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Sample records for adsorbed surfactant molecules

  1. Interactions of organic contaminants with mineral-adsorbed surfactants.

    PubMed

    Zhu, Lizhong; Chen, Baoliang; Tao, Shu; Chiou, Cary T

    2003-09-01

    Sorption of organic contaminants (phenol, p-nitrophenol, and naphthalene) to natural solids (soils and bentonite) with and without myristylpyridinium bromide (MPB) cationic surfactant was studied to provide novel insightto interactions of contaminants with the mineral-adsorbed surfactant. Contaminant sorption coefficients with mineral-adsorbed surfactants, Kss, show a strong dependence on surfactant loading in the solid. At low surfactant levels, the Kss values increased with increasing sorbed surfactant mass, reached a maximum, and then decreased with increasing surfactant loading. The Kss values for contaminants were always higher than respective partition coefficients with surfactant micelles (Kmc) and natural organic matter (Koc). At examined MPB concentrations in water the three organic contaminants showed little solubility enhancement by MPB. At low sorbed-surfactant levels, the resulting mineral-adsorbed surfactant via the cation-exchange process appears to form a thin organic film, which effectively "adsorbs" the contaminants, resulting in very high Kss values. At high surfactant levels, the sorbed surfactant on minerals appears to form a bulklike medium that behaves essentially as a partition phase (rather than an adsorptive surface), with the resulting Kss being significantly decreased and less dependent on the MPB loading. The results provide a reference to the use of surfactants for remediation of contaminated soils/sediments or groundwater in engineered surfactant-enhanced washing.

  2. Interactions of organic contaminants with mineral-adsorbed surfactants

    USGS Publications Warehouse

    Zhu, L.; Chen, B.; Tao, S.; Chiou, C.T.

    2003-01-01

    Sorption of organic contaminants (phenol, p-nitrophenol, and naphthalene) to natural solids (soils and bentonite) with and without myristylpyridinium bromide (MPB) cationic surfactant was studied to provide novel insight to interactions of contaminants with the mineral-adsorbed surfactant. Contaminant sorption coefficients with mineral-adsorbed surfactants, Kss, show a strong dependence on surfactant loading in the solid. At low surfactant levels, the Kss values increased with increasing sorbed surfactant mass, reached a maximum, and then decreased with increasing surfactant loading. The Kss values for contaminants were always higher than respective partition coefficients with surfactant micelles (Kmc) and natural organic matter (Koc). At examined MPB concentrations in water the three organic contaminants showed little solubility enhancement by MPB. At low sorbed-surfactant levels, the resulting mineral-adsorbed surfactant via the cation-exchange process appears to form a thin organic film, which effectively "adsorbs" the contaminants, resulting in very high Kss values. At high surfactant levels, the sorbed surfactant on minerals appears to form a bulklike medium that behaves essentially as a partition phase (rather than an adsorptive surface), with the resulting Kss being significantly decreased and less dependent on the MPB loading. The results provide a reference to the use of surfactants for remediation of contaminated soils/sediments or groundwater in engineered surfactant-enhanced washing.

  3. 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.

  4. 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.

  5. Miscibility of Hydrocarbon and Fluorocarbon Surfactants in Adsorbed Film and Micelle.

    PubMed

    Villeneuve, Masumi; Nomura, Teruko; Matsuki, Hitoshi; Kaneshina, Shoji; Aratono, Makoto

    2001-02-01

    We investigated the miscibility of nonionic hydrocarbon and fluorocarbon surfactants in the adsorbed film and the micelle by surface tension measurements of the aqueous solution. The combination of tetraethyleneglycol monodecyl ether (C10E4) and tetraethyleneglycol mono-1,1,7-trihydrododecafluoroheptyl ether (FC7E4) was chosen because they have the same hydrophilic groups and about the same surface activity. The extent of nonideal mixing was estimated quantitatively in terms of the excess Gibbs energy in the adsorbed film g(H,E) and that in the micelle g(M,E). The excess area per adsorbed molecule, A(H,E), was also evaluated and discussed. The ionic hydrocarbon and fluorocarbon mixed surfactant systems, lithium dodecyl sulfate (LiDS)/lithium perfluorooctane sulfonate (LiFOS) and lithium tetradecyl sulfate (LiTS)/LiFOS systems are also investigated from the standpoint of excess Gibbs energy and excess area. It is also clearly shown that the regular solution approach does not fit in the systems that contain ionic species. Copyright 2001 Academic Press.

  6. Imaging the wave functions of adsorbed molecules.

    PubMed

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

    2014-01-14

    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.

  7. Selection and evaluation of adsorbents for the removal of anionic surfactants from laundry rinsing water.

    PubMed

    Schouten, Natasja; van der Ham, Louis G J; Euverink, Gert-Jan W; de Haan, André B

    2007-10-01

    Low-cost adsorbents were tested to remove anionic surfactants from laundry rinsing water to allow re-use of water. Adsorbents were selected corresponding to the different surfactant adsorption mechanisms. Equilibrium adsorption studies of linear alkyl benzene sulfonate (LAS) show that ionic interaction results in a high maximum adsorption capacity on positively charged adsorbents of 0.6-1.7 gLAS/g. Non-ionic interactions, such as hydrophobic interactions of LAS with non-ionic resins or activated carbons, result in a lower adsorption capacity of 0.02-0.6 gLAS/g. Negatively charged materials, such as cation exchange resins or bentonite clay, have negligible adsorption capacities for LAS. Similar results are obtained for alpha olefin sulfonate (AOS). Cost comparison of different adsorbents shows that an inorganic anion exchange material (layered double hydroxide) and activated carbons are the most cost-effective materials in terms of the amount of surfactant adsorbed per dollar worth of adsorbent.

  8. Enhanced CO2 adsorptive performance of PEI/SBA-15 adsorbent using phosphate ester based surfactants as additives.

    PubMed

    Cheng, Dandan; Liu, Yue; Wang, Haiqiang; Weng, Xiaole; Wu, Zhongbiao

    2015-12-01

    In this study, a series of polyetherimide/SBA-15: 2-D hexagonal P6mm, Santa Barbara USA (PEI/SBA-15) adsorbents modified by phosphoric ester based surfactants (including tri(2-ethylhexyl) phosphate (TEP), bis(2-ethylhexyl) phosphate (BEP) and trimethyl phosphonoacetate (TMPA)) were prepared for CO2 adsorption. Experimental results indicated that the addition of TEP and BEP had positive effects on CO2 adsorption capacity over PEI/SBA-15. In particular, the CO2 adsorption amount could be improved by around 20% for 45PEI-5TEP/SBA-15 compared to the additive-free adsorbent. This could be attributed to the decrease of CO2 diffusion resistance in the PEI bulk network due to the interactions between TEP and loaded PEI molecules, which was further confirmed by adsorption kinetics results. In addition, it was also found that the cyclic performance of the TEP-modified adsorbent was better than the surfactant-free one. This could be due to two main reasons, based on the results of in situ DRIFT and TG-DSC tests. First and more importantly, adsorbed CO2 species could be desorbed more rapidly over TEP-modified adsorbent during the thermal desorption process. Furthermore, the enhanced thermal stability after TEP addition ensured lower degradation of amine groups during adsorption/desorption cycles.

  9. Fabrication of novel microstructures based on orientation-dependent adsorption of surfactant molecules in a TMAH solution

    NASA Astrophysics Data System (ADS)

    Pal, Prem; Sato, K.; Gosalvez, M. A.; Tang, B.; Hida, H.; Shikida, M.

    2011-01-01

    In this work, the orientation-dependent adsorption of surfactant molecules on the silicon surface during etching in surfactant-added tetramethylammonium hydroxide (TMAH) is investigated. Triton X-100 (C14H22O(C2H4O)n, n = 9-10) and 25 wt% TMAH are used as surfactant and main etchant, respectively. The crystallographic planes affected by the surfactant molecules are determined by analyzing the etching behavior of different mask patterns on Si{1 0 0} wafers and silicon hemispheres in pure and surfactant-added TMAH. Taken together, the shapes of the etched profiles and the analysis of the hemispherical etch rates confirm that thick and dense adsorbed surfactant layers are typically formed on both the exact and vicinal Si{1 1 0} surfaces. In addition, the results indicate that the adsorbed surfactant layer behaves as a permeable mask, partially slowing down the etch rate of the affected surface orientation/s and thus enforcing their appearance on the etching front. The peculiar etching properties of surfactant-added and surfactant-free TMAH are then utilized for the fabrication of advanced micromechanical structures with new shapes on Si{1 0 0} wafers and polydimethylsiloxane based on complex Si{1 0 0} molds.

  10. Sacrificial adsorbate for surfactants utilized in chemical floods of enhanced oil recovery operations

    DOEpatents

    Johnson, J.S. Jr.; Westmoreland, C.G.

    1980-08-20

    The present invention is directed to a sacrificial or competitive adsorbate for surfactants contained in chemical flooding emulsions for enhanced oil recovery operations. The adsorbate to be utilized in the method of the present invention is a caustic effluent from the bleach stage or the weak black liquor from the digesters and pulp washers of the kraft pulping process. This effluent or weak black liquor is injected into an oil-bearing subterranean earth formation prior to or concurrent with the chemical flood emulsion and is adsorbed on the active mineral surfaces of the formation matrix so as to effectively reduce adsorption of surfactant in the chemical flood. Alternatively, the effluent or liquor can be injected into the subterranean earth formation subsequent to a chemical flood to displace the surfactant from the mineral surfaces for the recovery thereof.

  11. Sacrificial adsorbate for surfactants utilized in chemical floods of enhanced oil recovery operations

    DOEpatents

    Johnson, Jr., James S.; Westmoreland, Clyde G.

    1982-01-01

    The present invention is directed to a sacrificial or competitive adsorbate for surfactants contained in chemical flooding emulsions for enhanced oil recovery operations. The adsorbate to be utilized in the method of the present invention is a caustic effluent from the bleach stage or the weak black liquor from the digesters and pulp washers of the kraft pulping process. This effluent or weak black liquor is injected into an oil-bearing subterranean earth formation prior to or concurrent with the chemical flood emulsion and is adsorbed on the active mineral surfaces of the formation matrix so as to effectively reduce adsorption of surfactant in the chemical flood. Alternatively, the effluent or liquor can be injected into the subterranean earth formation subsequent to a chemical flood to displace the surfactant from the mineral surfaces for the recovery thereof.

  12. Chiral switching by spontaneous conformational change in adsorbed organic molecules.

    PubMed

    Weigelt, Sigrid; Busse, Carsten; Petersen, Lars; Rauls, Eva; Hammer, Bjørk; Gothelf, Kurt V; Besenbacher, Flemming; Linderoth, Trolle R

    2006-02-01

    Self-assembly of adsorbed organic molecules is a promising route towards functional surface nano-architectures, and our understanding of associated dynamic processes has been significantly advanced by several scanning tunnelling microscopy (STM) investigations. Intramolecular degrees of freedom are widely accepted to influence ordering of complex adsorbates, but although molecular conformation has been identified and even manipulated by STM, the detailed dynamics of spontaneous conformational change in adsorbed molecules has hitherto not been addressed. Molecular surface structures often show important stereochemical effects as, aside from truly chiral molecules, a large class of so-called prochiral molecules become chiral once confined on a surface with an associated loss of symmetry. Here, we investigate a model system in which adsorbed molecules surprisingly switch between enantiomeric forms as they undergo thermally induced conformational changes. The associated kinetic parameters are quantified from time-resolved STM data whereas mechanistic insight is obtained from theoretical modelling. The chiral switching is demonstrated to enable an efficient channel towards formation of extended homochiral surface domains. Our results imply that appropriate prochiral molecules may be induced (for example, by seeding) to assume only one enantiomeric form in surface assemblies, which is of relevance for chiral amplification and asymmetric heterogenous catalysis.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

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

    2016-12-05

    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.

  15. Forces from periodic charging of adsorbed molecules

    NASA Astrophysics Data System (ADS)

    Kocić, N.; Decurtins, S.; Liu, S.-X.; Repp, J.

    2017-03-01

    In a recent publication [Kocić et al., Nano Lett. 15, 4406 (2015)], it was shown that gating of molecular levels in the field of an oscillating tip of an atomic force microscope can enable a periodic charging of individual molecules synchronized to the tip's oscillatory motion. Here we discuss further implications of such measurements, namely, how the force difference associated with the single-electron charging manifests itself in atomic force microscopy images and how it can be detected as a function of tip-sample distance. Moreover, we discuss how the critical voltage for the charge-state transition depends on distance and how that relates to the local contact potential difference. These measurements allow also for an estimate of the absolute tip-sample distance.

  16. Surfactant molecules to promote removal of cadmium ions from solid surfaces: A complementary experimental-simulational study

    NASA Astrophysics Data System (ADS)

    Pacheco-Blas, María del Alba; Dominguez, Hector; Rivera, Margarita

    2017-03-01

    Sodium dodecyl sulfate (SDS) was used to interact with metallic ions to demonstrate the efficiency of surfactant molecules to promote desorption of metals from solid surfaces. Scanning electron and atomic force microscopy were employed to study desorption of cadmium ions from highly oriented pyrolytic graphite (HOPG), as a model to understand the removal of metallic ions from carbon substrates. Contact angle measurements were carried out to investigate the wettability behavior of the surfactant on the contaminated surface. The desorption mechanism from a microscopic level was studied by using molecular dynamic simulations. Density profiles and pair correlation functions were analyzed to determine the cadmium-surface interaction in the presence of surfactant molecules to improve ion detachment. Simulations showed that surfactant molecules moved in between the adsorbed cadmium ions and the graphite surface pushing up the metallic groups to improve metal desorption. The experimental and theoretical results agree with atomic absorption spectroscopy results.

  17. Controlling the magnetism of adsorbed metal-organic molecules.

    PubMed

    Kuch, Wolfgang; Bernien, Matthias

    2017-01-18

    Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule's magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

  18. Controlling the magnetism of adsorbed metal-organic molecules

    NASA Astrophysics Data System (ADS)

    Kuch, Wolfgang; Bernien, Matthias

    2017-01-01

    Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule’s magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    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 O2 molecules adsorbed on the surface. Using density functional theory calculations, we find that an O2 molecule adsorbed on an α-alumina surface has a magnetic moment of ˜1.8 μB . 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 X Y spins on a square lattice find 1 /f magnetization noise, consistent with flux noise in Al SQUIDs.

  20. Resonant vibrational excitation of adsorbed molecules by electron impact

    NASA Astrophysics Data System (ADS)

    Djamo, V.; Teillet-Billy, D.; Gauyacq, J. P.

    1993-11-01

    The vibrational excitation of N2 molecules adsorbed on a silver surface by low energy electron impact is studied within the newly developed coupled angular mode method. The process involves the formation of a transient negative molecular ion. The results account well for the observations of Demuth and co-workers. They also reveal that most of the vibrational excitation corresponds to electrons scattered into the metal and thus unobservable in a scattering experiment.

