cascade laser and an astigmatic multi-pass cell. At least 6 bands have been observed from 1650 to 1680 Cm-1. Based on the previous microwave spectroscopic studies, these bands have been assigned to the blue-shifted water bending (ν_2) vibration modes associated with both the syn- and anti- conformers of the binary (C3H6O-H2O) and ternary (C3H6O-(H2O)2) complexes. This report shows the power of high resolution infrared spectroscopy to study multi-conformers of relatively large organic molecule complexes produced in a jet expansion. M. Losada, P. Nguyen, and Y .Xu, J. Phys. Chem. A, 112, 5621, (2008) Z. Su, Q. Wen, and Y. Xu, J. Am. Chem. Soc., 128, 6755, (2006) Z. Su and Y. Xu, Angew. Chem. Int. Ed., 46, 6163, (2007)

  9. All-electron scalar relativistic calculation of water molecule adsorption onto small gold clusters.

    PubMed

    Kuang, Xiang-Jun; Wang, Xin-Qiang; Liu, Gao-Bin

    2011-08-01

    An all-electron scalar relativistic calculation was performed on Au( n )H(2)O (n = 1-13) clusters using density functional theory (DFT) with the generalized gradient approximation at PW91 level. The calculation results reveal that, after adsorption, the small gold cluster would like to bond with oxygen and the H(2)O molecule prefers to occupy the single fold coordination site. Reflecting the strong scalar relativistic effect, Au( n ) geometries are distorted slightly but still maintain a planar structure. The Au-Au bond is strengthened and the H-O bond is weakened, as manifested by the shortening of the Au-Au bond-length and the lengthening of the H-O bond-length. The H-O-H bond angle becomes slightly larger. The enhancement of reactivity of the H(2)O molecule is obvious. The Au-O bond-lengths, adsorption energies, VIPs, HLGs, HOMO (LUMO) energy levels, charge transfers and the highest vibrational frequencies of the Au-O mode for Au( n )H(2)O clusters exhibit an obvious odd-even oscillation. The most favorable adsorption between small gold clusters and the H(2)O molecule takes place when the H(2)O molecule is adsorbed onto an even-numbered Au( n ) cluster and becomes an Au( n )H(2)O cluster with an even number of valence electrons. The odd-even alteration of magnetic moments is observed in Au( n )H(2)O clusters and may serve as material with a tunable code capacity of "0" and "1" by adsorbing a H(2)O molecule onto an odd or even-numbered small gold cluster. PMID:21140279

  10. Water disinfection: microbes versus molecules - an introduction of issues

    SciTech Connect

    Fowle, J.R. III, Kopfler, F.C.

    1986-11-01

    If the chemicals used to rid drinking water of disease-causing microbes are themselves potentially harmful, is drinking water safe. What trade-offs are acceptable with respect to microbial versus chemical water quality. This conference deals with current thinking about these topics. The subjects discussed reflect the evolution of thinking, both scientifically and socially, about how best to supply the public with safe, pure potable water. The goal of this paper is to introduce the issues associated with disinfectants and disinfectant by-products in water. This will be done by presenting a historical overview of the use of chemical disinfectants to purify drinking water and the subsequent awareness of potential health concerns. Historically, the major health issue associated with water has been the demonstrated role that water has played in spreading infectious disease. Waterborne infectious agents remain in the environment, and new ones emerge through evolution of humans and microorganisms and because of changing exposure patterns.

  11. Direct visual evidence for chemical mechanism of SERRS of the S-complex of pyrimidine molecule adsorbed on silver nanoparticle via charge transfer.

    PubMed

    Zhang, Xin; Wang, Peijie; Sheng, Shaoxiang; Zhang, Lisheng; Fang, Yan

    2014-01-01

    In this paper, the S-complex of pyrimidine molecule absorbed on silver clusters was employed as a model molecule to study the enhancement mechanism in surface-enhanced resonance Raman scattering (SERRS). We described the chemical enhancement of SERRS through charge transfer (CT) from Ag20 to pyrimidine on resonance excitation, and electromagnetic enhancement through intracluster charge redistribution (CR) on the electronic intracluster collective oscillation excitation. It is shown that SERRS process of the pyrimidine molecule absorbed on silver clusters with different incident wavelength are dominated by different enhancement mechanisms. Both experimental and theoretical works have been performed to understand the CT process in SERRS. PMID:24287052

  12. Implication of crystal water molecules in inhibitor binding at ALR2 active site.

    PubMed

    Hymavati; Kumar, Vivek; Sobhia, M Elizabeth

    2012-01-01

    Water molecules play a crucial role in mediating the interaction between a ligand and a macromolecule. The solvent environment around such biomolecule controls their structure and plays important role in protein-ligand interactions. An understanding of the nature and role of these water molecules in the active site of a protein could greatly increase the efficiency of rational drug design approaches. We have performed the comparative crystal structure analysis of aldose reductase to understand the role of crystal water in protein-ligand interaction. Molecular dynamics simulation has shown the versatile nature of water molecules in bridge H bonding during interaction. Occupancy and life time of water molecules depend on the type of cocrystallized ligand present in the structure. The information may be useful in rational approach to customize the ligand, and thereby longer occupancy and life time for bridge H-bonding. PMID:22649481

  13. A study of the potential application of nano-Mg(OH)2 in adsorbing low concentrations of uranyl tricarbonate from water.

    PubMed

    Cao, Qing; Huang, Feng; Zhuang, Zanyong; Lin, Zhang

    2012-04-01

    This work aims at the investigation of nano-Mg(OH)(2) as a promising adsorbent for uranium recovery from water. Systematic analysis including the uranium adsorption isotherm, the kinetics and the thermodynamics of adsorption of low concentrations of uranyl tricarbonate (0.1-20 mg L(-1)) by nano-Mg(OH)(2) was carried out. The results showed a spontaneous and exothermic uranium adsorption process by Mg(OH)(2), which could be well described with pseudo second order kinetics. Surface site calculation and zeta potential measurement further demonstrated that UO(2)(CO(3))(3)(4-) was a monolayer adsorbed onto nano-Mg(OH)(2) by electrostatic forces. Accordingly, the adsorption behavior met the conditions of the Langmuir isotherm. Moreover, in most of the reported literature, nano-Mg(OH)(2) had a higher UO(2)(CO(3))(3)(4-) adsorption affinity b, which implied a higher adsorption amount at equilibrium in a dilute adsorbate system. The significance of the adsorption affinity b for choosing and designing adsorbents with respect to low concentration of resources/pollutants treatment has also been assessed. PMID:22367227

  14. Adsorption of organic matter at mineral/water interfaces: I. ATR-FTIR spectroscopic and quantum chemical study of oxalate adsorbed at boehmite/water and corundum/water interfaces

    NASA Astrophysics Data System (ADS)

    Yoon, Tae Hyun; Johnson, Stephen B.; Musgrave, Charles B.; Brown, Gordon E.

    2004-11-01

    The types and structures of adsorption complexes formed by oxalate at boehmite (γ-AlOOH)/water and corundum (α-Al 2O 3)/water interfaces were determined using in situ attenuated total reflectance fourier transform infrared (ATR-FTIR) spectroscopy and quantum chemical simulation methods. At pH 5.1, at least four different oxalate species were found at or near the boehmite/water interface for oxalate surface coverages (Γ ox) ranging from 0.25 to 16.44 μmol/m 2. At relatively low coverages (Γ ox < 2.47), strongly adsorbed inner-sphere oxalate species (IR peaks at 1286, 1418, 1700, and 1720 cm -1) replace weakly adsorbed carbonate species, and a small proportion of oxalate anions are adsorbed in an outer-sphere mode (IR peaks at 1314 and 1591 cm -1). IR peaks indicative of inner-sphere adsorbed oxalate are also observed for oxalate at the corundum/water interface at Γ ox = 1.4 μmol/m 2. With increasing oxalate concentration (Γ ox > 2.47 μmol/m 2), the boehmite surface binding sites for inner-sphere adsorbed oxalate become saturated, and excess oxalate ions are present dominantly as aqueous species (IR peaks at 1309 and 1571 cm -1). In addition to these adsorption processes, oxalate-promoted dissolution of boehmite following inner-sphere oxalate adsorption becomes increasingly pronounced with increasing Γ ox and results in an aqueous Al(III)-oxalate species, as indicated by shifted IR peaks (1286 → 1297 cm -1 and 1418 → 1408 cm -1). At pH 2.5, no outer-sphere adsorbed oxalate or aqueous oxalate species were observed. The similarity of adsorbed oxalate spectral features at pH 2.5 and 5.1 implies that the adsorption mechanism of aqueous HOx - species involves loss of protons from this species during the ligand-exchange reaction. As a consequence, adsorbed inner-sphere oxalate and aqueous Al(III)-oxalate complexes formed at pH 2.5 have coordination geometries very similar to those formed at pH 5.1. The coordination geometry of inner-sphere adsorbed oxalate

  15. Development of magnetic graphene oxide adsorbent for the removal and preconcentration of As(III) and As(V) species from environmental water samples.

    PubMed

    Rashidi Nodeh, Hamid; Wan Ibrahim, Wan Aini; Ali, Imran; Sanagi, Mohd Marsin

    2016-05-01

    New-generation adsorbent, Fe3O4@SiO2/GO, was developed by modification of graphene oxide (GO) with silica-coated (SiO2) magnetic nanoparticles (Fe3O4). The synthesized adsorbent was characterized using Fourier transform infrared spectroscopy, X-ray diffractometry, energy-dispersive X-ray spectroscopy, and field emission scanning electron microscopy. The developed adsorbent was used for the removal and simultaneous preconcentration of As(III) and As(V) from environmental waters prior to ICP-MS analysis. Fe3O4@SiO2/GO provided high adsorption capacities, i.e., 7.51 and 11.46 mg g(-1) for As(III) and As(V), respectively, at pH 4.0. Adsorption isotherm, kinetic, and thermodynamic were investigated for As(III) and As(V) adsorption. Preconcentration of As(III) and As(V) were studied using magnetic solid-phase extraction (MSPE) method at pH 9.0 as the adsorbent showed selective adsorption for As(III) only in pH range 7-10. MSPE using Fe3O4@SiO2/GO was developed with good linearities (0.05-2.0 ng mL(-1)) and high coefficient of determination (R (2) = 0.9992 and 0.9985) for As(III) and As(V), respectively. The limits of detection (LODs) (3× SD/m, n = 3) obtained were 7.9 pg mL(-1) for As(III) and 28.0 pg mL(-1) for As(V). The LOD obtained is 357-1265× lower than the WHO maximum permissible limit of 10.0 ng mL(-1). The developed MSPE method showed good relative recoveries (72.55-109.71 %) and good RSDs (0.1-4.3 %, n = 3) for spring water, lake, river, and tap water samples. The new-generation adsorbent can be used for the removal and simultaneous preconcentration of As(III) and As(V) from water samples successfully. The adsorbent removal for As(III) is better than As(V). PMID:26850098

  16. Quantifying the Entropy of Binding for Water Molecules in Protein Cavities by Computing Correlations

    PubMed Central

    Huggins, David J.

    2015-01-01

    Protein structural analysis demonstrates that water molecules are commonly found in the internal cavities of proteins. Analysis of experimental data on the entropies of inorganic crystals suggests that the entropic cost of transferring such a water molecule to a protein cavity will not typically be greater than 7.0 cal/mol/K per water molecule, corresponding to a contribution of approximately +2.0 kcal/mol to the free energy. In this study, we employ the statistical mechanical method of inhomogeneous fluid solvation theory to quantify the enthalpic and entropic contributions of individual water molecules in 19 protein cavities across five different proteins. We utilize information theory to develop a rigorous estimate of the total two-particle entropy, yielding a complete framework to calculate hydration free energies. We show that predictions from inhomogeneous fluid solvation theory are in excellent agreement with predictions from free energy perturbation (FEP) and that these predictions are consistent with experimental estimates. However, the results suggest that water molecules in protein cavities containing charged residues may be subject to entropy changes that contribute more than +2.0 kcal/mol to the free energy. In all cases, these unfavorable entropy changes are predicted to be dominated by highly favorable enthalpy changes. These findings are relevant to the study of bridging water molecules at protein-protein interfaces as well as in complexes with cognate ligands and small-molecule inhibitors. PMID:25692597

  17. Fast transport of water molecules across carbon nanotubes induced by static electric fields

    NASA Astrophysics Data System (ADS)

    Zhang, Qi-Lin; Yang, Rong-Yao

    2016-01-01

    Water permeation across a single-walled carbon nanotube has been studied in the presence of static electric fields (SEFs) with different directions under hydrostatic pressures. With the angle between the SEF direction and tube axis increasing from 0∘ to 90∘, the water flux decreases gradually until almost vanishes, and the maximum value at 0∘ is approximately four times the case without SEFs. The phenomenon is attributed to the alignment of the polar water molecules along the SEF direction. We also show that water permeation properties are dependent on the field strength due mainly to thermal fluctuations of water molecules.

  18. Shape of a water molecule as function of OH separation

    NASA Astrophysics Data System (ADS)

    Gabbay, I.; March, N. H.

    1980-02-01

    For small O-H separation the water molecule becomes linear. The Murrell-Sorbie potential energy surface affords a basis to study the shape of the molecule for larger OH separation. The possible relevance to H 2O outside a metal surface is discussed.

  19. The putative role of some conserved water molecules in the structure and function of human transthyretin.

    PubMed

    Banerjee, Avik; Dasgupta, Subrata; Mukhopadhyay, Bishnu P; Sekar, Kanagaraj

    2015-11-01

    Human transthyretin (hTTR) is a multifunctional protein that is involved in several neurodegenerative diseases. Besides the transportation of thyroxin and vitamin A, it is also involved in the proteolysis of apolipoprotein A1 and Aβ peptide. Extensive analyses of 32 high-resolution X-ray and neutron diffraction structures of hTTR followed by molecular-dynamics simulation studies using a set of 15 selected structures affirmed the presence of 44 conserved water molecules in its dimeric structure. They are found to play several important roles in the structure and function of the protein. Eight water molecules stabilize the dimeric structure through an extensive hydrogen-bonding network. The absence of some of these water molecules in highly acidic conditions (pH ≤ 4.0) severely affects the interfacial hydrogen-bond network, which may destabilize the native tetrameric structure, leading to its dissociation. Three pairs of conserved water molecules contribute to maintaining the geometry of the ligand-binding cavities. Some other water molecules control the orientation and dynamics of different structural elements of hTTR. This systematic study of the location, absence, networking and interactions of the conserved water molecules may shed some light on various structural and functional aspects of the protein. The present study may also provide some rational clues about the conserved water-mediated architecture and stability of hTTR. PMID:26527142

  20. Unraveling the Sc(3+) Hydration Geometry: The Strange Case of the Far-Coordinated Water Molecule.

    PubMed

    Migliorati, Valentina; D'Angelo, Paola

    2016-07-01

    The hydration structure and dynamics of Sc(3+) in aqueous solution have been investigated using a combined approach based on quantum mechanical (QM) calculations, molecular dynamics (MD) simulations, and extended X-ray absorption fine structure (EXAFS) spectroscopy. An effective Sc-water two-body potential has been generated from QM calculations and then used in the MD simulation of Sc(3+) in water, and the reliability of the entire procedure has been assessed by comparing the theoretical structural results with the EXAFS experimental data. The outstanding outcome of this work is that the Sc(3+) ion forms a well-defined capped square antiprism (SAP) complex in aqueous solution, where the eight water molecules closest to the ion are located at the vertexes of a SAP polyhedron, while the ninth water molecule occupying the capping position is unusually found at a very long distance from the ion. This far-coordinated water molecule possesses a degree of structure comparable with the other first shell molecules surrounding the ion at much shorter distances, and its presence gave us the unique opportunity to easily identify the geometry of the Sc(3+) coordination polyhedron. Despite very strong ion-water interactions, the Sc(3+) hydration shell is very labile, as the far-coordinated ligand allows first shell water molecules to easily exchange their positions both inside the solvation shell and with the rest of the solvent molecules. PMID:27300102

  1. Amino-functionalized mesoporous MCM-41 silica as an efficient adsorbent for water treatment: batch and fixed-bed column adsorption of the nitrate anion

    NASA Astrophysics Data System (ADS)

    Ebrahimi-Gatkash, Mehdi; Younesi, Habibollah; Shahbazi, Afsaneh; Heidari, Ava

    2015-11-01

    In the present study, amino-functionalized Mobil Composite Material No. 41 (MCM-41) was used as an adsorbent to remove nitrate anions from aqueous solutions. Mono-, di- and tri-amino functioned silicas (N-MCM-41, NN-MCM-41 and NNN-MCM-41) were prepared by post-synthesis grafting method. The samples were characterized by means of X-ray powder diffraction, FTIR spectroscopy, thermogravimetric analysis, scanning electron microscopy and nitrogen adsorption-desorption. The effects of pH, initial concentration of anions, and adsorbent loading were examined in batch adsorption system. Results of adsorption experiments showed that the adsorption capacity increased with increasing adsorbent loading and initial anion concentration. It was found that the Langmuir mathematical model indicated better fit to the experimental data than the Freundlich. According to the constants of the Langmuir equation, the maximum adsorption capacity for nitrate anion by N-MCM-41, NN-MCM-41 and NNN-MCM-41 was found to be 31.68, 38.58 and 36.81 mg/g, respectively. The adsorption kinetics were investigated with pseudo-first-order and pseudo-second-order model. Adsorption followed the pseudo-second-order rate kinetics. The coefficients of determination for pseudo-second-order kinetic model are >0.99. For continuous adsorption experiments, NNN-MCM-41 adsorbent was used for the removal of nitrate anion from solutions. Breakthrough curves were investigated at different bed heights, flow rates and initial nitrate anion concentrations. The Thomas and Yan models were utilized to calculate the kinetic parameters and to predict the breakthrough curves of different bed height. Results from this study illustrated the potential utility of these adsorbents for nitrate removal from water solution.

  2. Asymmetric self-diffusion with orientation-dependence of water molecule in finite timescale

    NASA Astrophysics Data System (ADS)

    Wei, Xu; Sheng, Nan; Wan, RongZheng; Hu, GuoHui; Fang, HaiPing

    2016-07-01

    Self-diffusion of water has been investigated by molecular dynamics simulations. It was found that the preference of the direction in self-diffusion of water is orientation dependent in a finite time. For a time of ~100 ps, there are more possibilities for water molecules moving along the initial dipole orientation than in the opposite direction. This reveals that self-diffusion of water molecules is asymmetric in a finite time. We tested four water models and found that they all show similar asymmetric diffusion, indicating that asymmetric diffusion of water is intrinsic behavior rather than induced by the water model. These results are important for understanding and application of asymmetric diffusion in research fields such as biological water and confined water in small dimensions.

  3. Free energy barriers for escape of water molecules from protein hydration layer.

    PubMed

    Roy, Susmita; Bagchi, Biman

    2012-03-01

    Free energy barriers separating interfacial water molecules from the hydration layer at the surface of a protein to the bulk are obtained by using the umbrella sampling method of free energy calculation. We consider hydration layer of chicken villin head piece (HP-36) which has been studied extensively by molecular dynamics simulations. The free energy calculations reveal a strong sensitivity to the secondary structure. In particular, we find a region near the junction of first and second helix that contains a cluster of water molecules which are slow in motion, characterized by long residence times (of the order of 100 ps or more) and separated by a large free energy barrier from the bulk water. However, these "slow" water molecules constitute only about 5-10% of the total number of hydration layer water molecules. Nevertheless, they play an important role in stabilizing the protein conformation. Water molecules near the third helix (which is the important helix for biological function) are enthalpically least stable and exhibit the fastest dynamics. Interestingly, barrier height distributions of interfacial water are quite broad for water surrounding all the three helices (and the three coils), with the smallest barriers found for those near the helix-3. For the quasi-bound water molecules near the first and second helices, we use well-known Kramers' theory to estimate the residence time from the free energy surface, by estimating the friction along the reaction coordinate from the diffusion coefficient by using Einstein relation. The agreement found is satisfactory. We discuss the possible biological function of these slow, quasi-bound (but transient) water molecules on the surface. PMID:22288939

  4. Work function variation of MoS{sub 2} atomic layers grown with chemical vapor deposition: The effects of thickness and the adsorption of water/oxygen molecules

    SciTech Connect

    Kim, Jong Hun; Kim, Jae Hyeon; Park, Jeong Young E-mail: jeongypark@kaist.ac.kr; Lee, Jinhwan; Hwang, C. C.; Lee, Changgu E-mail: jeongypark@kaist.ac.kr

    2015-06-22

    The electrical properties of two-dimensional atomic sheets exhibit remarkable dependences on layer thickness and surface chemistry. Here, we investigated the variation of the work function properties of MoS{sub 2} films prepared with chemical vapor deposition (CVD) on SiO{sub 2} substrates with the number of film layers. Wafer-scale CVD MoS{sub 2} films with 2, 4, and 12 layers were fabricated on SiO{sub 2}, and their properties were evaluated by using Raman and photoluminescence spectroscopies. In accordance with our X-ray photoelectron spectroscopy results, our Kelvin probe force microscopy investigation found that the surface potential of the MoS{sub 2} films increases by ∼0.15 eV when the number of layers is increased from 2 to 12. Photoemission spectroscopy (PES) with in-situ annealing under ultra high vacuum conditions was used to directly demonstrate that this work function shift is associated with the screening effects of oxygen or water molecules adsorbed on the film surface. After annealing, it was found with PES that the surface potential decreases by ∼0.2 eV upon the removal of the adsorbed layers, which confirms that adsorbed species have a role in the variation in the work function.

  5. Vibrational analysis of water adsorbed on Pd(100): sensitivity of the isotope shifts of bending modes to the bonding site. Technical report

    SciTech Connect

    Lloyd, K.G.; Banse, B.A.; Hemminger, J.C.

    1986-02-15

    A harmonic picture of the vibrations of water adsorbed on Pd(100) is presented. The shift of the water-bending mode (against the surface plane) upon deuteration is well described by this purely harmonic picture. Normal-mode calculations in which the Pd(100) substrate is described by a finite cluster of 66 atoms were used to study the sensitivity of the isotope shift of the bending-mode frequency to the bonding site. The on-top and two-fold bridge sites are consistent with experimental results whereas the four-fold hollow site is not.

  6. Some observations on the development of superior photocatalytic systems for application to water purification by the "adsorb and shuttle" or the interphase charge transfer mechanisms.

    PubMed

    Langford, Cooper; Izadifard, Maryam; Radwan, Emad; Achari, Gopal

    2014-01-01

    Adsorb and shuttle (A/S) and interfacial charge transfer are the two major strategies for overcoming recombination in photocatalysis in this era of nanoparticle composites. Their relationships are considered here. A review of key literature is accompanied by a presentation of three new experiments within the overall aim of assessing the relation of these strategies. The cases presented include: A/S by a high silica zeolite/TiO2 composite, charge transfer (CT) between phases in a TiO2/WO3 composite and both A/S and CT by composites of TiO2 with powered activated carbon (AC) and single-walled carbon nanotubes (SWCNT). The opportunities presented by the two strategies for moving toward photocatalysts that could support applications for the removal of contaminants from drinking water or that lead to a practical adsorbent for organics that could be regenerated photocatalytically link this discussion to ongoing research here. PMID:25432008

  7. Roles of water molecules in bacteria and viruses

    NASA Astrophysics Data System (ADS)

    Cox, C. S.

    1993-02-01

    In addition to water, microbes mainly comprise lipids, carbohydrates, proteins and nucleic acids. Their structure and function singularly and conjointly is affected by water activity. Desiccation leads to dramatic lipid phase changes whereas carbohydrates, proteins and nucleic acids initially suffer spontaneous, reversible low activation energy Maillard reactions forming products that more slowly re-arrange, cross-link etc. to give non-native states. While initial products spontaneously may reverse to native states by raising water activity, later products only do so through energy consumption and enzymatic activity eg. repair. Yet, native states of lipid membranes and associated enzymes are required to generate energy. Consequently, good reserves of high energy compounds (e.g. ATP) and of membrane stabilisers (e.g. trehalose) may be expected to enhance survival following drying and rehydration (e.g. anhydrobiotic organisms).

  8. The density and refractive index of adsorbing protein layers.

    PubMed

    Vörös, Janos

    2004-07-01

    The structure of the adsorbing layers of native and denatured proteins (fibrinogen, gamma-immunoglobulin, albumin, and lysozyme) was studied on hydrophilic TiO(2) and hydrophobic Teflon-AF surfaces using the quartz crystal microbalance with dissipation and optical waveguide lightmode spectroscopy techniques. The density and the refractive index of the adsorbing protein layers could be determined from the complementary information provided by the two in situ instruments. The observed density and refractive index changes during the protein-adsorption process indicated the presence of conformational changes (e.g., partial unfolding) in general, especially upon contact with the hydrophobic surface. The structure of the formed layers was found to depend on the size of the proteins and on the experimental conditions. On the TiO(2) surface smaller proteins formed a denser layer than larger ones and the layer of unfolded proteins was less dense than that adsorbed from the native conformation. The hydrophobic surface induced denaturation and resulted in the formation of thin compact protein films of albumin and lysozyme. A linear correlation was found between the quartz crystal microbalance measured dissipation factor and the total water content of the layer, suggesting the existence of a dissipative process that is related to the solvent molecules present inside the adsorbed protein layer. Our measurements indicated that water and solvent molecules not only influence the 3D structure of proteins in solution but also play a crucial role in their adsorption onto surfaces. PMID:15240488

  9. Preparation, characterization and application of Saussurea tridactyla Sch-Bip as green adsorbents for preconcentration of rare earth elements in environmental water samples

    NASA Astrophysics Data System (ADS)

    Zhang, Qiangying; He, Man; Chen, Beibei; Hu, Bin

    2016-07-01

    This paper deals with preparation, characterization and application of the Saussurea tridactyla Sch-Bip (STSB) as a new green adsorbent for separation of matrix elements and preconcentration of rare earth elements (REEs) in environmental water samples. The pretreated STSB adsorbent with 2 mol L- 1 NaOH is characterized with higher surface area and adsorption capacities in comparison with a raw STSB material. The new adsorbent was used for the development of on-line solid phase extraction (SPE) for the determination of REEs by radial viewing 27 MHz inductively coupled plasma optical emission spectrometry (ICP-OES). Various parameters affecting the adsorption/desorption procedure were optimized. The adsorption capacities for the STSB were found to be 62.2 (Y)-153 mg g- 1 (Tm). Under the optimized conditions, the limits of detection (LODs, 3σ) for REEs were in the range of 0.06 (Yb)-8.77 (Sm) ng mL- 1. The relative standard deviations (RSDs) for 7 replicate determinations of target REEs at low concentration level ranged from 2.4 (Yb) to 8.9 (Sm)%. The adsorption isotherm fitted Langmuir model and the adsorption kinetics fitted well with both Pseudo-first order and Pseudo-second order models. The predominant adsorption mechanism is ion exchange. The STSB pretreated with 2 mol L- 1 NaOH has been demonstrated to be low cost, green and environment friendly adsorbent, featuring with high adsorption capacity, wide pH range, and fast adsorption/desorption kinetics for target REEs with long lifetime. The proposed method was applied to the determination of REEs in East Lake, Yangtze River and rain water samples.

  10. Ionic liquid coated carbon nanospheres as a new adsorbent for fast solid phase extraction of trace copper and lead from sea water, wastewater, street dust and spice samples.

    PubMed

    Tokalıoğlu, Şerife; Yavuz, Emre; Şahan, Halil; Çolak, Süleyman Gökhan; Ocakoğlu, Kasım; Kaçer, Mehmet; Patat, Şaban

    2016-10-01

    In this study a new adsorbent, ionic liquid (1,8-naphthalene monoimide bearing imidazolium salt) coated carbon nanospheres, was synthesized for the first time and it was used for the solid phase extraction of copper and lead from various samples prior to determination by flame atomic absorption spectrometry. The ionic liquid, carbon nanospheres and ionic liquid coated carbon nanospheres were characterized by using Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, (1)H NMR and (13)C NMR, Brunauer, Emmett and Teller surface area and zeta potential measurements. Various parameters for method optimization such as pH, adsorption and elution contact times, eluent volume, type and concentration, centrifuge time, sample volume, adsorption capacity and possible interfering ion effects were tested. The optimum pH was 6. The preconcentration factor, detection limits, adsorption capacity and precision (as RSD%) of the method were found to be 300-fold, 0.30µgL(-1), 60mgg(-1) and 1.1% for copper and 300-fold, 1.76µgL(-1); 50.3mgg(-1) and 2.2%, for lead, respectively. The effect of contact time results showed that copper and lead were adsorbed and desorbed from the adsorbent without vortexing. The equilibrium between analyte and adsorbent is reached very quickly. The method was rather selective for matrix ions in high concentrations. The accuracy of the developed method was confirmed by analyzing certified reference materials (LGC6016 Estuarine Water, Reference Material 8704 Buffalo River Sediment, and BCR-482 Lichen) and by spiking sea water, wastewater, street dust and spice samples. PMID:27474302

  11. Analytical model for three-dimensional Mercedes-Benz water molecules.

    PubMed

    Urbic, T

    2012-06-01

    We developed a statistical model which describes the thermal and volumetric properties of water-like molecules. A molecule is presented as a three-dimensional sphere with four hydrogen-bonding arms. Each water molecule interacts with its neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of a model developed before for a two-dimensional Mercedes-Benz model of water. We explored properties such as molar volume, density, heat capacity, thermal expansion coefficient, and isothermal compressibility as a function of temperature and pressure. We found that the volumetric and thermal properties follow the same trends with temperature as in real water and are in good general agreement with Monte Carlo simulations, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds upon increasing the temperature. PMID:23005100

  12. Analytical model for three-dimensional Mercedes-Benz water molecules

    NASA Astrophysics Data System (ADS)

    Urbic, T.

    2012-06-01

    We developed a statistical model which describes the thermal and volumetric properties of water-like molecules. A molecule is presented as a three-dimensional sphere with four hydrogen-bonding arms. Each water molecule interacts with its neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of a model developed before for a two-dimensional Mercedes-Benz model of water. We explored properties such as molar volume, density, heat capacity, thermal expansion coefficient, and isothermal compressibility as a function of temperature and pressure. We found that the volumetric and thermal properties follow the same trends with temperature as in real water and are in good general agreement with Monte Carlo simulations, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds upon increasing the temperature.

  13. Analytical model for three-dimensional Mercedes-Benz water molecules

    PubMed Central

    Urbic, T.