  1. Interaction of sodium polyacrylate adsorbed on TiO2 with cationic and anionic surfactants.

    PubMed

    Li, Haiyan; Tripp, Carl P

    2004-11-23

    Attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) was used to identify the structures formed during the adsorption of sodium polyacrylate (NaPA) on charged TiO2 particles and to determine the subsequent interaction of the adsorbed polymer structure with cationic and anionic surfactants. The nature of the polymer structure was deduced from the adsorbed amount in tandem with the information obtained from monitoring the change in the relative intensity of the COO- and COOH infrared bands. In particular, it is found that the relative number of COO- and COOH groups on the polymer backbone for the adsorbed state differs from that of the same polymer in solution. This difference is due to a shift in the population of COO-/COOH groups on the polymer backbone that arises when the COO- groups bind to positively charged sites on the surface. A change in the number COO-/COOH groups on the polymer is thus related to a change in the bound fraction of polymer. It is shown that the initial NaPA approaching the bare surface adopts a flat conformation with high bound fraction. Once the bare sites on the surface are covered, the accommodation of additional polymer on the surface requires the existing adsorbed layer to adopt a conformation with a lower bound fraction. When the adsorbed NaPA is probed with a solution containing the anionic surfactant sodium dodecyl sulfate (SDS), the SDS competes for surface sites and displaces some of the bound NaPA segments from the surface, giving rise to an polymer layer adsorbed with an even lower bound fraction. In contrast, addition of a solution containing the cationic surfactant cetyltrimethylammonium bromide (CTAB) results in the binding of the surfactant directly to the free COO- sites on the adsorbed polymer backbone. Confirmation of a direct interaction of the CTAB headgroup with the free COO- groups of the polymer is provided by intensity changes in the headgroup IR bands of the CTAB.

  2. 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.

  3. Multiple species of noninteracting molecules adsorbed on a Bethe lattice.

    PubMed

    Cohen, Michael; Harris, A B

    2008-10-01

    A simple method, previously used to calculate the equilibrium concentration of dimers adsorbed on a Bethe lattice as a function of the dimer activity, is generalized to solve the problem of a Bethe lattice in contact with a reservoir containing a mixture of molecules. The molecules may have arbitrary sizes and shapes consistent with the geometry of the lattice and the molecules do not interact with one another except for the hard-core restriction that two molecules cannot touch the same site. We obtain a set of simultaneous nonlinear equations, one equation for each species of molecule, which determines the equilibrium concentration of each type of molecule as a function of the (arbitrary) activities of the various species. Surprisingly, regardless of the number of species, the equilibrium concentrations are given explicitly in terms of the solution of a single equation in one unknown which can be solved numerically, if need be. Some numerical examples show that increasing the activity of one species need not necessarily decrease the equilibrium concentration of all other species. We also calculate the adsorption isotherm of an "annealed" Bethe lattice consisting of two types of sites which differently influence the activity of an adsorbed molecule. We prove that if the reservoir contains a finite number of molecular species, regions of two different polymer densities cannot simultaneously exist on the lattice. The widely used Guggenheim theory of mixtures, which can also be construed as a theory of adsorption, assumes for simplicity that the molecules in the mixture are composed of elementary units, which occupy sites of a lattice of coordination number q . Guggenheim's analysis relies on approximate combinatorial formulas which become exact on a Bethe lattice of the same coordination number, as we show in an appendix. Our analysis involves no combinatorics and relies only on recognizing the statistical independence of certain quantities. Despite the nominal

  4. Detection of individual gas molecules adsorbed on graphene.

    PubMed

    Schedin, F; Geim, A K; Morozov, S V; Hill, E W; Blake, P; Katsnelson, M I; Novoselov, K S

    2007-09-01

    The ultimate aim of any detection method is to achieve such a level of sensitivity that individual quanta of a measured entity can be resolved. In the case of chemical sensors, the quantum is one atom or molecule. Such resolution has so far been beyond the reach of any detection technique, including solid-state gas sensors hailed for their exceptional sensitivity. The fundamental reason limiting the resolution of such sensors is fluctuations due to thermal motion of charges and defects, which lead to intrinsic noise exceeding the sought-after signal from individual molecules, usually by many orders of magnitude. Here, we show that micrometre-size sensors made from graphene are capable of detecting individual events when a gas molecule attaches to or detaches from graphene's surface. The adsorbed molecules change the local carrier concentration in graphene one by one electron, which leads to step-like changes in resistance. The achieved sensitivity is due to the fact that graphene is an exceptionally low-noise material electronically, which makes it a promising candidate not only for chemical detectors but also for other applications where local probes sensitive to external charge, magnetic field or mechanical strain are required.

  5. 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

  6. Coalescence behavior of oil droplets coated in irreversibly-adsorbed surfactant layers.

    PubMed

    Reichert, Matthew D; Walker, Lynn M

    2015-07-01

    Coalescence between oil caps with irreversibly adsorbed layers of nonionic surfactant is characterized in deionized water and electrolyte solution. The coalescence is characterized using a modified capillary tensiometer allowing for accurate measurement of the coalescence time. Results suggest two types of coalescence behavior, fast coalescence at low surface coverages that are independent of ionic strength and slow coalescence at high coverage. These slow coalescence events (orders of magnitude slower) are argued to be due to electric double layer forces or more complicated stabilization mechanisms arising from interfacial deformation and surface forces. A simple film drainage model is used in combination with measured values for interfacial properties to quantify the interaction potential between the two interfaces. Since this approach allows the two caps to have the same history, interfacial coverage and curvature, the results offer a tool to better understand a mechanism that is important to emulsion stability.

  7. Theory of surface light scattering from a fluid-fluid interface with adsorbed polymeric surfactants

    NASA Astrophysics Data System (ADS)

    Buzza, D. M. A.; Jones, J. L.; McLeish, T. C. B.; Richards, R. W.

    1998-09-01

    We present a microscopic theory for the interfacial rheology of a fluid-fluid interface with adsorbed surfactant and calculate the effect of this on surface light scattering from the interface. We model the head and tail groups of the surfactant as polymer chains, a description that becomes increasingly accurate for large molecular weight surfactants, i.e., polymeric surfactants. Assuming high surface concentrations so that we have a double-sided polymer brush monolayer, we derive microscopic scaling expressions for the surface viscoelastic constants using the Alexander-deGennes model. Our results for the surface elastic constants agree with those in the literature, while the results for the viscous constants are new. We find that four elastic constants, i.e., γ (surface tension), ɛ (dilational elasticity), κ (bending modulus), λ (coupling constant), and three viscous constants, i.e., ɛ',κ',λ' (the viscous counterparts of ɛ, κ, and λ, respectively) are required for a general description of interfacial viscoelasticity (neglecting in-plane shear). In contrast to current phenomenological models, we find (1) there is no viscous counterpart to γ, i.e., γ'≡0; (2) there are two additional complex surface constants (i.e., λ+iωλ' and κ+iωκ') due to the finite thickness of the monolayer. Excellent agreement is found comparing our microscopic theory with measurements on diblock copolymer monolayers. We further derive the dispersion relation governing surface hydrodynamic modes and the power spectrum for surface quasielastic light scattering (SQELS) for a general interface parameterized by all the surface viscoelastic constants. Limiting results are presented for (1) liquid-air interfaces; (2) liquid-liquid interfaces with ultralow γ. The significant contribution of κ in the latter case opens up the possibility for a direct measurement of κ using SQELS for polymeric surfactant monolayers. Finally, we show that the coupling constant λ can lead to

  8. Procedure for freeze-drying molecules adsorbed to mica flakes.

    PubMed

    Heuser, J E

    1983-09-05

    The quick-freeze, deep-etch, rotary-replication technique is useful for visualizing cells and cell fractions but does not work with suspensions of macromolecules. These inevitably clump or collapse during deep-etching, presumably due to surface tension forces that develop during their transfer from ice to vacuum. Previous protocols have attempted to overcome such forces by attaching macromolecules to freshly cleaved mica before drying and replication. I describe here an adaptation of this procedure to the deep-etch technique as otherwise practiced. My innovation is to mix the molecules with an aqueous suspension of tiny flakes of mica and then to quick-freeze and freeze-fracture the suspension exactly as if one were dealing with cells. The fracture inevitably strikes the surfaces of many mica flakes and thereby cleaves the adsorbed macromolecules cleanly enough to reveal interesting substructure within them. The subsequent step of deep-etching exposes large expanses of unfractured mica and thus reveals intact macromolecules. These macromolecules are not obscured by salt deposits, even if they were frozen in hypertonic solutions, apparently because the fracturing step removes nearly all of the overlying electrolyte. Moreover, these macromolecules are minimally freeze-dried (since exposure is sufficient after only 3 min of etching at -102 degrees C) so they retain their three-dimensional topology. I show that molluscan hemocyanin is a good internal standard for this new technique. It is available commercially in stable solutions, mixes well with all sizes of macromolecules, and consists of particles that display distinct five-start surface helices, which have been measured carefully in the past and which possess a known handedness, useful for determining the orientation of micrographs when examining the various helical patterns possessed by most types of extended macromolecules. The fractured hemocyanin particles also display characteristic internal structures, which

  9. Surfactant-modified alumina: an efficient adsorbent for malachite green removal from water environment.

    PubMed

    Das, Asit K; Saha, Sandip; Pal, Anjali; Maji, Sanjoy K

    2009-07-15

    Surface of alumina was modified with sodium dodecyl sulfate (SDS), an anionic surfactant. The surfactant-modified alumina (SMA) was characterized by FTIR and thermal analysis. The SMA was then used for the removal of malachite green (MG; Basic Green 4), a well-known toxic cationic dye from aqueous environment. The removal of MG takes place in the micellar structure formed on alumina surface, and the process is called adsolubilization. All the studies were carried out in batch mode. The kinetic studies showed that 1 h contact time was sufficient to attain equilibrium. SMA was very efficient to remove MG up to 99% under optimum conditions. The concentration range of MG was 20-100 mg/L. The isotherm studies showed that it follows Langmuir model better than the Freundlich model. The maximum adsorption capacity was 185 mg/g. The effects of various parameters such as pH, presence of interfering ions (Cl-, NO3-, H2PO4-, SO4(2-), Fe2+, Ca2+) and organics (pesticides such as 2,4-dichlorophenoxyacetic acid, atrazine, endosulfan, and humic acid) are evaluated. It was observed that H2PO4-, Fe2+, endosulfan, and humic acid have maximum interference. Desorption of MG from exhausted SMA using acetone, and its reuse was studied. The regenerated adsorbent shows approximately 80% efficiency on the removal of MG. The usability of SMA for the removal of MG from real wastewater was also examined. The kinetic equilibrium was attained within 1 h and the removal could be achieved up to approximately 95% at a dose of 20 g/L. The adsorption followed Freundlich isotherm model better than the Langmuir model.

  10. Molecule-specific interactions of diatomic adsorbates at metal-liquid interfaces

    PubMed Central

    Kraack, Jan Philip; Kaech, Andres; Hamm, Peter

    2017-01-01

    Ultrafast vibrational dynamics of small molecules on platinum (Pt) layers in water are investigated using 2D attenuated total reflectance IR spectroscopy. Isotope combinations of carbon monoxide and cyanide are used to elucidate inter-adsorbate and substrate-adsorbate interactions. Despite observed cross-peaks in the CO spectra, we conclude that the molecules are not vibrationally coupled. Rather, strong substrate-adsorbate interactions evoke rapid (∼2 ps) vibrational relaxation from the adsorbate into the Pt layer, leading to thermal cross-peaks. In the case of CN, vibrational relaxation is significantly slower (∼10 ps) and dominated by adsorbate-solvent interactions, while the coupling to the substrate is negligible.

  11. Around a camphoric-acid boat, is the surfactant adsorbed on to the interface or dissolved in the bulk?

    NASA Astrophysics Data System (ADS)

    Mandre, Shreyas; Akella, Sathish; Singh, Dhiraj; Singh, Ravi; Bandi, Mahesh

    2016-11-01

    A camphoric-acid boat (c-boat for short), a cylindrical gel tablet infused with camphoric acid, moves spontaneously when placed on an air-water interface. This system is a classic example of propulsion driven by Marangoni forces. Despite rich history on particles propelled by Marangoni forces, including contributions by figures such as Benjamin Franklin, Allesandro Volta, and Giovanni Venturi, the underlying fluid dynamics remains poorly understood. A key missing piece is the nature of the surfactant; in our case, the question is whether the camphoric acid is dissolved in the bulk or adsorbed on to the interface. We gain insight into this piece by holding the c-boat stationary and measuring the surrounding axisymmetric flow velocity to a precision needed to distinguish between the two possibilities. For soluble surfactants, it is known that the velocity field decays as r - 2 / 3, where r is the distance from the center of the c-boat. Whereas, for surfactant adsorbed on to the air-water interface, we derive that the surrounding velocity fields decays as r - 3 / 5. Based on our measurements we deduce that, even though soluble in water, the Marangoni flow results from a layer of camphoric acid adsorbed to the air-water interface.

  12. Surfactant-modified montmorillonite as a nanosized adsorbent for removal of an insecticide: kinetic and isotherm studies.

    PubMed

    Hassani, Aydin; Khataee, Alireza; Karaca, Semra; Shirzad-Siboni, Mehdi

    2015-01-01

    Surfactant-modified montmorillonites (MMT) were prepared using trimethyloctylammonium bromide (TMOAB) and employed as a nanosized adsorbent to remove diazinon from aqueous solutions. The prepared adsorbent was characterized using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX). The dependence of removal efficiency on initial diazinon concentration, amount of adsorbent, pH of the solution and ionic strength was investigated. The affinity sequence for ion adsorption on TMOAB/MMT was in the order: without anion> sodium carbonate> sodium bicarbonate> sodium sulphate> sodium chloride. The adsorption kinetic and isotherm were best fit by a pseudo-second-order kinetic and Langmuir isotherm models, respectively.

  13. Substrate-mediated interactions and intermolecular forces between molecules adsorbed on surfaces.

    PubMed

    Sykes, E Charles H; Han, Patrick; Kandel, S Alex; Kelly, Kevin F; McCarty, Gregory S; Weiss, Paul S

    2003-12-01

    Adsorbate interactions and reactions on metal surfaces have been investigated using scanning tunneling microscopy. The manners in which adsorbates perturb the surface electronic structure in their vicinity are discussed. The effects these perturbations have on other molecules are shown to be important in overlayer growth. Interactions of molecules with surface steps are addressed, and each molecule's electron affinity is shown to dictate its adsorption sites at step edges. Standing waves emanating from steps are demonstrated to effect transient molecular adsorption up to 40 A away from the step edge. Halobenzene derivatives are used to demonstrate how the surface is important in aligning reactive intermediates.

  14. 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.

  15. 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.

  16. Unconventional superconductivity induced in Nb films by adsorbed chiral molecules

    NASA Astrophysics Data System (ADS)

    Alpern, H.; Katzir, E.; Yochelis, S.; Katz, N.; Paltiel, Y.; Millo, O.

    2016-11-01

    Motivated by recent observations of chiral-induced magnetization and spin-selective transport we studied the effect of chiral molecules on conventional BCS superconductors. By applying scanning tunneling spectroscopy, we demonstrate that the singlet-pairing s-wave order parameter of Nb is significantly altered upon adsorption of chiral polyalanine alpha-helix molecules on its surface. The tunneling spectra exhibit zero-bias conductance peaks embedded inside gaps or gap-like features, suggesting the emergence of unconventional triplet-pairing components with either d-wave or p-wave symmetry at the Nb organic-molecules interface, as corroborated by simulations. These results may open a way for realizing simple superconducting spintronics devices.

  17. 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].

  18. Resonant electron scattering by molecules adsorbed on a surface: N2-Ag system

    NASA Astrophysics Data System (ADS)

    Teillet-Billy, D.; Djamo, V.; Gauyacq, J. P.

    1992-05-01

    A model study of resonant electron scattering by static molecules adsorbed on a metal surface is presented, using the recently developed coupled angular mode (CAM) method. It is applied to the case of N2 molecules adsorbed on an Ag surface. The N2-2πg resonance characteristics (energy position and width) are determined and shown to be modified by the presence of the surface in qualitative agreement with the experimental results of Demuth et al. [Phys. Rev. Lett. 47 (1981) 1166].

  19. 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.

  20. Surfactant modified coir pith, an agricultural solid waste as adsorbent for phosphate removal and fertilizer carrier to control phosphate release.

    PubMed

    Namasivayam, C; Kumar, M V Suresh

    2005-10-01

    The surface of coir pith, an agricultural solid waste was modified using a cationic surfactant, hexadecyltrimethylammonium bromide (HDTMA) and the modified coir pith was investigated to assess the capacity for the removal of phosphate from aqueous solution. Optimum pH for maximum phosphate adsorption was found to be 4.0. Langmuir and Freundlich isotherms were used to model the adsorption equilibrium data. Kinetic studies showed that the adsorption obeyed second order kinetics. Thermodynamic parameters were evaluated and the overall adsorption process was spontaneous and endothermic. Effect of coexisting anions has also been studied. The feasibility of using spent adsorbent as fertilizer carrier to control phosphate release was also investigated.

  1. Structure-property relationship of quinuclidinium surfactants--Towards multifunctional biologically active molecules.

    PubMed

    Skočibušić, Mirjana; Odžak, Renata; Štefanić, Zoran; Križić, Ivana; Krišto, Lucija; Jović, Ozren; Hrenar, Tomica; Primožič, Ines; Jurašin, Darija

    2016-04-01

    Motivated by diverse biological and pharmacological activity of quinuclidine and oxime compounds we have synthesized and characterized novel class of surfactants, 3-hydroxyimino quinuclidinium bromides with different alkyl chains lengths (CnQNOH; n=12, 14 and 16). The incorporation of non conventional hydroxyimino quinuclidinium headgroup and variation in alkyl chain length affects hydrophilic-hydrophobic balance of surfactant molecule and thereby physicochemical properties important for its application. Therefore, newly synthesized surfactants were characterized by the combination of different experimental techniques: X-ray analysis, potentiometry, electrical conductivity, surface tension and dynamic light scattering measurements, as well as antimicrobial susceptibility tests. Comprehensive investigation of CnQNOH surfactants enabled insight into structure-property relationship i.e., way in which the arrangement of surfactant molecules in the crystal phase correlates with their solution behavior and biologically activity. The synthesized CnQNOH surfactants exhibited high adsorption efficiency and relatively low critical micelle concentrations. In addition, all investigated compounds showed very potent and promising activity against Gram-positive and clinically relevant Gram-negative bacterial strains compared to conventional antimicrobial agents: tetracycline and gentamicin. The overall results indicate that bicyclic headgroup with oxime moiety, which affects both hydrophilicity and hydrophobicity of CnQNOH molecule in addition to enabling hydrogen bonding, has dominant effect on crystal packing and physicochemical properties. The unique structural features of cationic surfactants with hydroxyimino quinuclidine headgroup along with diverse biological activity have made them promising structures in novel drug discovery. Obtained fundamental understanding how combination of different functionalities in a single surfactant molecule affects its physicochemical

  2. A surfactant-based, regularly arrayed nanostructure gel matrix for migration of small molecules.

    PubMed

    Kato, Masaru; Suwanai, Yusuke; Shimojima, Atsushi; Santa, Tomofumi

    2012-11-01

    The preparation of nanometer-scale pores, or nanopores, has become easy because of the progress in nanotechnology. Surfactants are promising materials for the preparation of nanostructures containing nanopores, because surfactants form many different phase structures, including cubic, micellar, and lamellar structures. We prepared a gel matrix with a cubic structure from a commercially available surfactant, polyoxyethylene(50) lauryl ether (C12EO50, Adekatol LA-50). This gel matrix had regularly arrayed nanopores between the packed spherical micelles. We used the gel to separate biomolecules by means of slab gel electrophoresis. The gel was applicable to migration of amino acids and peptides; however, larger molecules, such as proteins and single-walled carbon nanotubes, did not migrate through the gel. We concluded that the pore size was too small for the penetration of large molecules, and that only small molecules could penetrate the gel matrix. The migration mechanism of small molecules was similar to that observed in conventional gel electrophoresis. We concluded that the gel matrix prepared from surfactant is a promising matrix for migration and purification of small molecules. We also expect that the gel can be used as a nanoscale filter to trap large molecules, allowing only small molecules to pass.

  3. Method for removing strongly adsorbed surfactants and capping agents from metal to facilitate their catalytic applications

    DOEpatents

    Adzic, Radoslav R.; Gong, Kuanping; Cai, Yun; Wong, Stanislaus; Koenigsmann, Christopher

    2016-11-08

    A method of synthesizing activated electrocatalyst, preferably having a morphology of a nanostructure, is disclosed. The method includes safely and efficiently removing surfactants and capping agents from the surface of the metal structures. With regard to metal nanoparticles, the method includes synthesis of nanoparticle(s) in polar or non-polar solution with surfactants or capping agents and subsequent activation by CO-adsorption-induced surfactant/capping agent desorption and electrochemical oxidation. The method produces activated macroparticle or nanoparticle electrocatalysts without damaging the surface of the electrocatalyst that includes breaking, increasing particle thickness or increasing the number of low coordination sites.

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

    NASA Astrophysics Data System (ADS)

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

    2011-07-01

    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.

  5. Adsorption and adsolubilization of polymerizable surfactants on aluminum oxide.

    PubMed

    Attaphong, Chodchanok; Asnachinda, Emma; Charoensaeng, Ampira; Sabatini, David A; Khaodhiar, Sutha

    2010-04-01

    Surfactant-based adsorption processes have been widely investigated for environmental applications. A major problem facing surfactant-modified adsorbents is surfactant loss from the adsorbent due to loss of monomers from solution and subsequent surfactant desorption. For this study, a bilayer of anionic polymerizable surfactant (Hitenol BC 05, Hitenol BC 10 and Hitenol BC 20) and non-polymerizable surfactant (Hitenol N 08) was adsorbed onto alumina. The results of adsorption studies showed that as the number of ethylene oxide (EO) groups of the surfactants increased, the area per molecule increased and the maximum adsorption decreased. The lowest maximum adsorption onto alumina was for Hitenol BC 20 (20 EO groups) corresponding to 0.08 mmol/g or 0.34 molecule/nm(2) while the highest level of adsorption was 0.30 mmol/g or 1.28 molecule/nm(2) for Hitenol BC 05 (5 EO groups). This variation in adsorption was attributed to the increased bulkiness of the head group with increasing number of EO groups. Relative to the adsolubilization capacity of organic solutes, ethylcyclohexane adsolubilizes more than styrene. Styrene and ethylcyclohexane adsolubilization were both independent of the number of EO groups of the surfactant. For surfactant desorption studies, the polymerization of polymerizable surfactants increased the stability of surfactants adsorbed onto the alumina surface and reduced surfactant desorption from the alumina surface. These results provide useful information on surfactant-based surface modification to enhance contaminant remediation and industrial applications.

  6. Spectroscopic observations of the displacement dynamics of physically adsorbed molecules-CO on C60

    NASA Astrophysics Data System (ADS)

    Yuan, Chunqing; Yates, John T.

    2016-10-01

    In this paper, we observed physically adsorbed CO molecules on C60 surface being displaced by impinging noble gas atoms (He, Ne, Ar, Kr), either through a dynamic displacement process or an exothermic replacement process, depending on their adsorption energies. This displacement mechanism could shift from one to the other depending on the surface coverage and temperature. Furthermore, rotational energy of the impinging molecules may also contribute to the dynamic displacement process by supplying additional energy.

  7. Vibrational excitation of adsorbed molecules by low-energy photon-emitted electrons: A dynamical model

    NASA Astrophysics Data System (ADS)

    González Ureña, A.; Telle, H. H.; Tornero, J.

    2013-01-01

    A simple, inelastic electron-scattering dynamical model is presented to account for vibrational excitation in molecular adsorbates. The basic two ingredients of the theoretical model are: (i) the conservation of the total angular momentum, and (ii) the requirement of a critical time to allow for the intra-molecular energy re-arrangement of the transient negative-ion complex. The model is applied to the vibrational excitation dynamics of molecules chemisorbed at sub-monolayer conditions on ordered metal surfaces. This was exemplified for Acrylonitrile adsorbed on Cu(1 0 0), whose vibrational excitation was studied via energy loss spectra of low-energy two-photon photoemission (2PPE) electrons, and for ammonia (NH3 and ND3) adsorbed on Cu(1 0 0), being probed in a STM experiment. Fits of the model to the data allowed for deducing the energy threshold of the vibrational excitation of the Cdbnd C and Ctbnd N bonds of the ACN adsorbate molecules, and the threshold for the symmetric ν1-stretch mode excitation of adsorbed NH3/ND3. Also, information about the temporal dynamics underlying the inelastic electron scattering was gained.

  8. Structure, Dynamics, and Thermodynamics of Small Molecules Adsorbed in Zeolite Micropores: Simulation and Statistical Mechanics.

    NASA Astrophysics Data System (ADS)

    van Tassel, Paul Robert

    1993-01-01

    This thesis describes a fully detailed molecular simulation and modeling effort aimed at understanding the fundamentals of adsorption and diffusion of small molecules in zeolite micropores. The primary emphasis is on determining the relationship between the structure and chemistry of the zeolite adsorbent and the structure, dynamics, and thermodynamics of the adsorbed phase. Further emphasis is on developing simple, predictive models of zeolite adsorption and diffusion. We begin by presenting a Monte Carlo simulation of single component adsorption of xenon, methane, and argon in zeolite NaA. The form of the adsorbate density distribution indicates the presence of discrete adsorption sites which arrange in polyhedra whose geometry depends on the number and position of zeolite framework ions. Isotherm plateaus are attributed to either (i) a low energy adsorbate configuration or (ii) the saturation of polyhedral sites. Viewing the adsorbed phase as an ordered arrangement differs from the conventional delocalized model, yet it helps explain certain experimental observations. Next, a study of binary mixtures of small molecules in zeolite NaA using the Monte Carlo method is presented. The mixing in the pore is determined to be highly nonideal by comparison to a simple pore volume filling model. Strong selectivity for a more polarizable molecule (xenon) is observed only at low pore loading. At higher pore loading, a smaller, less polarizable molecule (argon) adsorbs selectively at a significantly lower pressure than predicted by the model. This enhanced selectivity is due to the ability of the smaller molecule to pack more efficiently inside of the pore. Finally, we present two simple lattice models whose forms are arrived at following careful consideration of simulation results. The first describes the adsorption of small molecules in a zeolite. A polyhedral lattice is postulated whose neighboring sites interact energetically and entropically. The second model describes

  9. 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.

  10. 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.

  11. VERUCLAY – a new type of photo-adsorbent active in the visible light range: modification of montmorillonite surface with organic surfactant

    EPA Science Inventory

    Montmorillonite K10 was treated with VeruSOL-3, a biodegradable and food-grade surfactant mixture of coconut oil, castor oil and citrus extracts, to manufacture a benign catalytic adsorbent that is active in the visible light. Veruclay was characterized by SEM, XRD, TGA, UVDRS, a...

  12. Chemical effects on vibrational properties of adsorbed molecules on metal surfaces: Coverage dependence

    NASA Astrophysics Data System (ADS)

    Ueba, H.

    1987-10-01

    Vibrational properties of chemisorbed molecules on metal surfaces are studied with a focus on the coverage dependent chemical shift of the frequencies. Available experimental data of a CO adsorption on transition metal and noble metal surfaces are analyzed in the light of the coverage dependent back-donation into the 2 π* orbitals of chemisorbed CO molecules. The vibrational frequency ωCO of the intramolecular stretching mode exhibits a downward shift of varying magnitude, depending on the amount of back-donation into the 2 π* orbitals of the chemisorbed CO. On increasing the coverage θ, ωCO usually increases due to the dipole-dipole interaction. On Cu surfaces, however, the shifts are relatively small, or in some cases, negative. So far, this anomalous frequency shift with θ is understood as a result of competitive effect between the upward dipole Ωdip and the downward chemical shift Ωchem associated with back-donation. The purpose of this paper is to establish the possible origin of the downward frequency shift through the electronic properties of an incomplete monolayer of adsorbates. The adsorbate density of states ρa is calculated by means of the coherent potential approximation, in which the electron hopping between the adsorbates (band formation effect) and the depolarization effect due to the proximity of ionized adsorbed molecules are taken into account. The change of the occupied portion of ρa and ρa ( ɛF) at the Fermi level ɛF with increasing θ then manifests itself in the coverage dependent Ωchem not only due to the static back-donation, but also due to the dynamical charge fluctuation during vibrational excitation. It is found that in a weakly chemisorbed system, such as CO/Cu, the negative Ωchem amounts to Ωdip at low θ. Consequently the apparent total frequency shift remains almost constant. As the coverage increases, Ωchem becomes larger than Ωdip due to the band effect. It is also shown that the variation of the back

  13. Formation of Adsorbed Oxygen Radicals on Minerals at the Martian Surface and the Decomposition of Organic Molecules

    NASA Technical Reports Server (NTRS)

    Yen, A. S.; Kim, S. S.; Freeman, B. A.; Hecht, M. H.

    2000-01-01

    We present experimental evidence that superoxide ions form on mineral grains at the martian surface and show that these adsorbates can explain the unusual reactivity of the soil as well as the apparent absence of organic molecules.

  14. 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.

  15. The submitochondrial particle assay as a screening test for acute aquatic toxicity of surfactant molecules

    SciTech Connect

    Bookland, E.A.; Bettermann, A.D.

    1995-12-31

    Two complementary protocols of the submitochondrial particle assay (SMP) were evaluated as screening tools for predicting the acute aquatic toxicity of various classes and chain lengths of surfactant molecules. SMP contain the functionally intact mitochondrial enzyme systems responsible for electron transport and oxidative phosphorylation. Both the Electron Transfer Assay (ETR) and the Reverse Electron Transfer Assay (RET) have been shown in prior work to generally be sensitive to agents capable of membrane and protein interactions, both suspected mechanisms of action for surfactants. The toxicity of ten compounds; four anionic surfactants, C{sub 12} alkyl sulfate (C{sub 12}AS), C{sub 12} and C{sub 15} alkyl ethoxy sulfate (C{sub 12}E{sub 4}S, C{sub 15}E{sub 4}S), linear alkyl benzene sulfonate (C{sub 12.3}LAS); one nonionic surfactant, alkyl ethoxylate (C{sub 12}E{sub 3}); three cationic surfactants, C{sub 8}, C{sub 12}, and C{sub 16} alkyl trimethyl ammonium chloride (C{sub 8}TMAC, C{sub 12}TMAC, C{sub 16}TMAC); an alcohol (C{sub 12}OH); and an amine, alkyl dimethylamine (C{sub 12}DMA); was determined. In all cases, both the ETR and the RET gave results showing equal or greater sensitivity than previously reported acute fish and invertebrate LC{sub 50}`s. In addition, increasing toxicity with increasing alkyl chain length was observed. As a rapid screening tool, the SMP bioassay avoids exposure concerns such as degradation of test material, a common concern for acute in vivo toxicity testing with rapidly degradable materials. Results indicate that the SMP bioassay can be useful as a predictive screening tool for the aquatic toxicity of surfactants.

  16. 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.