    2013-01-01

    We developed a statistical model which describes the thermal and volumetric properties of water-like molecules. A molecule is presented as a three-dimensional sphere with four hydrogen-bonding arms. Each water molecule interacts with its neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of a model developed before for a two-dimensional Mercedes-Benz model of water. We explored properties such as molar volume, density, heat capacity, thermal expansion coefficient, and isothermal compressibility as a function of temperature and pressure. We found that the volumetric and thermal properties follow the same trends with temperature as in real water and are in good general agreement with Monte Carlo simulations, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds upon increasing the temperature. PMID:23005100

  14. Enhanced Raman spectroscopy of molecules adsorbed on carbon-doped TiO₂ obtained from titanium carbide: a visible-light-assisted renewable substrate.

    PubMed

    Kiran, Vankayala; Sampath, Srinivasan

    2012-08-01

    Titanium carbide (TiC) is an electrically conducting material with favorable electrochemical properties. In the present studies, carbon-doped TiO(2) (C-TiO(2)) has been synthesized from TiC particles, as well as TiC films coated on stainless steel substrate via thermal annealing under various conditions. Several C-TiO(2) substrates are synthesized by varying experimental conditions and characterized by UV-visible spectroscopy, photoluminescence, X-ray diffraction, and X-ray photoelectron spectroscopic techniques. C-TiO(2) in the dry state (in powder form as well as in film form) is subsequently used as a substrate for enhancing Raman signals corresponding to 4-mercaptobenzoic acid and 4-nitrothiophenol by utilizing chemical enhancement based on charge-transfer interactions. Carbon, a nonmetal dopant in TiO(2), improves the intensities of Raman signals, compared to undoped TiO(2). Significant dependence of Raman intensity on carbon doping is observed. Ameliorated performance obtained using C-TiO(2) is attributed to the presence of surface defects that originate due to carbon as a dopant, which, in turn, triggers charge transfer between TiO(2) and analyte. The C-TiO(2) substrates are subsequently regenerated for repetitive use by illuminating an analyte-adsorbed substrate with visible light for a period of 5 h. PMID:22738214

  15. Disulfuric acid dissociated by two water molecules: ab initio and density functional theory calculations.

    PubMed

    Kim, Seong Kyu; Lee, Han Myoung; Kim, Kwang S

    2015-11-21

    We have studied geometries, energies and vibrational spectra of disulfuric acid (H2S2O7) and its anion (HS2O7(-)) hydrated by a few water molecules, using density functional theory (M062X) and ab initio theory (SCS-MP2 and CCSD(T)). The most noteworthy result is found in H2S2O7(H2O)2 in which the lowest energy conformer shows deprotonated H2S2O7. Thus, H2S2O7 requires only two water molecules, the fewest number of water molecules for deprotonation among various hydrated monomeric acids reported so far. Even the second deprotonation of the first deprotonated species HS2O7(-) needs only four water molecules. The deprotonation is supported by vibration spectra, in which acid O-H stretching peaks disappear and specific three O-H stretching peaks for H3O(+) (eigen structure) appear. We have also kept track of variations in several geometrical parameters, atomic charges, and hybrid orbital characters upon addition of water. As the number of water molecules added increases, the S-O bond weakens in the case of H2S2O7, but strengthens in the case of HS2O7(-). It implies that the decomposition leading to H2SO4 and SO3 hardly occurs prior to the 2nd deprotonation at low temperatures. PMID:26400266

  16. Wide pH range for fluoride removal from water by MHS-MgO/MgCO₃ adsorbent: kinetic, thermodynamic and mechanism studies.

    PubMed

    Zhang, Kaisheng; Wu, Shibiao; Wang, Xuelong; He, Junyong; Sun, Bai; Jia, Yong; Luo, Tao; Meng, Fanli; Jin, Zhen; Lin, Dongyue; Shen, Wei; Kong, Lingtao; Liu, Jinhuai

    2015-05-15

    A novel environment friendly adsorbent, micro-nano hierarchical structured flower-like MgO/MgCO3 (MHS-MgO/MgCO3), was developed for fluoride removal from water. The adsorbent was characterized and its defluoridation properties were investigated. Adsorption kinetics fitted well the pseudo-second-order model. Kinetic data revealed that the fluoride adsorption was rapid, more than 83-90% of fluoride could be removed within 30 min, and the adsorption equilibrium was achieved in the following 4 h. The fluoride adsorption isotherm was well described by Freundlich model. The maximum adsorption capacity was about 300 mg/g at pH=7. Moreover, this adsorbent possessed a very wide available pH range of 5-11, and the fluoride removal efficiencies even reached up to 86.2%, 83.2% and 76.5% at pH=11 for initial fluoride concentrations of 10, 20 and 30 mg/L, respectively. The effects of co-existing anions indicated that the anions had less effect on adsorption of fluoride except phosphate. In addition, the adsorption mechanism analysis revealed that the wide available pH range toward fluoride was mainly resulted from the exchange of the carbonate and hydroxyl groups on the surface of the MHS-MgO/MgCO3 with fluoride anions. PMID:25668780

  17. Auger spectrum of a water molecule after single and double core ionization

    SciTech Connect

    Inhester, L.; Burmeister, C. F.; Groenhof, G.; Grubmueller, H.

    2012-04-14

    The high intensity of free electron lasers opens up the possibility to perform single-shot molecule scattering experiments. However, even for small molecules, radiation damage induced by absorption of high intense x-ray radiation is not yet fully understood. One of the striking effects which occurs under intense x-ray illumination is the creation of double core ionized molecules in considerable quantity. To provide insight into this process, we have studied the dynamics of water molecules in single and double core ionized states by means of electronic transition rate calculations and ab initio molecular dynamics (MD) simulations. From the MD trajectories, photoionization and Auger transition rates were computed based on electronic continuum wavefunctions obtained by explicit integration of the coupled radial Schroedinger equations. These rates served to solve the master equations for the populations of the relevant electronic states. To account for the nuclear dynamics during the core hole lifetime, the calculated electron emission spectra for different molecular geometries were incoherently accumulated according to the obtained time-dependent populations, thus neglecting possible interference effects between different decay pathways. We find that, in contrast to the single core ionized water molecule, the nuclear dynamics for the double core ionized water molecule during the core hole lifetime leaves a clear fingerprint in the resulting electron emission spectra. The lifetime of the double core ionized water was found to be significantly shorter than half of the single core hole lifetime.

  18. Fast phase transition of water molecules in a defective carbon nanotube under an electric field

    NASA Astrophysics Data System (ADS)

    Meng, Xianwen; Huang, Jiping

    2016-02-01

    We utilize molecular dynamics simulations to study the effect of an electric field on the permeation of water molecules through a defective single-walled carbon nanotube (DSWCNT). Compared with a perfect single-walled carbon nanotube (PSWCNT), the behaviors of water molecules respond more quickly under the same electric field in a DSWCNT. Wet-dry phase transition of water molecules occurs when the electric field reaches 0.32 V/nm, which is much lower than the case of the PSWCNT. Besides, the critical electric field is affected by the number of defects. These results pave a way for designing fast wet-dry transition devices and provide a new insight into water permeation through a defective nanochannel.

  19. Vibrational states of a water molecule in a nano-cavity of beryl crystal lattice

    NASA Astrophysics Data System (ADS)

    Zhukova, Elena S.; Torgashev, Victor I.; Gorshunov, Boris P.; Lebedev, Vladimir V.; Shakurov, Gil'man S.; Kremer, Reinhard K.; Pestrjakov, Efim V.; Thomas, Victor G.; Fursenko, Dimitry A.; Prokhorov, Anatoly S.; Dressel, Martin

    2014-06-01

    Low-energy excitations of a single water molecule are studied when confined within a nano-size cavity formed by the ionic crystal lattice. Optical spectra are measured of manganese doped beryl single crystal Mn:Be3Al2Si6O18, that contains water molecules individually isolated in 0.51 nm diameter voids within the crystal lattice. Two types of orientation are distinguished: water-I molecules have their dipole moments aligned perpendicular to the c axis and dipole moments of water-II molecules are parallel to the c-axis. The optical conductivity σ(ν) and permittivity ɛ'(ν) spectra are recorded in terahertz and infrared ranges, at frequencies from several wavenumbers up to ν = 7000 cm-1, at temperatures 5-300 K and for two polarizations, when the electric vector E of the radiation is parallel and perpendicular to the c-axis. Comparative experiments on as-grown and on dehydrated samples allow to identify the spectra of σ(ν) and ɛ'(ν) caused exclusively by water molecules. In the infrared range, well-known internal modes ν1, ν2, and ν3 of the H2O molecule are observed for both polarizations, indicating the presence of water-I and water-II molecules in the crystal. Spectra recorded below 1000 cm-1 reveal a rich set of highly anisotropic features in the low-energy response of H2O molecule in a crystalline nano-cavity. While for E∥c only two absorption peaks are detected, at ˜90 cm-1 and ˜160 cm-1, several absorption bands are discovered for E⊥c, each consisting of narrower resonances. The bands are assigned to librational (400-500 cm-1) and translational (150-200 cm-1) vibrations of water-I molecule that is weakly coupled to the nano-cavity "walls." A model is presented that explains the "fine structure" of the bands by a splitting of the energy levels due to quantum tunneling between the minima in a six-well potential relief felt by a molecule within the cavity.

  20. Effect of the adsorbate (Bromacil) equilibrium concentration in water on its adsorption on powdered activated carbon. Part 1. Equilibrium parameters.

    PubMed

    Al Mardini, Fadi; Legube, Bernard

    2009-10-30

    This study was carried out to investigate the adsorption equilibrium and kinetics of a pesticide of the uracil group on powdered activated carbon (PAC). The experiments were conducted at a wide range of initial pesticide concentrations (approximately 5 microg L(-1) to approximately 500 microg L(-1) at pH 7.8), corresponding to equilibrium concentrations of less than 0.1 microg L(-1) for the weakest, which is compatible with the tolerance limits of drinking water. Such a very broad range of initial solute concentrations resulting powdered activated carbon (PAC) concentrations (0.1-5 mg L(-1)) is the main particularity of our study. The application of several monosolute equilibrium models (two, three or more parameters) has generally shown that Bromacil adsorption is probably effective on two types of sites. High reactivity sites (K(L) approximately 10(3) Lmg(-1)) which are 10-20 less present in a carbon surface than lower reactivity sites (K(L) approximately 10 Lmg(-1)), according to the q(m) values calculated by two- or three-parameter models. The maximum capacity of the studied powdered activated carbon (PAC), corresponding to monolayer adsorption, compared to the Bromacil molecule surface, would be between 170 mg g(-1) and 190 mg g(-1). This theoretical value is very close to the experimental q(m) values obtained when using linearized forms of Langmuir, Tóth and Fritz-Schluender models. PMID:19539425

  1. Water and Small-Molecule Permeation of Dormant Bacillus subtilis Spores

    PubMed Central

    Cermak, Nathan; Feijó Delgado, Francisco; Setlow, Barbara; Setlow, Peter

    2015-01-01

    ABSTRACT We use a suspended microchannel resonator to characterize the water and small-molecule permeability of Bacillus subtilis spores based on spores' buoyant mass in different solutions. Consistent with previous results, we found that the spore coat is not a significant barrier to small molecules, and the extent to which small molecules may enter the spore is size dependent. We have developed a method to directly observe the exchange kinetics of intraspore water with deuterium oxide, and we applied this method to wild-type spores and a panel of congenic mutants with deficiencies in the assembly or structure of the coat. Compared to wild-type spores, which exchange in approximately 1 s, several coat mutant spores were found to have relatively high water permeability with exchange times below the ∼200-ms temporal resolution of our assay. In addition, we found that the water permeability of the spore correlates with the ability of spores to germinate with dodecylamine and with the ability of TbCl3 to inhibit germination with l-valine. These results suggest that the structure of the coat may be necessary for maintaining low water permeability. IMPORTANCE Spores of Bacillus species cause food spoilage and disease and are extremely resistant to standard decontamination methods. This hardiness is partly due to spores' extremely low permeability to chemicals, including water. We present a method to directly monitor the uptake of molecules into B. subtilis spores by weighing spores in fluid. The results demonstrate the exchange of core water with subsecond resolution and show a correlation between water permeability and the rate at which small molecules can initiate or inhibit germination in coat-damaged spores. The ability to directly measure the uptake of molecules in the context of spores with known structural or genetic deficiencies is expected to provide insight into the determinants of spores' extreme resistance. PMID:26483518

  2. Hydroxyl and water molecule orientations in trypsin: Comparison to molecular dynamics structures

    SciTech Connect

    McDowell, R.S.; Kossiakoff, A.A.

    1994-12-31

    A comparison is presented of experimentally observed hydroxyl and water hydrogens in trypsin determined from neutron density maps with the results of a 140ps molecular dynamics (MD) simulation. Experimental determination of hydrogen and deuterium atom positions in molecules as large as proteins is a unique capability of neutron diffraction. The comparison addresses the degree to which a standard force-field approach can adequately describe the local electrostatic and van der Waals forces that determine the orientations of these hydrogens. Neutron densities, derived from 2.1{Angstrom} D{sub 2}O-H{sub 2}O difference Fourier maps, provide a database of 27 well-ordered hydroxyl hydrogens. Most of the simulated hydroxyl orientations are within a standard deviation of the experimentally-observed positions, including several examples in which both the simulation and the neutron density indicate that a hydroxyl group is shifted from a {open_quote}standard{close_quote} rotamer. For the most highly ordered water molecules, the hydrogen distributions calculated from the trajectory were in good agreement with neutron density; simulated water molecules that displayed multiple hydrogen bonding networks had correspondingly broadened neutron density profiles. This comparison was facilitated by development of a method to construct a pseudo 2{Angstrom} density map based on the hydrogen atom distributions from the simulation. The degree of disorder of internal water molecules is shown to result primarily from the electrostatic environment surrounding that water molecule as opposed to the cavity size available to the molecule. A method is presented for comparing the discrete observations sampled in a dynamics trajectory with the time- averaged data obtained from X-ray or neutron diffraction studies. This method is particularly useful for statically-disordered water molecules, in which the average location assigned from a trajectory may represent a site of relatively low occupancy.

  3. Improving protein-ligand docking with flexible interfacial water molecules using SWRosettaLigand.

    PubMed

    Li, Linqing; Xu, Weiwei; Lü, Qiang

    2015-11-01

    Computational protein-ligand docking is of great importance in drug discovery and design. Conformational changes greatly affect the results of protein-ligand docking, especially when water molecules take part in mediating protein ligand interactions or when large conformational changes are observed in the receptor backbone interface. We have developed an improved protocol, SWRosettaLigand, based on the RosettaLigand protocol. This approach incorporates the flexibility of interfacial water molecules and modeling of the interface of the receptor into the original RosettaLigand. In a coarse sampling step, SWRosettaLigand pre-optimizes the initial position of the water molecules, docks the ligand to the receptor with explicit water molecules, and minimizes the predicted structure with water molecules. The receptor backbone interface is treated as a loop and perturbed and refined by kinematic closure, or cyclic coordinate descent algorithm, with the presence of the ligand. In two cross-docking test sets, it was identified that for 8 out of 14, and 16 out of 22, test instances, the top-ranked structures by SWRosettaLigand achieved better accuracy than other protocols. PMID:26515196

  4. Water molecules inside protein structure affect binding of monosaccharides with HIV-1 antibody 2G12.

    PubMed

    Ueno-Noto, Kaori; Takano, Keiko

    2016-10-01

    Water molecules inside biomolecules constitute integral parts of their structure and participate in the functions of the proteins. Some of the X-ray crystallographic data are insufficient for analyzing a series of ligand-protein complexes in the same condition. We theoretically investigated antibody binding abilities of saccharide ligands and the effects of the inner water molecules of ligand-antibody complexes. Classical molecular dynamics and quantum chemical simulations using a model with possible water molecules inside the protein were performed with saccharide ligands and Human Immunodeficiency Virus 1 neutralizing antibody 2G12 complexes to estimate how inner water molecules of the protein affect the dynamics of the complexes as well as the ligand-antibody interaction. Our results indicate the fact that d-fructose's strong affinity to the antibody was partly due to the good retentiveness of solvent water molecules of the ligand and its stability of the ligand's conformation and relative position in the active site. © 2016 Wiley Periodicals, Inc. PMID:27388036

  5. Enhanced permeation of single-file water molecules across a noncylindrical nanochannel

    NASA Astrophysics Data System (ADS)

    Meng, X. W.; Huang, J. P.

    2013-07-01

    We utilize molecular dynamics simulations to study the effect of noncylindrical shapes of a nanochannel (which are inspired from the shape of real biological water nanochannels) on the permeation of single-file water molecules across the nanochannel. Compared with the cylindrical shape that has been tremendously adopted in the literature, the noncylindrical shapes play a crucial role in enhancing water permeation. Remarkably, the maximal enhancement ratio reaches a value of 6.28 (enhancement behavior). Meanwhile, the enhancement becomes saturated when the volume of the noncylindrical shape continues to increase (saturation behavior). The analysis of average diffusivity of water molecules helps to reveal the mechanism underlying the two behaviors whereas Poiseuille's law fails to explain them. These results pave a way for designing high-flow nanochannels and provide insight into water permeation across biological water nanochannels.

  6. Giant pumping of single-file water molecules in a carbon nanotube.

    PubMed

    Wang, Y; Zhao, Y J; Huang, J P

    2011-11-17

    Achieving a fast, unidirectional flow of single-file water molecules (UFSWM) across nanochannels is important for membrane-based water purification or seawater desalination. For this purpose, electro-osmosis methods are recognized as a very promising approach and have been extensively discussed in the literature. Utilizing molecular dynamics simulations, here we propose a design for pumping water molecules in a single-walled carbon nanotube in the presence of a linearly gradient electric (GE) field. Such a GE field is inspired by GE fields generated from charged ions located adjacent to biological membrane water nanochannels that can conduct water in and out of cells and can be experimentally achieved by using the charged tip of an atomic force microscope. As a result, the maximum speed of the UFSWM can be 1 or 2 orders of magnitude larger than that in a uniform electric (UE) field. Also, inverse transportation of water molecules does not exist in case of the GE field but can appear for the UE field. Thus, the GE field yields a much more efficient UFSWM than the UE field. The giant pumping ability as revealed is attributed to the nonzero net electrostatic force acting on each water molecule confined in the nanotube. These observations have significance for the design of nanoscale devices for readily achieving controllable UFSWM at high speed. PMID:21977917

  7. Interactions of carbon nanotubes with the nitromethane-water mixture governing selective adsorption of energetic molecules from aqueous solution.

    PubMed

    Liu, Yingzhe; Lai, Weipeng; Yu, Tao; Kang, Ying; Ge, Zhongxue

    2015-03-14

    The structure and dynamics of the nitromethane-water (NM-WT) binary mixture surrounding single walled carbon nanotubes (SWNTs) have been investigated by molecular dynamics simulations. The simulation trajectories show that the NM molecules can be selectively adsorbed both outside the surface and inside the cavity of SWNTs mainly dominated by van der Waals attractions because SWNTs have a higher binding affinity for NM than WT. The binding energies of SWNTs with NM and WT obtained from electronic structure calculations at the M06-2X/6-31+G* level are 15.31 and 5.51 kcal mol(-1), respectively. Compared with the SWNT exterior, the selective adsorption of NM is preferentially occurred in the SWNT interior due to the hydrophobic interactions and the dipole-dipole interactions, which induces the decrease of the hydrogen-bond number of NM with WT and ordered structures of NM with preferred intermolecular orientation in the SWNT cavity. Furthermore, the selective adsorption dynamics of NM from the aqueous solution is regardless of the chirality and radius of SWNTs. The SWNT radius plays a negligible role in the mass density distributions of NM outside the SWNTs, while the mass density of NM in the SWNT interior decreases gradually as the SWNT radius increases. The structural arrangements and intermolecular orientations of NM in the SWNT cavity are greatly dependent on the SWNT radius due to the size effect. PMID:25684688

  8. Formation of Organic Molecules and Water in Warm Disk Atmospheres

    NASA Astrophysics Data System (ADS)

    Najita, Joan R.; Ádámkovics, Máté; Glassgold, Alfred E.

    2011-12-01

    Observations from Spitzer and ground-based infrared spectroscopy reveal significant diversity in the molecular emission from the inner few AU of T Tauri disks. We explore theoretically the possible origin of this diversity by expanding on our earlier thermal-chemical model of disk atmospheres. We consider how variations in grain settling, X-ray irradiation, accretion-related mechanical heating, and the oxygen-to-carbon ratio can affect the thermal and chemical properties of the atmosphere at 0.25-40 AU. We find that these model parameters can account for many properties of the detected molecular emission. The column density of the warm (200-2000 K) molecular atmosphere is sensitive to grain settling and the efficiency of accretion-related heating, which may account, at least in part, for the large range in molecular emission fluxes that have been observed. The dependence of the atmospheric properties on the model parameters may also help to explain trends that have been reported in the literature between molecular emission strength and mid-infrared color, stellar accretion rate, and disk mass. We discuss whether some of the differences between our model results and the observations (e.g., for water) indicate a role for vertical transport and freezeout in the disk midplane. We also discuss how planetesimal formation in the outer disk (beyond the snowline) may imprint a chemical signature on the inner few AU of the disk and speculate on possible observational tracers of this process.

  9. Water-mediated influence of a crowded environment on internal vibrations of a protein molecule.

    PubMed

    Kuffel, Anna; Zielkiewicz, Jan

    2016-02-01

    The influence of crowding on the protein inner dynamics is examined by putting a single protein molecule close to one or two neighboring protein molecules. The presence of additional molecules influences the amplitudes of protein fluctuations. Also, a weak dynamical coupling of collective velocities of surface atoms of proteins separated by a layer of water is detected. The possible mechanisms of these phenomena are described. The cross-correlation function of the collective velocities of surface atoms of two proteins was decomposed into the Fourier series. The amplitude spectrum displays a peak at low frequencies. Also, the results of principal component analysis suggest that the close presence of an additional protein molecule influences the high-amplitude, low-frequency modes in the most prominent way. This part of the spectrum covers biologically important protein motions. The neighbor-induced changes in the inner dynamics of the protein may be connected with the changes in the velocity power spectrum of interfacial water. The additional protein molecule changes the properties of solvation water and in this way it can influence the dynamics of the second protein. It is suggested that this phenomenon may be described, at first approximation, by a damped oscillator driven by an external random force. This model was successfully applied to conformationally rigid Choristoneura fumiferana antifreeze protein molecules. PMID:26805932

  10. Photo-active and dynamical properties of hematite (Fe2O3)-water interfaces: an experimental and theoretical study.

    PubMed

    English, Niall J; Rahman, Mahfujur; Wadnerkar, Nitin; MacElroy, J M D

    2014-07-28

    The dynamical properties of physically and chemically adsorbed water molecules at pristine hematite-(001) surfaces have been studied by means of equilibrium Born-Oppenheimer molecular dynamics (BOMD) in the NVT ensemble at 298 K. The dissociation of water molecules to form chemically adsorbed species was scrutinised, in addition to 'hopping' or swapping events of protons between water molecules. Particular foci have been dynamical properties of the adsorbed water molecules and OH(-) and H3O(+) ions, the hydrogen bonds between protons in water molecules and the bridging oxygen atoms at the hematite surface, as well as the interactions between oxygen atoms in adsorbed water molecules and iron atoms at the hematite surface. Experimental results for photoelectrical current generation complement simulation findings of water dissociation. PMID:24525830

  11. Rotation of water molecules in plastic phase at extreme conditions from first principles molecular dynamics method

    NASA Astrophysics Data System (ADS)

    Tasaka, Tomofumi; Tsumuraya, Kazuo

    2014-03-01

    Water has a variety of polymorphs in wide ranges of temperature and pressure. Ice VII phase transforms to ice X with increased pressure. However the ice VII transforms to a superionic phase at higher temperatures around 2000K and pressure 30GPa in which the protons migrate in the body centered cubic lattice of oxygens. The ice VII transforms into rotator phase (so called plastic phase at lower temperatures around 600K and 5 to 50GPa. The formation of the phase has been confirmed only with the empirical potentials, whereas the experimental confirmation has been postponed until now. The present study elucidates the mechanism of the rotation of the water molecules and the correlation between the molecules during the rotation with the first principles molecular dynamics method. The water molecules rotate around each oxygen atom to conserve the ice VII positions of the protons.

  12. Interaction of water molecules with hexagonal 2D systems. A DFT study

    NASA Astrophysics Data System (ADS)

    Rojas, Ángela; Rey, Rafael

    Over the years water sources have been contaminated with many chemical agents, becoming issues that affect health of the world population. The advances of the nanoscience and nanotechnology in the development new materials constitute an alternative for design molecular filters with great efficiencies and low cost for water treatment and purification. In the nanoscale, the process of filtration or separation of inorganic and organic pollutants from water requires to study interactions of these atoms or molecules with different nano-materials. Specifically, it is necessary to understand the role of these interactions in physical and chemical properties of the nano-materials. In this work, the main interest is to do a theoretical study of interaction between water molecules and 2D graphene-like systems, such as silicene (h-Si) or germanene (h-Ge). Using Density Functional Theory we calculate total energy curves as function of separation between of water molecules and 2D systems. Different spatial configurations of water molecules relative to 2D systems are considered. Structural relaxation effects and changes of electronic charge density also are reported. Universidad Nacional de Colombia.

  13. Chemical interaction of water molecules with framework Al in acid zeolites: a periodic ab initio study on H-clinoptilolite.

    PubMed

    Valdiviés-Cruz, Karell; Lam, Anabel; Zicovich-Wilson, Claudio M

    2015-09-28

    Periodic quantum-chemistry methods as implemented in the CRYSTAL14 code were considered to analyse the interaction of acid clinoptilolite with water. Initially adsorbed molecules hydrolyse the Al-O bonds, giving rise to defective dealuminated materials. A suitable and representative periodic model of the partially disordered hydrated H-zeolite is the primitive cell (18 T sites) of a decahydrated trialuminated structure of HEU topology. The water distribution inside the material cavities was initially investigated. The model considered for further dealumination was the most stable one from those generated through a combined force field Monte Carlo and ab initio optimization strategy. Optimizations and energy estimations were made at the hybrid DFT level of theory (PBE0 functional) with an atomic basis set of VDZP quality. The energetics of the different pathways involved in the dealumination process was addressed by considering the Gibbs free energy with thermal and zero-point corrections through phonon analysis. It arises that hydrated models exhibit protonated water clusters stabilized by different kinds of H-bonds. The first Al extraction is slightly more energetically favourable from T3 than T2 sites, but at the same time the latter is more probable owing to its larger Al population. However, concerning the second dealumination step, it is more favourable removing the Al atom from both remaining sites after a starting abstraction from T2 rather than T3. These facts determine that the most probable overall pathways go through a first Al removal from T2. The agreement with experimental results is discussed. PMID:26299763

  14. Solvation of a probe molecule by fluid supercooled water in a hydrogel at 200 K.

    PubMed

    Santangelo, Maria Grazia; Levantino, Matteo; Cupane, Antonio; Jeschke, Gunnar

    2008-12-11

    By combining electron paramagnetic resonance (EPR) measurements on a nitroxide probe and differential scanning calorimetry (DSC), we demonstrate existence of liquid supercooled water in a silica hydrogel with high hydration level down to temperatures of at least 198 K. Besides the major fraction of liquid supercooled water, a minor fraction crystallizes at about 236 K during cooling and melts at 246 K during heating. The liquid domains are of sufficient size to solvate the nearly spherical paramagnetic probe molecule TEMPO with a diameter of about 6 A. Analysis of EPR spectra provides the rotational correlation time of the probe that is further used to compare the viscosity of the supercooled water with the one of bulk water. In the temperature interval investigated, the supercooled water behaves as a fragile liquid and eventually solidifies at 120 K to a glass that incorporates the probe molecules. PMID:19053683

  15. Impact of temperature and electrical potentials on the stability and structure of collagen adsorbed on the gold electrode

    NASA Astrophysics Data System (ADS)

    Meiners, Frank; Ahlers, Michael; Brand, Izabella; Wittstock, Gunther

    2015-01-01

    The morphology and structure of collagen type I adsorbed on gold electrodes were studied as a function of electrode potential and temperature by means of capacitance measurements, polarization modulation infrared reflection-absorption spectroscopy and scanning force microscopy at temperatures of 37 °C, 43 °C and 50 °C. The selected temperatures corresponded to the normal body temperature, temperature of denaturation of collagen molecules and denaturation of collagen fibrils, respectively. Independently of the solution temperature, collagen was adsorbed on gold electrodes in the potential range - 0.7 V < E < 0.4 V vs. Ag/AgCl, where the protein film was very stable. Fragments of collagen molecules made a direct contact to the gold surface and water was present in the film. Protein molecules were oriented preferentially with their long axis towards the gold surface. Collagen molecules in the adsorbed state preserved their native triple helical structure even at temperatures corresponding to collagen denaturation in aqueous solutions. Application of E < - 0.75 V vs. Ag/AgCl leads to the swelling of the protein film by water and desorption from the electrode surface. IR spectra provided no evidence of the thermal denaturation of adsorbed collagen molecules. A temperature increase to 50 °C leads to a distortion of the collagen film. The processes of aggregation and fibrilization were preferred over thermal denaturation for collagen adsorbed on the electrode surface and exposed to changing potentials.

  16. Shear-stress-induced structural arrangement of water molecules in nanoscale Couette flow with slipping at wall boundary

    SciTech Connect

    Lin, Jau-Wen

    2014-08-07

    This study investigated the structuring of water molecules in a nanoscale Couette flow with the upper plate subjected to lateral forces with various magnitudes and water slipping against a metal wall. It was found that when the upper plate is subjected to a force, the water body deforms into a parallelepiped. Water molecules in the channel are then gradually arranged into lattice positions, creating a layered structure. The structural arrangement of water molecules is caused by the water molecules accommodating themselves to the increase in energy under the application of a lateral force on the moving plate. The ordering arrangement of water molecules increases the rotational degree of freedom, allowing the molecules to increase their Coulomb potential energy through polar rotation that accounts for the energy input through the upper plate. With a force continuously applied to the upper plate, the water molecules in contact with the upper plate move forward until slip between the water and upper plate occurs. The relation between the structural arrangement of water molecules, slip at the wall, and the shear force is studied. The relation between the slip and the locking/unlocking of water molecules to metal atoms is also studied.

  17. Sum Frequency Generation Vibrational Spectroscopy of Adsorbed Amino Acids, Peptides and Proteins of Hydrophilic and Hydrophobic Solid-Water Interfaces

    SciTech Connect

    Holinga IV, George Joseph

    2010-09-01

    Sum frequency generation (SFG) vibrational spectroscopy was used to investigate the interfacial properties of several amino acids, peptides, and proteins adsorbed at the hydrophilic polystyrene solid-liquid and the hydrophobic silica solid-liquid interfaces. The influence of experimental geometry on the sensitivity and resolution of the SFG vibrational spectroscopy technique was investigated both theoretically and experimentally. SFG was implemented to investigate the adsorption and organization of eight individual amino acids at model hydrophilic and hydrophobic surfaces under physiological conditions. Biointerface studies were conducted using a combination of SFG and quartz crystal microbalance (QCM) comparing the interfacial structure and concentration of two amino acids and their corresponding homopeptides at two model liquid-solid interfaces as a function of their concentration in aqueous solutions. The influence of temperature, concentration, equilibration time, and electrical bias on the extent of adsorption and interfacial structure of biomolecules were explored at the liquid-solid interface via QCM and SFG. QCM was utilized to quantify the biological activity of heparin functionalized surfaces. A novel optical parametric amplifier was developed and utilized in SFG experiments to investigate the secondary structure of an adsorbed model peptide at the solid-liquid interface.

  18. Arsenic Re-Mobilization in Water Treatment Adsorbents Under Reducing Conditions: Part II, XAS and Modeling Study

    SciTech Connect

    Liu,S.; Jing, C.; Meng, X.

    2008-01-01

    The mechanism of arsenic re-mobilization in spent adsorbents under reducing conditions was studied using X-ray absorption spectroscopy and surface complexation model calculations. X-ray absorption near edge structure (XANES) spectroscopy demonstrated that As(V) was partially reduced to As(III) in spent granular ferric hydroxide (GFH), titanium dioxide (TiO2), activated alumina (AA) and modified activated alumina (MAA) adsorbents after 2 years of anaerobic incubation. As(V) was completely reduced to As(III) in spent granular ferric oxide (GFO) under 2-year incubation. The extended X-ray absorption fine structure (EXAFS) spectroscopy analysis showed that As(III) formed bidentate binuclear surface complexes on GFO as evidenced by an average As(III)-O bond distance of 1.78 Angstroms and As(III)-Fe distance of 3.34 Angstroms . The release of As from the spent GFO and TiO2 was simulated using the charge distribution multi-site complexation (CD-MUSIC) model. The observed redox ranges for As release and sulfate mobility were described by model calculations.

  19. Graphene-modified TiO2 nanotube arrays as an adsorbent in micro-solid phase extraction for determination of carbamate pesticides in water samples.

    PubMed

    Zhou, Qingxiang; Fang, Zhi

    2015-04-15

    Graphene is a good adsorbent for organic pollutants, especially for compounds containing benzene rings. When used in TiO2 nanotube arrays for micro-solid phase extraction (μ-SPE), the combination of graphene's strong adsorptive properties with its good separation capabilities results in excellent sample preconcentration performance. In the present study, graphene-modified TiO2 nanotube arrays were prepared by electrodeposition using a cyclic voltammetric reduction method. Four carbamate pesticides, including metolcarb, carbaryl, isoprocarb, and diethofencarb, were used as model analytes to validate the enrichment properties of the prepared adsorbent in μ-SPE. Factors affecting the enrichment efficiency of the μ-SPE procedure were optimized and included sample pH, elution solvents, salting-out effect, adsorption time and desorption time. Under optimal conditions, graphene-modified TiO2 nanotube arrays exhibited excellent enrichment efficiency for carbamate pesticides. The detection limits of these carbamate pesticides ranged from 2.27 to 3.26 μg L(-1). The proposed method was validated using four environmental water samples, and yields of pesticides recovered from spiked test samples of the four analytes were in the range of 83.9-108.8%. These results indicate that graphene-modified TiO2 nanotube arrays exhibit good adsorption to the target pollutants, and the method described in this work could be used as a faster and easier alternative procedure for routine analysis of carbamate pesticides in real water samples. PMID:25818138

  20. Evaluation of the use of performance reference compounds in an oasis-HLB adsorbent based passive sampler for improving water concentration estimates of polar herbicides in freshwater

    USGS Publications Warehouse

    Mazzella, N.; Lissalde, S.; Moreira, S.; Delmas, F.; Mazellier, P.; Huckins, J.N.

    2010-01-01

    Passive samplers such as the Polar Organic Chemical Integrative Sampler (POCIS) are useful tools for monitoring trace levels of polar organic chemicals in aquatic environments. The use of performance reference compounds (PRC) spiked into the POCIS adsorbent for in situ calibration may improve the semiquantitative nature of water concentration estimates based on this type of sampler. In this work, deuterium labeled atrazine-desisopropyl (DIA-d5) was chosen as PRC because of its relatively high fugacity from Oasis HLB (the POCIS adsorbent used) and our earlier evidence of its isotropic exchange. In situ calibration of POCIS spiked with DIA-d5was performed, and the resulting time-weighted average concentration estimates were compared with similar values from an automatic sampler equipped with Oasis HLB cartridges. Before PRC correction, water concentration estimates based on POCIS data sampling ratesfrom a laboratory calibration exposure were systematically lower than the reference concentrations obtained with the automatic sampler. Use of the DIA-d5 PRC data to correct POCIS sampling rates narrowed differences between corresponding values derived from the two methods. Application of PRCs for in situ calibration seems promising for improving POCIS-derived concentration estimates of polar pesticides. However, careful attention must be paid to the minimization of matrix effects when the quantification is performed by HPLC-ESI-MS/MS. ?? 2010 American Chemical Society.

  1. Magnetized graphene layers synthesized on the carbon nanofibers as novel adsorbent for the extraction of polycyclic aromatic hydrocarbons from environmental water samples.

    PubMed

    Rezvani-Eivari, Mostafa; Amiri, Amirhassan; Baghayeri, Mehdi; Ghaemi, Ferial

    2016-09-23

    The application of magnetized graphene (G) layers synthesized on the carbon nanofibers (CNFs) (m-G/CNF) was investigated as novel adsorbent for the magnetic solid-phase extraction (MSPE) of polycyclic aromatic hydrocarbons (PAHs) in water samples followed by gas chromatography-flame ionization detector (GC-FID). Six important parameters, affecting the extraction efficiency of PAHs, including: amount of adsorbent, adsorption and desorption times, type and volume of the eluent solvent and salt content of the sample were evaluated. The optimum extraction conditions were obtained as: 5min for extraction time, 20mg for sorbent amount, dichloromethane as desorption solvent, 1mL for desorption solvent volume, 5min for desorption time and 15% (w/v) for NaCl concentration. Good performance data were obtained at the optimized conditions. The calibration curves were linear over the concentration ranges from 0.012 to 100ngmL(-1) with correlation coefficients (r) between 0.9950 and 0.9967 for all the analytes. The limits of detection (LODs, S/N=3) of the proposed method for the studied PAHs were 0.004-0.03ngmL(-1). The relative standard deviations (RSDs) for five replicates at two concentration levels (0.1 and 50ngmL(-1)) of PAHs were ranged from 3.4 to 5.7%. Appropriate relative recovery values, in the range of 95.5-99.9%, were also obtained for the real water sample analysis. PMID:27578405

  2. Local lateral environment of the molecules at the surface of DMSO-water mixtures.

    PubMed

    Fábián, Balázs; Idrissi, Abdenacer; Marekha, Bogdan; Jedlovszky, Pál

    2016-10-12

    Molecular dynamics simulations of the liquid-vapour interface of dimethyl sulphoxide (DMSO)-water mixtures of 11 different compositions, including two neat systems are performed on the canonical (N, V, T) ensemble at 298 K. The molecules constituting the surface layer of these systems are selected by means of the identification of the truly interfacial molecules (ITIM) method, and their local lateral environment at the liquid surface is investigated by performing Voronoi analysis. The obtained results reveal that both molecules prefer to be in a mixed local environment, consisting of both kinds of molecules, at the liquid surface, and this preference is even stronger here than in the bulk liquid phase. Neat-like patches, in which a molecule is surrounded by like neighbours, are not found. However, vacancies that are surrounded solely by water molecules are observed at the liquid surface. Our results show that strongly hydrogen bonded DMSO·H2O complexes, known to exist in the bulk phase of these mixtures, are absent from the liquid surface. PMID:27506283

  3. An ab initio molecular dynamics study on hydrogen bonds between water molecules

    NASA Astrophysics Data System (ADS)

    Pan, Zhang; Chen, Jing; Lü, Gang; Geng, Yi-Zhao; Zhang, Hui; Ji, Qing

    2012-04-01

    The quantitative estimation of the total interaction energy of a molecular system containing hydrogen bonds (H bonds) depends largely on how to identify H bonding. The conventional geometric criteria of H bonding are simple and convenient in application, but a certain amount of non-H bonding cases are also identified as H bonding. In order to investigate the wrong identification, we carry out a systematic calculation on the interaction energy of two water molecules at various orientation angles and distances using ab initio molecular dynamics method with the dispersion correction for the Becke-Lee-Yang-Parr (BLYP) functionals. It is shown that, at many orientation angles and distances, the interaction energies of the two water molecules exceed the energy criterion of the H bond, but they are still identified as H-bonded by the conventional "distance-angle" criteria. It is found that in these non-H bonding cases the wrong identification is mainly caused by short-range interaction between the two neighbouring water molecules. We thus propose that, in addition to the conventional distance and angle criteria of H bonding, the distance dHṡṡṡH between the two neighbouring hydrogen atoms of the two water molecules should also be taken as a criterion, and the distance rOṡṡṡH between the hydrogen atom of the H-bond donor molecule and the oxygen atom of the acceptor molecule should be restricted by a lower limit. When dHṡṡṡH and rOṡṡṡH are small (e.g., dHṡṡṡH < 2.0 Å and rOṡṡṡH < 1.62 Å), the repulsion between the two neighbouring atoms increases the total energy of the two water molecules dramatically and apparently weakens the binding of the water dimer. A statistical analysis and comparison of the numbers of the H bonds identified by using different criteria have been conducted on a Car-Parrinello ab initio molecular dynamics simulation with dispersion correction for a system of 64 water molecules at near-ambient temperature. They

  4. Ultralayered Co3O4 as a new adsorbent for preconcentration of Pb(II) from water, food, sediment and tobacco samples.

    PubMed

    Yavuz, Emre; Tokalıoğlu, Serife; Sahan, Halil; Patat, Saban

    2013-10-15

    In this study, ultralayered Co3O4 adsorbent was synthesized and characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The surface area of the solid material was found to be 75.5m(2)g(-1) by BET method. The ultralayered Co3O4 was used for the first time as an effective adsorbent for the preconcentration of the Pb(II) ions in various samples prior to flame atomic absorption detection. Analytical parameters affecting the solid phase extraction of Pb(II) such as pH, adsorption and elution contact time, eluent volume and concentration, sample volume and common matrix ions were investigated. The recovery values for Pb(II) were found to be ≥ 92% even in the presence of 75,000 mg L(-1) Na(I), 75,000 mg L(-1) K(I), and 75,000 mg L(-1) Ca(II) ions. 10s vortexing time was enough for both adsorption and elution contact times. The elution was easily made with 2 mL of 2.0 mol L(-1) HNO3. The reusability (170 cycles) and adsorption capacity (35.5 mg g(-1)) of ultralayered Co3O4 were excellent. The preconcentration factor of the method and detection limit were found to be 175 and 0.72 µg L(-1), respectively. The described method was validated with certified reference material (RM 8704 Buffalo River Sediment, BCR-482 Licken and SPS-WW1 Batch 111-Wastewater) and spiked real samples. It was also applied for the preconcentration of Pb(II) ions in various water (well water, mineral water, waste water and sea water), food (cauliflower and barley), street sediment and tobacco samples. PMID:24054654

  5. DFTr optimization and DFTr-MD studies of glucose, ten explicit water molecules enclosed by an implicit solvent, COSMO

    Technology Transfer Automated Retrieval System (TEKTRAN)

    DFTr optimization studies are carried out on alpha/beta-glucose surrounded by ten explicit water molecules and the glucose/water super-molecule completely enclosed by an implicit solvation model, COSMO. Twenty one starting configurations of the explicit waters were first optimized empirically with t...

  6. Rapid nanosheets and nanowires formation by thermal oxidation of iron in water vapour and their applications as Cr(VI) adsorbent

    NASA Astrophysics Data System (ADS)

    Budiman, Faisal; Bashirom, Nurulhuda; Tan, Wai Kian; Razak, Khairunisak Abdul; Matsuda, Atsunori; Lockman, Zainovia

    2016-09-01

    Thermal oxidation of iron foil was done at 400 °C and 500 °C in for 2 h to form multilayered oxide scale with outer oxide layer of α-Fe2O3 comprising of nanowires and nanosheets respectively. Iron oxidized at 300 °C formed a rather compact film with no noticeable nanostructures. The morphologies of oxide formed in different oxidation environment (water vapour or dry air) were compared; densely packed nanostructures were produced in water vapour compared to dry air. Time variation study indicated rapid growth of nanostructure whereby for 1 min at 500 °C dense nanowires with some noticeable nanosheets were already observed. The nanowires and nanosheets were used to adsorb Cr(VI) from aqueous solution. Adsorption of 10 ppm of Cr(VI) on the nanowires and nanosheets was found to be successful with much faster removal efficiency for the nanosheets. Both samples displayed complete adsorption for less than 1 h.

  7. Chemically accurate energy barriers of small gas molecules moving through hexagonal water rings.

    PubMed

    Hjertenæs, Eirik; Trinh, Thuat T; Koch, Henrik

    2016-07-21

    We present chemically accurate potential energy curves of CH4, CO2 and H2 moving through hexagonal water rings, calculated by CCSD(T)/aug-cc-pVTZ with counterpoise correction. The barriers are extracted from a potential energy surface obtained by allowing the water ring to expand while the gas molecule diffuses through. State-of-the-art XC-functionals are evaluated against the CCSD(T) potential energy surface. PMID:27345929

  8. Water/carbonate stripping for CO.sub.2 capture adsorber regeneration and CO.sub.2 delivery to photoautotrophs

    DOEpatents

    Chance, Ronald; Koros, William J.; McCool, Benjamin; Noel, James

    2015-08-11

    The invention provides systems and methods for the delivery of carbon to photoautotrophs. The invention utilizes low energy regeneration of adsorbent for CO.sub.2 capture and provides for effective CO.sub.2 loading into liquids useful for photoautotroph growth and/or production of photosynthetic products, such as biofuels, via photoautotrophic culture media. The inventive system comprises a fluid/membrane/fluid contactor that provides selective transfer of molecular CO.sub.2 via a dense (non-porous) membrane from a carbonate-based CO.sub.2 snipping solution to a culture medium where the CO.sub.2 is consumed by a photoautotroph for the production of biofuels, biofuel precursors or other commercial products.

  9. Theoretical study of the decomposition of formamide in the presence of water molecules.

    PubMed

    Nguyen, Vinh Son; Orlando, Thomas M; Leszczynski, Jerzy; Nguyen, Minh Tho

    2013-03-28

    Formamide (NH2CHO, FM) has been considered an active key precursor in prebiotic chemistry on early Earth. Under certain conditions such as dry lagoons, FM can decompose to produce reactants that lead to formation of more complex biomolecules. Specifically, FM decomposition follows many reactive channels producing small molecules such as H2, CO, H2O, HCN, HNC, NH3, and HNCO with comparable energy barriers in the range of 73-82 kcal/mol. Due to the likely presence of water on prebiotic Earth and the intrinsic presence of water following FM decomposition, we explore the effects of water oligomers, (H2O)n with n = 1-3, on its dehydration, dehydrogenation, and decarbonylation reactions using quantum chemical computations. Geometries are optimized using MP2/aug-cc-pVxZ calculations (x = D,T), and relative energies are evaluated using coupled-cluster theory CCSD(T) with the aug-cc-pVxZ basis sets (x = D, T, Q). Where possible the coupled-cluster energies are extrapolated to the complete basis set limit (CBS). Water classically acts as an efficient bifunctional catalyst for decomposition. With the presence of one water molecule, the dehydration pathway leading to HCN is favored. When two and three water molecules are involved, dehydration remains energetically favored over other channels and attains an energy barrier of ~30 kcal/mol. PMID:23461351

  10. Size, separation, structural order, and mass density of molecules packing in water and ice

    PubMed Central

    Huang, Yongli; Zhang, Xi; Ma, Zengsheng; Li, Wen; Zhou, Yichun; Zhou, Ji; Zheng, Weitao; Sun, Chang Q.

    2013-01-01

    The structural symmetry and molecular separation in water and ice remain uncertain. We present herewith a solution to unifying the density, the structure order and symmetry, the size (H-O length dH), and the separation (dOO = dL + dH or the O:H length dL) of molecules packing in water and ice in terms of statistic mean. This solution reconciles: i) the dL and the dH symmetrization of the O:H-O bond in compressed ice, ii) the dOO relaxation of cooling water and ice and, iii) the dOO expansion of a dimer and between molecules at water surface. With any one of the dOO, the density ρ(g·cm−3), the dL, and the dH, as a known input, one can resolve the rest quantities using this solution that is probing conditions or methods independent. We clarified that: i) liquid water prefers statistically the mono-phase of tetrahedrally-coordinated structure with fluctuation, ii) the low-density phase (supersolid phase as it is strongly polarized with even lower density) exists only in regions consisting molecules with fewer than four neighbors and, iii) repulsion between electron pairs on adjacent oxygen atoms dictates the cooperative relaxation of the segmented O:H-O bond, which is responsible for the performance of water and ice. PMID:24141643

  11. Temperature dependence of the transport of single-file water molecules through a hydrophobic channel.

    PubMed

    Su, Jiaye; Yang, Keda

    2016-05-01

    Although great effort has been made on the transport properties of water molecules through nanometer channels, our understanding on the effect of some basic parameters are still rather poor. In this article, we use molecular dynamics simulations to study the temperature effect on the transport of single-file water molecules through a hydrophobic channel. Of particular interest is that the water flow and average translocation time both exhibit exponential relations with the temperature. Based on the continuous-time random-walk model and Arrhenius equation, we explore some new physical insights on these exponential behaviors. With the increase of temperature, the water dipoles flip more frequently, since the estimated flipping barrier is less than 2 kB T. Specifically, the flipping frequency also shows an exponential relation with the temperature. Furthermore, the water-water interaction and water occupancy demonstrate linear relations with the temperature, and the water density profiles along the channel axis can be slightly affected by the temperature. These results not only enhance our knowledge about the temperature effect on the single-file water transport, but also have potential implications for the design of controllable nanofluidic machines. © 2016 Wiley Periodicals, Inc. PMID:26777386

  12. The Dynamics, energetics and selectivity of water chain-containing aquapores created by the self-assembly of aquafoldamer molecules.

    PubMed

    Ma, Wenliang; Wang, Chunquan; Li, Juntong; Zhang, Kun; Lu, Yu-Jing; Huo, Yanping; Zeng, Huaqiang

    2015-11-21

    Through a series of crystallographic snapshots of water chain-containing aquapores formed from numerous one-dimensionally aligned aquafoldamer molecules 2, we demonstrated here (1) a preferential recognition of the water molecules over methanol molecules by the assembled cavity-containing aquapores with a selectivity factor of at least 17.7, (2) the dynamic nature of the water chains and the aquapores in response to varying external stimuli that exert the most influential impact on the aromatic π-π stacking in the aquapores and (3) the aquapores undergo a significant rearrangement in order to accommodate water, rather than methanol, molecules. PMID:26381358

  13. Simultaneous removal of multiple pesticides from water: effect of organically modified clays as coagulant aid and adsorbent in coagulation-flocculation process.

    PubMed

    Shabeer, T P Ahammed; Saha, Ajoy; Gajbhiye, V T; Gupta, Suman; Manjaiah, K M; Varghese, Eldho

    2014-01-01

    Contamination of drinking water sources with agrochemical residues became a major concern in the twenty-first century. Coagulation-flocculation is the most widely used water-treatment process, but the efficiency to remove pesticides and other organic pollutants are limited compared to adsorption process. Thus, simultaneous action of adsorption on normal bentonite or organo-modified montmorillonite clays [modified with octadecylamine (ODA-M) and octadecylamine + amino-propyltriethoxysilane (ODAAPS-M)] followed by coagulation-flocculation by alum and poly aluminium chloride has been evaluated for removal of 10 different pesticides, namely atrazine, lindane, metribuzin, aldrin, chlorpyriphos, pendimethalin, alpha-endosulphan, beta-endosulphan, p,p'-DDT, cypermethrin and two of its metabolites, endosulphan sulphate and p,p'-DDE, from water. The coagulation without integration of adsorption was less effective (removal % varies from 12 to 49) than the adsorption-coagulation integrated system (removal % varies from 71 to 100). Further, coagulation integrated with adsorption was more effective when organically modified montmorillonite was used as adsorbent compared to normal bentonite. The removal efficiency of organic clay depends upon the concentration of pesticides, doses of clay minerals, and efficiency was more for ODAAPS-M as compared to ODA-M. The combination of ODAAPS-M-clay with coagulants was also used efficiently for the removal of pesticides from natural and fortified natural water collected and the results exhibit the usefulness of this remediation technique for application in water decontamination and in treatment of industrial and agricultural waste waters. PMID:25145219

  14. A novel fiber-based adsorbent technology

    SciTech Connect

    Reynolds, T.A.

    1997-10-01

    In this Phase I Small Business Innovation Research program, Chemica Technologies, Inc. is developing an economical, robust, fiber-based adsorbent technology for removal of heavy metals from contaminated water. The key innovation is the development of regenerable adsorbent fibers and adsorbent fiber cloths that have high capacity and selectivity for heavy metals and are chemically robust. The process has the potential for widespread use at DOE facilities, mining operations, and the chemical process industry.

  15. Trapped water molecule in the charge separation of a bacterial reaction center.

    PubMed

    Ivashin, Nikolai; Larsson, Sven

    2008-09-25

    Low-frequency oscillations in the absorption spectrum at 1020 nm, connected to the primary charge separation process in Rhodobacter sphaeroides, have been shown by Yakovlev et al. to be caused by rotational motion of an interstitial water molecule called "water-A". The same water molecule was shown by Potter et al. to increase the rate of charge separation by a factor of 8. We have carried out geometry optimization of water-A and its nearest atoms in the protein pocket, using density functional theory (DFT). There are strong hydrogen bonds to the axial imidazol group of the B part of the special pair (P=PAPB) and to the keto carbonyl group of ring V of the accessory chlorophyll (BA). Rotation of water-A is thus impossible in the electronic ground state. We have tried to support our speculations on other possible mechanisms by calculations. The P(+)BA(-) charge transfer state is stabilized by proton transfer from water-A and simultaneous proton transfer from the axial group of PB to water-A. After double proton transfer the hydrogen bond to the keto group disappears whereby a possibility opens up for almost free water rotation. The results therefore would explain the 32 cm(-1) oscillation of Yakovlev et al. The proposed mechanism assumes, however, that the general assumption that the activation energy disappears in the primary charge separation of bacterial photosynthesis, holds also for this special case. PMID:18761433

  16. Disintegration of water molecules in a steam-plasma torch powered by microwaves

    SciTech Connect

    Uhm, Han S.; Kim, Jong H.; Hong, Yong C.

    2007-07-15

    A pure steam torch is generated by making use of 2.45 GHz microwave. Steam from a steam generator enters the discharge tube as a swirl gas at a temperature higher than 150 deg. C. This steam becomes a working gas and produces a stable steam torch. The torch volume is almost linearly proportional to the microwave power. The temperature of the torch flame is measured by making use of optical spectroscopy and a thermocouple device. Two distinctive regions are exhibited, a bright, whitish region of a high-temperature zone and a reddish, dimmer region of a relatively low-temperature zone. The bright, whitish region is a typical torch based on plasma species and the reddish, dimmer region is hydrogen burning in oxygen. Study of water molecule disintegration and gas temperature effects on the molecular fraction characteristics in steam-plasma of a microwave plasma torch at the atmospheric pressure is carried out. An analytical investigation of water disintegration indicates that a substantial fraction of water molecules disintegrate and form other compounds at high temperatures in the steam-plasma torch. Emission profiles of the hydroxide radical and water molecules confirm the theoretical predictions of water disintegration in the torch.

  17. A systematic method for studying the spatial distribution of water molecules around nucleic acid bases.

    PubMed Central

    Schneider, B; Cohen, D M; Schleifer, L; Srinivasan, A R; Olson, W K; Berman, H M

    1993-01-01

    A new method to analyze the distribution of water molecules around the bases in DNA is presented. This method relies on the notion of a "hydrated building block," which represents the joint observed hydration around all bases of a particular type, in structures of a particular conformation type. The hydrated building blocks were constructed using atomic coordinates from 40 structures contained in the Nucleic Acid Database. Pseudoelectron densities were calculated for water molecules in each hydrated building block using standard crystallographic procedures. The electron densities were fitted to obtain "average building blocks," which represent bases with waters only at average or probable positions. Both types of building blocks were used to construct models of hydrated DNA oligomers. The essential features of the solvent structure around d(CGCGAATTCGCG)2 in the B form and d(CGCGCG)2 in the Z form were reproduced. Images FIGURE 4 FIGURE 5 PMID:8312469

  18. Bamboo charcoal as adsorbent for SPE coupled with monolithic column-HPLC for rapid determination of 16 polycyclic aromatic hydrocarbons in water samples.

    PubMed

    Ma, Jiping; Li, Mo; Li, Jinhua; Rui, Cuijie; Xin, Yanping; Xue, Qinzhao; Chen, Lingxin

    2011-10-01

    The coupling of solid-phase extraction (SPE) using bamboo charcoal (BC) as an adsorbent with a monolithic column-high performance liquid chromatography (MC-HPLC) method was developed for the high-efficiency enrichment and rapid determination of 16 polycyclic aromatic hydrocarbons (PAHs) in water. Key influence factors, such as the type and the volume of the elution solvent, and the flow rate and the volume of the sample loading, were optimized to obtain a high SPE recovery and extraction efficiency. BC as an SPE adsorbent presented a high extraction efficiency due to its large specific surface area and high adsorption capacity; MC as an HPLC column accelerated the separation within 8 min because of its high porosity, fast mass transfer, and low-pressure resistance. The calibration curves for the PAHs extracted were linear in the range of 0.2-15 µg/L, with the correlation coefficients (r(2)) between 0.9970-0.9999. This method attained good precisions (relative standard deviation, RSD) from 3.5 to 10.9% for the standard PAHs I aqueous solutions at 5 µg/L; the method recoveries ranged in 52.6-121.6% for real spiked river water samples with 0.4 and 4 µg/L. The limits of detection (LODs, S/N = 3) of the method were determined from 11 and 87 ng/L. The developed method was demonstrated to be applicable for the rapid and sensitive determination of 16 PAHs in real environmental water samples. PMID:22586244

  19. Monte Carlo simulation of several biologically relevant molecules and zwitterions in water

    NASA Astrophysics Data System (ADS)

    Patuwo, Michael Y.; Bettens, Ryan P. A.

    2012-02-01

    In this work, we study the hydration free energies of butane, zwitterionic alanine, valine, serine, threonine, and asparagine, and two neuraminidase inhibitors by means of Monte Carlo (MC) simulation. The solute molecule, represented in the form of distributed multipoles and modified 6-12 potential, was varied from a non-interacting 'ghost' molecule to its full potential functions in TIP4P water. Intermediate systems with soft-core solute-solvent interaction potentials are simulated separately and then subjected to Bennett's Acceptance ratio (BAR) for the free energy calculation. Hydration shells surrounding the solute particles were used to assess the quality of potential functions.

  20. Structure detection in a libration vibration spectrum of water molecules by methods of nonlinear optics

    SciTech Connect

    Babenko, V A; Sychev, Andrei A

    2012-09-30

    In exciting water possessing an enhanced optical strength by the radiation of a YAG : Nd{sup 3+} laser with 20-ps pulses, nonlinear scattering of light was detected in the frequency range of the optical second harmonic. A relationship was established of the signal of the nonlinear scattering with a stimulated Raman scattering (SRS) of the laser radiation in water. Near the SRS threshold, the structure was observed in the spectrum of nonlinear scattering, which is related to intermolecular libration vibrations of water molecules. (laser applications and other topics in quantum electronics)

  1. Water-inducing molecular self-assembly of amphiphilic molecules into nanofibers

    SciTech Connect

    Zhang, Weiguang; Zhao, Pusu; Song, Jie

    2011-12-15

    Graphical abstract: TPDP nanofibers with smooth surfaces can be obtained by reprecipitation method using ethanol as good solvent and water as poor solvent. In the self-assembly process, during the water adding to the amphiphilic molecules' saturated solution, the amphiphilic molecules firstly assembled into needle-like small rods. With an increase in the self-assembled time, a large number of the nanofibers are produced. The assembly behavior was revealed in the course of direct in situ monitoring of its growth with optical microscopy. Highlights: Black-Right-Pointing-Pointer 2,3,6,7-Tetramethoxy-9,10-di(4-pyridyl)-9,10-dihydroanthracen (TPDP) was synthesized. Black-Right-Pointing-Pointer TPDP nanofibers can be obtained by reprecipitation method. Black-Right-Pointing-Pointer The assembly behavior was revealed in situ monitoring with optical microscopy. -- Abstract: We present investigations on the microcosmic self-assembly process of new synthesized amphiphilic TPDP molecules. It can be seen that pure TPDP nanofibers with smooth surfaces can be obtained by reprecipitation method using ethanol as good solvent and water as poor solvent. In the self-assembly process, during the water adding to the amphiphilic molecules' saturated solution, the amphiphilic molecules firstly assembled into needle-like small rods. With an increase in the self-assembled time, a large number of the nanofibers are produced. The assembly behavior was revealed in the course of direct in situ monitoring of its growth with optical microscopy. Field emission scanning electron microscopy was adopted to characterize the morphologies of the products.