  17. 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

  18. Magnetization switching in ferromagnets by adsorbed chiral molecules without current or external magnetic field

    PubMed Central

    Ben Dor, Oren; Yochelis, Shira; Radko, Anna; Vankayala, Kiran; Capua, Eyal; Capua, Amir; Yang, See-Hun; Baczewski, Lech Tomasz; Parkin, Stuart Stephen Papworth; Naaman, Ron; Paltiel, Yossi

    2017-01-01

    Ferromagnets are commonly magnetized by either external magnetic fields or spin polarized currents. The manipulation of magnetization by spin-current occurs through the spin-transfer-torque effect, which is applied, for example, in modern magnetoresistive random access memory. However, the current density required for the spin-transfer torque is of the order of 1 × 106 A·cm−2, or about 1 × 1025 electrons s−1 cm−2. This relatively high current density significantly affects the devices' structure and performance. Here we demonstrate magnetization switching of ferromagnetic thin layers that is induced solely by adsorption of chiral molecules. In this case, about 1013 electrons per cm2 are sufficient to induce magnetization reversal. The direction of the magnetization depends on the handedness of the adsorbed chiral molecules. Local magnetization switching is achieved by adsorbing a chiral self-assembled molecular monolayer on a gold-coated ferromagnetic layer with perpendicular magnetic anisotropy. These results present a simple low-power magnetization mechanism when operating at ambient conditions. PMID:28230054

  19. Magnetization switching in ferromagnets by adsorbed chiral molecules without current or external magnetic field.

    PubMed

    Ben Dor, Oren; Yochelis, Shira; Radko, Anna; Vankayala, Kiran; Capua, Eyal; Capua, Amir; Yang, See-Hun; Baczewski, Lech Tomasz; Parkin, Stuart Stephen Papworth; Naaman, Ron; Paltiel, Yossi

    2017-02-23

    Ferromagnets are commonly magnetized by either external magnetic fields or spin polarized currents. The manipulation of magnetization by spin-current occurs through the spin-transfer-torque effect, which is applied, for example, in modern magnetoresistive random access memory. However, the current density required for the spin-transfer torque is of the order of 1 × 10(6) A·cm(-2), or about 1 × 10(25) electrons s(-1) cm(-2). This relatively high current density significantly affects the devices' structure and performance. Here we demonstrate magnetization switching of ferromagnetic thin layers that is induced solely by adsorption of chiral molecules. In this case, about 10(13) electrons per cm(2) are sufficient to induce magnetization reversal. The direction of the magnetization depends on the handedness of the adsorbed chiral molecules. Local magnetization switching is achieved by adsorbing a chiral self-assembled molecular monolayer on a gold-coated ferromagnetic layer with perpendicular magnetic anisotropy. These results present a simple low-power magnetization mechanism when operating at ambient conditions.

  20. Induced IR overtone and fundamental bands of isotopic H 2 molecules adsorbed in NaCaA zeolites

    NASA Astrophysics Data System (ADS)

    Förster, H.; Frede, W.

    1984-05-01

    NIR spectroscopy has been successfully applied to surface chemical problems, using the FT transmission technique. Vibrational spectra of H 2 and D 2, adsorbed in NaA and NaCaA zeolites, have been recorded in the fundamental regions of both adsorbates and, for the first time, in the overtone region of D 2. Useful information on the properties of the adsorbed molecules can be derived from the overtone spectra of D 2 and the fine structure of the H 2 fundamental. It turns out that the properties of the D 2 molecules, e.g. dissociation energy and anharmonicity, are hardly affected by adsorption. The fine structure of the H 2 fundamental, however, indicates the rotation to be strongly hindered. The ortho-para splitting is decreased with respect to the free molecule value and approaches that for planarly rotating molecules. Due to this hindrance, the corresponding D 2 splitting is not resolved.

  1. Spins of adsorbed molecules investigated by the detection of Kondo resonance

    NASA Astrophysics Data System (ADS)

    Komeda, Tadahiro

    2014-12-01

    Surface magnetism has been one of the platforms to explore the magnetism in low dimensions. It is also a key component for the development of quantum information processes, which utilizes the spin degree of freedom. The Kondo resonance is a phenomenon that is caused by an interaction between an isolated spin and conduction electrons. First observed in the 1930s as an anomalous increase in the low-temperature resistance of metals embedded with magnetic atoms, the Kondo physics mainly studied the effects of bulk magnetic impurities in the resistivity. In the last 15 years it has undergone a revival by a scanning tunneling microscope (STM) which enables the measurement of the Kondo resonance at surfaces using an atomic scale point contact. The detection of the Kondo resonance can be a powerful tool to explore surface magnetism. In this article, I review recent studies of the surface spin of adsorbed molecules by the detection of the Kondo resonance. Researches on metal phthalocyanine (MPc) and porphyrin molecules will be examined. In addition, the Kondo resonance for double-decker lanthanoide Pc molecules will be discussed. Some of the double-decker Pc molecules show single-molecule magnet (SMM) behavior, which attracts attention as a material for electronic devices. For both classes, the ligand plays a crucial role in determining the parameters of the Kondo resonance, such as the Kondo temperature and the change of the shape from peak to Fano-dip. In addition, the spin in delocalized molecular orbital forms the Kondo resonance, which shows significant differences from the Kondo resonance formed by the metal spins. Since molecular orbital can be tuned in a flexible manner by the design of the molecule, the Kondo resonance formed by delocalized molecular orbital might expand the knowledge of this field.

  2. Hygroscopic Growth of Self-Assembled Layered Surfactant Molecules at the Interface between Air and Organic Salts

    SciTech Connect

    Shin, Yongsoon; Wang, Li Q.; Fryxell, Glen E.; Exarhos, Gregory J.; Lu, Yunfeng

    2003-12-15

    In this paper, we report a self-assembly of surfactant molecules at the interface of air/hygroscopic quaternary ammonium salts such as tetrabutylammonium acetate (TBAAc), tetrabutylammonium bromide (TBAB), and tetrabutylammonium nitrate (TBAN), where they show different hygroscopicity, TBAAc > TBAB TBAN. Homogeneously dissolved surfactants rearrange themselves when they contact air due to high moisture adsorption behavior of such organic salts. Highly ordered lamellar phases with different lattice spacings have been observed when surfactants with long alkyl chains were used. Alkylammonium halides form monolayers, while neutral alkylamines forms bilayers based upon basal spacings of their X-ray diffraction patterns. The change in basal spacings in lamellar patterns, the alkyl chain conformation of surfactants, and H-bonding property of neutral amine surfactants are discussed in detail.

  3. Density functional analysis of gaseous molecules adsorbed on metal ion/defective nano-sheet graphene

    NASA Astrophysics Data System (ADS)

    Deng, Jin-Pei; Chuang, Wen-Hua; Tai, Chin-Kuen; Kao, Hsien-Chang; Pan, Jiunn-Hung; Wang, Bo-Cheng

    2016-11-01

    Density functional theory was applied to calculate the adsorption property of metal/hexa-vacancy defective graphene (denoted as HDG-M, M: Fe2+, Co2+, Ni2+, Cu2+ and Zn2+) with O- and N-dopants. We investigate the adsorption properties of these complexes between gaseous molecules and HDG-M. Our results show that HDG-Cu has a high selectivity for O2, but HDG-Fe has a good ability to capture many gases such as CO, NO and O2. Our calculations could provide useful information for designing new graphene-based adsorbents to remove undesired gases, which may poison the metal catalysts in reaction processes.

  4. Transport and Stability of Biological Molecules in Surfactant-Alginate Composite Hydrogels

    PubMed Central

    Stoppel, Whitney L.; White, Joseph C.; Horava, Sarena D.; Bhatia, Surita R.; Roberts, Susan C.

    2013-01-01

    Obstructed transport of biological molecules can result in improper release of pharmaceuticals or biologics from biomedical devices. Recent studies have shown that nonionic surfactants, such as Pluronic® F68 (F68), positively alter biomaterial properties, such as mesh size and microcapsule diameter. To further understand the effect of F68 (incorporated at concentrations well above the critical micelle concentration (CMC)) in traditional biomaterials, the transport properties of BSA and riboflavin were investigated in F68-alginate composite hydrogels. Results indicate that small molecule transport (represented by riboflavin) was not significantly hindered by F68 in homogeneously crosslinked hydrogels (up to an 11% decrease in loading capacity and 14% increase in effective diffusion coefficient, Deff), while protein transport in homogeneously crosslinked hydrogels (represented by BSA) was significantly affected (up to a 43% decrease in loading capacity and 40% increase in Deff). For inhomogeneously crosslinked hydrogels (CaCl2 or BaCl2 gelation), the Deff increased up to 50% and 83% for small molecule and proteins, respectively. Variation in the alginate gelation method was shown to affect transport through measurable changes in swelling ratio (30% decrease) and observable changes in crosslinking structure as well as up to a 3.6 and 11.8-fold difference in Deff for riboflavin and BSA, respectively. The change in protein transport properties is a product of mesh size restrictions (10–25 nm estimated by mechanical properties) and BSA-F68 interaction (DLS). Taken as a whole, these results show that incorporation of a nonionic surfactant at concentrations above the CMC can affect device functionality by impeding the transport of large biological molecules. PMID:21798381

  5. Adsorption of polyoxyethylenic surfactants on quartz, kaolin, and dolomite: A correlation between surfactant structure and solid surface nature

    SciTech Connect

    Nevskaia, D.M.; Guerrero-Ruiz, A.; Lopez-Gonzalez, J.deD.

    1996-08-10

    Adsorption of a surfactant at a liquid-solid interface makes up the basis of many technological processes such as detergency, flotation, water treatment, and enhanced oil recovery. The influence of variables such as adsorption temperature, polar chain length, and nature of functional groups on the adsorption, from aqueous solutions, of various surfactants (TX-114, TX-100, TX-165, TX-305, NP1P4E, NP4P1E, NP4S, NP10S, and NP25S) has been investigated. Several nonporous solids, including various samples of quartz, kaolin, and dolomite, were studied. Conformational changes of adsorbed surfactant molecules on one quartz, when the oxyethylenic length of Tritons increases, have been detected. For all the other solid samples the surface is not completely covered by Tritons. On quartz, the surfactants are adsorbed by hydrogen bonds between the surfactant`s ether groups and the silanol groups of the solid surface. These hydroxyl groups must be free and sufficiently separated from other hydroxyls of the solid surface. When the number of propoxy groups increases (from NP1P4E to NP4P1E) the adsorbed amount of surfactant on the solid studied decreases. Anionic surfactants are adsorbed on quartz in lower amounts than the corresponding nonionic surfactants. However, the adsorbed amounts of Tritons and sulfated Tritons on kaolin are similar, probably due to the positive charges on the edges of this material.

  6. Biobased surfactant-like molecules from organic wastes: the effect of waste composition and composting process on surfactant properties and on the ability to solubilize Tetrachloroethene (PCE).

    PubMed

    Quadri, Giorgia; Chen, Xiaosong; Jawitz, James W; Tambone, Fulvia; Genevini, Pierluigi; Faoro, Franco; Adani, Fabrizio

    2008-04-01

    In this work, four surfactant-like humic acids (HAs) obtained from garden lignocellulose wastes and kitchen food wastes mixed with garden-lignocellulose wastes, both before and after composting, were tested for surfactant properties and the ability to solubilize tetrachloroethene (PCE). The waste-derived HAs showed good surfactant properties, lowering the water surface tension from 74 mN m(-1) to 45.4 +/- 4.4 mN m(-1), with a critical micelle concentration (CMC) of 1.54 +/- 1.68 g L(-1), which is lower than many synthetic ionic surfactants. CMC was affected by both waste origin and composting processes. The addition of food waste and composting reduced CMC by adding alkyl-C (measured by CP MAS 13C NMR) and N- and S-HA contents (amide molecules), so that a multistep regression was found [CMC = 24.6 - 0.189 alkyl C - 2.64 (N + S); R2 = 0.77, P < 0.10, n = 6]. The four HAs solubilized PCE at the rate of 0.18-0.47 g PCE/g aqueous biosurfactant. These results were much higher than those reported in the literature for a commercial HA (0.026 g/g), but they were in line with those measured in this work for nonionic surfactants such as Tween-80 (0.69 g/g) and Triton X-100 (1.08 g/g).

  7. 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

  8. Ro-vibrational Stark effect on H2 and D2 molecules adsorbed in NaA zeolite

    NASA Astrophysics Data System (ADS)

    Bras, N.

    1999-03-01

    In order to explain the induced infrared bands of H2 and D2 adsorbed in NaA zeolites the Stark effect on the ro-vibrational levels of these molecules is considered for electric fields created by various charge distributions. The shift and intensity of the induced ro-vibration transitions are calculated.

  9. Micro-differential thermal analysis detection of adsorbed explosive molecules using microfabricated bridges.

    PubMed

    Senesac, Larry R; Yi, Dechang; Greve, Anders; Hales, Jan H; Davis, Zachary J; Nicholson, Don M; Boisen, Anja; Thundat, Thomas

    2009-03-01

    Although micromechanical sensors enable chemical vapor sensing with unprecedented sensitivity using variations in mass and stress, obtaining chemical selectivity using the micromechanical response still remains as a crucial challenge. Chemoselectivity in vapor detection using immobilized selective layers that rely on weak chemical interactions provides only partial selectivity. Here we show that the very low thermal mass of micromechanical sensors can be used to produce unique responses that can be used for achieving chemical selectivity without losing sensitivity or reversibility. We demonstrate that this method is capable of differentiating explosive vapors from nonexplosives and is additionally capable of differentiating individual explosive vapors such as trinitrotoluene, pentaerythritol tetranitrate, and cyclotrimethylenetrinitromine. This method, based on a microfabricated bridge with a programmable heating rate, produces unique and reproducible thermal response patterns within 50 ms that are characteristic to classes of adsorbed explosive molecules. We demonstrate that this micro-differential thermal analysis technique can selectively detect explosives, providing a method for fast direct detection with a limit of detection of 600x10(-12) g.

  10. Micro differential thermal analysis detection of adsorbed explosive molecules using microfabricated bridges

    SciTech Connect

    Senesac, Larry R; Yi, Dechang; Greve, Anders; Hales, Jan; Davis, Zachary; Nicholson, Don M; Boisen, Anja; Thundat, Thomas George

    2009-01-01

    Although micromechanical sensors enable chemical vapor sensing with unprecedented sensitivity using variations in mass and stress, obtaining chemical selectivity using the micromechanical response still remains as a crucial challenge. Chemoselectivity in vapor detection using immobilized selective layers that rely on weak chemical interactions provides only partial selectivity. Here we show that the very low thermal mass of micromechanical sensors can be used to produce unique responses that can be used for achieving chemical selectivity without losing sensitivity or reversibility. We demonstrate that this method is capable of differentiating explosive vapors from nonexplosives and is additionally capable of differentiating individual explosive vapors such as trinitrotoluene, pentaerythritol tetranitrate, and cyclotrimethylenetrinitromine. This method, based on a microfabricated bridge with a programmable heating rate, produces unique and reproducible thermal response patterns within 50 ms that are characteristic to classes of adsorbed explosive molecules. We demonstrate that this micro-differential thermal analysis technique can selectively detect explosives, providing a method for fast direct detection with a limit of detection of 600 x 10{sup -12} g.

  11. Classical and quantum studies of the photodissociation of a HX (X=Cl,F) molecule adsorbed on ice.

    PubMed

    Woittequand, S; Duflot, D; Monnerville, M; Pouilly, B; Toubin, C; Briquez, S; Meyer, H-D

    2007-10-28

    The photodissociation dynamics of a HX (X = Cl,F) molecule adsorbed on a hexagonal ice surface at T = 0 K is studied using time-dependent quantum wave packets and quasiclassical trajectories. The relevant potential energy surfaces are calculated using high-level ab initio methods. We present here two dimensional calculations for the dynamics of the hydrogen photofragment for both HCl and HF molecules. The purpose of this paper is to compare the photodissociation dynamics of the two molecules which are adsorbed on the ice surface with different equilibrium geometries. The total photodissociation cross section and the angular distribution are calculated. The comparison with classical trajectory calculations provides evidence for typical quantum effects and reveals rainbow structures.

  12. Electric field effect observed on the infrared spectra of the N2O molecule adsorbed in NaA zeolite

    NASA Astrophysics Data System (ADS)

    Bras, N.; Cohen de Lara, E.