  2. Molecular mimicry of substrate oxygen atoms by water molecules in the beta-amylase active site.

    PubMed

    Pujadas, G; Palau, J

    2001-08-01

    Soybean beta-amylase (EC 3.2.1.2) has been crystallized both free and complexed with a variety of ligands. Four water molecules in the free-enzyme catalytic cleft form a multihydrogen-bond network with eight strategic residues involved in enzyme-ligand hydrogen bonds. We show here that the positions of these four water molecules are coincident with the positions of four potential oxygen atoms of the ligands within the complex. Some of these waters are displaced from the active site when the ligands bind to the enzyme. How many are displaced depends on the shape of the ligand. This means that when one of the four positions is not occupied by a ligand oxygen atom, the corresponding water remains. We studied the functional/structural role of these four waters and conclude that their presence means that the conformation of the eight side chains is fixed in all situations (free or complexed enzyme) and preserved from unwanted or forbidden conformational changes that could hamper the catalytic mechanism. The water structure at the active pocket of beta-amylase is therefore essential for providing the ligand recognition process with plasticity. It does not affect the protein active-site geometry and preserves the overall hydrogen-bonding network, irrespective of which ligand is bound to the enzyme. We also investigated whether other enzymes showed a similar role for water. Finally, we discuss the potential use of these results for predicting whether water molecules can mimic ligand atoms in the active center. PMID:11468361

  3. Nanovalved Adsorbents for CH4 Storage.

    PubMed

    Song, Zhuonan; Nambo, Apolo; Tate, Kirby L; Bao, Ainan; Zhu, Minqi; Jasinski, Jacek B; Zhou, Shaojun J; Meyer, Howard S; Carreon, Moises A; Li, Shiguang; Yu, Miao

    2016-05-11

    A novel concept of utilizing nanoporous coatings as effective nanovalves on microporous adsorbents was developed for high capacity natural gas storage at low storage pressure. The work reported here for the first time presents the concept of nanovalved adsorbents capable of sealing high pressure CH4 inside the adsorbents and storing it at low pressure. Traditional natural gas storage tanks are thick and heavy, which makes them expensive to manufacture and highly energy-consuming to carry around. Our design uses unique adsorbent pellets with nanoscale pores surrounded by a coating that functions as a valve to help manage the pressure of the gas and facilitate more efficient storage and transportation. We expect this new concept will result in a lighter, more affordable product with increased storage capacity. The nanovalved adsorbent concept demonstrated here can be potentially extended for the storage of other important gas molecules targeted for diverse relevant functional applications. PMID:27124722

  4. Single-molecule redox blinking of perylene diimide derivatives in water.

    PubMed

    Cordes, Thorben; Vogelsang, Jan; Anaya, Milena; Spagnuolo, Carla; Gietl, Andreas; Summerer, Wolfram; Herrmann, Andreas; Müllen, Klaus; Tinnefeld, Philip

    2010-02-24

    Dynamic developments in ultrasensitive and superresolution fluorescence microscopy call for improved fluorescence markers with increased photostability and new functionalities. We used single-molecule spectroscopy to study water-soluble perylene dicarboximide fluorophores (PDI), which were immobilized in aqueous buffer by attaching the fluorophore to DNA. Under these conditions bright fluorescence, comparable to that of single-molecule compatible organic fluorophores, is observed with homogeneous spectral and fluorescence decay time distributions. We additionally show how the fluorescence of the PDI can be controlled through photoinduced electron-transfer reactions by using different concentrations of reductants and oxidants, yielding either blinking or stable emission. We explain these properties by the redox potentials of PDI and the recently introduced ROXS (reducing and oxidizing system) concept. Finally, we evaluate how this fluorescence control of PDIs can be used for superresolution "Blink-Microscopy" in aqueous or organic media and more generally for single-molecule spectroscopy. PMID:20121094

  5. INTERSTELLAR ICES AS WITNESSES OF STAR FORMATION: SELECTIVE DEUTERATION OF WATER AND ORGANIC MOLECULES UNVEILED

    SciTech Connect

    Cazaux, S.; Spaans, M.; Caselli, P.

    2011-11-10

    Observations of star-forming environments revealed that the abundances of some deuterated interstellar molecules are markedly larger than the cosmic D/H ratio of 10{sup -5}. Possible reasons for this pointed to grain surface chemistry. However, organic molecules and water, which are both ice constituents, do not enjoy the same deuteration. For example, deuterated formaldehyde is very abundant in comets and star-forming regions, while deuterated water rarely is. In this paper, we explain this selective deuteration by following the formation of ices (using the rate equation method) in translucent clouds, as well as their evolution as the cloud collapses to form a star. Ices start with the deposition of gas-phase CO and O onto dust grains. While reaction of oxygen with atoms (H or D) or molecules (H{sub 2}) yields H{sub 2}O (HDO), CO only reacts with atoms (H and D) to form H{sub 2}CO (HDCO, D{sub 2}CO). As a result, the deuteration of formaldehyde is sensitive to the gas D/H ratio as the cloud undergoes gravitational collapse, while the deuteration of water strongly depends on the dust temperature at the time of ice formation. These results reproduce well the deuterium fractionation of formaldehyde observed in comets and star-forming regions and can explain the wide spread of deuterium fractionation of water observed in these environments.

  6. Bias-dependent local structure of water molecules at an electrochemical interface

    NASA Astrophysics Data System (ADS)

    Pedroza, Luana; Brandimarte, Pedro; Rocha, Alexandre R.; Fernandez-Serra, Marivi

    2015-03-01

    Following the need for new - and renewable - sources of energy worldwide, fuel cells using electrocatalysts can be thought of as a viable option. Understanding the local structure of water molecules at the interfaces of the metallic electrodes is a key problem. Notably the system is under an external potential bias, which makes the task of simulating this setup difficult. A first principle description of all components of the system is the most appropriate methodology in order to advance understanding of electrochemical processes. There, the metal is usually charged. To correctly compute the effect of an external bias potential applied to electrodes, we combine density functional theory (DFT) and non-equilibrium Green's functions methods (NEGF), with and without van der Waals interactions. In this work, we apply this methodology to study the electronic properties and forces of one water molecule and water monolayer at the interface of gold electrodes. We find that the water molecule has a different torque direction depending on the sign of the bias applied. We also show that it changes the position of the most stable configuration indicating that the external bias plays an important role in the structural properties of the interface. We acknowledge financial support from FAPESP.

  7. Theoretical and experimental investigation of the interactions between [emim]Ac and water molecules

    NASA Astrophysics Data System (ADS)

    Ding, Zhen-Dong; Chi, Zhen; Gu, Wen-Xiu; Gu, Sheng-Ming; Wang, Hai-Jun

    2012-05-01

    Density functional theory (DFT) calculations, atom in molecules (AIM) theory, natural bond orbital (NBO) analysis and infrared (IR) spectroscopy were performed to investigate the interactions between water molecules and ionic liquid 1-ethyl-3-methylimidazolium acetate ([emim]Ac). It was found that [emim]Ac interacts with water molecules mainly via H-bonds, and the anionic part of [emim]Ac plays a major role in the interaction with H2O. The energies of H-bonds were estimated from spectral shifts of hydroxy antisymmetric stretching vibration. Moreover, the experimental results also indicated that hydroxy of water mainly interacts with the COO- of [emim]Ac. Further studies indicated that the intensity of hydroxy stretching vibrations tend to be stronger with the increase of the concentration of water. In addition, the frequency of hydroxy stretching vibrations showed clearly red-shift, and the COO- vibrational frequency gradually shifted to the lower wavenumber region, which were indicative of extended hydrogen bonded network.

  8. Magnetic solid-phase extraction using poly(para-phenylenediamine) modified with magnetic nanoparticles as adsorbent for analysis of monocyclic aromatic amines in water and urine samples.

    PubMed

    Amiri, Amirhassan; Baghayeri, Mehdi; Nori, Somayeh

    2015-10-01

    In the present work, a simple and effective method based on magnetic separation has been developed for the extraction of monocyclic aromatic amines in water and urine samples using poly(para-phenylenediamine) modified with Fe3O4 nanoparticles (PpPD/Fe3O4) as an adsorbent. The chemical structures of the sorbent were characterized by field emission scanning electron microscopy (FESEM) and Fourier transform infrared spectrophotometer (FT-IR). Various parameters affecting on the extraction efficiency of desired analytes, such as pH of solution, desorption conditions, extraction time, salt effect and amount of adsorbent have been investigated and optimized. The obtained optimal conditions were: sample pH, 6; amount of sorbent, 20mg; sorption time, 2min; elution solvent and its volume, dichloromethane and chloroform (3:1 v/v), 250μL; elution time, 30s and without addition of NaCl. Under the optimum conditions, detection limits in the range of 0.007-0.01ngmL(-1) were obtained by gas chromatography-flame ionization detector (GC-FID). The calibration curves were linear in the range 0.05-100ngmL(-1) with a correlation coefficient better than 0.9953. In addition, a satisfactory reproducibility was achieved by evaluating the intra- and inter-day precisions with relative standard deviations (RSDs) less than 5.9 and 7.3%, respectively. The proposed procedure has been successfully applied to the determination of target analytes in water and urine samples. The results demonstrated that the developed method is simple, inexpensive, accurate and remarkably free from interference effects. PMID:26341590

  9. Anomalous and anisotropic nanoscale diffusion of hydration water molecules in fluid lipid membranes.

    PubMed

    Toppozini, Laura; Roosen-Runge, Felix; Bewley, Robert I; Dalgliesh, Robert M; Perring, Toby; Seydel, Tilo; Glyde, Henry R; García Sakai, Victoria; Rheinstädter, Maikel C

    2015-11-14

    We have studied nanoscale diffusion of membrane hydration water in fluid-phase lipid bilayers made of 1,2-dimyristoyl-3-phosphocholine (DMPC) using incoherent quasi-elastic neutron scattering. Dynamics were fit directly in the energy domain using the Fourier transform of a stretched exponential. By using large, 2-dimensional detectors, lateral motions of water molecules and motions perpendicular to the membranes could be studied simultaneously, resulting in 2-dimensional maps of relaxation time, τ, and stretching exponent, β. We present experimental evidence for anomalous (sub-diffusive) and anisotropic diffusion of membrane hydration water molecules over nanometer distances. By combining molecular dynamics and Brownian dynamics simulations, the potential microscopic origins for the anomaly and anisotropy of hydration water were investigated. Bulk water was found to show intrinsic sub-diffusive motion at time scales of several picoseconds, likely related to caging effects. In membrane hydration water, however, the anisotropy of confinement and local dynamical environments leads to an anisotropy of relaxation times and stretched exponents, indicative of anomalous dynamics. PMID:26338138

  10. The reaction of clean Li surfaces with small molecules in ultrahigh vacuum. 2: Water

    SciTech Connect

    Zhuang, G.; Ross, P.N. Jr.; Kong, F.P.; McLarnon, F. |

    1998-01-01

    Reactions at the Li/H{sub 2}O interface were studied at 160 to 290 K in ultrahigh vacuum by a combination of spectroscopic ellipsometry and Auger electron spectroscopy. Ice multilayers, ca. 100 ML thick, were deposited on clean Li at 160 K. The evaporation rate of water at 160 K is sufficiently slow that the ice layer remains on the surface for about 1 h. After 10 min at 160 k, a pure LiOH layer ca. 70 {angstrom} thick is produced, and after 1 h there is evidence of a slow conversion to LiOH to Li{sub 2}O in the layer, probably at the Li/LiOH interface. Raising the temperature to 240 K results in desorption of the adsorbed water and conversion of all the LiOH to a porous (60% void) layer composed mostly of Li{sub 2}O (35%) with some metallic Li mixed in. Raising the temperature further to 290 K results in densification of the layer by both collapse of the voids and by diffusion of Li into the interstices of the Li{sub 2}O, increasing the Li content to 27% and shrinking the film thickness to 26 {angstrom}. Based on these results, a model for the behavior of small amounts of water in Li battery electrolyte is presented.

  11. Structure and dynamics of water and lipid molecules in charged anionic DMPG lipid bilayer membranes

    NASA Astrophysics Data System (ADS)

    Rønnest, A. K.; Peters, G. H.; Hansen, F. Y.; Taub, H.; Miskowiec, A.

    2016-04-01

    Molecular dynamics simulations have been used to investigate the influence of the valency of counter-ions on the structure of freestanding bilayer membranes of the anionic 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol (DMPG) lipid at 310 K and 1 atm. At this temperature, the membrane is in the fluid phase with a monovalent counter-ion and in the gel phase with a divalent counter-ion. The diffusion constant of water as a function of its depth in the membrane has been determined from mean-square-displacement calculations. Also, calculated incoherent quasielastic neutron scattering functions have been compared to experimental results and used to determine an average diffusion constant for all water molecules in the system. On extrapolating the diffusion constants inferred experimentally to a temperature of 310 K, reasonable agreement with the simulations is obtained. However, the experiments do not have the sensitivity to confirm the diffusion of a small component of water bound to the lipids as found in the simulations. In addition, the orientation of the dipole moment of the water molecules has been determined as a function of their depth in the membrane. Previous indirect estimates of the electrostatic potential within phospholipid membranes imply an enormous electric field of 108-109 V m-1, which is likely to have great significance in controlling the conformation of translocating membrane proteins and in the transfer of ions and molecules across the membrane. We have calculated the membrane potential for DMPG bilayers and found ˜1 V (˜2 ṡ 108 V m-1) when in the fluid phase with a monovalent counter-ion and ˜1.4 V (˜2.8 ṡ 108 V m-1) when in the gel phase with a divalent counter-ion. The number of water molecules for a fully hydrated DMPG membrane has been estimated to be 9.7 molecules per lipid in the gel phase and 17.5 molecules in the fluid phase, considerably smaller than inferred experimentally for 1,2-dimyristoyl-sn-glycero-3-phosphorylcholine (DMPC

  12. Adsorbate-induced curvature and stiffening of graphene.

    PubMed

    Svatek, Simon A; Scott, Oliver R; Rivett, Jasmine P H; Wright, Katherine; Baldoni, Matteo; Bichoutskaia, Elena; Taniguchi, Takashi; Watanabe, Kenji; Marsden, Alexander J; Wilson, Neil R; Beton, Peter H

    2015-01-14

    The adsorption of the alkane tetratetracontane (TTC, C44H90) on graphene induces the formation of a curved surface stabilized by a gain in adsorption energy. This effect arises from a curvature-dependent variation of a moiré pattern due to the mismatch of the carbon-carbon separation in the adsorbed molecule and the period of graphene. The effect is observed when graphene is transferred onto a deformable substrate, which in our case is the interface between water layers adsorbed on mica and an organic solvent, but is not observed on more rigid substrates such as boron nitride. Our results show that molecular adsorption can be influenced by substrate curvature, provide an example of two-dimensional molecular self-assembly on a soft, responsive interface, and demonstrate that the mechanical properties of graphene may be modified by molecular adsorption, which is of relevance to nanomechanical systems, electronics, and membrane technology. PMID:25469625

  13. Versatile Small Molecule Motifs for Self-assembly in Water and Formation of Biofunctional Supramolecular Hydrogels

    PubMed Central

    Zhang, Ye; Kuang, Yi; Gao, Yuan; Xu, Bing

    2010-01-01

    This article introduces new structural motifs (referred as “samogen”) that serve as the building blocks of hydrogelators for molecular self-assembly in water to result in a series of supramolecular hydrogels. Using a compound that consists of two phenylalanine residues and a naphthyl group (also abbreviated as NapFF (1) in this text) as an example of the samogens, we demonstrated the ability of the samogens to convert bioactive molecules into molecular hydrogelators that self-assemble in water to result in nanofibers. By briefly summarizing the properties and applications (e.g., wound healing, drug delivery, controlling cell fate, typing bacteria, and catalysis) of these molecular hydrogelators derived from the samogens, we intend to illustrate the basic requirements and promises of the small molecule hydrogelators for applications in chemistry, materials science, and biomedicine. PMID:20608718

  14. Orientation and alignment effects in electron-induced ionization of a single oriented water molecule

    SciTech Connect

    Champion, C.; Rivarola, R. D.

    2010-10-15

    We here report a theoretical study about the orientation effect on the total ionization cross sections for a single oriented water molecule. The theoretical description of the ionization process is performed within the first Born framework with a collisional system including an initial state composed of a projectile and a water target molecule described by a plane wave and an accurate one-center molecular wave function, respectively, and a final state constituted by a slow ejected electron represented by a Coulomb wave and a scattered (fast) electron projectile described by a plane wave. Secondary electron energetic distributions as well as total cross sections are then compared for particular target configurations pointing out strong alignment and orientation effects on the description of the ionization process.

  15. Water molecule-enhanced CO{sub 2} insertion in lanthanide coordination polymers

    SciTech Connect

    Luo Liushan; Huang Xiaoyuan; Wang Ning; Wu Hongyan; Chen Wenbin; Feng Zihao; Zhu Huiping; Peng Xiaoling; Li Yongxian; Huang Ling; Yue Shantang; Liu Yingliang

    2009-08-15

    Two new lanthanide coordination polymers H{sub 2}N(CH{sub 3}){sub 2}.[Eu{sup III}{sub 2}(L{sub 1}){sub 3}(L{sub 2})] (1, L{sub 1}=isophthalic acid dianion, L{sub 2}=formic acid anion) and [La{sup III}(2,5-PDC)(L{sub 2})](2, 2,5-PDC=2,5-pyridinedicarboxylate dianion) were synthesized under solvothermal conditions. It is of interest that the formic ligand (L{sub 2}) is not contained in the stating materials, but arises from the water molecule-enhanced CO{sub 2} insertion during the solvothermal process. Both of the two compounds exhibit complicated three dimensional sandwich-like frameworks. - Graphical abstract: Two new lanthanide coordination polymers involving water molecule-enhanced CO{sub 2} insertion resulting in the formation of formic anion and dimethylammonium cation were synthesized under solvothermal conditions.

  16. Influences of Dilute Organic Adsorbates on the Hydration of Low-Surface-Area Silicates.

    PubMed

    Sangodkar, Rahul P; Smith, Benjamin J; Gajan, David; Rossini, Aaron J; Roberts, Lawrence R; Funkhouser, Gary P; Lesage, Anne; Emsley, Lyndon; Chmelka, Bradley F

    2015-07-01

    Competitive adsorption of dilute quantities of certain organic molecules and water at silicate surfaces strongly influence the rates of silicate dissolution, hydration, and crystallization. Here, we determine the molecular-level structures, compositions, and site-specific interactions of adsorbed organic molecules at low absolute bulk concentrations on heterogeneous silicate particle surfaces at early stages of hydration. Specifically, dilute quantities (∼0.1% by weight of solids) of the disaccharide sucrose or industrially important phosphonic acid species slow dramatically the hydration of low-surface-area (∼1 m(2)/g) silicate particles. Here, the physicochemically distinct adsorption interactions of these organic species are established by using dynamic nuclear polarization (DNP) surface-enhanced solid-state NMR techniques. These measurements provide significantly improved signal sensitivity for near-surface species that is crucial for the detection and analysis of dilute adsorbed organic molecules and silicate species on low-surface-area particles, which until now have been infeasible to characterize. DNP-enhanced 2D (29)Si{(1)H}, (13)C{(1)H}, and (31)P{(1)H} heteronuclear correlation and 1D (29)Si{(13)C} rotational-echo double-resonance NMR measurements establish hydrogen-bond-mediated adsorption of sucrose at distinct nonhydrated and hydrated silicate surface sites and electrostatic interactions with surface Ca(2+) cations. By comparison, phosphonic acid molecules are found to adsorb electrostatically at or near cationic calcium surface sites to form Ca(2+)-phosphonate complexes. Although dilute quantities of both types of organic molecules effectively inhibit hydration, they do so by adsorbing in distinct ways that depend on their specific architectures and physicochemical interactions. The results demonstrate the feasibility of using DNP-enhanced NMR techniques to measure and assess dilute adsorbed molecules and their molecular interactions on low

  17. Diagrammatic perturbation theory applied to the ground state of the water molecule

    NASA Technical Reports Server (NTRS)

    Silver, D. M.; Wilson, S.

    1977-01-01

    The diagrammatic many-body perturbation theory is applied to the ground state of the water molecule within the algebraic approximation. Using four different basis sets, the total energy, the equilibrium OH bond length, and the equilibrium HOH bond angle are examined. The latter is found to be a particularly sensitive test of the convergence of perturbation expansions. Certain third-order results, which incorporate all two-, three-, and four-body effects, show evidence of good convergence properties.

  18. Double ionization of single oriented water molecules by electron impact: Second-order Born description

    SciTech Connect

    Dal Cappello, C.; Champion, C.; Kada, I.; Mansouri, A.

    2011-06-15

    The double ionization of isolated water molecules fixed in space is investigated within a theoretical approach based on the second-order Born approximation. Electron angular distributions have been studied for specific kinematical conditions. The three usual mechanisms, the shake-off and the two two-step mechanisms, have been identified. A significant contribution of the two-step mechanism is clearly visible for some particular kinematics.

  19. Organic and inorganic contaminants removal from water with biochar, a renewable, low cost and sustainable adsorbent--a critical review.

    PubMed

    Mohan, Dinesh; Sarswat, Ankur; Ok, Yong Sik; Pittman, Charles U

    2014-05-01

    Biochar is used for soil conditioning, remediation, carbon sequestration and water remediation. Biochar application to water and wastewater has never been reviewed previously. This review focuses on recent applications of biochars, produced from biomass pyrolysis (slow and fast), in water and wastewater treatment. Slow and fast pyrolysis biochar production is briefly discussed. The literature on sorption of organic and inorganic contaminants by biochars is surveyed and reviewed. Adsorption capacities for organic and inorganic contaminants by different biochars under different operating conditions are summarized and, where possible, compared. Mechanisms responsible for contaminant remediation are briefly discussed. Finally, a few recommendations for further research have been made in the area of biochar development for application to water filtration. PMID:24636918

  20. Organic molecules and water in the planet formation region of young circumstellar disks.

    PubMed

    Carr, John S; Najita, Joan R

    2008-03-14

    The chemical composition of protoplanetary disks is expected to hold clues to the physical and chemical processes that influence the formation of planetary systems. However, characterizing the gas composition in the planet formation region of disks has been a challenge to date. We report here that the protoplanetary disk within 3 astronomical units of AA Tauri possesses a rich molecular emission spectrum in the mid-infrared, indicating a high abundance of simple organic molecules (HCN, C2H2, and CO2), water vapor, and OH. These results suggest that water is abundant throughout the inner disk and that the disk supports an active organic chemistry. PMID:18339932

  1. Experimental Evaluation of Proposed Small-Molecule Inhibitors of Water Channel Aquaporin-1.

    PubMed

    Esteva-Font, Cristina; Jin, Byung-Ju; Lee, Sujin; Phuan, Puay-Wah; Anderson, Marc O; Verkman, A S

    2016-06-01

    The aquaporin-1 (AQP1) water channel is a potentially important drug target, as AQP1 inhibition is predicted to have therapeutic action in edema, tumor growth, glaucoma, and other conditions. Here, we measured the AQP1 inhibition efficacy of 12 putative small-molecule AQP1 inhibitors reported in six recent studies, and one AQP1 activator. Osmotic water permeability was measured by stopped-flow light scattering in human and rat erythrocytes that natively express AQP1, in hemoglobin-free membrane vesicles from rat and human erythrocytes, and in plasma membrane vesicles isolated from AQP1-transfected Chinese hamster ovary cell cultures. As a positive control, 0.3 mM HgCl2 inhibited AQP1 water permeability by >95%. We found that none of the tested compounds at 50 µM significantly inhibited or increased AQP1 water permeability in these assays. Identification of AQP1 inhibitors remains an important priority. PMID:26993802

  2. WScore: A Flexible and Accurate Treatment of Explicit Water Molecules in Ligand-Receptor Docking.

    PubMed

    Murphy, Robert B; Repasky, Matthew P; Greenwood, Jeremy R; Tubert-Brohman, Ivan; Jerome, Steven; Annabhimoju, Ramakrishna; Boyles, Nicholas A; Schmitz, Christopher D; Abel, Robert; Farid, Ramy; Friesner, Richard A

    2016-05-12

    We have developed a new methodology for protein-ligand docking and scoring, WScore, incorporating a flexible description of explicit water molecules. The locations and thermodynamics of the waters are derived from a WaterMap molecular dynamics simulation. The water structure is employed to provide an atomic level description of ligand and protein desolvation. WScore also contains a detailed model for localized ligand and protein strain energy and integrates an MM-GBSA scoring component with these terms to assess delocalized strain of the complex. Ensemble docking is used to take into account induced fit effects on the receptor conformation, and protein reorganization free energies are assigned via fitting to experimental data. The performance of the method is evaluated for pose prediction, rank ordering of self-docked complexes, and enrichment in virtual screening, using a large data set of PDB complexes and compared with the Glide SP and Glide XP models; significant improvements are obtained. PMID:27054459

  3. Isolation of enteroviruses from water, suspended solids, and sediments from Galveston Bay: survival of poliovirus and rotavirus adsorbed to sediments.

    PubMed Central

    Rao, V C; Seidel, K M; Goyal, S M; Metcalf, T G; Melnick, J L

    1984-01-01

    The distribution and quantitation of enteroviruses among water, suspended solids, and compact sediments in a polluted estuary are described. Samples were collected sequentially from water, suspended solids, fluffy sediments (uppermost layer of bottom sediments), and compact sediment. A total of 103 samples were examined of which 27 (26%) were positive for virus. Polioviruses were recovered most often, followed by coxsackie B viruses and echoviruses 7 and 29. Virus was found most often attached to suspended solids: 72% of these samples were positive, whereas only 14% of water samples without solids yielded virus. Fluffy sediments yielded virus in 47% of the samples, whereas only 5% of compact bottom-sediment samples were positive. When associated with solids, poliovirus and rotavirus retained their infectious quality for 19 days. The same viruses remained infectious for only 9 days when freely suspended in seawater. Collection of suspended solids at ambient water pH appears to be very useful for the detection of virus; it has advantages over collecting and processing large volumes of water, with accompanying pH adjustment and salt addition for processing. PMID:6091548

  4. Ultrafast Raman-induced Kerr-effect of water: Single molecule versus collective motions

    NASA Astrophysics Data System (ADS)

    Winkler, Kathrin; Lindner, Jörg; Bürsing, Helge; Vöhringer, Peter

    2000-09-01

    The ultrafast optical Kerr-response of water and heavy water has been measured at 1 bar in the temperature range between 273 and 373 K. The nuclear Kerr response of the liquid exhibits a pronounced double exponential decay on longer time scales after dephasing of impulsively perturbed acoustic modes is completed. The time constant, τ2, characterizing the slowly decaying exponential component of the Kerr-response function is in quantitative agreement with rotational diffusion time constants of the water molecules obtained form nuclear magnetic resonance (NMR) spin-lattice relaxation rates. A detailed comparison with THz time domain spectroscopy demonstrates that the reorientational dynamics responsible for the long time tail of the Kerr response are due to single molecule as opposed to collective effects. Furthermore, a good agreement between the single molecule rotational diffusion and the Stokes-Einstein-Debye equation is found in the temperature range of thermodynamic stability of the liquid. The time constant, τ1, characterizing the fast exponential component of the Kerr-response of water is found to be in qualitative agreement with central Lorentzian linewidths obtained from frequency-domain, depolarized Raman scattering experiments. The temperature dependence of τ2 does not follow an Arrhenius-type behavior, which was previously taken as evidence for thermally activated crossing of a librational barrier with concomitant hydrogen-bond breakage. Instead, the temperature dependence of the fast relaxation time constant can be represented adequately by the Speedy-Angell relation which has been shown to accurately describe a number of transport parameters and thermodynamic properties of water.

  5. Nitrogen cycling between sediment and the shallow-water column in the transition zone of the Potomac River and Estuary. II. The role of wind-driven resuspension and adsorbed ammonium

    NASA Astrophysics Data System (ADS)

    Simon, N. S.

    1989-05-01

    During periods of sediment resuspension, desorption of ammonium from sediment solids can be the major pathway for enriching the water column with the ammonium that is produced by bacterial degradation of organic matter in the bottom material. This hyopthesis is based on a three-year study of diffusive flux in the transition zone of the Potomac River at a site 35 m from the Virginia shore where the average water-column depth is approximately 1 m over sandy sediment. A diffusion-controlled sampler was used to collect water samples at the interface between the water column and sediment and at several tens of centimeters into the sediment. Interstitial water concentration gradients showed that diffusive flux of ammonium from the sandy shallow-water sediments was approximately 1% of the diffusive flux of ammonium from the silty channel sediments in the same zone of the Potomac River. Organic nitrogen and bound or adsorbed ammonium were the predominant nitrogen forms in the sediment. Adsorbed ammonium concentrations ranged from nondetectable to 3·7 μmol g -1 of sediment. Concentrations of adsorbed ammonium per gram of sediment were one to three orders of magnitude more than interstitial water ammonium concentrations. Desorption of ammonium from sediment solids appeared to be the controlling factor in the degree of water-column ammonium enrichment. In laboratory experiments that simulated sediment resuspension, 40-80% of the adsorbed ammonium predicted to desorb did so after approximately 30 min of mixing. Based on calculations for 1 m 2 to a depth of 4 cm, one resuspenion event lasting minutes could mix more ammonium into the water column from desorption of ammonium from sediment solids than could be delivered to the water column by diffusive flux from shallow-water sediments in 10-1000 days and would be comparable to enrichment by ammonium diffusive flux for 5-50 days from channel sediments in the same river zone.

  6. Nitrogen cycling between sediment and the shallow-water column in the transition zone of the Potomac River and Estuary. II. The role of wind-driven resuspension and adsorbed ammonium

    USGS Publications Warehouse

    Simon, N.S.

    1989-01-01

    During periods of sediment resuspension, desorption of ammonium from sediment solids can be the major pathway for enriching the water column with the ammonium that is produced by bacterial degradation of organic matter in the bottom material. This hyopthesis is based on a three-year study of diffusive flux in the transition zone of the Potomac River at a site 35 m from the Virginia shore where the average water-column depth is approximately 1 m over sandy sediment. A diffusion-controlled sampler was used to collect water samples at the interface between the water column and sediment and at several tens of centimeters into the sediment. Interstitial water concentration gradients showed that diffusive flux of ammonium from the sandy shallow-water sediments was approximately 1% of the diffusive flux of ammonium from the silty channel sediments in the same zone of the Potomac River. Organic nitrogen and bound or adsorbed ammonium were the predominant nitrogen forms in the sediment. Adsorbed ammonium concentrations ranged from nondetectable to 3??7 ??mol g-1 of sediment. Concentrations of adsorbed ammonium per gram of sediment were one to three orders of magnitude more than interstitial water ammonium concentrations. Desorption of ammonium from sediment solids appeared to be the controlling factor in the degree of water-column ammonium enrichment. In laboratory experiments that simulated sediment resuspension, 40-80% of the adsorbed ammonium predicted to desorb did so after approximately 30 min of mixing. Based on calculations for 1 m2 to a depth of 4 cm, one resuspenion event lasting minutes could mix more ammonium into the water column from desorption of ammonium from sediment solids than could be delivered to the water column by diffusive flux from shallow-water sediments in 10-1000 days and would be comparable to enrichment by ammonium diffusive flux for 5-50 days from channel sediments in the same river zone. ?? 1989.

  7. Ligand-free gold atom clusters adsorbed on graphene nano sheets generated by oxidative laser fragmentation in water

    NASA Astrophysics Data System (ADS)

    Lau, Marcus; Haxhiaj, Ina; Wagener, Philipp; Intartaglia, Romuald; Brandi, Fernando; Nakamura, Junji; Barcikowski, Stephan

    2014-08-01

    Over three decades after the first synthesis of stabilized Au55-clusters many scientific questions about gold cluster properties are still unsolved and ligand-free colloidal clusters are difficult to fabricate. Here we present a novel route to produce ultra-small gold particles by using a green technique, the laser ablation and fragmentation in water, without using reductive or stabilizing agents at any step of the synthesis. For fabrication only a pulsed laser, a gold-target, pure water, sodium hydroxide and hydrogen peroxide are deployed. The particles are exemplarily hybridized to graphene supports showing that these carbon-free colloidal clusters might serve as versatile building blocks.

  8. Single-Molecule Imaging of DNAs with Sticky Ends at Water/Fused Silica Interface

    SciTech Connect

    Slavica Isailovic

    2005-12-17

    Total internal reflection fluorescence microscopy (TIRFM) was used to study intermolecular interactions of DNAs with unpaired (sticky) ends of different lengths at water/fused silica interface at the single-molecule level. Evanescent field residence time, linear velocity and adsorption/desorption frequency were measured in a microchannel for individual DNA molecules from T7, Lambda, and PSP3 phages at various pH values. The longest residence times and the highest adsorption/desorption frequencies at the constant flow at pH 5.5 were found for PSP3 DNA, followed by lower values for Lambda DNA, and the lowest values for T7 DNA. Since T7, Lambda, and PSP3 DNA molecules contain none, twelve and nineteen unpaired bases, respectively, it was concluded that the affinity of DNAs for the surface increases with the length of the sticky ends. This confirms that hydrophobic and hydrogen-bonding interactions between sticky ends and fused-silica surface are driving forces for DNA adsorption at the fused-silica surface. Described single-molecule methodology and results therein can be valuable for investigation of interactions in liquid chromatography, as well as for design of DNA hybridization sensors and drug delivery systems.

  9. Volumetric Interpretation of Protein Adsorption: Capacity Scaling with Adsorbate Molecular Weight and Adsorbent Surface Energy

    PubMed Central

    Parhi, Purnendu; Golas, Avantika; Barnthip, Naris; Noh, Hyeran; Vogler, Erwin A.

    2009-01-01

    Silanized-glass-particle adsorbent capacities are extracted from adsorption isotherms of human serum albumin (HSA, 66 kDa), immunoglobulin G (IgG, 160 kDa), fibrinogen (Fib, 341 kDa), and immunoglobulin M (IgM, 1000 kDa) for adsorbent surface energies sampling the observable range of water wettability. Adsorbent capacity expressed as either mass-or-moles per-unit-adsorbent-area increases with protein molecular weight (MW) in a manner that is quantitatively inconsistent with the idea that proteins adsorb as a monolayer at the solution-material interface in any physically-realizable configuration or state of denaturation. Capacity decreases monotonically with increasing adsorbent hydrophilicity to the limit-of-detection (LOD) near τo = 30 dyne/cm (θ~65o) for all protein/surface combinations studied (where τo≡γlvocosθ is the water adhesion tension, γlvo is the interfacial tension of pure-buffer solution, and θ is the buffer advancing contact angle). Experimental evidence thus shows that adsorbent capacity depends on both adsorbent surface energy and adsorbate size. Comparison of theory to experiment implies that proteins do not adsorb onto a two-dimensional (2D) interfacial plane as frequently depicted in the literature but rather partition from solution into a three-dimensional (3D) interphase region that separates the physical surface from bulk solution. This interphase has a finite volume related to the dimensions of hydrated protein in the adsorbed state (defining “layer” thickness). The interphase can be comprised of a number of adsorbed-protein layers depending on the solution concentration in which adsorbent is immersed, molecular volume of the adsorbing protein (proportional to MW), and adsorbent hydrophilicity. Multilayer adsorption accounts for adsorbent capacity over-and-above monolayer and is inconsistent with the idea that protein adsorbs to surfaces primarily through protein/surface interactions because proteins within second (or higher

  10. Atomic force microscopy study of nitrogen molecule self-assembly at the HOPG-water interface

    NASA Astrophysics Data System (ADS)

    Lu, Yi-Hsien; Yang, Chih-Wen; Hwang, Ing-Shouh

    2014-06-01

    In this work, we investigated the evolution of the graphite-water interface in a nitrogen atmosphere by using frequency-modulation atomic force microscopy (FM-AFM). A highly ordered pyrolytic graphite (HOPG) sample was immersed in pre-degassed water and subsequently placed in the nitrogen environment. The dissolved nitrogen molecules diffused in water and self-assembled into ordered row-like structural domains at the interface. Nucleation and growth processes of the domains were observed. When the coverage of the ordered structure surpassed 50%, small clusters began to appear on the ordered structure. The number density of the clusters increases as the coverage of the ordered structures increases and these clusters may hop on the ordered structures. A model is proposed to explain the evolution of the nitrogen molecule self-assembly process at the interface. The observation of nitrogen clusters may shed light on the nature and nucleation of the so-called nanobubbles at hydrophobic-water interfaces.

  11. CVRQD ab initio ground-state adiabatic potential energy surfaces for the water molecule.

    PubMed

    Barletta, Paolo; Shirin, Sergei V; Zobov, Nikolai F; Polyansky, Oleg L; Tennyson, Jonathan; Valeev, Edward F; Császár, Attila G

    2006-11-28

    The high accuracy ab initio adiabatic potential energy surfaces (PESs) of the ground electronic state of the water molecule, determined originally by Polyansky et al. [Science 299, 539 (2003)] and called CVRQD, are extended and carefully characterized and analyzed. The CVRQD potential energy surfaces are obtained from extrapolation to the complete basis set of nearly full configuration interaction valence-only electronic structure computations, augmented by core, relativistic, quantum electrodynamics, and diagonal Born-Oppenheimer corrections. We also report ab initio calculations of several quantities characterizing the CVRQD PESs, including equilibrium and vibrationally averaged (0 K) structures, harmonic and anharmonic force fields, harmonic vibrational frequencies, vibrational fundamentals, and zero-point energies. They can be considered as the best ab initio estimates of these quantities available today. Results of first-principles computations on the rovibrational energy levels of several isotopologues of the water molecule are also presented, based on the CVRQD PESs and the use of variational nuclear motion calculations employing an exact kinetic energy operator given in orthogonal internal coordinates. The variational nuclear motion calculations also include a simplified treatment of nonadiabatic effects. This sophisticated procedure to compute rovibrational energy levels reproduces all the known rovibrational levels of the water isotopologues considered, H(2) (16)O, H(2) (17)O, H(2) (18)O, and D(2) (16)O, to better than 1 cm(-1) on average. Finally, prospects for further improvement of the ground-state adiabatic ab initio PESs of water are discussed. PMID:17144700

  12. Vibrational spectra and molecular dynamics of hydrogen peroxide molecules at quartz/water interfaces

    NASA Astrophysics Data System (ADS)

    Lv, Ye-qing; Zheng, Shi-li; Wang, Shao-na; Yan, Wen-yi; Zhang, Yi; Du, Hao

    2016-06-01

    The influence of H2O2 on the water vibration at quartz interface was examined using sum-frequency generation (SFG) spectroscopy, and the effect of H2O2 concentration has been systematically studied. Further, the number density and radical distribution of water molecules, H2O2 molecules, and quartz surface silanol groups were calculated using molecular dynamics (MD) simulation to provide molecular level interpretation for the SFG spectra. It is concluded from this study that the hydrogen peroxide molecules prefers to donate H-bonds to the in-plane silanol groups rather than accepting H-bonds from out-of-plane silanol groups, as evidenced by the strengthening of the peak located at 3400 cm-1 assigned to "liquid-like" hydrogen-bonding network. The SFG results have been supported by the MD calculation results, which demonstrate that the relative intensity of the peak located at 3400 cm-1 to that of located at 3200 cm-1 increases monotonously with the increase in the number of hydrogen peroxide in the first hydration shell of silanol.

  13. Effect of the adsorbate (Bromacil) equilibrium concentration in water on its adsorption on powdered activated carbon. Part 3: Competition with natural organic matter.

    PubMed

    Al Mardini, Fadi; Legube, Bernard

    2010-10-15

    This study (part 3) was carried out to investigate the effect of the natural organic matter (NOM) concentration on Bromacil (pesticide) adsorption on powdered activated carbon (PAC) in the same experimental conditions as in our previous studies (parts 1 and 2). Our previous findings showed that Bromacil adsorption in buffered pure water (pH 7.8) occurred at two types of site. In the presence of NOM (three kinds), we noted a significant reduction in Bromacil adsorption capacities due to the competitive effects exerted by NOM. Highly reactive sites (or pores) in PAC appeared to be blocked by NOM adsorption, as demonstrated by the application of a pseudo-single solute isotherm and of the simplified ideal adsorbed solution theory (IAST), regardless of the initial Bromacil and NOM concentrations. The competing effect of low-molecular weight NOM was found to be greater than the competing effect of high-molecular weight NOM. The pseudo-second order surface-reaction model fitted Bromacil adsorption particularly well, even in the presence of NOM. However, the adsorption-kinetic constant values were found to be independent of the aqueous equilibrium concentration of the target compound, contrary to that observed in pure water. The kinetic data thus confirmed that high reactivity PAC sites were blocked by NOM adsorption. A practical approach concluded this work. PMID:20619963

  14. Preparation of iron nanoparticles-loaded Spondias purpurea seed waste as an excellent adsorbent for removal of phosphate from synthetic and natural waters.

    PubMed

    Arshadi, M; Foroughifard, S; Etemad Gholtash, J; Abbaspourrad, A

    2015-08-15

    The synthesis and characterization of nanoscale zerovalent iron particles (NZVI) supported on Spondias purpurea seed waste (S-NaOH-NZVI) was performed for the adsorption of phosphate (P) ions from waste waters. The effects of various parameters, such as contact time, pH, concentration, reusability and temperature were studied. The adsorption of phosphate ions has been studied in terms of pseudo-first- and -second-order kinetics, and the Freundlich, and Langmuir isotherms models have also been used to the equilibrium adsorption data. The adsorption kinetics followed the mechanism of the pseudo-second-order equation. The thermodynamic parameters (ΔG, ΔH and ΔS) indicated that the adsorption of phosphate ions were feasible, spontaneous and endothermic at 25-80 °C. No significant loss of activity was observed; confirming that the S-NaOH-NZVI has high stability during the adsorption process even after 12th runs. The suggested adsorbent in this paper was also implemented to remove P from the Persian Gulf water. XRD, FTIR and EDX analysis indicated the presence of Fe3 (PO4)2⋅8H2O (vivianite) on the S-NaOH-NZVI@P surface. PMID:25919431

  15. Spectrophotometric determination of basic fuchsin from various water samples after vortex assisted solid phase extraction using reduced graphene oxide as an adsorbent.

    PubMed

    Tokalıoğlu, Şerife; Yavuz, Emre; Aslantaş, Ayşe; Şahan, Halil; Taşkın, Ferhat; Patat, Şaban

    2015-10-01

    In this study, a fast and simple vortex assisted solid phase extraction method was developed for the separation/preconcentration of basic fuchsin in various water samples. The determination of basic fuchsin was carried out at a wavelength of 554 nm by spectrophotometry. Reduced graphene oxide which was used as a solid phase extractor was synthesized and characterized by X-ray diffraction, scanning electron microscopy and the Brunauer, Emmett and Teller. The optimum conditions are as follows: pH 2, contact times for adsorption and elution of 30 s and 90 s, respectively, 10 mg adsorbent, and eluent (ethanol) volume of 1 mL. The effects of some interfering ions and dyes were investigated. The method was linear in the concentration range of 50-250 μg L(-1). The adsorption capacity was 34.1 mg g(-1). The preconcentration factor, limit of detection and precision (RSD, %) of the method were found to be 400, 0.07 μg L(-1) and 1.2%, respectively. The described method was validated by analyzing basic fuchsin spiked certified reference material (SPS-WW1 Batch 114-Wastewater) and spiked real water samples. PMID:25974670

  16. The effects of adsorbed water on tensile strength and Young's modulus of moldings determined by means of a three-point bending method.

    PubMed

    Tsukamoto, T; Chen, C Y; Okamoto, H; Danjo, K

    2000-06-01

    Young's moduli (E) of three representative tableting excipients and their mix powders were measured for compressed rectangular beam specimens over a range of porosities using a three-point bending technique. We also examined the effects of the amount of water adsorbed on the tensile strength of these specimens. The maximal tensile strength (sigma(max)) decreased with increasing water vapor adsorption for microcrystalline cellulose (MCC) and mixed powders of lactose and MCC. Sigma(max) increased with increasing compression stress and specimen weight for all samples. Sigma(max) of an alpha-lactose and cornstarch mixture with a ratio of 7:3 showed a large value. Young's modulus (E) and the crushing energy (CE) of MCC were larger than those of the other samples. Young's modulus of specimens decreased as the proportion of alpha-lactose increased. Disintegration time (DT) of tablets comprised of lactose and MCC mixture was much faster than those of tablets comprised of individual powders. This appeared to demonstrate the effect of MCC swelling on the disintegration time of the tablet. The disintegration time of the lactose/cornstarch series increased only when Young's modulus increased sharply. PMID:10866134

  17. Novel DGT method with tri-metal oxide adsorbent for in situ spatiotemporal flux measurement of fluoride in waters and sediments.

    PubMed

    Zhou, Chun-Yang; Guan, Dong-Xing; Williams, Paul N; Luo, Jun; Ma, Lena Q

    2016-08-01

    Natural mineral-water interface reactions drive ecosystem/global fluoride (F(-)) cycling. These small-scale processes prove challenging to monitoring due to mobilization being highly localized and variable; influenced by changing climate, hydrology, dissolution chemistries and pedogenosis. These release events could be captured in situ by the passive sampling technique, diffusive gradients in thin-films (DGT), providing a cost-effective and time-integrated measurement of F(-) mobilization. However, attempts to develop the method for F(-) have been unsuccessful due to the very restrictive operational ranges that most F(-)-absorbents function within. A new hybrid-DGT technique for F(-) quantification containing a three-phase fine particle composite (FeAlCe, FAC) adsorbent was developed and evaluated. Sampler response was validated in laboratory and field deployments, passing solution chemistry QC within ionic strength and pH ranges of 0-200 mmol L(-1) and 4.3-9.1, respectively, and exhibiting high sorption capacities (98 ± 8 μg cm(-2)). FAC-DGT measurements adequately predicted up to weeklong averaged in situ F(-) fluvial fluxes in a freshwater river and F(-) concentrations in a wastewater treatment flume determined by high frequency active sampling. While, millimetre-scale diffusive fluxes across the sediment-water interface were modeled for three contrasting lake bed sediments from a F(-)-enriched lake using the new FAC-DGT platform. PMID:27161886

  18. Effects of a single water molecule on the OH + H2O2 reaction.

    PubMed

    Buszek, Robert J; Torrent-Sucarrat, Miquel; Anglada, Josep M; Francisco, Joseph S

    2012-06-21

    The effect of a single water molecule on the reaction between H(2)O(2) and HO has been investigated by employing MP2 and CCSD(T) theoretical approaches in connection with the aug-cc-PVDZ, aug-cc-PVTZ, and aug-cc-PVQZ basis sets and extrapolation to an ∞ basis set. The reaction without water has two elementary reaction paths that differ from each other in the orientation of the hydrogen atom of the hydroxyl radical moiety. Our computed rate constant, at 298 K, is 1.56 × 10(-12) cm(3) molecule(-1) s(-1), in excellent agreement with the suggested value by the NASA/JPL evaluation. The influence of water vapor has been investigated by considering either that H(2)O(2) first forms a complex with water that reacts with hydroxyl radical or that H(2)O(2) reacts with a previously formed H(2)O·OH complex. With the addition of water, the reaction mechanism becomes much more complex, yielding four different reaction paths. Two pathways do not undergo the oxidation reaction but an exchange reaction where there is an interchange between H(2)O(2)·H(2)O and H(2)O·OH complexes. The other two pathways oxidize H(2)O(2), with a computed total rate constant of 4.09 × 10(-12) cm(3) molecule(-1) s(-1) at 298 K, 2.6 times the value of the rate constant of the unassisted reaction. However, the true effect of water vapor requires taking into account the concentration of the prereactive bimolecular complex, namely, H(2)O(2)·H(2)O. With this consideration, water can actually slow down the oxidation of H(2)O(2) by OH between 1840 and 20.5 times in the 240-425 K temperature range. This is an example that demonstrates how water could be a catalyst in an atmospheric reaction in the laboratory but is slow under atmospheric conditions. PMID:22455374

  19. Mesoporous ZnAl2O4: an efficient adsorbent for the removal of arsenic from contaminated water.

    PubMed

    Kumari, Vandana; Bhaumik, Asim

    2015-07-14

    We report, for the first time, an efficient soft-templating strategy for the synthesis of mesoporous ZnAl2O4 using the supramolecular assembly of lauric acid (surfactant) as a template under alkaline pH conditions. A 50 : 50 (v/v) mixture of water-ethanol has been found to be a very efficient synthesis medium for the dissolution of inorganic precursors, retaining the supramolecular assembly of the lauric acid surfactant and adjusting the necessary pH of the synthesis gel, which are very crucial parameters to obtain the stable mesophase of zinc aluminate. This mesoporous ZnAl2O4 material has retained the mesophase upon calcination, showed good BET surface area and electron microscopic results revealed that the material is composed of tiny spherical nanoparticles of dimensions ca. 5-7 nm size. Mesoporous ZnAl2O4 showed very good adsorption efficiency for the removal of arsenic from contaminated water. An efficient synthesis strategy, high BET surface area, stable mesophase and good adsorption efficiency for AsO4(3-) from arsenic-contaminated water by the mesoporous ZnAl2O4 material have huge potential to be explored in the large scale purification of groundwater. PMID:26053110

  20. Influence of water on the mobility of small molecules dispersed in a polymeric system.

    PubMed

    Le Meste, M; Voilley, A; Colas, B

    1991-01-01

    The rotational mobility of paramagnetic solutes dispersed in partially hydrated macromolecules (proteins, polysaccharides, synthetic polymers) was measured using Electron Spin Resonance. A critical minimum amount of water was observed to be necessary for these molecules to reach a level of mobility of the same order as in dilute solutions. This amount of water depended on the size of the diffusing solute and on the microporosity of the macromolecule. Above this critical moisture range, a progressive increase of the proportion of mobile solute occurred over a hydration range determined by the size of the diffusing solute. At the same time, the rotational diffusivity of the mobile solute increased linearly with water content. The mobilization pattern of spin-labelled side chains of caseinates was observed to be similar to that of the solute. Results are discussed with reference to free volume theory. PMID:1660672

  1. Single molecule force spectroscopy by AFM indicates helical structure of poly(ethylene-glycol) in water

    NASA Astrophysics Data System (ADS)

    Oesterhelt, F.; Rief, M.; Gaub, H. E.

    1999-03-01

    We elongated individual poly(ethylene-glycol) (PEG) molecules tethered at one end to an AFM cantilever. We observed the resistive force as a function of elongation in different solvents. In all cases the molecular response was found to be fully reversible and thus in thermodynamic equilibrium. In hexadecane the stretched PEG acts like an ideal entropy spring and can be well described as a freely jointed chain. In water we observed marked deviations in the transition region from entropic to enthalpic elasticity, indicating the deformation of a supra-structure within the polymer. An analysis based on elastically coupled Markovian two-level systems agrees well with recent ab initio calculations predicting that PEG in water forms a non-planar supra-structure which is stabilized by water bridges. We obtained a binding free energy of 3.0+/-0.3 kT.

  2. Separation of the attractive and repulsive contributions to the adsorbate-adsorbate interactions of polar adsorbates on Si(100)

    NASA Astrophysics Data System (ADS)

    Lin, Ying-Hsiu; Jeng, Horng-Tay; Lin, Deng-Sung

    2015-11-01

    Dissociative adsorption of H2O, NH3, CH3OH and CH3NH2 polar molecules on the Si(100) surface results in a 1:1 mixture of two adsorbates (H and multi-atomic fragment A = OH, NH2, CH3O, CH3NH, respectively) on the surface. By using density functional theory (DFT) calculations, the adsorption geometry, the total energies and the charge densities for various possible ordered structures of the mixed adsorbate layer have been found. Analyzing the systematic trends in the total energies unveils concurrently the nearest-neighbor interactions ENN and the next nearest-neighbor interactions ENNN between two polar adsorbates A. In going from small to large polar adsorbates, ENN's exhibit an attractive-to-repulsive crossover behavior, indicating that they include competing attractive and repulsive contributions. Exploration of the charge density distributions allows the estimation of the degree of charge overlapping between immediately neighboring A's, the resulting contribution of the steric repulsions, and that of the attractive interactions to the corresponding ENN's. The attractive contributions to nearest neighboring adsorbate-adsorbate interactions between the polar adsorbates under study are shown to result from hydrogen bonds or dipole-dipole interactions.

  3. Influence of the water molecules near surface of viral protein on virus activation process

    NASA Astrophysics Data System (ADS)

    Shepelenko, S. O.; Salnikov, A. S.; Rak, S. V.; Goncharova, E. P.; Ryzhikov, A. B.

    2009-06-01

    The infection of a cell with influenza virus comprises the stages of receptor binding to the cell membrane, endocytosis of virus particle, and fusion of the virus envelope and cell endosome membrane, which is determined by the conformational changes in hemagglutinin, a virus envelope protein, caused by pH decrease within the endosome. The pH value that induces conformation rearrangements of hemagglutinin molecule considerably varies for different influenza virus strains, first and foremost, due to the differences in amino acid structure of the corresponding proteins. The main goal of this study was to construct a model making it possible to assess the critical pH value characterizing the fusogenic activity of influenza virus hemagglutinin from the data on hemagglutinin structure and experimental verification of this model. Under this model, we assume that when the electrostatic force between interacting hemagglutinin molecules in the virus envelop exceeds a certain value, the hemagglutinin HA1 subunits are arranged so that they form a cavity sufficient for penetration of water molecules. This event leads to an irreversible hydration of the inner fragments of hemagglutinin molecule in a trimer and to the completion of conformational changes. The geometry of electrostatic field in hemagglutinin trimer was calculated taking into account the polarization effects near the interface of two dielectrics, aqueous medium and protein macromolecule. The critical pH values for the conformational changes in hemagglutinin were measured by the erythrocyte hemolysis induced by influenza virus particles when decreasing pH. The critical pH value conditionally separating the pH range into the regions with and without the conformational changes was calculated for several influenza virus H1N1 and H3N2 strains based on the data on the amino acid structure of the corresponding hemagglutinin molecules. Comparison of the theoretical and experimental values of critical pH values for

  4. Spectral properties of mixtures of montmorillonite and dark grains - Implications for remote sensing minerals containing chemically and physically adsorbed water

    NASA Technical Reports Server (NTRS)

    Clark, R. N.

    1983-01-01

    The spectral properties from 0.4 to 3 microns of montmorillonite plus dark carbon grains (called opaques) of various sizes are studied as a function of the weight fraction of opaques present. The reflectance level and band depths of the 1.4-, 1.9-, 2.2-, and 2.8-micron water and/or OH absorption features are analyzed using derived empirical relationships and scattering theory. It is found that the absorption band depths and reflectance level are a very nonlinear function of the weight fraction of opaques present but can be predicted in many cases by simple scattering theory. The 2.8-micron bound water fundamental band is the most difficult absorption feature to suppress. The overtone absorptions are suppressed a greater amount than the fundamental but are still apparent even when 10-20 wt pct opaques are present. The relationships observed and the simple scattering theory presented show that quantitative compositional remote sensing studies are feasible for surfaces containing complex mineral mixtures.

  5. The Effect of Water Molecules on Mechanical Properties of Bamboo Microfibrils

    NASA Astrophysics Data System (ADS)

    Rahbar, Nima

    Bamboo fibers have higher strength-to-weight ratios than steel and concrete. The unique properties of bamboo fibers come from their natural composite structures that comprise mainly cellulose nanofibrils in a matrix of intertwined hemicellulose and lignin called lignin-carbohydrate complex (LCC). Here, we have utilized atomistic simulations to investigate the mechanical properties and mechanisms of interactions between these materials, in the presence of water molecules. Our results suggest that hemicellulose exhibits better mechanical properties and lignin shows greater tendency to adhere to cellulose nanofibrils. Consequently, the role of hemicellulose found to be enhancing the mechanical properties and lignin found to be providing the strength of bamboo fibers. The abundance of Hbonds in hemicellulose chains is responsible for improving the mechanical behavior of LCC. The strong van der Waals forces between lignin molecules and cellulose nanofibrils is responsible for higher adhesion energy between LCC/cellulose nanofibrils. We also found out that the amorphous regions of cellulose nanofibrils is the weakest interface in bamboo Microfibrils. In presence of water, the elastic modulus of lignin increases at low water content (less than 10 NSF CAREER Grant No. 1261284.

  6. Test conditions greatly influence permeation of water soluble molecules through the intestinal mucosa: need for standardisation.

    PubMed Central

    Peeters, M; Hiele, M; Ghoos, Y; Huysmans, V; Geboes, K; Vantrappen, G; Rutgeerts, P

    1994-01-01

    Permeability tests are widely used to investigate the pathogenesis of various gastrointestinal diseases including coeliac disease, infectious diarrhoea, and inflammatory bowel disease. In Crohn's disease they are used as activity parameters by some investigators. Lack of standardisation, however, makes it very difficult to compare data reported in different studies. The aim of this study was to gather permeation data in well controlled test conditions to standardise the methods. Nine healthy volunteers each received five consecutive permeability tests by mouth using polyethylene glycol-400 (PEG-400) and 51Cr-EDTA as probe molecules. The probes were dissolved in water, a glucose solution, a starch solution, a hyperosmolar lactulose-mannitol solution, and a liquid meal. A significantly decreased permeation for both probes was found when given with the hyperosmolar solution. The 51Cr-EDTA permeation was also decreased with water. The permeability index, 51Cr-EDTA/PEG-400, corrected for influencing factors, confirmed that the lactulose-mannitol solution and plain water yield lower values of macro-molecule permeation than starch, glucose or liquid meal. Hyperosmolarity was clearly accompanied by a decrease in permeability probably caused by reversed solvent drag. Interindividual variability of probe permeation and permeability index is very low with a standard liquid meal. It is proposed that for permeability studies a standard liquid meal is always used. PMID:7959195

  7. Test conditions greatly influence permeation of water soluble molecules through the intestinal mucosa: need for standardisation.

    PubMed

    Peeters, M; Hiele, M; Ghoos, Y; Huysmans, V; Geboes, K; Vantrappen, G; Rutgeerts, P

    1994-10-01

    Permeability tests are widely used to investigate the pathogenesis of various gastrointestinal diseases including coeliac disease, infectious diarrhoea, and inflammatory bowel disease. In Crohn's disease they are used as activity parameters by some investigators. Lack of standardisation, however, makes it very difficult to compare data reported in different studies. The aim of this study was to gather permeation data in well controlled test conditions to standardise the methods. Nine healthy volunteers each received five consecutive permeability tests by mouth using polyethylene glycol-400 (PEG-400) and 51Cr-EDTA as probe molecules. The probes were dissolved in water, a glucose solution, a starch solution, a hyperosmolar lactulose-mannitol solution, and a liquid meal. A significantly decreased permeation for both probes was found when given with the hyperosmolar solution. The 51Cr-EDTA permeation was also decreased with water. The permeability index, 51Cr-EDTA/PEG-400, corrected for influencing factors, confirmed that the lactulose-mannitol solution and plain water yield lower values of macro-molecule permeation than starch, glucose or liquid meal. Hyperosmolarity was clearly accompanied by a decrease in permeability probably caused by reversed solvent drag. Interindividual variability of probe permeation and permeability index is very low with a standard liquid meal. It is proposed that for permeability studies a standard liquid meal is always used. PMID:7959195

  8. Intramolecular cyclization of aspartic acid residues assisted by three water molecules: a density functional theory study

    NASA Astrophysics Data System (ADS)

    Takahashi, Ohgi; Kirikoshi, Ryota

    2014-01-01

    Aspartic acid (Asp) residues in peptides and proteins (l-Asp) are known to undergo spontaneous nonenzymatic reactions to form l-β-Asp, d-Asp, and d-β-Asp residues. The formation of these abnormal Asp residues in proteins may affect their three-dimensional structures and hence their properties and functions. Indeed, the reactions have been thought to contribute to aging and pathologies. Most of the above reactions of the l-Asp residues proceed via a cyclic succinimide intermediate. In this paper, a novel three-water-assisted mechanism is proposed for cyclization of an Asp residue (forming a gem-diol precursor of the succinimide) by the B3LYP/6-31 + G(d,p) density functional theory calculations carried out for an Asp-containing model compound (Ace-Asp-Nme, where Ace = acetyl and Nme = NHCH3). The three water molecules act as catalysts by mediating ‘long-range’ proton transfers. In the proposed mechanism, the amide group on the C-terminal side of the Asp residue is first converted to the tautomeric iminol form (iminolization). Then, reorientation of a water molecule and a conformational change occur successively, followed by the nucleophilic attack of the iminol nitrogen on the carboxyl carbon of the Asp side chain to form the gem-diol species. A satisfactory agreement was obtained between the calculated and experimental energetics.

  9. Examining Adsorbed Polymer Conformations with Fluorescence Imaging

    NASA Astrophysics Data System (ADS)

    Parkes, Maria; Chennaoui, Mourad; Wong, Janet; Tribology Group, Dept. of Mechanical Engineering Team

    2011-03-01

    The conformation of adsorbed polymers can have significant impact on their properties such as dynamics and elasticity as well as their ability to take part in reactions with other molecules. Experimental research to determine adsorbed polymer conformation has relied mainly on atomic force microscopy (AFM) studies. During an AFM scan, the contact between the scanning probe and the polymer could affect the polymer conformation, particularly where parts of the polymer might have formed projected loops and tails. In this work, conformations of model polymers are examined with total internal reflection fluorescence microscopy (TIRFM). The advantage of TIRFM over AFM is that TIRFM is a non contact technique. Lambda DNA labelled along its length with fluorescent probes was adsorbed in a projected 2D -- 3D state. With TIRFM, the relationship between intensity and depth was used as a basis to determine how the conformation of the adsorbed polymers evolved with time using our custom algorithm.

  10. Cassava root husks powder as green adsorbent for the removal of Cu(II) from natural river water

    NASA Astrophysics Data System (ADS)

    Jorgetto, A. O.; Silva, R. I. V.; Saeki, M. J.; Barbosa, R. C.; Martines, M. A. U.; Jorge, S. M. A.; Silva, A. C. P.; Schneider, J. F.; Castro, G. R.

    2014-01-01

    Through a series of simple processes, cassava root husks were turned into a fine powder of controlled particle size (63-75 μm). FTIR spectrum demonstrated the existence of alcohol, amine and carboxylic groups; and elemental analysis confirmed the presence of elements of interest such as sulphur, nitrogen and oxygen. Cross-polarized {1H}13C NMR technique indicated the existence of methionine and thiamine through the signals observed at 55 ppm and 54 ppm, respectively, and the point of zero charge (pHpzc) was achieved at pH 5.2. The material was applied in solid-phase extraction of Cu(II) via batch experiments. Optimum adsorption pH was found to be in range of 3-6 and in the kinetic experiment the equilibrium was attained in 1 min. The highest adsorption capacity was 0.14 mmol g-1. The adsorption data were fit to the modified Langmuir equation, and the maximum amount of metal species extracted from the solution, Ns, was determined to be ˜0.14 mmol g-1, which is an indicative that the main adsorption mechanism is through chemisorption. Under optimized conditions, the material was utilized in preconcentration experiments, which culminated in an enrichment factor of 41.3-fold. With the aid of the enrichment factor, experiments were carried out to determine the Cu(II) content in tap water and natural water. Preconcentration method was also applied to a certified reference material (1643e) and the concentration found was 23.03 ± 0.79 μg L-1, whereas the specified Cu(II) concentration was 22.7 ± 0.31 μg L-1.