    1995-05-01

    The spectrum of the N2O molecule adsorbed in the cavity of NaA zeolite presents two main components for each of the stretching vibrational modes. It is assumed that they correspond to molecules parallel and antiparallel to the electric field of the inner surface of the zeolite cavity. In order to verify this assumption, the frequency shifts and the intensities of these components have been calculated for the two orientations of the molecule with respect to the field, by applying the model of Bishop for the vibrational Stark effect. These calculations require the knowledge of molecular quantities such as derivatives of permanent electric moments and polarizability.

  13. 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.

  14. 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.

  15. 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

  16. Impact of model perfume molecules on the self-assembly of anionic surfactant sodium dodecyl 6-benzene sulfonate.

    PubMed

    Bradbury, Robert; Penfold, Jeffrey; Thomas, Robert K; Tucker, Ian M; Petkov, Jordan T; Jones, Craig; Grillo, Isabelle

    2013-03-12

    The impact of two model perfumes with differing degrees of hydrophobicity/hydrophilicity, linalool (LL) and phenylethanol (PE), on the solution structure of anionic surfactant sodium dodecyl 6-benzene sulfonate, LAS-6, has been studied by small angle neutron scattering, SANS. For both types of perfume molecules, complex phase behavior is observed. The phase behavior depends upon the concentration, surfactant/perfume composition, and type of perfume. The more hydrophilic perfume PE promotes the formation of more highly curved structures. At relatively low surfactant concentrations, small globular micelles, L1, are formed. These become perfume droplets, L(sm), stabilized by the surfactant at much higher perfume solution compositions. At higher surfactant concentrations, the tendency of LAS-6 to form more planar structures is evident. The more hydrophobic linalool promotes the formation of more planar structures. Combined with the greater tendency of LAS-6 to form planar structures, this results in the planar structures dominating the phase behavior for the LAS-6/linalool mixtures. For the LAS-6/linalool mixture, the self-assembly is in the form of micelles only at the lowest surfactant and perfume concentrations. Over most of the concentration-composition space explored, the structures are predominantly lamellar, L(α), or vesicle, L(v), or in the form of a lamellar/micellar coexistence. At low and intermediate amounts of LL, a significantly different structure is observed, and the aggregates are in the form of small, relatively monodisperse vesicles (i.e., nanovesicles), L(sv).

  17. Selective binding of single-stranded DNA-binding proteins onto DNA molecules adsorbed on single-walled carbon nanotubes.

    PubMed

    Nii, Daisuke; Hayashida, Takuya; Yamaguchi, Yuuki; Ikawa, Shukuko; Shibata, Takehiko; Umemura, Kazuo

    2014-09-01

    Single-stranded DNA-binding (SSB) proteins were treated with hybrids of DNA and single-walled carbon nanotubes (SWNTs) to examine the biological function of the DNA molecules adsorbed on the SWNT surface. When single-stranded DNA (ssDNA) was used for the hybridization, significant binding of the SSB molecules to the ssDNA-SWNT hybrids was observed by using atomic force microscopy (AFM) and agarose gel electrophoresis. When double-stranded DNA (dsDNA) was used, the SSB molecules did not bind to the dsDNA-SWNT hybrids in most of the conditions that we evaluated. A specifically modified electrophoresis procedure was used to monitor the locations of the DNA, SSB, and SWNT molecules. Our results clearly showed that ssDNA/dsDNA molecules on the SWNT surfaces retained their single-stranded/double-stranded structures.

  18. Infrared-Laser Excitation of the Internal Vibrational Mode of a Diatomic Molecule Adsorbed on a Metal Surface.

    DTIC Science & Technology

    1986-11-01

    Excitation of the Internal Vibrational Mode of a Diatomic Molecule Adsorbed on a Metal Surface m by ’ Andre Peremans, Jacques Darville , Jean-Marie...Andre Peremans, Jacques Darville , Jean-Marie Gilles and Thomas F. George 13. TYPE OF REPORT 13b. TIME COVERED 14. DATE OF REPORT (Yr. Mo.. Dayl As...ON A METAL SURFACE h Andr& Peremans , Jacques Darville and Jean-Marie Gilles _ _ _ _ Laboratoire de Spectroscopie Mol6culaire de Surface Accesnion

  19. REUSABLE ADSORBENTS FOR DILUTE SOLUTIONS SEPARATION. 5: PHOTODEGRADATION OF ORGANIC COMPOUNDS ON SURFACTANT-MODIFIED TITANIA. (R828598C753)

    EPA Science Inventory

    A semiconductor titania (TiO2) surface was modified by surfactant adsorption to make it more hydrophobic and to increase the adsorption of hydrophobic organic compounds (HOCs) and their photodegradation rates under UV irradiation. Photocatalytic experiments using Ti...

  20. Phase Segregation and Dynamics in Strongly Interacting Small Molecule Additive - Block Copolymer Surfactant Complexes

    NASA Astrophysics Data System (ADS)

    Kothari, Rohit; Khalil, Ahmed; Henning Winter, H.; Watkins, James J.

    2012-02-01

    Rheology and Small Angle X-Ray Scattering (SAXS) were used to investigate order to disorder transitions (ODTs) and disorder to order transitions (DOTs) of poly(ethyleneoxide-b-propyleneoxide-b-ethyleneoxide) block copolymer surfactants mixed with hydrogen-bond-donating small molecule additives. A series of additives having a core benzene ring and systematic variation in the number of carboxylic or hydroxyl groups attached to the ring were of particular interest. Ordered cylindrical morphologies, confirmed using SAXS, were obtained only in a certain additive concentration region. ODTs were characterized by sudden changes in the linear viscoelastic properties in low frequency region upon increasing temperature. The locations of ODTs varied widely with hydrogen-bond-donating ability of the functional group and were found to be strongly dependent on the number of functional groups attached to the ring. For a given additive, the temperature at which ODT occur was strong function of the additive loading, whereas the linear viscoelastic properties of the ordered state were little changed upon varying additive concentration in ordered region. The location and dynamics of DOTs upon cooling were comparable to the ODTs upon heating. Studies using these model systems provide insight into the design of well-ordered hybrid materials.

  1. A discrete interaction model/quantum mechanical method for describing response properties of molecules adsorbed on metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Morton, Seth Michael; Jensen, Lasse

    2010-08-01

    A new polarizable quantum mechanics/molecular mechanics method for the calculation of response properties of molecules adsorbed on metal nanoparticles is presented. This method, which we denote the discrete interaction model/quantum mechanics (DIM/QM) method, represents the nanoparticle atomistically which enables the modeling of the influence of the local environment of a nanoparticle surface on the optical properties of a molecule. Using DIM/QM, we investigate the excitation energies of rhodamine-6G (R6G) and crystal violet (CV) adsorbed on silver and gold nanoparticles of different quasispherical shapes and sizes. The metal nanoparticle is characterized by its static total polarizability, a reasonable approximation for frequencies far from the plasmon resonance. We observe that for both R6G and CV, the presence of the nanoparticle shifts the strongest excitation to the red ˜40 nm and also increases the oscillator strength of that excitation. The shifts in excitation energies due to the nanoparticle surface are found to be comparable to those due to solvation. We find that these shifts decay quickly as the molecule is moved away from the surface. We also find that the wavelength shift is largest when the transition dipole moment is aligned with the edges of the nanoparticle surface where the electric field is expected to be the largest. These results show that the molecular excitations are sensitive to the local environment on the nanoparticle as well as the specific orientation of the molecule relative to the surface.

  2. Surfactant-enhanced cellulose nanocrystal Pickering emulsions.

    PubMed

    Hu, Zhen; Ballinger, Sarah; Pelton, Robert; Cranston, Emily D

    2015-02-01

    The effect of surfactants on the properties of Pickering emulsions stabilized by cellulose nanocrystals (CNCs) was investigated. Electrophoretic mobility, interfacial tension, confocal microscopy and three-phase contact angle measurements were used to elucidate the interactions between anionic CNCs and cationic alkyl ammonium surfactants didecyldimethylammonium bromide (DMAB) and cetyltrimethylammonium bromide (CTAB). Both surfactants were found to adsorb onto CNCs with concentration-dependent morphology. At low concentrations, individual surfactant molecules adsorbed with alkyl tails pointing outward leading to hydrophobic CNCs. At higher concentrations, above the surfactant's apparent critical micelle concentration, surfactant aggregate morphologies on CNCs were inferred and the hydrophobicity of CNCs decreased. DMAB, which has two alkyl tails, rendered the CNCs more hydrophobic than CTAB which has only a single alkyl tail, at all surfactant concentrations. The change in CNC wettability from surfactant adsorption was directly linked to emulsion properties; adding surfactant increased the emulsion stability, decreased the droplet size, and controlled the internal phase of CNC Pickering emulsions. More specifically, a double transitional phase inversion, from oil-in-water to water-in-oil and back to oil-in-water, was observed for emulsions with CNCs and increasing amounts of DMAB (the more hydrophobic surfactant). With CNCs and CTAB, no phase inversion was induced. This work represents the first report of CNC Pickering emulsions with surfactants as well as the first CNC Pickering emulsions that can be phase inverted. The ability to surface modify CNCs in situ and tailor emulsions by adding surfactants may extend the potential of CNCs to new liquid formulations and extruded/spray-dried materials.

  3. Entropy of adsorption of mixed surfactants from solutions onto the air/water interface

    USGS Publications Warehouse

    Chen, L.-W.; Chen, J.-H.; Zhou, N.-F.

    1995-01-01

    The partial molar entropy change for mixed surfactant molecules adsorbed from solution at the air/water interface has been investigated by surface thermodynamics based upon the experimental surface tension isotherms at various temperatures. Results for different surfactant mixtures of sodium dodecyl sulfate and sodium tetradecyl sulfate, decylpyridinium chloride and sodium alkylsulfonates have shown that the partial molar entropy changes for adsorption of the mixed surfactants were generally negative and decreased with increasing adsorption to a minimum near the maximum adsorption and then increased abruptly. The entropy decrease can be explained by the adsorption-orientation of surfactant molecules in the adsorbed monolayer and the abrupt entropy increase at the maximum adsorption is possible due to the strong repulsion between the adsorbed molecules.

  4. 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.

  5. Self-organization of surfactant molecules on solid surface: an STM study of sodium alkyl sulfonates [rapid communication

    NASA Astrophysics Data System (ADS)

    Yin, Xiu-Li; Wan, Li-Jun; Yang, Zheng-Yu; Yu, Jia-Yong

    2005-02-01

    Adsorption and self-organization of sodium alkyl sulfonates (STS and SHS) on HOPG have been studied by using in situ scanning tunneling microscopy (STM). Both SHS and STS molecules adsorb on HOPG surface and form long-range well-ordered monolayers. The molecular rows and the axes of alkyl chain of the molecules cross each other at angles of 60° and 90° in the STS and SHS layers, respectively. Molecular details such as sulfonate functional group (head) and alkyl chain are clearly imaged. The neighboring molecules in different rows form a "head to head" configuration. Structural models for the molecular arrangement of the two adlayers are proposed.

  6. Sensitivity of photoelectron diffraction to conformational changes of adsorbed molecules: Tetra-tert-butyl-azobenzene/Au(111)

    PubMed Central

    Schuler, A.; Greif, M.; Seitsonen, A. P.; Mette, G.; Castiglioni, L.; Osterwalder, J.; Hengsberger, M.

    2017-01-01

    Electron diffraction is a standard tool to investigate the atomic structure of surfaces, interfaces, and adsorbate systems. In particular, photoelectron diffraction is a promising candidate for real-time studies of structural dynamics combining the ultimate time resolution of optical pulses and the high scattering cross-sections for electrons. In view of future time-resolved experiments from molecular layers, we studied the sensitivity of photoelectron diffraction to conformational changes of only a small fraction of molecules in a monolayer adsorbed on a metallic substrate. 3,3′,5,5′-tetra-tert-butyl-azobenzene served as test case. This molecule can be switched between two isomers, trans and cis, by absorption of ultraviolet light. X-ray photoelectron diffraction patterns were recorded from tetra-tert-butyl-azobenzene/Au(111) in thermal equilibrium at room temperature and compared to patterns taken in the photostationary state obtained by exposing the surface to radiation from a high-intensity helium discharge lamp. Difference patterns were simulated by means of multiple-scattering calculations, which allowed us to determine the fraction of molecules that underwent isomerization. PMID:28217715

  7. Sensitivity of photoelectron diffraction to conformational changes of adsorbed molecules: Tetra-tert-butyl-azobenzene/Au(111).

    PubMed

    Schuler, A; Greif, M; Seitsonen, A P; Mette, G; Castiglioni, L; Osterwalder, J; Hengsberger, M

    2017-01-01

    Electron diffraction is a standard tool to investigate the atomic structure of surfaces, interfaces, and adsorbate systems. In particular, photoelectron diffraction is a promising candidate for real-time studies of structural dynamics combining the ultimate time resolution of optical pulses and the high scattering cross-sections for electrons. In view of future time-resolved experiments from molecular layers, we studied the sensitivity of photoelectron diffraction to conformational changes of only a small fraction of molecules in a monolayer adsorbed on a metallic substrate. 3,3',5,5'-tetra-tert-butyl-azobenzene served as test case. This molecule can be switched between two isomers, trans and cis, by absorption of ultraviolet light. X-ray photoelectron diffraction patterns were recorded from tetra-tert-butyl-azobenzene/Au(111) in thermal equilibrium at room temperature and compared to patterns taken in the photostationary state obtained by exposing the surface to radiation from a high-intensity helium discharge lamp. Difference patterns were simulated by means of multiple-scattering calculations, which allowed us to determine the fraction of molecules that underwent isomerization.

  8. Synthetic high-charge organomica: effect of the layer charge and alkyl chain length on the structure of the adsorbed surfactants.

    PubMed

    Pazos, M Carolina; Castro, Miguel A; Orta, M Mar; Pavón, Esperanza; Valencia Rios, Jesús S; Alba, María D

    2012-05-15

    A family of organomicas was synthesized using synthetic swelling micas with high layer charge (Na(n)Si(8-n)Al(n)Mg(6)F(4)O(20)·XH(2)O, where n = 2, 3, and 4) exchanged with dodecylammonium and octadecylammonium cations. The molecular arrangement of the surfactant was elucidated on the basis on XRD patterns and DTA. The ordering conformation of the surfactant molecules into the interlayer space of micas was investigated by (13)C, (27)Al, and (29)Si MAS NMR. The arrangement of alkylammonium ions in these high-charge synthetic micas depends on the combined effects of the layer charge of the mica and the chain length of the cation. In the organomicas with dodecylammonium, a transition from a parallel layer to a bilayer-paraffin arrangement is observed when the layer charge of the mica increases. However, when octadecylammonium is the interlayer cation, the molecular arrangement of the surfactant was found to follow the bilayer-paraffin model for all values of layer charge. The amount of ordered conformation all-trans is directly proportional of layer charge.