  11. Two-dimensional interlocked pentagonal bilayer ice: how do water molecules form a hydrogen bonding network?

    PubMed

    Zhu, Weiduo; Zhao, Wen-Hui; Wang, Lu; Yin, Di; Jia, Min; Yang, Jinlong; Zeng, Xiao Cheng; Yuan, Lan-Feng

    2016-06-01

    The plethora of ice structures observed both in bulk and under nanoscale confinement reflects the extraordinary ability of water molecules to form diverse forms of hydrogen bonding networks. An ideal hydrogen bonding network of water should satisfy three requirements: (1) four hydrogen bonds connected with every water molecule, (2) nearly linear hydrogen bonds, and (3) tetrahedral configuration for the four hydrogen bonds around an O atom. However, under nanoscale confinement, some of the three requirements have to be unmet, and the selection of the specific requirement(s) leads to different types of hydrogen bonding structures. According to molecular dynamics (MD) simulations for water confined between two smooth hydrophobic walls, we obtain a phase diagram of three two-dimensional (2D) crystalline structures and a bilayer liquid. A new 2D bilayer ice is found and named the interlocked pentagonal bilayer ice (IPBI), because its side view comprises interlocked pentagonal channels. The basic motif in the top view of IPBI is a large hexagon composed of four small pentagons, resembling the top view of a previously reported "coffin" bilayer ice [Johnston, et al., J. Chem. Phys., 2010, 133, 154516]. First-principles optimizations suggest that both bilayer ices are stable. However, there are fundamental differences between the two bilayer structures due to the difference in the selection among the three requirements. The IPBI sacrifices the linearity of hydrogen bonds to retain locally tetrahedral configurations of the hydrogen bonds, whereas the coffin structure does the opposite. The tradeoff between the conditions of an ideal hydrogen bonding network can serve as a generic guidance to understand the rich phase behaviors of nanoconfined water. PMID:27063210

  12. Calculating Partition Coefficients of Small Molecules in Octanol/Water and Cyclohexane/Water.

    PubMed

    Bannan, Caitlin C; Calabró, Gaetano; Kyu, Daisy Y; Mobley, David L

    2016-08-01

    Partition coefficients describe how a solute is distributed between two immiscible solvents. They are used in drug design as a measure of a solute's hydrophobicity and a proxy for its membrane permeability. We calculate partition coefficients from transfer free energies using molecular dynamics simulations in explicit solvent. Setup is done by our new Solvation Toolkit which automates the process of creating input files for any combination of solutes and solvents for many popular molecular dynamics software packages. We calculate partition coefficients between octanol/water and cyclohexane/water with the Generalized AMBER Force Field (GAFF) and the Dielectric Corrected GAFF (GAFF-DC). With similar methods in the past we found a root-mean-squared error (RMSE) of 6.3 kJ/mol in hydration free energies which would correspond to an error of around 1.6 log units in partition coefficients if solvation free energies in both solvents were estimated with comparable accuracy. Here we find an overall RMSE of about 1.2 log units with both force fields. Results from GAFF and GAFF-DC seem to exhibit systematic biases in opposite directions for calculated cyclohexane/water partition coefficients. PMID:27434695

  13. Development and characterization of activated hydrochars from orange peels as potential adsorbents for emerging organic contaminants.

    PubMed

    Fernandez, M E; Ledesma, B; Román, S; Bonelli, P R; Cukierman, A L

    2015-05-01

    Activated hydrochars obtained from the hydrothermal carbonization of orange peels (Citrus sinensis) followed by various thermochemical processing were assessed as adsorbents for emerging contaminants in water. Thermal activation under flows of CO2 or air as well as chemical activation with phosphoric acid were applied to the hydrochars. Their characteristics were analyzed and related to their ability to uptake three pharmaceuticals (diclofenac sodium, salicylic acid and flurbiprofen) considered as emerging contaminants. The hydrothermal carbonization and subsequent activations promoted substantial chemical transformations which affected the surface properties of the activated hydrochars; they exhibited specific surface areas ranging from 300 to ∼620 m(2)/g. Morphological characterization showed the development of coral-like microspheres dominating the surface of most hydrochars. Their ability to adsorb the three pharmaceuticals selected was found largely dependent on whether the molecules were ionized or in their neutral form and on the porosity developed by the new adsorbents. PMID:25742754

  14. First-principles study of water adsorption on α-SiO2 [110] surface

    NASA Astrophysics Data System (ADS)

    Mankad, Venu; Jha, Prafulla K.

    2016-08-01

    We have investigated the structural and electronic properties of water molecule adsorbed silicon dioxide (α-SiO2) [110] surface and analyzed the influence of water molecule on its energetics, structure and elctronic propertes using density functional theory based first principles calculations. The inhomogeneous topology of the α-SiO2 clean surface promotes a total charge density displacement on the adsorbed water molecule and giving rise to electron-rich as well as hole-rich region. The electronic charge transfer from a α-SiO2 to the water molecule occurs upon the formation of a partially occupied level laying above conduction band level.

  15. Explicit Consideration of Water Molecules to Study Vibrational Circular DICHROÎSM of Monosaccharide's

    NASA Astrophysics Data System (ADS)

    Moussi, Sofiane; Ouamerali, Ourida

    2014-06-01

    Carbohydrates have multiples roles in biological systems. It has been found that the glycoside bond is fundamentally important in many aspects of chemistry and biology and forms the basis of carbohydrate chemistry. That means the stereochemical information, namely, glycosidic linkages α or β, gives an significant features of the carbohydrate glycosidation position of the glycosylic acceptor. For these reasons, much effort was made for the synthesis and analysis of the glycoside bond. Vibrational circular dichroism VCD has some advantages over conventional electronic circular dichroism (ECD) due to the applicability to all organic molecules and the reliability of ab initio quantum calculation. However, for a molecule with many chiral centers such as carbohydrates, determination of the absolute configuration tends to be difficult because the information from each stereochemical center is mixed and averaged over the spectrum. In the CH stretching region, only two VCD studies on carbohydrates have been reported and spectra--structure correlation, as determined for the glycoside band, remains to be investigated. T. Taniguchi and collaborators report that methyl glycosides exhibit a characteristic VCD peak, the sign of which solely reflects the C-1 absolute configuration. This work is a theoretical contribution to study the behaviour of VCD spectrum's of the monosaccharides when the water molecules are taken explicitly. This study is focused on six different monosaccharides in theirs absolute configuration R and S. We used the method of density functional theory DFT by means of the B3LYP hybrid functional and 6-31G * basis set.

  16. Mesoporous carbon nanomaterials as environmental adsorbents.

    PubMed

    Tripathi, Pranav K; Gan, Lihua; Liu, Mingxian; Rao, Nageswara N

    2014-02-01

    The transportation and diffusion of the guest objects or molecules in the porous carbon nanomaterials can be facilitated by reducing the pathway and resistance. The reduced pathway depends on the porous nature of carbon nanomaterials. Classification of porous carbon materials by the International Union of Pure and Applied Chemistry (IUPAC) has given a new opportunity to design the pores as per their applicability and to understand the mobility of ions, atoms, and molecules in the porous network of carbon materials and also advanced their countless applicability. However, synthesis of carbon nanomaterials with a desired porous network is still a great challenge. Although, remarkable developments have taken place in the recent years, control over the pores size and/or hierarchical porous architectures, especially in the synthesis of carbon nanospheres (CNSs) and ordered mesoporous carbon (OMCs) is still intriguing. The micro and mesoporous CNSs and OMCs have been prepared by a variety of procedures and over a wide range of compositions using various different surfactant templates and carbon precursors etc. The mechanisms of formation of micromesopore in the CNSs and OMCs are still evolving. On the other hand, the urge for adsorbents with very high adsorption capacities for removing contaminants from water is growing steadily. In this review, we address the state-of-the-art synthesis of micro and mesoporous CNSs and OMCs, giving examples of their applications for adsorptive removals of contaminants including our own research studies. PMID:24749459

  17. Carbon nanotube sponges as a solid-phase extraction adsorbent for the enrichment and determination of polychlorinated biphenyls at trace levels in environmental water samples.

    PubMed

    Wang, Lei; Wang, Xia; Zhou, Jia-Bin; Zhao, Ru-Song

    2016-11-01

    Carbon nanotube (CNT) sponges has recently attracted considerable attention in numerous fields because of its excellent properties, such as high porosity, light weight, and large surface area. The potential of CNT sponges for the solid-phase extraction (SPE) of organic pollutants at trace levels was investigated in this study for the first time. Seven polychlorinated biphenyls (PCBs) were selected as analytes, and gas chromatography-tandem mass spectrometry was employed for the detection. We optimized important parameters that may influence the efficiency of SPE, including the kind and volume of elution solvent, sample pH, and sample flow rate and volume. Under optimized conditions, low limits of detection (0.72-1.98ngL(-1)), wide range of linearity (10-1000ngL(-1)) and good repeatability (2.69-6.85%, n=5) were obtained. CNT sponges exhibited higher extraction performance than other adsorbent materials under the optimized conditions. Real environmental water samples were analyzed, and satisfactory recoveries (81.1-119.1%) were achieved. All these results demonstrated that CNT sponges are suitable SPE material for the enrichment and sensitive determination of PCBs at trace levels. PMID:27591590

  18. Magnetic porous carbon derived from a Zn/Co bimetallic metal-organic framework as an adsorbent for the extraction of chlorophenols from water and honey tea samples.

    PubMed

    Li, Menghua; Wang, Junmin; Jiao, Caina; Wang, Chun; Wu, Qiuhua; Wang, Zhi

    2016-05-01

    A novel magnetic porous carbon derived from a bimetallic metal-organic framework, Zn/Co-MPC, was prepared by introducing cobalt into ZIF-8. Magnetic porous carbon that possesses magnetic properties and a large specific surface area was firstly fabricated by the direct carbonization of Zn/Co-ZIF-8. The prepared magnetic porous carbon material was characterized by scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, N2 adsorption, and vibrating sample magnetometry. The prepared magnetic porous carbon was used as a magnetic solid-phase extraction adsorbent for the enrichment of chlorophenols from water and honey tea samples before high-performance liquid chromatography analysis. Several experimental parameters that could influence the extraction efficiency were investigated and optimized. Under the optimum conditions, good linearities (r > 0.9957) for all calibration curves were obtained with low limits of detection, which are in the range of 0.1-0.2 ng mL(-1) for all the analytes. The results showed that the prepared magnetic porous carbon had an excellent adsorption capability toward the target analytes. PMID:26991637

  19. Application of Graphene Oxide-MnFe2O4 Magnetic Nanohybrids as Magnetically Separable Adsorbent for Highly Efficient Removal of Arsenic from Water

    NASA Astrophysics Data System (ADS)

    Huong, Pham Thi Lan; Huy, Le Thanh; Phan, Vu Ngoc; Huy, Tran Quang; Nam, Man Hoai; Lam, Vu Dinh; Le, Anh-Tuan

    2016-05-01

    In this work, a functional magnetic nanohybrid consisting of manganese ferrite magnetic nanoparticles (MnFe2O4) deposited onto graphene oxide (GO) nanosheets was successfully synthesized using a modified co-precipitation method. The as-prepared GO-MnFe2O4 magnetic nanohybrids were characterized using x-ray diffraction, transmission electron microscopy, Fourier transformed infrared spectroscopy, and vibrating sample magnetometer measurements. Adsorption experiments were performed to evaluate the adsorption capacities and efficient removal of arsenic of the nanohybrid and compared with bare MnFe2O4 nanoparticles and GO nanosheets. Our obtained results reveal that the adsorption process of the nanohybrids was well fitted with a pseudo-second-order kinetic equation and a Freundlich isotherm model; the maximum adsorption capacity and removal efficiency of the nanohybrids obtained ~240.385 mg/g and 99.9% with a fast response of equilibrium adsorption time ~20 min. The larger adsorption capacity and shorter equilibrium time of the GO-MnFe2O4 nanohybrids showed better performance than that of bare MnFe2O4 nanoparticles and GO nanosheets. The advantages of reusability, magnetic separation, high removal efficiency, and quick kinetics make these nanohybrids very promising as low-cost adsorbents for fast and effective removal of arsenic from water.

  20. Energy deposition model based on electron scattering cross section data from water molecules

    NASA Astrophysics Data System (ADS)

    Muñoz, A.; Oiler, J. C.; Blanco, F.; Gorfinkiel, J. D.; Limão-Vieira, P.; Maira-Vidal, A.; Borge, M. J. G.; Tengblad, O.; Huerga, C.; Téllez, M.; García, G.

    2008-10-01

    A complete set of electrons scattering cross sections by water molecules over a broad energy range, from the me V to the Me V ranges, is presented in this study. These data have been obtained by combining experiments and calculations and cover most relevant processes, both elastic and inelastic, which can take place in the considered energy range. A new Monte Carlo simulation programme has been developed using as input parameter these cross sectional data as well as experimental energy loss spectra. The simulation procedure has been applied to obtain electron tracks and energy deposition plots in water when irradiated by a Ru-106 plaque as those used for brachyteraphy of ocular tumours. Finally, the low energy electron tracks provided by the present model have been compared with those obtained with other codes available in the literature

  1. Dipole and quadrupole polarizabilities of the water molecule as a function of geometry.

    PubMed

    Loboda, Oleksandr; Ingrosso, Francesca; Ruiz-López, Manuel F; Reis, Heribert; Millot, Claude

    2016-09-01

    Dipolar, dipole-quadrupole and quadrupole-quadrupole static polarizabilities of the water molecule have been determined by ab initio calculations at coupled cluster level of theory with single, double and perturbative triple excitations CCSD(T) with an aug-cc-pVTZ basis set using a finite field and field-gradient method. The geometry dependence of polarizability tensor components has been explored and modeled by power series expansion in bond length and angle variations up to sum of powers equal to 4. The results provide a very detailed description of the static polarizability of water up to quadrupolar rank which can be used for the test and development of novel accurate polarizable interaction potentials for modeling aqueous solutions. © 2016 Wiley Periodicals, Inc. PMID:27354163

  2. Water and complex organic molecules in the warm inner regions of solar-type protostars

    NASA Astrophysics Data System (ADS)

    Coutens, A.; Jørgensen, J. K.; Persson, M. V.; Lykke, J. M.; Taquet, V.; van Dishoeck, E. F.; Vastel, C.; Wampfler, S. F.

    2015-12-01

    Water and complex organic molecules play an important role in the emergence of Life. They have been detected in different types of astrophysical environments (protostars, prestellar cores, outflows, protoplanetary disks, comets, etc). In particular, they show high abundances towards the warm inner regions of protostars, where the icy grain mantles thermally desorb. Can a part of the molecular content observed in these regions be preserved during the star formation process and incorporated into asteroids and comets, that can deliver it to planetary embryos through impacts? By comparison with cometary studies, interferometric observations of solar-type protostars can help to address this important question. We present recent results obtained with the Plateau de Bure interferometer about water deuteration, glycolaldehyde and ethylene glycol towards the low-mass protostar NGC 1333 IRAS2A.

  3. Effect of the adsorbate (Bromacil) equilibrium concentration in water on its adsorption on powdered activated carbon. Part 2: Kinetic parameters.

    PubMed

    Al Mardini, Fadi; Legube, Bernard

    2009-10-30

    The application of several monosolute equilibrium models has previously shown that Bromacil adsorption on SA-UF (Norit) powdered activated carbon (PAC) is probably effective on two types of sites. High reactivity sites were found to be 10-20 less present in a carbon surface than lower reactivity sites, according to the q(m) values calculated by isotherm models. The aims of this work were trying, primarily, to identify the kinetic-determinant stage of the sorption of Bromacil at a wide range of initial pesticide concentrations (approximately 5 to approximately 500 microg L(-1) at pH 7.8), and secondly, to specify the rate constants and other useful design parameters for the application in water treatment. It was therefore not possible to specify a priori whether the diffusion or surface reaction is the key step. It shows that many of the tested models which describe the stage of distribution or the surface reaction are correctly applied. However, the diffusivity values (D and D(0)) were found to be constant only constants for some specific experimental concentrations. The HSDM model of surface diffusion in pores was also applied but the values of the diffusion coefficient of surface (D(s)) were widely scattered and reduce significantly with the initial concentration or the equilibrium concentration in Bromacil. The model of surface reaction of pseudo-second order fitted particularly well and led to constant values which are independent of the equilibrium concentration, except for the low concentrations where the constants become significantly more important. This last observation confirms perfectly the hypothesis based on two types of sites as concluded by the equilibrium data (part 1). PMID:19560269

  4. Conserved hydrogen bonds and water molecules in MDR HIV-1 protease substrate complexes

    SciTech Connect

    Liu, Zhigang; Wang, Yong; Yedidi, Ravikiran S.; Dewdney, Tamaria G.; Reiter, Samuel J.; Brunzelle, Joseph S.; Kovari, Iulia A.; Kovari, Ladislau C.

    2012-12-19

    Success of highly active antiretroviral therapy (HAART) in anti-HIV therapy is severely compromised by the rapidly developing drug resistance. HIV-1 protease inhibitors, part of HAART, are losing their potency and efficacy in inhibiting the target. Multi-drug resistant (MDR) 769 HIV-1 protease (resistant mutations at residues 10, 36, 46, 54, 62, 63, 71, 82, 84, 90) was selected for the present study to understand the binding to its natural substrates. The nine crystal structures of MDR769 HIV-1 protease substrate hepta-peptide complexes were analyzed in order to reveal the conserved structural elements for the purpose of drug design against MDR HIV-1 protease. Our structural studies demonstrated that highly conserved hydrogen bonds between the protease and substrate peptides, together with the conserved crystallographic water molecules, played a crucial role in the substrate recognition, substrate stabilization and protease stabilization. Additionally, the absence of the key flap-ligand bridging water molecule might imply a different catalytic mechanism of MDR769 HIV-1 protease compared to that of wild type (WT) HIV-1 protease.

  5. The binding energies of one and two water molecules to the first transition-row metal positive ions. II

    NASA Technical Reports Server (NTRS)

    Rosi, Marzio; Bauschlicher, Charles W., Jr.

    1990-01-01

    The present investigation of H2O's binding energy to transition-metal ions proceeds from the D(2h) structure and bends the two water molecules out of plane. The molecule is constrained to have C(2v) symmetry, so that each water molecule and metal ion lies on a plane. The ground states are bent only for Mn(H2O)2(+) and Zn(H2O)2(+), where only 4s4p hybridization is energetically favorable; 4s4p hybridization reduces repulsion.

  6. Pillared Interlayered Clays as Adsorbents of Gases and Vapors

    NASA Astrophysics Data System (ADS)

    Pires, J.; Pinto, M. L.

    This chapter reviews recent works where porous materials prepared from clays, particularly pillared interlayered clays (PILCs), were studied as gas phase adsorbents. It also includes the cases which used the adsorption of gases and vapors for the nanotextural characterization of the materials, other than the usual low temperature nitrogen adsorption. This is, for instance, the case of the adsorption of molecules of volatile organic compounds (VOCs), with various dimensions and shapes, which can be used as probe molecules for the characterization of the porosity or concerning the topic of the VOCs abatement. A similar situation occurs with water adsorption, whose results can be informative not only on the desiccant properties of the materials but also on their surface chemistry. A more recent line of studies of adsorption by materials prepared from clays, namely, the hydrocarbon purification from natural gas or biogas, was also addressed.

  7. The effects of water molecules on the electronic and structural properties of peptide nanotubes.

    PubMed

    Andrade-Filho, T; Ferreira, Fabio Furlan; Alves, Wendel Andrade; Rocha, Alexandre Reily

    2013-05-28

    The self-assembly of short amino acid chains appears to be one of the most promising strategies for the fabrication of nanostructures. Their solubility in water and the possibility of chemical modification by targeting the amino or carboxyl terminus give peptide-based nanostructures several advantages over carbon nanotube nanostructures. However, because these systems are synthesized in aqueous solution, a deeper understanding is needed on the effects of water especially with respect to the electronic, structural and transport properties. In this work, the electronic properties of L-diphenylalanine nanotubes (FF-NTs) have been studied using the Self-Consistent Charge Density-Functional-based Tight-Binding method augmented with dispersion interaction. The presence of water molecules in the central hydrophilic channel and their interaction with the nanostructures are addressed. We demonstrate that the presence of water leads to significant changes in the electronic properties of these systems decreasing the band gap which can lead to an increase in the hopping probability and the conductivity. PMID:23588391

  8. Hydrodynamic and nonhydrodynamic contributions to the bimolecular collision rates of solute molecules in supercooled bulk water.

    PubMed

    Peric, Ida; Merunka, Dalibor; Bales, Barney L; Peric, Miroslav

    2014-06-26

    Bimolecular collision rate constants of a model solute are measured in water at T = 259-303 K, a range encompassing both normal and supercooled water. A stable, spherical nitroxide spin probe, perdeuterated 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, is studied using electron paramagnetic resonance spectroscopy (EPR), taking advantage of the fact that the rotational correlation time, τ(R), the mean time between successive spin exchanges within a cage, τ(RE), and the long-time-averaged spin exchange rate constants, K(ex), of the same solute molecule may be measured independently. Thus, long- and short-time translational diffusion behavior may be inferred from K(ex) and τ(RE), respectively. In order to measure K(ex), the effects of dipole-dipole interactions (DD) on the EPR spectra must be separated, yielding as a bonus the DD broadening rate constants that are related to the dephasing rate constant due to DD, W(dd). We find that both K(ex) and W(dd) behave hydrodynamically; that is to say they vary monotonically with T/η or η/T, respectively, where η is the shear viscosity, as predicted by the Stokes-Einstein equation. The same is true of the self-diffusion of water. In contrast, τ(RE) does not follow hydrodynamic behavior, varying rather as a linear function of the density reaching a maximum at 276 ± 2 K near where water displays a maximum density. PMID:24874024

  9. Hydrodynamic and Nonhydrodynamic Contributions to the Bimolecular Collision Rates of Solute Molecules in Supercooled Bulk Water

    PubMed Central

    2015-01-01

    Bimolecular collision rate constants of a model solute are measured in water at T = 259–303 K, a range encompassing both normal and supercooled water. A stable, spherical nitroxide spin probe, perdeuterated 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, is studied using electron paramagnetic resonance spectroscopy (EPR), taking advantage of the fact that the rotational correlation time, τR, the mean time between successive spin exchanges within a cage, τRE, and the long-time-averaged spin exchange rate constants, Kex, of the same solute molecule may be measured independently. Thus, long- and short-time translational diffusion behavior may be inferred from Kex and τRE, respectively. In order to measure Kex, the effects of dipole–dipole interactions (DD) on the EPR spectra must be separated, yielding as a bonus the DD broadening rate constants that are related to the dephasing rate constant due to DD, Wdd. We find that both Kex and Wdd behave hydrodynamically; that is to say they vary monotonically with T/η or η/T, respectively, where η is the shear viscosity, as predicted by the Stokes–Einstein equation. The same is true of the self-diffusion of water. In contrast, τRE does not follow hydrodynamic behavior, varying rather as a linear function of the density reaching a maximum at 276 ± 2 K near where water displays a maximum density. PMID:24874024

  10. ORGANIC MOLECULES AND WATER IN THE INNER DISKS OF T TAURI STARS

    SciTech Connect

    Carr, John S.; Najita, Joan R. E-mail: najita@noao.edu

    2011-06-01

    We report high signal-to-noise Spitzer Infrared Spectrograph spectra of a sample of 11 classical T Tauri stars. Molecular emission from rotational transitions of H{sub 2}O and OH and rovibrational bands of simple organic molecules (CO{sub 2}, HCN, C{sub 2}H{sub 2}) is common among the sources in the sample. The emission shows a range in both flux and line-to-continuum ratio for each molecule and in the flux ratios of different molecular species. The gas temperatures (200-800 K) and emitting areas we derive are consistent with the emission originating in a warm disk atmosphere in the inner planet formation region at radii <2 AU. The H{sub 2}O emission appears to form under a limited range of excitation conditions, as demonstrated by the similarity in relative strengths of H{sub 2}O features from star to star and the narrow range in derived temperature and column density. Emission from highly excited rotational levels of OH is present in all stars; the OH emission flux increases with the stellar accretion rate, and the OH/H{sub 2}O flux ratio shows a relatively small scatter. We interpret these results as evidence for OH production via FUV photodissociation of H{sub 2}O in the disk surface layers. No obvious explanation is found for the observed range in the relative emission strengths of different organic molecules or in their strength with respect to water. We put forward the possibility that these variations reflect a diversity in organic abundances due to star-to-star differences in the C/O ratio of the inner disk gas. Stars with the largest HCN/H{sub 2}O flux ratios in our sample have the largest disk masses. While larger samples are required to confirm this, we speculate that such a trend could result if higher mass disks are more efficient at planetesimal formation and sequestration of water in the outer disk, leading to enhanced C/O ratios and abundances of organic molecules in the inner disk. A comparison of our derived HCN-to-H{sub 2}O column density ratio

  11. Sn(II) oxy-hydroxides as potential adsorbents for Cr(VI)-uptake from drinking water: An X-ray absorption study.

    PubMed

    Pinakidou, Fani; Kaprara, Efthimia; Katsikini, Maria; Paloura, Eleni C; Simeonidis, Konstantinos; Mitrakas, Manassis

    2016-05-01

    The feasibility of implementing a Sn(II) oxy-hydroxide (Sn6O4(OH)4) for the reduction and adsorption of Cr(VI) in drinking water treatment was investigated using XAFS spectroscopies at the Cr-K-edge. The analysis of the Cr-K-edge XANES and EXAFS spectra verified the effective use of Sn6O4(OH)4 for successful Cr(VI) removal. Adsorption isotherms, as well as dynamic Rapid Small Scale Test (RSSCT) in NSF water matrix showed that Sn6O4(OH)4 can decrease Cr(VI) concentration below the upcoming regulation limit of 10μg/L for drinking water. Moreover, an uptake capacity of 7.2μg/mg at breakthrough concentration of 10μg/L was estimated from the RSSCT, while the residual Cr(VI) concentration ranged at sub-ppb level for a significant period of the experiment. Furthermore, no evidence for the formation of Cr(OH)3 precipitates was found. On the contrary, Cr(III)-oxyanions were chemisorbed onto SnO2, which was formed after Sn(II)-oxidation during Cr(VI)-reduction. Nevertheless, changes in the type of Cr(III)-inner sphere complexes were observed after increasing surface coverage: Cr(III)-oxyanions preferentially sorb in a geometry which combines both bidentate binuclear ((2)C) and monodentate ((1)V) geometries, at the expense of the present bidentate mononuclear ((2)E) contributions. On the other hand, the pH during sorption does not affect the adsorption mechanism of Cr(III)-species. The implementation of Sn6O4(OH)4 in water treatment technology combines the advantage of rapidly reducing a large amount of Cr(VI) due to donation of two electrons by Sn(II) and also the strong chemisorption of Cr(III) in a combination of the (2)C and (1)V configurations, which enhances the safe disposal of spent adsorbents. PMID:26878637

  12. Dynamic and Static Water Molecules Complement the TN16 Conformational Heterogeneity inside the Tubulin Cavity.

    PubMed

    Majumdar, Sarmistha; Maiti, Satyabrata; Ghosh Dastidar, Shubhra

    2016-01-19

    TN16 is one of the most promising inhibitors of α, β dimer of tubulin that occupies the cavity in the β-subunit located at the dimeric interface, known as the colchicine binding site. The experimentally determined structure of the complex (Protein Data Bank entry 3HKD) presents the conformation and position of the ligand based on the "best fit", keeping the controversy of other significant binding modes open for further investigation. Computation has already revealed that TN16 experiences fluctuations within the binding pocket, but the insight from that previous report was limited by the shorter windows of sampling and by the approximations on the surrounding environment by implicit solvation. This article reports that in most of the cases straightforward MMGBSA calculations of binding energy revealed a gradual loss of stabilization that was inconsistent with the structural observations, and thus, it indicated the lack of consideration of stabilizing factors with appropriate weightage. Consideration of the structurally packed water molecules in the space between the ligand and receptor successfully eliminated such discrepancies between the structure and stability, serving as the "litmus test" of the importance of explicit consideration of such structurally packed water in the calculations. Such consideration has further evidenced a quasi-degenerate character of the different binding modes of TN16 that has rationalized the observed intrinsic fluctuations of TN16 within the pocket, which is likely to be the most critical insight into its entropy-dominated binding. Quantum mechanical calculations have revealed a relay of electron density from TN16 to the protein via a water molecule in a concerted manner. PMID:26666704

  13. Vasoactive properties of CORM-3, a novel water-soluble carbon monoxide-releasing molecule.

    PubMed

    Foresti, Roberta; Hammad, Jehad; Clark, James E; Johnson, Tony R; Mann, Brian E; Friebe, Andreas; Green, Colin J; Motterlini, Roberto

    2004-06-01

    1 Carbon monoxide (CO), one of the end products of heme catabolism by heme oxygenase, possesses antihypertensive and vasodilatory characteristics. We have recently discovered that certain transition metal carbonyls are capable of releasing CO in biological fluids and modulate physiological functions via the delivery of CO. Because the initial compounds identified were not water soluble, we have synthesized new CO-releasing molecules that are chemically modified to allow solubility in water. The aim of this study was to assess the vasoactive properties of tricarbonylchloro(glycinato)ruthenium(II) (CORM-3) in vitro and in vivo. 2 CORM-3 produced a concentration-dependent relaxation in vessels precontracted with phenylephrine, exerting significant vasodilatation starting at concentrations of 25-50 microm. Inactive CORM-3, which does not release CO, did not affect vascular tone. 3 Blockers of ATP-dependent potassium channels (glibenclamide) or guanylate cyclase activity (ODQ) considerably reduced CORM-3-dependent relaxation, confirming that potassium channels activation and cGMP partly mediate the vasoactive properties of CO. In fact, increased levels of cGMP were detected in aortas following CORM-3 stimulation. 4 The in vitro and in vivo vasorelaxant activities of CORM-3 were further enhanced in the presence of YC-1, a benzylindazole derivative which is known to sensitize guanylate cyclase to activation by CO. Interestingly, inhibiting nitric oxide production or removing the endothelium significantly decreased vasodilatation by CORM-3, suggesting that factors produced by the endothelium influence CORM-3 vascular activities. 5 These results, together with our previous findings on the cardioprotective functions of CORM-3, indicate that this molecule is an excellent prototype of water-soluble CO carriers for studying the pharmacological and biological features of CO. PMID:15148243

  14. Vasoactive properties of CORM-3, a novel water-soluble carbon monoxide-releasing molecule

    PubMed Central

    Foresti, Roberta; Hammad, Jehad; Clark, James E; Johnson, Tony R; Mann, Brian E; Friebe, Andreas; Green, Colin J; Motterlini, Roberto

    2004-01-01

    Carbon monoxide (CO), one of the end products of heme catabolism by heme oxygenase, possesses antihypertensive and vasodilatory characteristics. We have recently discovered that certain transition metal carbonyls are capable of releasing CO in biological fluids and modulate physiological functions via the delivery of CO. Because the initial compounds identified were not water soluble, we have synthesized new CO-releasing molecules that are chemically modified to allow solubility in water. The aim of this study was to assess the vasoactive properties of tricarbonylchloro(glycinato)ruthenium(II) (CORM-3) in vitro and in vivo. CORM-3 produced a concentration-dependent relaxation in vessels precontracted with phenylephrine, exerting significant vasodilatation starting at concentrations of 25–50 μM. Inactive CORM-3, which does not release CO, did not affect vascular tone. Blockers of ATP-dependent potassium channels (glibenclamide) or guanylate cyclase activity (ODQ) considerably reduced CORM-3-dependent relaxation, confirming that potassium channels activation and cGMP partly mediate the vasoactive properties of CO. In fact, increased levels of cGMP were detected in aortas following CORM-3 stimulation. The in vitro and in vivo vasorelaxant activities of CORM-3 were further enhanced in the presence of YC-1, a benzylindazole derivative which is known to sensitize guanylate cyclase to activation by CO. Interestingly, inhibiting nitric oxide production or removing the endothelium significantly decreased vasodilatation by CORM-3, suggesting that factors produced by the endothelium influence CORM-3 vascular activities. These results, together with our previous findings on the cardioprotective functions of CORM-3, indicate that this molecule is an excellent prototype of water-soluble CO carriers for studying the pharmacological and biological features of CO. PMID:15148243

  15. Unintended consequences? Water molecules at biological and crystallographic protein-protein interfaces.

    PubMed

    Ahmed, Mostafa H; Habtemariam, Mesay; Safo, Martin K; Scarsdale, J Neel; Spyrakis, Francesca; Cozzini, Pietro; Mozzarelli, Andrea; Kellogg, Glen E

    2013-12-01

    The importance of protein-protein interactions (PPIs) is becoming increasingly appreciated, as these interactions lie at the core of virtually every biological process. Small molecule modulators that target PPIs are under exploration as new therapies. One of the greatest obstacles faced in crystallographically determining the 3D structures of proteins is coaxing the proteins to form "artificial" PPIs that lead to uniform crystals suitable for X-ray diffraction. This work compares interactions formed naturally, i.e., "biological", with those artificially formed under crystallization conditions or "non-biological". In particular, a detailed analysis of water molecules at the interfaces of high-resolution (≤2.30 Å) X-ray crystal structures of protein-protein complexes, where 140 are biological protein-protein complex structures and 112 include non-biological protein-protein interfaces, was carried out using modeling tools based on the HINT forcefield. Surprisingly few and relatively subtle differences were observed between the two types of interfaces: (i) non-biological interfaces are more polar than biological interfaces, yet there is better organized hydrogen bonding at the latter; (ii) biological associations rely more on water-mediated interactions with backbone atoms compared to non-biological associations; (iii) aromatic/planar residues play a larger role in biological associations with respect to water, and (iv) Lys has a particularly large role at non-biological interfaces. A support vector machines (SVMs) classifier using descriptors from this study was devised that was able to correctly classify 84% of the two interface types. PMID:24076743

  16. The uranium from seawater program at PNNL: Overview of marine testing, adsorbent characterization, adsorbent durability, adsorbent toxicity, and deployment studies

    DOE PAGESBeta

    Gill, Gary A.; Kuo, Li -Jung; Janke, Christopher James; Park, Jiyeon; Jeters, Robert T.; Bonheyo, George T.; Pan, Horng -Bin; Wai, Chien; Khangaonkar, Tarang P.; Bianucci, Laura; et al

    2016-02-07

    The Pacific Northwest National Laboratory's (PNNL) Marine Science Laboratory (MSL) located along the coast of Washington State is evaluating the performance of uranium adsorption materials being developed for seawater extraction under realistic marine conditions with natural seawater. Two types of exposure systems were employed in this program: flow-through columns for testing of fixed beds of individual fibers and pellets and a recirculating water flume for testing of braided adsorbent material. Testing consists of measurements of the adsorption of uranium and other elements from seawater as a function of time, typically 42 to 56 day exposures, to determine the adsorbent capacitymore » and adsorption rate (kinetics). Analysis of uranium and other trace elements collected by the adsorbents was conducted following strong acid digestion of the adsorbent with 50% aqua regia using either Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) or Inductively Coupled Plasma Mass Spectrometer (ICP-MS). The ORNL 38H adsorbent had a 56 day adsorption capacity of 3.30 ± 0.68 g U/ kg adsorbent (normalized to a salinity of 35 psu), a saturation adsorption capacity of 4.89 ± 0.83 g U/kg of adsorbent material (normalized to a salinity of 35 psu) and a half-saturation time of 28 10 days. The AF1 adsorbent material had a 56 day adsorption capacity of 3.9 ± 0.2 g U/kg adsorbent material (normalized to a salinity of 35 psu), a saturation capacity of 5.4 ± 0.2 g U/kg adsorbent material (normalized to a salinity of 35 psu) and a half saturation time of 23 2 days. The ORNL amidoxime-based adsorbent materials are not specific for uranium, but also adsorb other elements from seawater. The major doubly charged cations in seawater (Ca and Mg) account for a majority of the cations adsorbed (61% by mass and 74% by molar percent). For the ORNL AF1 adsorbent material, U is the 4th most abundant element adsorbed by mass and 7th most abundant by molar percentage. Marine testing

  17. The Uranium from Seawater Program at PNNL: Overview of marine testing, adsorbent characterization, adsorbent durability, adsorbent toxicity, and deployment studies

    SciTech Connect

    Gill, Gary; Kuo, Li-Jung; Janke, Christopher James; Park, Jiyeon; Jeters, Robert T; Bonheyo, George; Pan, Horng-Bin; Wai, Chien; Khangaonkar, Tarang P; Bianucci, Laura; Wood, Jordana; Warner, Marvin G; Peterson, Sonja; Abrecht, David; Mayes, Richard T; Tsouris, Costas; Oyola, Yatsandra; Strivens, Jonathan E.; Schlafer, Nicholas; Addleman, Shane R; Chouyyok, Wilaiwan; Das, Sadananda; Kim, Jungseung; Buesseler, Dr. Ken; Breier, Crystalline; D'Alessandro, Dr. Evan

    2016-01-01

    The Pacific Northwest National Laboratory s (PNNL) Marine Science Laboratory (MSL) located along the coast of Washington State is evaluating the performance of uranium adsorption materials being developed for seawater extraction under realistic marine conditions with natural seawater. Two types of exposure systems were employed in this program: flow-through columns for testing of fixed beds of individual fibers and pellets and a recirculating water flume for testing of braided adsorbent material. Testing consists of measurements of the adsorption of uranium and other elements from seawater as a function of time, typically 42 to 56 day exposures, to determine the adsorbent capacity and adsorption rate (kinetics). Analysis of uranium and other trace elements collected by the adsorbents was conducted following strong acid digestion of the adsorbent with 50% aqua regia using either Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) or Inductively Coupled Plasma Mass Spectrometer (ICP-MS). The ORNL 38H adsorbent had a 56 day adsorption capacity of 3.30 0.68 g U/ kg adsorbent (normalized to a salinity of 35 psu), a saturation adsorption capacity of 4.89 0.83 g U/kg of adsorbent material (normalized to a salinity of 35 psu) and a half-saturation time of 28 10 days. The AF1 adsorbent material had a 56 day adsorption capacity of 3.9 0.2 g U/kg adsorbent material (normalized to a salinity of 35 psu), a saturation capacity of 5.4 0.2 g U/kg adsorbent material (normalized to a salinity of 35 psu) and a half saturation time of 23 2 days. The ORNL amidoxime-based adsorbent materials are not specific for uranium, but also adsorb other elements from seawater. The major doubly charged cations in seawater (Ca and Mg) account for a majority of the cations adsorbed (61% by mass and 74% by molar percent). For the ORNL AF1 adsorbent material, U is the 4th most abundant element adsorbed by mass and 7th most abundant by molar percentage. Marine testing at Woods Hole

  18. Orbiting Water Molecules Dance to Tune Of Galaxy's "Central Engine," Astronomers Say

    NASA Astrophysics Data System (ADS)

    2000-01-01

    A disk of water molecules orbiting a supermassive black hole at the core of a galaxy 60 million light-years away is "reverberating" in response to variations in the energy output from the galaxy's powerful "central engine" close to the black hole, astronomers say. The team of astronomers used the National Science Foundation's (NSF) Very Large Array (VLA) radio telescope in New Mexico and the 100-meter-diameter radio telescope of the Max Planck Institute for Radio Astronomy at Effelsberg, Germany, to observe the galaxy NGC 1068 in the constellation Cetus. They announced their findings today at the American Astronomical Society's meeting in Atlanta. The water molecules, in a disk some 5 light-years in diameter, are acting as a set of giant cosmic radio-wave amplifiers, called masers. Using energy radiated by the galaxy's "central engine," the molecules strengthen, or brighten, radio emission at a particular frequency as seen from Earth. "We have seen variations in the radio 'brightness' of these cosmic amplifiers that we believe were caused by variations in the energy output of the central engine," said Jack Gallimore, an astronomer at the National Radio Astronomy Observatory (NRAO) in Charlottesville, VA. "This could provide us with a valuable new tool for learning about the central engine itself," he added. Gallimore worked with Stefi Baum of the Space Telescope Science Institute in Baltimore, MD; Christian Henkel of the Max Planck Institute for Radio Astronomy in Bonn, Germany; Ian Glass of the South African Astronomical Observatory; Mark Claussen of the NRAO in Socorro, NM; and Almudena Prieto of the European Southern Observatory in Munich, Germany. "Our observations show that NGC 1068 is the second-known case of a giant disk of water molecules orbiting a supermassive black hole at a galaxy's core," Gallimore said. The first case was the galaxy NGC 4258 (Messier 106), whose disk of radio-amplifying water molecules was measured by the NSF's Very Long Baseline

  19. Mechanism of dialkyl phthalates removal from aqueous solution using γ-cyclodextrin and starch based polyurethane polymer adsorbents.

    PubMed

    Okoli, Chukwunonso Peter; Adewuyi, Gregory Olufemi; Zhang, Qian; Diagboya, Paul N; Guo, Qingjun

    2014-12-19

    Phthalate esters have been known as potent endocrine disruptors and carcinogens; and their removal from water have been of considerable concern recently. In the present study, γ-cyclodextrin polyurethane polymer (GPP), γ-cyclodextrin/starch polyurethane copolymer (GSP), and starch polyurethane polymer (SPP) have been synthesized and characterized. Their adsorption efficiencies for the removal of dimethyl phthalate (DMP) and diethyl phthalate (DEP) from aqueous solutions were investigated. The characterization results showed the success of the synthesis. The isotherms were L-type, and both the Langmuir and Freundlich adsorption isotherm gave good fittings to the adsorption data. Adsorption mechanisms suggested that these adsorbents spontaneously adsorb phthalate molecules driven mainly by enthalpy change, and the adsorption process was attributed to multiple adsorbent-adsorbate interactions such as hydrogen bonding, π-π stacking, and pore filling. The results showed that starch and γ-cyclodextrin polyurethane polymer adsorbents have excellent potential as adsorbent materials for the removal of phthalates from the contaminated water. PMID:25263912

  20. Rotations and vibrations of water molecule inside the fullerene cage: infrared study of H2O@C60

    NASA Astrophysics Data System (ADS)

    Room, Toomas; Shugai, A.; Nagel, U.; Mamone, S.; Krachmalnicoff, A.; Whitby, R. J.; Levitt, M. H.; Nishida, T.; Murata, Y.; Lei, Xuegong; Li, Yongjun; Turro, N. J.

    2015-03-01

    Water is the second molecule after hydrogen what has been trapped inside the cage of a C60 molecule by the molucular surgery method. We studied isolated water molecule isotopologs H2O, D2O, and HDO in the solid phase at cryogenic temperatures using IR spectroscopy. The water molecule rotation transitions were observed in the THz and vibration-rotation transitions in the mid-IR range. The slow conversion between para and ortho water allowed us to record the time evolution of spectra and to separate ortho and para absorption lines of water. The similarity of the rotation spectrum of caged water to water in the gas phase indicates that water is free to rotate in the C60 cage even at temperature as low as 3 K. However, spectral lines show a splitting of about 0.5 meV what is not compatible with the icosahedral symmetry of C60. Different models (e.g. crystal field effects in solid C60, C60 cage distortions) will be discussed. This work was supported by institutional research funding IUT23-3 of the Estonian Ministry of Education and Research.

  1. In situ laser Raman spectra of iron phthalocyanine adsorbed on copper and gold electrodes. [Electronic structure

    SciTech Connect

    Melendres, C.A.; Rios, C.B.; Feng, X.; McMasters, R.

    1983-01-01

    Raman spectra of iron phthalocyanine (FePc) and its tetrasulfonated derivative (FeTSPc) adsorbed on copper and gold electrodes have been observed in situ in 0.05 M H/sub 2/SO/sub 4/ solution. Results confirm the authors previous finding on the coordination of FePc to water molecules to solution. Evidence suggests that the iron phthalocyanines are probably oriented with their planes parallel to the electrode surface even in immersed electrodes. A decrease in intensity and broadening of some vibrational bands are observed on increasing cathodic polarization; these are attributed to a lifting of the degeneracy of the vibrational modes due to a change in symmetry of the adsorbed molecules brought about by polarization induced by the double-layer field. The effect of carbon on the Raman spectra is discussed. The iron phthalocyanines appear to be stable at potentials close to hydrogen evolution in the absence of oxygen. 18 references, 8 figures.

  2. In situ laser Raman spectra of iron phthalocyanine adsorbed on copper and gold electrodes

    SciTech Connect

    Melendres, C.A.; Rios, C.B.; Feng, X.; McMasters, R.

    1983-09-01

    Raman spectra of iron phthalocyanine (FePc) and its tetrasulfonated derivative (FeTSPc) adsorbed on copper and gold electrodes have been observed in situ in 0.05 M H/sub 2/SO/sub 4/ solution. Results confirm our previous finding on the coordination of FePc to water molecules to solution. Evidence suggests that the iron phthalocyanines are probably oriented with their planes parallel to the electrode surface even in immersed electrodes. A decrease in intensity and broadening of some vibrational bands are observed on increasing cathodic polarization; these are attributed to a lifting of the degeneracy of the vibrational modes due to a change in symmetry of the adsorbed molecules brought about by polarization induced by the double-layer field. The effect of carbon on the Raman spectra is discussed. The iron phthalocyanines appear to be stable at potentials close to hydrogen evolution in the absence of oxygen. 8 figures.

  3. Anisotropic conductivity tensor imaging in MREIT using directional diffusion rate of water molecules

    NASA Astrophysics Data System (ADS)

    In Kwon, Oh; Jeong, Woo Chul; Sajib, Saurav Z. K.; Kim, Hyung Joong; Woo, Eung Je

    2014-06-01

    Magnetic resonance electrical impedance tomography (MREIT) is an emerging method to visualize electrical conductivity and/or current density images at low frequencies (below 1 KHz). Injecting currents into an imaging object, one component of the induced magnetic flux density is acquired using an MRI scanner for isotropic conductivity image reconstructions. Diffusion tensor MRI (DT-MRI) measures the intrinsic three-dimensional diffusion property of water molecules within a tissue. It characterizes the anisotropic water transport by the effective diffusion tensor. Combining the DT-MRI and MREIT techniques, we propose a novel direct method for absolute conductivity tensor image reconstructions based on a linear relationship between the water diffusion tensor and the electrical conductivity tensor. We first recover the projected current density, which is the best approximation of the internal current density one can obtain from the measured single component of the induced magnetic flux density. This enables us to estimate a scale factor between the diffusion tensor and the conductivity tensor. Combining these values at all pixels with the acquired diffusion tensor map, we can quantitatively recover the anisotropic conductivity tensor map. From numerical simulations and experimental verifications using a biological tissue phantom, we found that the new method overcomes the limitations of each method and successfully reconstructs both the direction and magnitude of the conductivity tensor for both the anisotropic and isotropic regions.

  4. The hydrolytic water molecule in trypsin, revealed by time-resolved Laue crystallography

    SciTech Connect

    Singer, P.T. ); Smalaas, A. ); Carty, R.P. ); Mangel, W.F.; Sweet, R.M. )

    1993-01-29

    Crystals of bovine trypsin were acylated at the reactive residue, serine 195, to form the transiently stable p-guanidinobenzoate. Hydrolysis of this species was triggered in the crystals by a jump in pH. The hydrolysis was monitored by three-dimensional Laue crystallography, resulting in three x-ray diffraction structures, all from the same crystal and each representing approximately 5 seconds of x-ray exposure. The structures were analyzed at a nominal resolution of 1.8 angstroms and were of sufficient quality to reproduce subtle features in the electron-density maps for each of the structures. Comparison of the structures before and after the pH jump reveals that a water molecule has positioned itself to attack the acyl group in the initial step of the hydrolysis of this transient intermediate. 12 refs., 3 figs., 2 tabs.

  5. Switching of the magnetocaloric effect of Mn(II) glycolate by water molecules.

    PubMed

    Chen, Yan-Cong; Guo, Fu-Sheng; Liu, Jun-Liang; Leng, Ji-Dong; Vrábel, Peter; Orendáč, Martin; Prokleška, Jan; Sechovský, Vladimír; Tong, Ming-Liang

    2014-03-10

    The transformation of Mn(II) glycolates (glc) between the three-dimensional coordination polymer [Mn(glc)2]n (1) and discrete mononuclear phase [Mn(glc)2 (H2O)2] (2) can be reversibly switched by water molecules, which dramatically change the magnetocaloric effect (MCE) of Mn(II) glycolates from the maximum of 6.9 J kg(-1)  K(-1) in 1 to 60.3 J kg(-1)  K(-1) in 2. This case example reveals that the effect of magnetic coupling on MCE plays a dominant role over that of other factors such as magnetic density for 3d-type magnetic refrigerants. PMID:24532426

  6. Computing the energy of a water molecule using multideterminants: A simple, efficient algorithm

    NASA Astrophysics Data System (ADS)

    Clark, Bryan K.; Morales, Miguel A.; McMinis, Jeremy; Kim, Jeongnim; Scuseria, Gustavo E.

    2011-12-01

    Quantum Monte Carlo (QMC) methods such as variational Monte Carlo and fixed node diffusion Monte Carlo depend heavily on the quality of the trial wave function. Although Slater-Jastrow wave functions are the most commonly used variational ansatz in electronic structure, more sophisticated wave functions are critical to ascertaining new physics. One such wave function is the multi-Slater-Jastrow wave function which consists of a Jastrow function multiplied by the sum of Slater determinants. In this paper we describe a method for working with these wave functions in QMC codes that is easy to implement, efficient both in computational speed as well as memory, and easily parallelized. The computational cost scales quadratically with particle number making this scaling no worse than the single determinant case and linear with the total number of excitations. Additionally, we implement this method and use it to compute the ground state energy of a water molecule.

  7. Computing the energy of a water molecule using multideterminants: a simple, efficient algorithm.

    PubMed

    Clark, Bryan K; Morales, Miguel A; McMinis, Jeremy; Kim, Jeongnim; Scuseria, Gustavo E

    2011-12-28

    Quantum Monte Carlo (QMC) methods such as variational Monte Carlo and fixed node diffusion Monte Carlo depend heavily on the quality of the trial wave function. Although Slater-Jastrow wave functions are the most commonly used variational ansatz in electronic structure, more sophisticated wave functions are critical to ascertaining new physics. One such wave function is the multi-Slater-Jastrow wave function which consists of a Jastrow function multiplied by the sum of Slater determinants. In this paper we describe a method for working with these wave functions in QMC codes that is easy to implement, efficient both in computational speed as well as memory, and easily parallelized. The computational cost scales quadratically with particle number making this scaling no worse than the single determinant case and linear with the total number of excitations. Additionally, we implement this method and use it to compute the ground state energy of a water molecule. PMID:22225142

  8. Sense or no-sense of the sum parameter for water soluble "adsorbable organic halogens" (AOX) and "absorbed organic halogens" (AOX-S18) for the assessment of organohalogens in sludges and sediments.

    PubMed

    Müller, German

    2003-07-01

    "AOX" is the abbreviation of the sum parameter for water soluble "adsorbable organic halogens" in which 'A' stands for adsorbable, 'O' for organic and 'X' for the halogens chlorine, bromine and iodine. After the introduction of the AOX in 1976, this parameter has been correctly used for "real" AOX constituents (DDT and its metabolites, PCBs, etc.) but also misused for non-adsorbable adsorbed OX-compounds, mostly high molecular organohalogens in plants and even to inorganic compounds being neither organic nor adsorbable. The question of natural "Adsorbable Organic Halogens" (AOX) formed by living organisms and/or during natural abiogenic processes has been definitively solved by the known existence of already more than 3650 organohalogen compounds, amongst them the highly reactive, cancerogenic vinyl chloride (VC). The extension of the AOX to AOX-S18 for Sludges and Sediments, in which A stands for adsorbed (not for adsorbable) is questionable. It includes the most important water insoluble technical organochlorine product: polyvinyl chloride, PVC. In addition to organic halogens it also includes inorganic, mineralogenic halides, incorporated mainly in the crystal lattice of fine grained phyllosilicates, the typical clay minerals (kaolinite, montmorillonite, illite and chlorite) which are main constituents of sediments and sedimentary rocks representing the major part of the sedimentary cover of the earth. Other phyllosilicates, biotite and muscovite, major constituents of granites and many metamorphic rocks (gneiss and mica schist) will also contribute to the AOX-S18 especially in soils as result of weathering processes. Since chlorine is incorporated into the mineral structure and, as a consequence, not soluble by the nitric acid analytical step (pH 0.5) of the S18 determination, it will account to the AOX-S18 in the final charcoal combustion step at temperatures >950 degrees C. After heavy rainfalls sewage sludge composition is strongly influenced by

  9. Measurements of the number density of water molecules in plasma by using a combined spectral-probe method

    NASA Astrophysics Data System (ADS)

    Bernatskiy, A. V.; Ochkin, V. N.; Afonin, O. N.; Antipenkov, A. B.

    2015-09-01

    A novel method for measuring the number density of water molecules in low-temperature plasma is developed. The absolute intensities of rotational lines of the (0,0) band of the OH( A 2Σ- X 2П) transition are used. Lines with sufficiently large rotational quantum numbers referring to the so-called "hot" group of molecules produced by electron-impact dissociative excitation of water molecules are chosen for measurements. The excitation rate of a process with a known cross section is determined by measuring the parameters of plasma electrons by means of the probe method. The measured number densities of molecules are compared with those in the initial plasma-forming mixture. The time evolution of the particle densities in plasma is investigated. The problems of the sensitivity and applicability of the absolute spectral method are considered.

  10. Measurements of the number density of water molecules in plasma by using a combined spectral−probe method

    SciTech Connect

    Bernatskiy, A. V. Ochkin, V. N.; Afonin, O. N.; Antipenkov, A. B.

    2015-09-15

    A novel method for measuring the number density of water molecules in low-temperature plasma is developed. The absolute intensities of rotational lines of the (0,0) band of the OH(A{sup 2}Σ–X{sup 2}Π) transition are used. Lines with sufficiently large rotational quantum numbers referring to the so-called “hot” group of molecules produced by electron-impact dissociative excitation of water molecules are chosen for measurements. The excitation rate of a process with a known cross section is determined by measuring the parameters of plasma electrons by means of the probe method. The measured number densities of molecules are compared with those in the initial plasma-forming mixture. The time evolution of the particle densities in plasma is investigated. The problems of the sensitivity and applicability of the absolute spectral method are considered.

  11. How small polar molecules protect membrane systems against osmotic stress: the urea-water-phospholipid system.

    PubMed

    Costa-Balogh, Fátima O; Wennerström, Håkan; Wadsö, Lars; Sparr, Emma

    2006-11-30

    We investigate how a small polar molecule, urea, can act to protect a phospholipid bilayer system against osmotic stress. Osmotic stress can be caused by a dry environment, by freezing, or by exposure to aqueous systems with high osmotic pressure due to solutes like in saline water. A large number of organisms regularly experience osmotic stress, and it is a common response to produce small polar molecules intracellularly. We have selected a ternary system of urea-water-dimyristoyl phosphatidylcholine (DMPC) as a model to investigate the molecular mechanism behind this protective effect, in this case, of urea, and we put special emphasis on the applications of urea in skin care products. Using differential scanning calorimetry, X-ray diffraction, and sorption microbalance measurements, we studied the phase behavior of lipid systems exposed to an excess of solvent of varying compositions, as well as lipid systems exposed to water at reduced relative humidities. From this, we have arrived at a rather detailed thermodynamic characterization. The basic findings are as follows: (i) In excess solvent, the thermally induced lipid phase transitions are only marginally dependent on the urea content, with the exception being that the P(beta) phase is not observed in the presence of urea. (ii) For lipid systems with limited access to solvent, the phase behavior is basically determined by the amount (volume) of solvent irrespective of the urea content. (iii) The presence of urea has the effect of retaining the liquid crystalline phase at relative humidities down to 64% (at 27 degrees C), whereas, in the absence of urea, the transition to the gel phase occurs already at a relative humidity of 94%. This demonstrates the protective effect of urea against osmotic stress. (iv) In skin care products, urea is referred to as a moisturizer, which we find slightly misleading as it replaces the water while keeping the physical properties unaltered. (v) In other systems, urea is known to

  12. Molecular Adsorber Coating

    NASA Technical Reports Server (NTRS)

    Straka, Sharon; Peters, Wanda; Hasegawa, Mark; Hedgeland, Randy; Petro, John; Novo-Gradac, Kevin; Wong, Alfred; Triolo, Jack; Miller, Cory

    2011-01-01

    A document discusses a zeolite-based sprayable molecular adsorber coating that has been developed to alleviate the size and weight issues of current ceramic puck-based technology, while providing a configuration that more projects can use to protect against degradation from outgassed materials within a spacecraft, particularly contamination-sensitive instruments. This coating system demonstrates five times the adsorption capacity of previously developed adsorber coating slurries. The molecular adsorber formulation was developed and refined, and a procedure for spray application was developed. Samples were spray-coated and tested for capacity, thermal optical/radiative properties, coating adhesion, and thermal cycling. Work performed during this study indicates that the molecular adsorber formulation can be applied to aluminum, stainless steel, or other metal substrates that can accept silicate-based coatings. The coating can also function as a thermal- control coating. This adsorber will dramatically reduce the mass and volume restrictions, and is less expensive than the currently used molecular adsorber puck design.

  13. Site blocking effects on adsorbed polyacrylamide conformation

    NASA Astrophysics Data System (ADS)

    Brotherson, Brett A.

    The use of polymers as flocculating additives is a common practice in many manufacturing environments. However, exactly how these polymers interact with surfaces is relatively unknown. One specific topic which is thought to be very important to flocculation is an adsorbed polymer's conformation. Substantial amounts of previous work, mainly using simulations, have been performed to elucidate the theory surrounding adsorbed polymer conformations. Yet, there is little experimental work which directly verifies current theory. In order to optimize the use of polymer flocculants in industrial applications, a better understanding of an adsorbed polymer's conformation on a surface beyond theoretical simulations is necessary. This work looks specifically at site blocking, which has a broad impact on flocculation, adsorption, and surface modification, and investigated its effects on the resulting adsorbed polymer conformation. Experimental methods which would allow direct determination of adsorbed polymer conformational details and be comparable with previous experimental results were first determined or developed. Characterization of an adsorbed polymer's conformation was then evaluated using dynamic light scattering, a currently accepted experimental technique to examine this. This commonly used technique was performed to allow the comparison of this works results with past literature. Next, a new technique using atomic force microscopy was developed, building on previous experimental techniques, to allow the direct determination of an adsorbed polymer's loop lengths. This method also was able to quantify changes in the length of adsorbed polymer tails. Finally, mesoscopic simulation was attempted using dissipative particle dynamics. In order to determine more information about an adsorbed polymer's conformation, three different environmental factors were analyzed: an adsorbed polymer on a surface in water, an adsorbed polymer on a surface in aqueous solutions of varying

  14. The local environment of the molecules in water-DMSO mixtures, as seen from computer simulations and Voronoi polyhedra analysis.

    PubMed

    Idrissi, Abdenacer; Marekha, B; Kiselev, M; Jedlovszky, Pál

    2015-02-01

    Molecular dynamics simulations of water-DMSO mixtures, containing 10, 20, 30, 40, 50, 60, 70, 80, and 90 mol% DMSO, respectively, have been performed on the isothermal-isobaric (N,p,T) ensemble at T = 298 K and at the pressure equal to the experimental vapor pressure at each mixture composition. In addition, simulations of the two neat systems have also been performed for reference. The potential models used in the simulations are known to excellently reproduce the mixing properties of these compounds. The simulation results have been analyzed in detail by means of the Voronoi polyhedra (VP) of the molecules. Distributions of the VP volume and the asphericity parameter as well as that of the radius of the spherical intermolecular voids have been calculated. Detailed analyses of these distributions have revealed that both molecules prefer to be in an environment consisting of both types of molecules, but the affinity of DMSO for mixing with water is clearly stronger than that of water for mixing with DMSO. As a consequence, the dilution of the two neat liquids by the other component has been found to follow different mechanisms: when DMSO is added to neat water small domains of neat-like water persist up to the equimolar composition, whereas no such domains are found when neat DMSO is diluted by water. The observed behaviour is also in line with the fact that the main thermodynamic driving force behind the full miscibility of water and DMSO is the energy change accompanying their mixing, and that the entropy change accompanying this mixing is negative in systems of low and positive in systems of high DMSO mole fractions. Finally, we have found a direct evidence for the existence of strong hydrogen bonded complexes formed by one DMSO and two water molecules, but it has also been shown that these complexes are in equilibrium with single (monomeric) water and DMSO molecules in the mixed systems. PMID:25533427

  15. Effect of nanotube-length on the transport properties of single-file water molecules: Transition from bidirectional to unidirectional

    NASA Astrophysics Data System (ADS)

    Su, Jiaye; Guo, Hongxia

    2011-06-01

    We use molecular dynamics (MD) simulations to study the transport of single-file water molecules through carbon nanotubes (CNTs) with various lengths in an electric field. Most importantly, we find that even the water dipoles inside the CNT are maintained along the field direction, a large amount of water molecules can still transport against the field direction for short CNTs, leading to a low unidirectional transport efficiency (η). As the CNT length increases, the efficiency η will increase remarkably, and achieves the maximum value of 1.0 at or exceeding a critical CNT length. Consequently, the transition from bidirectional to unidirectional transport is observed and is found to be relevant to thermal fluctuations of the two reservoirs, which is explored by the interaction between water molecules inside and outside the CNT. We also find that the water flow vs CNT length follows an exponential decay of f ˜ exp ( - L/L0), and the average translocation time of individual water molecules yields to a power law of τtrans ˜ Lυ, where L0 and ν are constant and slightly depend on the field strength. We further compare our results with the continuous-time random-walk (CTRW) model and find that the water flow can also be described by a power law of f ˜ L-μ modified from CTRW. Our results provide some new physical insights into the biased transport of single-file water molecules, which show the feasibility of using CNTs with any length to pump water in an electric field. The mechanism is important for designing efficient nanofluidic apparatuses.