  9. Adsorption of cationic monomeric and gemini surfactants on montmorillonite and adsolubilization of vitamin E.

    PubMed

    Sakai, Kenichi; Nakajima, Erimi; Takamatsu, Yuichiro; Sharma, Suraj C; Torigoe, Kanjiro; Yoshimura, Tomokazu; Esumi, Kunio; Sakai, Hideki; Abe, Masahiko

    2008-01-01

    Adsorption of a cationic gemini surfactant (1,2-bis(dodecyldimethylammonio) ethane dibromide, 12-2-12) and the corresponding monomeric surfactant (dodecyltrimethylammonium bromide, DTAB) on montmorillonite has been characterized with a combination of adsorption isotherm, interlayer spacing and FT-IR spectroscopic data. Adsolubilization of vitamin E into the adsorbed surfactant layers has also been studied. The adsorption isotherm data reveal that the adsorption of the two surfactants is driven by the two factors: one is the cation exchange that occurs on the interlayer basal planes and the other is the hydrophobic interaction between hydrocarbon chains of the surfactants. Although the adsorbed amount measured in the saturation region (in mol g(-1)) is almost identical for the two surfactants, the conformation of the intercalated surfactant molecules differs significantly from each other. The adsorption of DTAB results in a lateral bilayer arrangement in the limited interlayer space, whereas 12-2-12 gives a normal bilayer arrangement in the expanded interlayer space. Adsolubilization of vitamin E takes place into the adsorbed surfactant layers, and interestingly, all the vitamin E molecules added in the montmorillonite suspensions are hybridized at lower surfactant concentrations due to the great specific surface area of the clay material. Since the maximum adsolubilization amount is usually obtained just below the critical micelle concentration, the gemini surfactant is deemed to be more efficient than the corresponding monomeric one to achieve the great adsolubilization amount.

  10. Sorption of organic molecules on surfaces of a microporous polymer adsorbent modified with different quantities of uracil

    NASA Astrophysics Data System (ADS)

    Gus'kov, V. Yu.; Ganieva, A. G.; Kudasheva, F. Kh.

    2016-11-01

    The sorption of organic molecules on the surfaces of a number of adsorbents based on a microporous copolymer of styrene and divinylbenzene modified with different quantities of uracil is studied by means of inverse gas chromatography at infinite dilution. Samples containing 10-6, 10-5, 10-4, 10-3, 10-2, and 0.5 × 10‒1 weight parts of uracil (the pC of uracil ranges from 1.3 to 6) are studied. The contributions from different intermolecular interactions to the Helmholtz energy of sorption are calculated via the linear free energy relationship. It is found that as the concentration of uracil on the surface of the polymer adsorbent grows, the contributions from different intermolecular interactions and the conventional polarity of the surface have a bend at pC = 3, due probably to the formation of a supramolecular structure of uracil. Based on the obtained results, it is concluded that the formation of the supramolecular structure of uracil on the surface of the polymer adsorbent starts when pC < 3.

  11. Hygroscopic Growth of Self-Assembled Layered Surfactant Molecules at the Interface between Air and Organic Salts

    SciTech Connect

    Shin, Yongsoon; Wang, Li Q.; Fryxell, Glen E.; Exarhos, Gregory J.

    2005-04-01

    We report here a self-assembly of surfactant molecules at the interface of air/hygroscopic quaternary ammonium salts, tetrabutylammonium acetate (TBAAc). Homogeneously dissolved surfactant molecules at 100 C self-assemble upon contacting air due to high moisture adsorption behavior of the organic salt when cooling down. Highly ordered lamellar phases with different lattice spacings have been observed when surfactants with various lengths of alkyl chains were used. CnTMAB/TBAAc systems showed all trans conformation of interior methylene carbons and interdigited bilayers with an average CH2 increment of 0.119nm, while CnNH2/TBAAc systems showed trans/gauche mixed conformations of interior methylene carbons and bilayers with an average CH2 increment of 0.247nm. CnNH2s in CnNH2/TBAAc formed bilayers through water-mediated intermolecular hydrogen bonds with a water layer thickness of 0.51-0.61nm. In CnTAB/TBAAc, as the head group of CnTAB is bigger, the interdigited bilayer thickness (d-spacing) is smaller because their bigger head groups accommodate enough space for alkyl tails to come in between them.

  12. Investigations on humic acid removal from water using surfactant-modified zeolite as adsorbent in a fixed-bed reactor

    NASA Astrophysics Data System (ADS)

    Elsheikh, Awad F.; Ahmad, Umi Kalthom; Ramli, Zainab

    2016-12-01

    Natural organic matter (NOM) is ubiquitous in aquatic environments and has recently become an issue of worldwide concern in drinking water treatment. The major component of NOM is humic acids (HA). In this study, a natural zeolite (mordenite) was modified employing hexadecyltrimethylammonium bromide (HDTMA) to enhance greater efficient sites for sorption of HA. The natural zeolite and surfactant-modified zeolite (SMZ) were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectrometer (FT-IR), N2 Adsorption-desorption isotherms and BET-specific surface area, thermographic analysis, derivative thermographic analysis (TGA-DTA) and Field emission scanning electron microscopy (FESEM). A fixed-bed reactor was used for the removal of HA and the effects of different experimental parameters such as HDTMA loading levels, HA solution flow rate, solution pH and eluent concentration were investigated. The results indicated that the SMZ bed with HDTMA loading of 75% of external cation exchange capacity (ECEC) at a flow rate of 2 BV/h and pH of 10 showed the greatest enhanced removal efficiency of HA while ethanol solutions (25%v/v) with feed flow rate of 2 BV/h were sufficient for complete regeneration of SMZ and desorption of HA. Measurements of surface area of SMZ indicated that a monolayer formation of the surfactant at those conditions allowed the optimum removal of HA.

  13. Microscopic resolution of the interplay of Kondo screening and superconducting pairing: Mn-phthalocyanine molecules adsorbed on superconducting Pb(111)

    NASA Astrophysics Data System (ADS)

    Bauer, Johannes; Pascual, Jose I.; Franke, Katharina J.

    2013-02-01

    Magnetic molecules adsorbed on a superconductor give rise to a local competition of Cooper pair and Kondo singlet formation inducing subgap bound states. For manganese-phthalocyanine molecules on a Pb(111) substrate, scanning tunneling spectroscopy resolves pairs of subgap bound states and two Kondo screening channels. We show in a combined approach of scaling and numerical renormalization group calculations that the intriguing relation between Kondo screening and superconducting pairing is solely determined by the hybridization strength with the substrate. We demonstrate that an effective one-channel Anderson impurity model with a sizable particle-hole asymmetry captures universal and nonuniversal observations in the system quantitatively. The model parameters and disentanglement of the two screening channels are elucidated by scaling arguments.

  14. Adsorption of micelle-forming surfactants from aqueous solutions on disperse titanium boride

    SciTech Connect

    Grodskii, A.S.; Komleva, E.A.; Frolov, Yu.G.

    1988-08-10

    Adsorption studies showed that nonionogenic and cationic surfactants are adsorbed on the surface of disperse titanium boride. Anionic surfactants are virtually not adsorbed due to the negative charge of the particles. It was found that in the region of low concentrations of surfactants in the solution, adsorption of Sintanols takes place in lyophobic regions and the surface of the particles becomes hydrophilic. The Sintamid molecules are adsorbed on the entire interface, including both hydrophobic and hydrophilic sections, with subsequent formation of bimolecular layers by adsorption on hydrophobic sections. Catamine-AB is adsorbed on hydrophilic sections of the surface also with the formation of bimolecular layers. Developed polymolecular layers up to 10-15 nm thick are formed on titanium boride particles from micellar solutions of nonionigenic and cationic surfactants.

  15. Control of the dipole layer of polar organic molecules adsorbed on metal surfaces via different charge-transfer channels

    NASA Astrophysics Data System (ADS)

    Lin, Meng-Kai; Nakayama, Yasuo; Zhuang, Ying-Jie; Su, Kai-Jun; Wang, Chin-Yung; Pi, Tun-Wen; Metz, Sebastian; Papadopoulos, Theodoros A.; Chiang, T.-C.; Ishii, Hisao; Tang, S.-J.

    2017-02-01

    Organic molecules with a permanent electric dipole moment have been widely used as a template for further growth of molecular layers in device structures. Key properties of the resulting organic films such as energy level alignment (ELA), work function, and injection/collection barrier are linked to the magnitude and direction of the dipole moment at the interface. Using angle-resolved photoemission spectroscopy (ARPES), we have systematically investigated the coverage-dependent work function and spectral line shapes of occupied molecular energy states (MESs) of chloroaluminium-phthalocyanine (ClAlPc) grown on Ag(111). We demonstrate that the dipole orientation of the first ClAlPc layer can be controlled by adjusting the deposition rate and postannealing conditions, and we find that the ELA at the interface differs by ˜0.4 eV between the Cl up and down configurations of the adsorbed ClAlPc molecules. These observations are rationalized by density functional theory (DFT) calculations based on a realistic model of the ClAlPc/Ag(111) interface, which reveal that the different orientations of the ClAlPc dipole layer lead to different charge-transfer channels between the adsorbed ClAlPc and Ag(111) substrate. Our findings provide a useful framework toward method development for ELA tuning.

  16. 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.

  17. In situ Fourier transform-infrared internal reflection spectroscopic analysis of hydrocarbon chain ordering of surfactants adsorbed at mineral oxide surfaces

    NASA Astrophysics Data System (ADS)

    Cross, William Murray

    The adsorption of surfactants at mineral oxide surfaces was investigated by in situ Fourier transform infrared internal reflection spectroscopy (FT-IR/IRS), and contact angle goniometry. FT-IR/IRS was used to determine both adsorption isotherms and the enthalpy of adsorption. Furthermore, the conformation and orientation of the hydrocarbon chain of SDS adsorbed at a sapphire internal reflection element (IRE) were determined. Contact angle goniometry was used to measure the effect of the surface phase of the surfactant on the hydrophobic character of sapphire surfaces in aqueous solutions. For SDS adsorbed by sapphire, in situ FT-IR/IRS experiments indicate that a surface phase transition occurs at an adsorption density of 2 to 3 x 10-10 mol/cm2 for both pD 2.9 and 6.9. This transition is characterized by a two to four wavenumber shift in the position of the asymmetric -CH2 stretching band. Based on solution spectroscopy studies, the surface phase was found to be similar to solution phase micelles and liquid crystals for adsorption densities less than the adsorption density of the surface phase transition. Whereas for adsorption densities in excess of the adsorption density of the surface phase transition, the surface phase resembled a solution phase coagel species. It was also found that the contact angle of an air bubble at the sapphire surface exhibited a sharp decrease at the adsorption density corresponding to the surface phase transition The effect of temperature on adsorption and phase behavior of SDS at the sapphire IRE surface was also determined. It was shown that a surface phase transition similar to that discussed occurred at approximately 298 K. The adsorption reaction was found to be exothermic, with a heat of adsorption of --1.3 kcal/mole for adsorption densities less than the adsorption density of the surface phase transition at 298 K and --4.1 kcal/mole for adsorption densities greater than the adsorption density of the surface phase transition

  18. Adsorbate-induced absorption redshift in an organic-inorganic cluster conjugate: Electronic effects of surfactants and organic adsorbates on the lowest excited states of a methanethiol-CdSe conjugate

    NASA Astrophysics Data System (ADS)

    Liu, Christopher; Chung, Sang-Yoon; Lee, Sungyul; Weiss, Shimon; Neuhauser, Daniel

    2009-11-01

    Bioconjugated CdSe quantum dots are promising reagents for bioimaging applications. Experimentally, the binding of a short peptide has been found to redshift the optical absorption of nanoclusters [J. Tsay et al., J. Phys. Chem. B 109, 1669 (2005)]. This study examines this issue by performing density functional theory (DFT) and time-dependent-DFT calculations to study the ground state and low-lying excited states of (CdSe)6[SCH3]-, a transition metal complex built by binding methanethiolate to a CdSe molecular cluster. Natural bond orbital results show that the redshift is caused by ligand-inorganic cluster orbital interaction. The highest occupied molecular orbital (HOMO) of (CdSe)6 is dominated by selenium 4p orbitals; in contrast, the HOMO of (CdSe)6[SCH3]- is dominated by sulfur 3p orbitals. This difference shows that [SCH3]- binding effectively introduces filled sulfur orbitals above the selenium 4p orbitals of (CdSe)6. The resulting smaller HOMO-LUMO gap of (CdSe)6[SCH3]- indeed leads to redshifts in its excitation energies compared to (CdSe)6. In contrast, binding of multiple NH3 destabilizes cadmium 5p orbitals, which contribute significantly to the lowest unoccupied molecular orbital (LUMO) of (CdSe)6, while leaving the selenium 4p orbitals near the HOMO relatively unaffected. This has the effect of widening the HOMO-LUMO gap of (CdSe)6ṡ6NH3 compared to (CdSe)6. As expected, the excitation energies of the passivated (CdSe)6ṡ6NH3 are also blueshifted compared to (CdSe)6. As far as NH3 is a faithful representation of a surfactant, the results clearly illustrate the differences between the electronic effects of an alkylthiolate versus those of surfactant molecules. Surface passivation of (CdSe)6[SCH3]- is then simulated by coating it with multiple NH3 molecules. The results suggest that the [SCH3]- adsorption induces a redshift in the excitation energies in a surfactant environment.

  19. Adsorbate-induced absorption redshift in an organic-inorganic cluster conjugate: Electronic effects of surfactants and organic adsorbates on the lowest excited states of a methanethiol-CdSe conjugate.

    PubMed

    Liu, Christopher; Chung, Sang-Yoon; Lee, Sungyul; Weiss, Shimon; Neuhauser, Daniel

    2009-11-07

    Bioconjugated CdSe quantum dots are promising reagents for bioimaging applications. Experimentally, the binding of a short peptide has been found to redshift the optical absorption of nanoclusters [J. Tsay et al., J. Phys. Chem. B 109, 1669 (2005)]. This study examines this issue by performing density functional theory (DFT) and time-dependent-DFT calculations to study the ground state and low-lying excited states of (CdSe)(6)[SCH(3)](-), a transition metal complex built by binding methanethiolate to a CdSe molecular cluster. Natural bond orbital results show that the redshift is caused by ligand-inorganic cluster orbital interaction. The highest occupied molecular orbital (HOMO) of (CdSe)(6) is dominated by selenium 4p orbitals; in contrast, the HOMO of (CdSe)(6)[SCH(3)](-) is dominated by sulfur 3p orbitals. This difference shows that [SCH(3)](-) binding effectively introduces filled sulfur orbitals above the selenium 4p orbitals of (CdSe)(6). The resulting smaller HOMO-LUMO gap of (CdSe)(6)[SCH(3)](-) indeed leads to redshifts in its excitation energies compared to (CdSe)(6). In contrast, binding of multiple NH(3) destabilizes cadmium 5p orbitals, which contribute significantly to the lowest unoccupied molecular orbital (LUMO) of (CdSe)(6), while leaving the selenium 4p orbitals near the HOMO relatively unaffected. This has the effect of widening the HOMO-LUMO gap of (CdSe)(6)6NH(3) compared to (CdSe)(6). As expected, the excitation energies of the passivated (CdSe)(6)6NH(3) are also blueshifted compared to (CdSe)(6). As far as NH(3) is a faithful representation of a surfactant, the results clearly illustrate the differences between the electronic effects of an alkylthiolate versus those of surfactant molecules. Surface passivation of (CdSe)(6)[SCH(3)](-) is then simulated by coating it with multiple NH(3) molecules. The results suggest that the [SCH(3)](-) adsorption induces a redshift in the excitation energies in a surfactant environment.

  20. [Sorption and mechanism of surfactants on bentonite in combined pollution].

    PubMed

    Sun, Xiao-Hui; Lu, Ying-Ying; Chen, Shu-Guang; Li, Ling-Jian; Shen, Xue-You

    2007-04-01

    Sorption of cationic surfactant cetyl pyridinium chloride (CPC), anionic surfactant sodium dodecylbenzene sulfonate (SDBS) and nonionic surfactant Triton X-100 (TX-100) on bentonite was studied. The influences of cation-exchange capacity (CEC), temperature and salinity on the sorption of CPC were also discussed. The results indicate that the sorption of CPC on Na-bentonite is greater than that of TX-100 and SDBS, and SDBS hardly shows any sorption. CPC is adsorbed to Na-bentonite through a combination of hydrophobic bonding and cation-exchange. While TX-100 is adsorbed to Na-bentonite via the formation of an adsorption layer of twain surfactant molecule and hydrogenolysis of silicon-oxygen surface of bentonite and TX-100. The amount of SDBS adsorbed on Ca-bentonite increases with increasing surfactant concentration, reaching a maximum at 1.5 critical micelle concentration (CMC), and then decreases with increasing surfactant loading. The mechanism of the retention appears to be formation of a sparingly soluble Ca-SDBS species, and dissolution in the micelle. The amount of CPC adsorbed on bentonite decreases with increasing temperature, and increases with increasing CEC. NaCl can enhance the sorption of CPC on bentonite.