  16. Carbon dioxide (C{sup 16}O{sub 2} and C{sup 18}O{sub 2}) adsorption in zeolite Y materials: effect of cation, adsorbed water and particle size

    SciTech Connect

    Pragati Galhotra; Juan G. Navea; Sarah C. Larsen; Vicki H. Grassian

    2009-07-01

    In this study, CO{sub 2} adsorption in the presence and absence of co-adsorbed H{sub 2}O was investigated in zeolite Y. Several different zeolite Y materials were investigated including commercial NaY, commercial NaY ion-exchanged with Ba{sup 2+} and nanocrystalline NaY; herein referred to as NaY, BaY and nano-NaY. Following heating of these zeolites to 573 K and cooling to room temperature, CO{sub 2} was adsorbed as a function of pressure. FTIR spectra show that a majority of CO{sub 2} adsorbs in the pores of these three zeolites (NaY, BaY and nano-NaY) in a linear complex with the exchangeable cation, as indicated by the intense absorption band near 2350 cm{sup -1}, assigned to the 3 asymmetric stretch of adsorbed CO{sub 2}. Most interestingly is the formation of carbonate and bicarbonate on the external surface of nano-NaY zeolites as indicated by the presence of several broad absorption bands in the 1200-1800 cm{sup -1} region, suggesting unique sites for CO{sub 2} adsorption on the surface of the nanomaterial. For the other two zeolite materials investigated, bicarbonate formation is only evident in BaY zeolite in the presence of co-adsorbed water. Adsorption of {sup 18}O-labeled carbon dioxide and theoretical quantum chemical calculations confirm these assignments and conclusions. 28 refs., 9 figs., 3 tabs.

  17. Transition energies of benzoquinone anions are immune to symmetry breaking by a single water molecule.

    PubMed

    Stockett, Mark H; Nielsen, Steen Brøndsted

    2016-03-14

    p-Benzoquinone is the prototypical member of the quinone class of molecules with a basic functionality relevant for the primary reactions of photosynthesis. As electronically excited quinone anions are formed in near-resonant electron transfer, key issues are how the local environment affects excited-state energy levels and deexcitation times. The former we address here with action spectroscopy of mass-selected bare radical anions (pBQ(-)) and one-water pBQ(-)·H2O complexes, isolated in vacuo. The complex represents a precursor for internal proton transfer to form the semiquinone free radical, the first chemical product in the light-driven electron transport chain. Both ions display bands in the visible and ultraviolet with, importantly, almost identical maxima. Despite localizing negative charge, thereby breaking the high orbital symmetries, water is surprisingly innocent. This finding implies that natural fluctuations in the quinone microenvironment cause only minor variations in excited-state energies and thus electron-transfer rates. Hence quinones are robust participants in electron transport. PMID:26490302

  18. A proactive role of water molecules in acceptor recognition by protein O-fucosyltransferase 2.

    PubMed

    Valero-González, Jessika; Leonhard-Melief, Christina; Lira-Navarrete, Erandi; Jiménez-Osés, Gonzalo; Hernández-Ruiz, Cristina; Pallarés, María Carmen; Yruela, Inmaculada; Vasudevan, Deepika; Lostao, Anabel; Corzana, Francisco; Takeuchi, Hideyuki; Haltiwanger, Robert S; Hurtado-Guerrero, Ramon

    2016-04-01

    Protein O-fucosyltransferase 2 (POFUT2) is an essential enzyme that fucosylates serine and threonine residues of folded thrombospondin type 1 repeats (TSRs). To date, the mechanism by which this enzyme recognizes very dissimilar TSRs has been unclear. By engineering a fusion protein, we report the crystal structure of Caenorhabditis elegans POFUT2 (CePOFUT2) in complex with GDP and human TSR1 that suggests an inverting mechanism for fucose transfer assisted by a catalytic base and shows that nearly half of the TSR1 is embraced by CePOFUT2. A small number of direct interactions and a large network of water molecules maintain the complex. Site-directed mutagenesis demonstrates that POFUT2 fucosylates threonine preferentially over serine and relies on folded TSRs containing the minimal consensus sequence C-X-X-S/T-C. Crystallographic and mutagenesis data, together with atomic-level simulations, uncover a binding mechanism by which POFUT2 promiscuously recognizes the structural fingerprint of poorly homologous TSRs through a dynamic network of water-mediated interactions. PMID:26854667

  19. Hyperfine coupling constants on inner-sphere water molecules of Gd(III)-based MRI contrast agents.

    PubMed

    Esteban-Gómez, David; de Blas, Andrés; Rodríguez-Blas, Teresa; Helm, Lothar; Platas-Iglesias, Carlos

    2012-11-12

    Herein we present a theoretical investigation of the hyperfine coupling constants (HFCCs) on the inner-sphere water molecules of [Gd(H(2)O)(8)](3+) and different Gd(III)-based magnetic resonance imaging contrast agents such as [Gd(DOTA)(H(2)O)](-), [Gd(DTPA)(H(2)O)](2-), [Gd(DTPA-BMA)(H(2)O)] and [Gd(HP-DO3A)(H(2)O)]. DFT calculations performed on the [Gd(H(2)O)(8)](3+) model system show that both hybrid-GGA functionals (BH&HLYP, B3PW91 and PBE1PBE) and the hybrid meta-GGA functional TPSSh provide (17)O HFCCs in close agreement with the experimental data. The use of all-electron relativistic approaches based on the DKH2 approximation and the use of relativistic effective core potentials (RECP) provide results of essentially the same quality. The accurate calculation of HFCCs on the [Gd(DOTA)(H(2)O)](-), [Gd(DTPA)(H(2)O)](2-), [Gd(DTPA-BMA)(H(2)O)] and [Gd(HP-DO3A)(H(2)O)] complexes requires an adequate description of solvent effects. This was achieved by using a mixed cluster/continuum approach that includes explicitly two second-sphere water molecules. The calculated isotropic (17)O HFCCs (A(iso)) fall within the range 0.40-0.56 MHz, and show deviations from the corresponding experimental values typically lower than 0.05 MHz. The A(iso) values are significantly affected by the distance between the oxygen atom of the coordinated water molecule and the Gd(III) ion, as well as by the orientation of the water molecule plane with respect to the Gd-O vector. (1)H HFCCs of coordinated water molecules and (17)O HFCCs of second-sphere water molecules take values close to zero. PMID:22927182

  20. Standoff Spectroscopy of Surface Adsorbed Chemicals

    SciTech Connect

    Van Neste, Charles W; Senesac, Larry R; Thundat, Thomas George

    2009-01-01

    Despite its immediate applications, selective detection of trace quantities of surface adsorbed chemicals, such as explosives, without physically collecting the sample molecules is a challenging task. Standoff spectroscopic techniques offer an ideal method of detecting chemicals without using a sample collection step. Though standoff spectroscopic techniques are capable of providing high selectivity, their demonstrated sensitivities are poor. Here we describe standoff detection of trace quantities of surface adsorbed chemicals using two quantum cascade lasers operated simultaneously, with tunable wavelength windows that match with absorption peaks of the analytes. This standoff method is a variation of photoacoustic spectroscopy, where scattered light from the sample surface is used for exciting acoustic resonance of the detector. We demonstrate a sensitivity of 100 ng/cm{sup 2} and a standoff detection distance of 20 m for surface adsorbed analytes such as explosives and tributyl phosphate.

  1. Physisorption of DNA molecules on chemically modified single-walled carbon nanotubes with and without sonication.

    PubMed

    Umemura, Kazuo; Ishibashi, Yu; Oura, Shusuke

    2016-09-01

    We investigated the physisorption phenomenon of single-stranded DNA (ssDNA) molecules onto two types of commercially available chemically functionalized single-walled carbon nanotubes (SWNTs) by atomic force microscopy (AFM) and agarose gel electrophoresis. We found that DNA molecules can adsorb on the water-soluble SWNT surfaces without sonication, although sonication treatment has been used for hybridization of DNA and SWNTs in many previous studies. Using our method, damage of DNA molecules by sonication can be avoided. On the other hand, the amount of DNA molecules adsorbed on SWNT surfaces increased when the samples were sonicated. This fact suggests that the sonication is effective not only at debundling of SWNTs, but also at assisting DNA adsorption. Furthermore, DNA adsorption was affected by the types of functionalized SWNTs. In the case of SWNTs functionalized with polyethylene glycol (PEG-SWNT), physisorption of ssDNA molecules was confirmed only by agarose-gel electrophoresis. In contrast, amino-terminated SWNTs (NH2-SWNTs) showed a change in the height distribution profile based on AFM observations. These results suggest that DNA molecules tended to adsorb to NH2-SWNT surfaces, although DNA molecules can also adsorb on PEG-SWNT surfaces. Our results revealed fundamental information for developing nanobiodevices using hybrids of DNA and SWNTs. PMID:26846296

  2. Black Molecular Adsorber Coatings for Spaceflight Applications

    NASA Technical Reports Server (NTRS)

    Abraham, Nithin Susan; Hasegawa, Mark Makoto; Straka, Sharon A.

    2014-01-01

    The molecular adsorber coating is a new technology that was developed to mitigate the risk of on-orbit molecular contamination on spaceflight missions. The application of this coating would be ideal near highly sensitive, interior surfaces and instruments that are negatively impacted by outgassed molecules from materials, such as plastics, adhesives, lubricants, epoxies, and other similar compounds. This current, sprayable paint technology is comprised of inorganic white materials made from highly porous zeolite. In addition to good adhesion performance, thermal stability, and adsorptive capability, the molecular adsorber coating offers favorable thermal control characteristics. However, low reflectivity properties, which are typically offered by black thermal control coatings, are desired for some spaceflight applications. For example, black coatings are used on interior surfaces, in particular, on instrument baffles for optical stray light control. Similarly, they are also used within light paths between optical systems, such as telescopes, to absorb light. Recent efforts have been made to transform the white molecular adsorber coating into a black coating with similar adsorptive properties. This result is achieved by optimizing the current formulation with black pigments, while still maintaining its adsorption capability for outgassing control. Different binder to pigment ratios, coating thicknesses, and spray application techniques were explored to develop a black version of the molecular adsorber coating. During the development process, coating performance and adsorption characteristics were studied. The preliminary work performed on black molecular adsorber coatings thus far is very promising. Continued development and testing is necessary for its use on future contamination sensitive spaceflight missions.

  3. Photochemistry of Nitrate Adsorbed on Mineral Dust

    NASA Astrophysics Data System (ADS)

    Gankanda, A.; Grassian, V. H.

    2013-12-01

    Mineral dust particles in the atmosphere are often associated with adsorbed nitrate from heterogeneous reactions with nitrogen oxides including HNO3 and NO2. Although nitrate ion is a well-studied chromophore in natural waters, the photochemistry of adsorbed nitrate on mineral dust particles is yet to be fully explored. In this study, wavelength dependence of the photochemistry of adsorbed nitrate on different model components of mineral dust aerosol has been investigated using transmission FTIR spectroscopy. Al2O3, TiO2 and NaY zeolite were used as model systems to represent non-photoactive oxides, photoactive semiconductor oxides and porous materials respectively, present in mineral dust aerosol. In this study, adsorbed nitrate is irradiated with 254 nm, 310 nm and 350 nm narrow band light. In the irradiation with narrow band light, NO2 is the only detectable gas-phase product formed from nitrate adsorbed on Al2O3 and TiO2. The NO2 yield is highest at 310 nm for both Al2O3 and TiO2. Unlike Al2O3 and TiO2, in zeolite, adsorbed nitrate photolysis to nitrite is observed only at 310 nm during narrow band irradiation. Moreover gas phase products were not detected during nitrate photolysis in zeolite at all three wavelengths. The significance of these differences as related to nitrate photochemistry on different mineral dust components will be highlighted.

  4. Two-dimensional description of surface-bounded exospheres with application to the migration of water molecules on the Moon

    NASA Astrophysics Data System (ADS)

    Schorghofer, Norbert

    2015-05-01

    On the Moon, water molecules and other volatiles are thought to migrate along ballistic trajectories. Here, this migration process is described in terms of a two-dimensional partial differential equation for the surface concentration, based on the probability distribution of thermal ballistic hops. A random-walk model, a corresponding diffusion coefficient, and a continuum description are provided. In other words, a surface-bounded exosphere is described purely in terms of quantities on the surface, which can provide computational and conceptual advantages. The derived continuum equation can be used to calculate the steady-state distribution of the surface concentration of volatile water molecules. An analytic steady-state solution is obtained for an equatorial ring; it reveals the width and mass of the pileup of molecules at the morning terminator.

  5. Single-molecule analysis of ultradilute solutions with guided streams of 1-{mu}m water droplets

    SciTech Connect

    Kung, C.; Barnes, M.D.; Lermer, N.; Whitten, W.B.; Ramsey, J.M.

    1999-03-01

    We describe instrumentation for real-time detection of single-molecule fluorescence in guided streams of 1-{mu}m (nominal) water droplets. In this technique, target molecules were confined to droplets whose volumes were comparable with illumination volumes in diffraction-limited fluorescence microscopy and guided to the waist of a cw probe laser with an electrostatic potential. Concentration detection limits for Rhodamine 6G in water were determined to be {approximately}1 fM, roughly 3 orders of magnitude lower than corresponding limits determined recently with diffraction-limited microscopy techniques for a chemical separation of similar dyes. In addition to its utility as a vehicle for probing single molecules, instrumentation for producing and focusing stable streams of 1{endash}2-{mu}m-diameter droplets may have other important analytical applications as well. {copyright} 1999 Optical Society of America

  6. Cardioprotective actions by a water-soluble carbon monoxide-releasing molecule.

    PubMed

    Clark, James E; Naughton, Patrick; Shurey, Sandra; Green, Colin J; Johnson, Tony R; Mann, Brian E; Foresti, Roberta; Motterlini, Roberto

    2003-07-25

    Carbon monoxide, which is generated in mammals during the degradation of heme by the enzyme heme oxygenase, is an important signaling mediator. Transition metal carbonyls have been recently shown to function as carbon monoxide-releasing molecules (CO-RMs) and to elicit distinct pharmacological activities in biological systems. In the present study, we report that a water-soluble form of CO-RM promotes cardioprotection in vitro and in vivo. Specifically, we found that tricarbonylchloro(glycinato)ruthenium(II) (CORM-3) is stable in water at acidic pH but in physiological buffers rapidly liberates CO in solution. Cardiac cells pretreated with CORM-3 (10 to 50 micromol/L) become more resistant to the damage caused by hypoxia-reoxygenation and oxidative stress. In addition, isolated hearts reperfused in the presence of CORM-3 (10 micromol/L) after an ischemic event displayed a significant recovery in myocardial performance and a marked and significant reduction in cardiac muscle damage and infarct size. The cardioprotective effects mediated by CORM-3 in cardiac cells and isolated hearts were totally abolished by 5-hydroxydecanoic acid, an inhibitor of mitochondrial ATP-dependent potassium channels. Predictably, cardioprotection is lost when CORM-3 is replaced by an inactive form (iCORM-3) that is incapable of liberating CO. Using a model of cardiac allograft rejection in mice, we also found that treatment of recipients with CORM-3 but not iCORM-3 considerably prolonged the survival rate of transplanted hearts. These data corroborate the notion that transition metal carbonyls could be used as carriers to deliver CO and highlight the bioactivity and potential therapeutic features of CO-RMs in the mitigation of cardiac dysfunction. The full text of this article is available online at http://www.circresaha.org. PMID:12842916

  7. Computing the energy of a water molecule using multideterminants: A simple, efficient algorithm

    SciTech Connect

    Clark, Bryan K.; Morales, Miguel A; Mcminis, Jeremy; Kim, Jeongnim; Scuseria, Gustavo E

    2011-01-01

    Quantum Monte Carlo (QMC) methods such as variational Monte Carlo and fixed node diffusion Monte Carlo depend heavily on the quality of the trial wave function. Although Slater-Jastrow wave functions are the most commonly used variational ansatz in electronic structure, more sophisticated wave functions are critical to ascertaining new physics. One such wave function is the multi-Slater- Jastrow wave function which consists of a Jastrow function multiplied by the sum of Slater deter- minants. In this paper we describe a method for working with these wave functions in QMC codes that is easy to implement, efficient both in computational speed as well as memory, and easily par- allelized. The computational cost scales quadratically with particle number making this scaling no worse than the single determinant case and linear with the total number of excitations. Addition- ally, we implement this method and use it to compute the ground state energy of a water molecule. 2011 American Institute of Physics. [doi:10.1063/1.3665391

  8. Association of Catechin Molecules in Water: Quantitative Binding Study and Complex Structure Analysis.

    PubMed

    Ujihara, Tomomi; Hayashi, Nobuyuki

    2016-01-22

    Associations between catechin molecules were investigated by (1)H NMR titration experiments. Eight green tea catechins formed self-assembled dimers in water, and gallate-type catechins had a greater tendency to self-associate than non-gallate-type catechins. All eight catechins also associated as 1:1 heterodimer complexes. Investigation of complex formation of epigallocatechin-3-O-gallate (EGCg) and epigallocatechin (EGC) with the other catechins showed that the affinity between EGCg and 2,3-trans-gallate-type catechins was remarkably high, and the binding affinity of EGCg for ECg was also rather strong. In contrast, the non-gallate-type catechin EGC exhibited generally low binding affinity for other catechins. Structural analyses of the complexes by ROESY experiments and density functional theory calculations demonstrated that the higher binding abilities of gallate-type catechins are due to providing multiple intermolecular interactions that remain effective in an aqueous environment, such as aromatic/aromatic or CH/π interactions. PMID:26720794

  9. Computer simulations of adsorbed liquid crystal films

    NASA Astrophysics Data System (ADS)

    Wall, Greg D.; Cleaver, Douglas J.

    2003-01-01

    The structures adopted by adsorbed thin films of Gay-Berne particles in the presence of a coexisting vapour phase are investigated by molecular dynamics simulation. The films are adsorbed at a flat substrate which favours planar anchoring, whereas the nematic-vapour interface favours normal alignment. On cooling, a system with a high molecule-substrate interaction strength exhibits substrate-induced planar orientational ordering and considerable stratification is observed in the density profiles. In contrast, a system with weak molecule-substrate coupling adopts a director orientation orthogonal to the substrate plane, owing to the increased influence of the nematic-vapour interface. There are significant differences between the structures adopted at the two interfaces, in contrast with the predictions of density functional treatments of such systems.

  10. Water adsorption on the LaMnO3 surface

    NASA Astrophysics Data System (ADS)

    Billman, Chris R.; Wang, Yan; Cheng, Hai-Ping

    2016-02-01

    Studying the adsorption of water on the metallic LaMnO3 surface can provide insight into this complicated surface-adsorbate interaction. Using density functional theory, we investigated the adsorption of a water monomer, dimer, trimer, and a monolayer on the surface. The electronic structure of ground state configurations is explored using analysis of density of states, charge density, and crystal orbital overlap populations. We found that the interaction between the surface and water molecules is stronger than hydrogen bonding between molecules, which facilitates wetting of the surface. Adsorbed water molecules form very strong hydrogen bonds, with substantially shifted OH stretch modes. For the monolayer of adsorbed water, a hint of a bilayer is observed with a height separation of only 0.2 A˚. However, simulated scanning tunneling microscopy images and vibrational spectra suggest a significant difference between the two layers due to intermolecular bonding and interaction with the substrate.

  11. Water Adsorption on the LaMnO3 Surface

    NASA Astrophysics Data System (ADS)

    Billman, Chris; Wang, Yan; Cheng, Hai-Ping

    Studying the adsorption of water on the metallic LaMnO3 surface can provide insight into this complicated surface-adsorbate interaction. Using density functional theory, we investigated the adsorption of a water monomer, dimer, trimer and a monolayer on the surface. The electronic structure of ground state configurations is explored using analysis of density of states, charge density, and crystal orbital overlap populations. We found that the interaction between the surface and water molecules is stronger than hydrogen bonding between molecules, which facilitates wetting of the surface. Adsorbed water molecules form very strong hydrogen bonds, with substantially shifted OH stretch modes. For the monolayer of adsorbed water, a hint of a bilayer is observed with a height separation of only 0.2 Å. However, simulated scanning tunneling microscopy (STM) images and vibrational spectra suggest a significant difference between the two layers due to intermolecular bonding and interaction with the substrate.

  12. About Some Of The Properties Of A Guest Molecule Confined In A Water Network, In Order To Form A Clathrate

    NASA Astrophysics Data System (ADS)

    Pérez, G. Bravo; Cruz-Torres, A.; Romero-Martínez, A.

    2008-03-01

    At conditions of high pressure and or low temperature, like a sea bottom from even 1 Km deep, hydrates formation may take place. Its presence is facilitated at the water/oil interface inside conducting oil pipelines. Once formed, the hydrates nucleate further to agglomerations, sticking to the inner surface of the tube. This represents a big problem to flow assurance. We present results contributing to a better understanding of the interaction of a guest molecule with a water cage confining it, that give rise to a hydrate formation. The hydrate structure, its formation energy, and the role that the H bond and its cooperative effect in the water network play in the electrostatic dipole moment of the hydrate, are presented. Molecular calculations using the HF/6-311g(d, p), B3LYP/6-311g(d, p), and B3LYP/6-311++g(d,p) methods, have been applied to compare three different hydrates, each one confining one, two CH4 molecules, and a CO2 molecule, requiring respectively n = 14, 35, and 15 water molecules for the confinement.

  13. Application of novel, low-cost, laterite-based adsorbent for removal of lead from water: Equilibrium, kinetic and thermodynamic studies.

    PubMed

    Chatterjee, Somak; De, Sirshendu

    2016-01-01

    Contamination of groundwater by carcinogenic heavy metal, e.g., lead is an important issue and possibility of using a natural rock, laterite, is explored in this work to mitigate this problem. Treated laterite (TL- prepared using hydrochloric acid and sodium hydroxide) was successfully utilized for this purpose. The adsorbent was characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray (EDX), and Fourier Transform Infrared Spectroscopy (FTIR) to highlight its physical and chemical properties. Optimized equilibrium conditions were 1 g L(-1) adsorbent concentration, 0.26 mm size and a pH of 7 ± 0.2. Monolayer adsorption capacity of lead on treated laterite was 15 mg/g, 14.5 and 13 mg g(-1) at temperatures of 303 K, 313 K and 323 K, respectively. The adsorption was exothermic and physical in nature. At 303 K, value of effective diffusivity of (De) and mass transfer co-efficient (Kf) of lead onto TL were 6.5 × 10(-10) m(2)/s and 3.3 × 10(-4) m/s, respectively (solved from shrinking core model of adsorption kinetics). Magnesium and sulphate show highest interference effect on the adsorption of lead by TL. Efficacy of the adsorbent has been verified using real-life contaminated groundwater. Thus, this work demonstrates performance of a cost-effective media for lead removal. PMID:26646980

  14. Bovine serum albumin-Cu(II) hybrid nanoflowers: An effective adsorbent for solid phase extraction and slurry sampling flame atomic absorption spectrometric analysis of cadmium and lead in water, hair, food and cigarette samples.

    PubMed

    Yilmaz, Erkan; Ocsoy, Ismail; Ozdemir, Nalan; Soylak, Mustafa

    2016-02-01

    Herein, the synthesis of bovine serum albumin-Cu(II) hybrid nanoflowers (BSA-NFs) through the building blocks of bovine serum albumin (BSA) and copper(II) ions in phosphate buffered saline (PBS) and their use as adsorbent for cadmium and lead ions are reported. The BSA-NFs, for the first time, were efficiently utilized as novel adsorbent for solid phase extraction (SPE) of cadmium and lead ions in water, food, cigarette and hair samples. The method is based on the separation and pre-concentration of Cd(II) and Pb(II) by BSA-NFs prior to determination by slurry analysis via flame atomic absorption spectrometry (FAAS). The analytes were adsorbed on BSA-NFs under the vortex mixing and then the ion-loaded slurry was separated and directly introduced into the flame AAS nebulizer by using a hand-made micro sample introduction system to eliminate a number of drawbacks. The effects of analytical key parameters, such as pH, amount of BSA-NFs, vortexing time, sample volume, and matrix effect of foreign ions on adsorbing of Cd(II) and Pb(II) were systematically investigated and optimized. The limits of detection (LODs) for Cd(II) and Pb(II) were calculated as 0.37 μg L(-)(1) and 8.8 μg L(-)(1), respectively. The relative standard deviation percentages (RSDs) (N = 5) for Cd(II) and Pb(II) were 7.2%, and 5.0%, respectively. The accuracy of the developed procedure was validated by the analysis of certified reference materials (TMDA-53.3 Fortified Water, TMDA-70 Fortified Water, SPS-WW2 Waste Water, NCSDC-73349 Bush Branches and Leaves) and by addition/recovery analysis. The quantitative recoveries were obtained for the analysis of certified reference materials and addition/recovery tests. The method was successfully applied to the analysis of cadmium and lead in water, food, cigarette and hair samples. PMID:26772130

  15. Adsorbent and adsorbent bed for materials capture and separation processes

    SciTech Connect

    Liu, Wei

    2011-01-25

    A method device and material for performing adsorption wherein a fluid mixture is passed through a channel in a structured adsorbent bed having a solid adsorbent comprised of adsorbent particles having a general diameter less than 100 um, loaded in a porous support matrix defining at least one straight flow channel. The adsorbent bed is configured to allow passage of a fluid through said channel and diffusion of a target material into said adsorbent under a pressure gradient driving force. The targeted molecular species in the fluid mixture diffuses across the porous support retaining layer, contacts the adsorbent, and adsorbs on the adsorbent, while the remaining species in the fluid mixture flows out of the channel.

  16. Superparamagnetic core-shells anchored onto graphene oxide grafted with phenylethyl amine as a nano-adsorbent for extraction and enrichment of organophosphorus pesticides from fruit, vegetable and water samples.

    PubMed

    Mahpishanian, Shokouh; Sereshti, Hassan; Baghdadi, Majid

    2015-08-01

    A novel adsorbent composed of silica coated magnetic microparticles (Fe3O4@SiO2) and graphene oxide (GO) functionalized with phenylethyl amine (PEA) was synthesized and characterized using Fourier transform-infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), vibrating sample magnetometry (VSM), and CHN elemental analysis techniques. The adsorbent (Fe3O4@SiO2@GO-PEA) was then used in a magnetic solid phase extraction (MSPE) of six organophosphorous pesticides (OPPs) including methyl parathion, fenitrothion, methidathion, ethion, methyl azinphos and coumaphos prior to gas chromatography-nitrogen phosphorus detection (GC-NPD). The fabricated adsorbent combines the advantages of superior adsorption capability of modified GO and magnetic separability of magnetite microparticles to provide high adsorption capacity, and easy isolation from sample solutions. The main experimental parameters affecting the extraction recovery of OPPs including extraction time, pH, adsorbent dosage, salt concentration, and desorption conditions were investigated and optimized. Under the optimal conditions, linear responses were obtained in the concentration range of 0.06-200μgL(-1) with the determination coefficients (R(2)) between 0.9945 and 0.9996. The limits of detection were from 0.02 to 0.1μgL(-1) and the intraday and inter-day relative standard deviations (RSDs) were less than 4.8 and 6.4%, respectively. The method was successfully applied for determination of the OPPs in apple, grape, pear, bell pepper, celery and water samples. The obtained recoveries were in the range of 90.4-108.0% (RSDs=1.9-6.6%, n=3) for fruits and vegetables, and 94.6-104.2% (RSDs=2.0-4.8%, n=3) for water samples. The excellent extraction performance of the adsorbent can be attributed to its structure characteristics where the phenyl rings of PEA grafted on the GO nanosheets are accessible to interact effectively with OPPs via delocalized π-electron system. PMID:26129984

  17. Differential flexibility of the secondary structures of lysozyme and the structure and ordering of surrounding water molecules

    NASA Astrophysics Data System (ADS)

    Sinha, Sudipta Kumar; Bandyopadhyay, Sanjoy

    2011-03-01

    We have performed an atomistic molecular dynamics simulation of an aqueous solution of hen egg-white lysozyme at room temperature with explicit water molecules. Several analyses have been carried out to explore the differential flexibility of the secondary structural segments of the protein and the structure and ordering of water around them. It is found that the overall flexibility of the protein molecule is primarily controlled by few large-amplitude bistable motions exhibited by two coils; one connecting two α-helical segments in domain-1 and the other connecting a 310 helix and a β-sheet in domain-2 of the protein. The heterogeneous structuring of water around the segments of the protein has been found to depend on the degree of exposure of the segments to water. The ordering of water molecules around the protein segments and their tagged potential energies have been found to be anticorrelated with each other. Some of these findings can be verified by suitable experimental studies.

  18. Label-Free Fluctuation Spectroscopy Based on Coherent Anti-Stokes Raman Scattering from Bulk Water Molecules.

    PubMed

    Rabasovic, M D; Sisamakis, E; Wennmalm, S; Widengren, J

    2016-04-01

    Nanoparticles (NPs) and molecules can be analyzed by inverse fluorescence correlation spectroscopy (iFCS) as they pass through an open detection volume, displacing fractions of the fluorescence-emitting solution in which they are dissolved. iFCS does not require the NPs or molecules to be labeled. However, fluorophores in μm-mm concentrations are needed for the solution signal. Here, we instead use coherent anti-Stokes Raman scattering (CARS) from plain water molecules as the signal from the solution. By this fully label-free approach, termed inverse CARS-based correlation spectroscopy (iCARS-CS), NPs that are a few tenths of nm in diameter and at pM concentrations can be analyzed, and their absolute volumes/concentrations can be determined. Likewise, lipid vesicles can be analyzed as they diffuse/flow through the detection volume by using CARS fluctuations from the surrounding water molecules. iCARS-CS could likely offer a broadly applicable, label-free characterization technique of, for example, NPs, small lipid exosomes, or microparticles in biomolecular diagnostics and screening, and can also utilize CARS signals from biologically relevant media other than