  1. Some features of raman scattering by molecules adsorbed on metal crystal faces and a fine light structure

    NASA Astrophysics Data System (ADS)

    Polubotko, A. M.

    2013-07-01

    The paper analyzes some experiments on Raman scattering by molecules adsorbed on the face (111) of silver monocrystals performed by A. Campion et al. From the existence of the forbidden line A 2 u of benzene, the conclusion about existence of the surface field, caused by atomic structure of the surface is made. The relatively large intensity of this line allows to make a conclusion about large influence of the electromagnetic field spatial inhomogeneity in crystals on their optical properties. The difference between this field and a regular plane wave, which usually describes propagation of electromagnetic field in solids is named as a fine light structure. The influence of this structure on optical properties of solids is pointed out.

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

    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.

  3. Enhanced Raman scattering by molecules adsorbed at the surface of colloidal spheroids

    NASA Astrophysics Data System (ADS)

    Wang, D.-S.; Kerker, M.

    1981-08-01

    Equations are derived and calculations are presented for the electrodynamic mechanism of enhanced Raman scattering by molecules at the surface of prolate and oblate spheroids in the small-particle limit. The molecules may be arbitrarily distributed; the particles may be arbitrarily oriented. Calculations are presented for a monolayer distributed over randomly oriented spheroids. The effects of particle shape are considered for Ag, Au, and Cu hydrosols. The peak enhancement moves to longer wavelengths, and in the case of Au and Cu the magnitude of the enhancement increases strikingly as the eccentricity increases. The relation between the dependence of the Raman enhancement upon excitation wavelength and the extinction spectra is discussed, including the precariousness of extrapolating such relations beyond the small-particle limit.

  4. 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.}

  5. Adsorption of anionic and non-ionic surfactants on carbon nanotubes in water with dissipative particle dynamics simulation

    NASA Astrophysics Data System (ADS)

    Vo, Minh D.; Shiau, Benjamin; Harwell, Jeffrey H.; Papavassiliou, Dimitrios V.

    2016-05-01

    The morphology of surfactants physically adsorbed on the surface of carbon nanotubes (CNTs) has a significant impact on the dispersion of CNTs in the solution. The adsorption of the surfactants alfoterra 123-8s (AF) and tergitol 15-s-40 (TG) on CNTs was investigated with dissipative particle dynamics (DPD) simulations, as well as the behavior of the binary surfactant system with CNTs. Properties of surfactants (i.e., critical micelle concentration, aggregation number, shape and size of micelle, and diffusivity) in water were determined to validate the simulation model. Results indicated that the assembly of surfactants (AF and TG) on CNTs depends on the interaction of the surfactant tail and the CNT surface, where surfactants formed mainly hemimicellar structures. For surfactants in solution, most micelles had spherical shape. The particles formed by the CNT and the adsorbed surfactant became hydrophilic, due to the outward orientation of the head groups of the surfactants that formed monolayer adsorption. In the binary surfactant system, the presence of TG on the CNT surface provided a considerable hydrophilic steric effect, due to the EO groups of TG molecules. It was also seen that the adsorption of AF was more favorable than TG on the CNT surface. Diffusion coefficients for the surfactants in the bulk and surface diffusion on the CNT were calculated. These results are applicable, in a qualitative sense, to the more general case of adsorption of surfactants on the hydrophobic surface of cylindrically shaped nanoscale objects.

  6. 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.

  7. 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.

  8. 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.

  9. Bile salt surfactants in micellar electrokinetic capillary chromatography: Application to hydrophobic molecule separations

    SciTech Connect

    Cole, R.O.; Sepaniak, M.J. . Dept. of Chemistry); Hinze, W.L. . Dept. of Chemistry); Gorse, J.; Oldiges, K. . Dept. of Chemistry)

    1990-01-01

    Bile Salt surfactants are used in the micellar electrokinetic capillary chromatography (MECC) separation of various hydrophobic compounds. The use of methanol in the mobile phase allows the separation of previously intractable compounds including polyaromatic hydrocarbons. The effects of methanol on critical micelle concentration is investigated for sodium dodecyl sulfate (SDS) and the bile salt sodium cholate. It is determined that the unique structure of the bile salt micelle is much more tolerant to the addition of organic solvents than SDS, thereby increasing the scope of applications of MECC to include hydrophobic compounds. 30 refs., 9 figs.

  10. Extended delivery of an anionic drug by contact lens loaded with a cationic surfactant.

    PubMed

    Bengani, Lokendrakumar C; Chauhan, Anuj

    2013-04-01

    Drug eluding contact lenses can be very effective vehicles for ophthalmic drug delivery, but are incapable of releasing drug for more than a few hours. We propose to optimize the interactions of the polymer matrix of the contact lens with the hydrophobic tails of ionic surfactants to adsorb the surfactant molecules on the polymer with high packing and thus create a high surface charge. Ionic drugs can then adsorb on the charged surfactant coated surfaces with high affinity to reduce the transport rates, leading to extended release. Specifically, we show control release of an anionic drug dexamethasone 21-disodium phosphate from poly-hydroxyethyl methacrylate (p-HEMA) contact lenses by utilizing cationic surfactant (cetalkonium chloride). The partition coefficient of the drug increase exponentially with surfactant loading in the gel in at least qualitative agreement with the Debye-Hückel theory. The drug adsorbs on the surfactant covered polymer, and can also diffuse along the surface with diffusivity lower than that for the free drug, leading to a reduction in the effective diffusivity, which is the weighted combination of the free and surface diffusivities. The addition of surfactant did not impact transparency of lenses, and had additional benefits of increase in wettability and significant reduction in protein absorption. With a surfactant loading of about 10%, the drug release duration was increased from about 2 h to 50 h in 1-day ACUVUE(®) contact lenses, proving the viability of using surfactant for increasing drug release durations.

  11. Study of IR laser photoacoustic spectra of organic molecules adsorbed on metal surface

    NASA Astrophysics Data System (ADS)

    Lu, Huizong; Chen, Kaitai; Wang, Zhaoyong

    1987-06-01

    Using a branch-tuning CW CO2 laser in the range of 0.2 to 10.8 microns, the IR photoacoustic spectra of organic molecules absorbed on a silver surface were studied. The absorbed molecular spectra of four layers of arachidic acid and cellulose diacetate with different surface densities was studied. No peak shift was found in a comparison between IR photoacoustic spectra of solid arachidic acid near 944/cm and the corresponding IR Fourier spectra of solid archidic acid. The IR photoacoustic spectra of cellulose diacetate with sigma sub 1 = 14,000/sq cm and sigma sub 1 = 5.5 x 10 to the 15th/sq cm respectively was compared with the corresponding transmission spectra of solid cellulose diacetate. It was found that the peak of the former near 1054/cm had a red shift of about 5/cm while the peak of the latter had no obvious shift within the range of accuracy of the experiment.

  12. Effect of substrate thickness on ejection of phenylalanine molecules adsorbed on free-standing graphene bombarded by 10 keV C60

    NASA Astrophysics Data System (ADS)

    Golunski, M.; Verkhoturov, S. V.; Verkhoturov, D. S.; Schweikert, E. A.; Postawa, Z.

    2017-02-01

    Molecular dynamics computer simulations have been employed to investigate the effect of substrate thickness on the ejection mechanism of phenylalanine molecules deposited on free-standing graphene. The system is bombarded from the graphene side by 10 keV C60 projectiles at normal incidence and the ejected particles are collected both in transmission and reflection directions. It has been found that the ejection mechanism depends on the substrate thickness. At thin substrates mostly organic fragments are ejected by direct collisions between projectile atoms and adsorbed molecules. At thicker substrates interaction between deforming topmost graphene sheet and adsorbed molecules becomes more important. As this process is gentle and directionally correlated, it leads predominantly to ejection of intact molecules. The implications of the results to a novel analytical approach in Secondary Ion Mass Spectrometry based on ultrathin free-standing graphene substrates and a transmission geometry are discussed.

  13. Thermally cleavable surfactants

    DOEpatents

    McElhanon, James R.; Simmons, Blake A.; Zifer, Thomas; Jamison, Gregory M.; Loy, Douglas A.; Rahimian, Kamyar; Long, Timothy M.; Wheeler, David R.; Staiger, Chad L.

    2009-11-24

    Two new surfactant molecules are reported which contain thermally labile Diels-Alder adducts connecting the polar and non-polar sections of each molecule. The two surfactants possess identical non-polar dodecyl tail segments but exhibit different polar headgroups. The surfactants become soluble in water when anionic salts are formed through the deprotonation of the surfactant headgroups by the addition of potassium hydroxide. When either surfactant is exposed to temperature above about 60.degree. C., the retro Diels-Alder reaction occurs, yielding hydrophilic and hydrophobic fragments or the aqueous solutions of the surfactants subsequently exhibit loss of all surface-active behavior.

  14. Thermally cleavable surfactants

    DOEpatents

    McElhanon, James R.; Simmons, Blake A.; Zifer, Thomas; Jamison, Gregory M.; Loy, Douglas A.; Rahimian, Kamyar; Long, Timothy M.; Wheeler, David R.; Staiger, Chad L.

    2006-04-04

    Two new surfactant molecules are reported which contain thermally labile Diels-Alder adducts connecting the polar and non-polar sections of each molecule. The two surfactants possess identical non-polar dodecyl tail segments but exhibit different polar headgroups. The surfactants become soluble in water when anionic salts are formed through the deprotonation of the surfactant headgroups by the addition of potassium hydroxide. When either surfactant is exposed to temperature above about 60.degree. C., the retro Diels-Alder reaction occurs, yielding hydrophilic and hydrophobic fragments and the aqueous solutions of the surfactants subsequently exhibit loss of all surface-active behavior.

  15. Thermally cleavable surfactants

    DOEpatents

    McElhanon, James R.; Simmons, Blake A.; Zifer, Thomas; Jamison, Gregory M.; Loy, Douglas A.; Rahimian, Kamyar; Long, Timothy M.; Wheeler, David R.; Staiger, Chad L.

    2009-09-29

    Two new surfactant molecules are reported which contain thermally labile Diels-Alder adducts connecting the polar and non-polar sections of each molecule. The two surfactants possess identical non-polar dodecyl tail segments but exhibit different polar headgroups. The surfactants become soluble in water when anionic salts are formed through the deprotonation of the surfactant headgroups by the addition of potassium hydroxide. When either surfactant is exposed to temperature above about 60.degree. C., the retro Diels-Alder reaction occurs, yielding hydrophilic and hydrophobic fragments or the aqueous solutions of the surfactants subsequently exhibit loss of all surface-active behavior.

  16. Adsorption of naphthalene and ozone on atmospheric air/ice interfaces coated with surfactants: a molecular simulation study.

    PubMed

    Liyana-Arachchi, Thilanga P; Valsaraj, Kalliat T; Hung, Francisco R

    2012-03-15

    The adsorption of gas-phase naphthalene and ozone molecules onto air/ice interfaces coated with different surfactant species (1-octanol, 1-hexadecanol, or 1-octanal) was investigated using classical molecular dynamics (MD) simulations. Naphthalene and ozone exhibit a strong preference to be adsorbed at the surfactant-coated air/ice interfaces, as opposed to either being dissolved into the bulk of the quasi-liquid layer (QLL) or being incorporated into the ice crystals. The QLL becomes thinner when the air/ice interface is coated with surfactant molecules. The adsorption of both naphthalene and ozone onto surfactant-coated air/ice interfaces is enhanced when compared to bare air/ice interface. Both naphthalene and ozone tend to stay dissolved in the surfactant layer and close to the QLL, rather than adsorbing on top of the surfactant molecules and close to the air region of our systems. Surfactants prefer to orient at a tilted angle with respect to the air/ice interface; the angular distribution and the most preferred angle vary depending on the hydrophilic end group, the length of the hydrophobic tail, and the surfactant concentration at the air/ice interface. Naphthalene prefers to have a flat orientation on the surfactant coated air/ice interface, except at high concentrations of 1-hexadecanol at the air/ice interface; the angular distribution of naphthalene depends on the specific surfactant and its concentration at the air/ice interface. The dynamics of naphthalene molecules at the surfactant-coated air/ice interface slow down as compared to those observed at bare air/ice interfaces. The presence of surfactants does not seem to affect the self-association of naphthalene molecules at the air/ice interface, at least for the specific surfactants and the range of concentrations considered in this study.

  17. 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

    2008-12-07

    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(+) 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.

  18. Effect of side by side interactions on the thermodynamic properties of adsorbed CO molecules on the Ni(111) surface: a cluster model study

    NASA Astrophysics Data System (ADS)

    Shamkhali, Amir N.; Parsafar, Gholamabbas

    2010-05-01

    The effect of electrostatic interactions on vibrational frequencies and thermodynamic properties of CO adsorbate on the Ni(111) surface is calculated by taking the first and second nearest-neighbour interactions into account. In order to obtain reasonable results, the cluster model of various surface adsorption sites with CO adsorbate is partially optimized, using Density Functional Theory and also the MP2 method for the hcp site. Comparison between DFT and MP2 results shows that DFT results are more reliable for this system. The stretching and bending frequencies of CO adsorbate are calculated using both Partial Hessian Analysis and Cluster-Adsorbate Coupling methods. Stretching and bending frequencies are both shifted by the side by side interactions. The coupling of surface phonons and adsorbate vibrations reduces the side effects. The largest side effects on the vibrational internal energy, isochoric heat capacity, entropy and total Helmholtz free energy of adsorbed CO molecule calculated using the CAC method are found for 0.5 ML coverage. The results of the CAC method are better, but the PHA method can be used as a simple upper bound estimation. The adsorptive phase acts as an intelligent material in such a way that it changes its configuration in order to reduce the side effects.

  19. Method for the calculation of the vibrational frequency shift of physisorbed molecules. Application to H2 adsorbed in NaA zeolite

    NASA Astrophysics Data System (ADS)

    Larin, A. V.; Cohen De Lara, E.

    1994-11-01

    The vibrational frequency shift of physisorbed diatomic molecules is related to the interaction with the adsorbent expressed in terms of the internuclear distance ρ. It is calculated by the Schrödinger equation, the perturbation theory, and a simplified method. We show that it is sufficient to calculate the interaction potential for the values of ρ in the ground and first vibrational states in order to get a precision of 10% on the frequency shift. The comparison between the theoretical and experimental frequency shift of H2 adsorbed in NaA zeolite is used to adjust the interaction potential, especially in terms of the ionicity of the crystal.

  20. Remobilizing surfactant retarded fluid particle interfaces. I. Stress-free conditions at the interfaces of micellar solutions of surfactants with fast sorption kinetics

    NASA Astrophysics Data System (ADS)

    Stebe, Kathleen J.; Lin, Shi-Yow; Maldarelli, Charles

    1991-01-01

    Surfactant molecules adsorb onto the interfaces of moving fluid particles and are convected to regions in which the surface flow converges. Accumulation of surfactant in these regions creates interfacial tension gradients that retard the surface flow. In this study it is argued theoretically and demonstrated experimentally that fluid movement on the surface of a drop or bubble can remain unhindered in the presence of a single adsorbed surfactant if, relative to the convective rate of transport of adsorbed surfactant along the surface, desorption is fast, and the bulk concentration is high enough so that diffusion away from the particle is fast. For this circumstance, a uniform surface concentration of surfactant is maintained, and no gradients in surface tension arise to retard the surface velocity. The fluid particle flow behaves as it would in the absence of surfactant save that it has a reduced, uniform surface tension. The remobilization of surfactant-laden interfaces of fluid particles is demonstrated experimentally in a three-phase periodic slug flow in a capillary tube in which a train of alternating air and aqueous slugs ride on an annular wetting film of fluorocarbon oil. Surfactant, dissolved in the aqueous slug phase, adsorbs onto and retards the aqueous-oil interface. The hydrodynamics of this flow is such that small changes in the mobility of this interface create large shear rates in the oil layer. This significantly increases the pressure drop required to drive the slug train at constant velocity. Three surface adsorbers are used to demonstrate surface remobilization: The polyethoxy, nonionic surfactants Triton X-100 and Brij-35, which have fast desorption kinetics and do not retard the surface flow at high concentrations and, as a counter example, the desorption hindered protein bovine serum albumin, which is shown to be unable to remobilize an interface even at high concentration.

  1. Changes in the surfaces on DDOAB organoclays adsorbed with paranitrophenol-An XRD, TEM and TG study

    SciTech Connect

    Zhou Qin; He Hongping; Frost, Ray L. Xi Yunfei

    2008-12-01

    The adsorption of paranitrophenol on organoclays synthesised by the ion exchange of the surfactant molecule dimethyldioctadecylammonium bromide (DDOAB) of formula (CH{sub 3}(CH{sub 2}){sub 17}){sub 2}NBr(CH{sub 3}){sub 2} has been studied by X-ray diffraction (XRD), transmission electron microscopy (TEM) and thermogravimetric analysis. The expansion of the montmorillonite depends on the loading of the montmorillonite with dimethyldioctadecylammonium bromide and is related to the arrangement of the surfactant molecules within the clay interlayer. This expansion is altered by the adsorbed paranitrophenol and is observed in the transmission electron microscopic images of the organoclay with adsorbed paranitrophenol. Changes in the surfactant molecular arrangements were analysed by thermogravimetry. The paranitrophenol is sublimed simultaneously with the loss of surfactant. The dehydroxylation temperature of the montmorillonite is decreased upon adsorption of the paranitrophenol indicating a bonding between the paranitrophenol and the hydroxyl units of the montmorillonite.

  2. A computer modelling study of the interaction of organic adsorbates with fluorapatite surfaces

    NASA Astrophysics Data System (ADS)

    Mkhonto, Donald; Ngoepe, Phuti E.; Cooper, Timothy G.; de Leeuw, Nora H.

    2006-08-01

    Computer modelling techniques were employed to investigate the adsorption of a selection of organic surfactant molecules to a range of fluorapatite surfaces, and new interatomic potential models for the apatite/adsorbate interactions are presented. The adsorbates coordinate mainly to the surfaces through interaction between their oxygen (or nitrogen) atoms to surface calcium ions, followed by hydrogen-bonded interactions to surface oxygen ions and, to a much lesser extent, surface fluorides. Bridging between two surface calcium ions is the preferred mode of adsorption, when the geometry of the adsorbates allows it, and multiple interactions between surfaces and adsorbate molecules lead to the largest adsorption energies. All adsorbates containing carbonyl and hydroxy groups interact strongly with the surfaces, releasing energies between approximately 100 and 215 kJ mol-1, but methylamine containing only the NH2 functional group adsorbs to the surfaces to a much lesser extent (25 95 kJ mol-1). Both hydroxy methanamide and hydroxy ethanal prefer to adsorb to some surfaces in an eclipsed conformation, which is a requisite for these functional groups. Sorption of the organic material by replacement of pre-adsorbed water at different surface features is calculated to be mainly exothermic for methanoic acid, hydroxy methanamide and hydroxy ethanal molecules, whereas methyl amine would not replace pre-adsorbed water at the fluorapatite surfaces. The efficacy of the surfactant molecules is calculated to be hydroxy aldehydes > alkyl hydroxamates > carboxylic acids ≫ alkyl amines. The results from this study suggest that computer simulations may provide a route to the identification or even design of particular organic surfactants for use in mineral separation by flotation.

  3. In situ STM imaging of bis-3-sodiumsulfopropyl-disulfide molecules adsorbed on copper film electrodeposited on Pt(111) single crystal electrode.

    PubMed

    Tu, HsinLing; Yen, PoYu; Chen, Sihzih; Yau, ShuehLin; Dow, Wei-Ping; Lee, Yuh-Lang

    2011-06-07

    The adsorption of bis-3-sodiumsulfopropyldi-sulfide (SPS) on metal electrodes in chloride-containing media has been intensively studied to unveil its accelerating effect on Cu electrodeposition. Molecular resolution scanning tunneling microscopy (STM) imaging technique was used in this study to explore the adsorption and decomposition of SPS molecules concurring with the electrodeposition of copper on an ordered Pt(111) electrode in 0.1 M HClO(4) + 1 mM Cu(ClO(4))(2) + 1 mM KCl. Depending on the potential of Pt(111), SPS molecules could react, adsorb, and decompose at chloride-capped Cu films. A submonolayer of Cu adatoms classified as the underpotential deposition (UPD) layer at 0.4 V (vs Ag/AgCl) was completely displaced by SPS molecules, possibly occurring via RSSR (SPS) + Cl-Cu-Pt → RS(-)-Pt(+) + RS(-) (MPS) + Cu(2+) + Cl(-), where MPS is 3-mercaptopropanesulfonate. By contrast, at 0.2 V, where a full monolayer of Cu was presumed to be deposited, SPS molecules were adsorbed in local (4 × 4) structures at the lower ends of step ledges. Bulk Cu deposition driven by a small overpotential (η < 50 mV) proceeded slowly to yield an atomically smooth Cu deposit at the very beginning (<5 layers). On a bilayer Cu deposit, the chloride adlayer was still adsorbed to afford SPS admolecules arranged in a unique 1D striped phase. SPS molecules could decompose into MPS upon further Cu deposition, as a (2 × 2)-MPS structure was observed with prolonged in situ STM imaging. It was possible to visualize either SPS admolecules in the upper plane or chloride adlayer sitting underneath upon switching the imaging conditions. Overall, this study established a MPS molecular film adsorbed to the chloride adlayer sitting atop the Cu deposit.

  4. Thermodynamics on soluble carbon nanotubes: how do DNA molecules replace surfactants on carbon nanotubes?

    PubMed

    Kato, Yuichi; Inoue, Ayaka; Niidome, Yasuro; Nakashima, Naotoshi

    2012-01-01

    Here we represent thermodynamics on soluble carbon nanotubes that enables deep understanding the interactions between single-walled carbon nanotubes (SWNTs) and molecules. We selected sodium cholate and single-stranded cytosine oligo-DNAs (dCn (n = 4, 5, 6, 7, 8, 10, 15, and 20)), both of which are typical SWNT solubilizers, and successfully determined thermodynamic properties (ΔG, ΔH and ΔS values) for the exchange reactions of sodium cholate on four different chiralities of SWNTs ((n,m) = (6,5), (7,5), (10,2), and (8,6)) for the DNAs. Typical results contain i) the dC5 exhibited an exothermic exchange, whereas the dC6, 8, 10, 15, and 20 materials exhibited endothermic exchanges, and ii) the energetics of the dC4 and dC7 exchanges depended on the associated chiral indices and could be endothermic or exothermic. The presented method is general and is applicable to any molecule that interacts with nanotubes. The study opens a way for science of carbon nanotube thermodynamics.

  5. Action mechanism of small and large molecule surfactant-based clove oil nanoemulsions against food-borne pathogens and real-time detection of their subpopulations.

    PubMed

    Majeed, Hamid; Antoniou, John; Shoemaker, Charles F; Fang, Zhong

    2015-01-01

    Flow cytometry exactly discriminated three subpopulations, i.e., viable, damage and sublethal cells of L. monocytogenes, S. aureus and E. coli when treated at their MIC values. Purity gum ultra (PGU) a large molecule surfactant-based CO nanoemulsion exerted significant impact on cellular subpopulations of L. monocytogenes and S. aureus, with more membrane-damaged cells. On the other hand, when compared with bulk CO the results showed minimum membrane damage and more viable cells, whereas PGU CO nanoemulsion showed minimum effect on cellular subpopulation and represented more viable than damaged cells in case of E. coli. Similarly, Tween 80 a small molecule surfactant-based CO nanoemulsion showed limited overall activity against three tested microorganisms with more viable cells. We conclude that it was due to sequestration of CO constituents in interfaces, less availability in aqueous phase and finally inhibit bactericidal activity. Moreover, both CO and CO nanoemulsions showed membrane damage as primary inactivation mechanism of tested bacterial cells.

  6. Genetic Complexity of the Human Innate Host Defense Molecules, Surfactant Protein A1 (SP-A1) and SP-A2—Impact on Function

    PubMed Central

    Floros, Joanna; Wang, Guirong; Mikerov, Anatoly N.

    2010-01-01

    Innate immunity mechanisms play a critical role in the primary response to invading pathogenic microorganisms and other insulting agents. The innate lung immune system includes lung surfactant, a lipoprotein complex that carries out a function essential for life, that is, reduction of the surface tension at the air–liquid interphase of the alveolar space. By means of this function, pulmonary surfactant prevents lung collapse, therefore ensuring normal lung function and lung health. Pulmonary surfactant contains a number of host-defense molecules that are involved in the elimination of pathogens, viruses, particles, allergens, and other insults, as well as in the control of inflammation. This review is concerned with one of the surfactant proteins, the human (h) surfactant protein A (hSP-A), which, in addition to its role in surfactant-related functions, plays an important role in the modulation of lung host defense. The hSP-A locus has been identified with extensive complexity that may have an impact on its function, structure, and regulation. In humans, two genes—SP-A1 (SFTPA1) and SP-A2 (SFTPA2)—encode SP-A, with SP-A2 gene products being more biologically active than SP-A1 in most of the in vitro assays investigated. Although the two hSP-A genes share a high level of sequence similarity, differences in the structure and function between SP-A1 and SP-A2 have been observed in recent studies. In this review, we discuss the human SP-A complexity and how this may affect SP-A function. PMID:19392648

  7. Metathesis depolymerizable surfactants

    DOEpatents

    Jamison, Gregory M.; Wheeler, David R.; Loy, Douglas A.; Simmons, Blake A.; Long, Timothy M.; McElhanon, James R.; Rahimian, Kamyar; Staiger, Chad L.

    2008-04-15

    A class of surfactant molecules whose structure includes regularly spaced unsaturation in the tail group and thus, can be readily decomposed by ring-closing metathesis, and particularly by the action of a transition metal catalyst, to form small molecule products. These small molecules are designed to have increased volatility and/or enhanced solubility as compared to the original surfactant molecule and are thus easily removed by solvent extraction or vacuum extraction at low temperature. By producing easily removable decomposition products, the surfactant molecules become particularly desirable as template structures for preparing meso- and microstructural materials with tailored properties.

  8. Silanization of polyelectrolyte-coated particles: an effective route to stabilize Raman tagging molecules adsorbed on micrometer-sized silver particles.

    PubMed

    Kim, Kwan; Lee, Hyang Bong; Shin, Kuan Soo

    2008-06-03

    Micrometer-sized Ag (microAg) powders are very efficient surface-enhanced Raman scattering (SERS) substrates. To use microAg powders as a core material for molecular sensors operating via SERS, it is necessary to stabilize the tagging (i.e., SERS-marker) molecules adsorbed onto them. We demonstrate in this work that once the tagging molecules are coated with aliphatic polyelectrolytes such as poly(allylamine hydrochloride), the base-catalyzed silanization can be readily carried out to form stable silica shells around the polyelectrolyte layers by a biomimetic process; any particle can therefore be coated with silica since polyelectrolytes can be deposited beforehand via a layer-by-layer deposition method. Even after silanization, the SERS peaks of marker molecules on microAg particles are the only observable peaks since aliphatic polyelectrolytes, as well as silica shells, are intrinsically weak Raman scatterers, and more importantly, the SERS signals must be derived mostly from the first layer of the adsorbates (i.e., the marker molecules) in direct contact with the microAg particles. Silica shells, once fabricated, can further be derivatized to possess biofunctional groups; therefore, the modified microAg particles can be used as platforms of highly stable SERS-based biological sensors, as well as barcoding materials.

  9. Ratio of the surface-enhanced anti-Stokes scattering to the surface-enhanced Stokes-Raman scattering for molecules adsorbed on a silver electrode

    NASA Astrophysics Data System (ADS)

    Brolo, A. G.; Sanderson, A. C.; Smith, A. P.

    2004-01-01

    Surface-enhanced Raman scattering (SERS) from oxazine 720 (oxa), rhodamine 6G (R6G), and pyridine (py) adsorbed on a rough silver surface was observed. The silver electrode was immersed in aqueous solutions permitting control of the potential bias applied to the surface. SERS spectra in the Stokes and anti-Stokes regions were obtained for several applied potentials and two laser excitation energies. Normalized ratios between the anti-Stokes and the Stokes intensities K were calculated from the SERS spectra. The K ratios differed from unity for all the systems investigated. A preferential enhancement of the (surface-enhanced) Stokes scattering was observed for oxa and py. In contrast, the K ratios were higher than unity for R6G, indicating an increase in the anti-Stokes signal. The K ratios measured in this work decreased with the excitation energy and showed a dependence on the energy of the vibrational modes. These results were satisfactorily explained using resonance models, based on the charge-transfer and electromagnetic theories for SERS. No evidence for a SERS-induced nonthermal population distribution among the vibrational states of the adsorbed molecules (vibrational optical pumping) was found. Therefore, we conclude that the main features of the preferential enhancement of the anti-Stokes scattering for an adsorbed molecule on rough silver can be fully understood in the context of current SERS theories.

  10. Mechanistic study of wettability alteration using surfactants with applications in naturally fractured reservoirs.

    PubMed

    Salehi, Mehdi; Johnson, Stephen J; Liang, Jenn-Tai

    2008-12-16

    In naturally fractured reservoirs, oil recovery from waterflooding relies on the spontaneous imbibition of water to expel oil from the matrix into the fracture system. The spontaneous imbibition process is most efficient in strongly water-wet rock where the capillary driving force is strong. In oil- or mixed-wet fractured carbonate reservoirs, however, the capillary driving force for the spontaneous imbibition process is weak, and therefore the waterflooding oil recoveries are low. The recovery efficiency can be improved by dissolving low concentrations of surfactants in the injected water to alter the wettability of the reservoir rock to a more water-wet state. This wettability alteration accelerates the spontaneous imbibition of water into matrix blocks, thereby increasing the oil recovery during waterflooding. Several mechanisms have been proposed to explain the wettability alteration by surfactants, but none have been verified experimentally. Understanding of the mechanisms behind wettability alteration could help to improve the performance of the process and aid in identification of alternative surfactants for use in field applications. Results from this study revealed that ion-pair formation and adsorption of surfactant molecules through interactions with the adsorbed crude oil components on the rock surface are the two main mechanisms responsible for the wettability alteration. Previous researchers observed that, for a given rock type, the effectiveness of wettability alteration is highly dependent upon the ionic nature of the surfactant involved. Our experimental results demonstrated that ion-pair formation between the charged head groups of surfactant molecules and the adsorbed crude oil components on rock surface was more effective in changing the rock wettability toward a more water-wet state than the adsorption of surfactant molecules as a monolayer on the rock surface through hydrophobic interaction with the adsorbed crude oil components. By comparing

  11. Light-controllable dispersion and recovery of graphenes and carbon nanotubes using a photo-switchable surfactant.

    PubMed

    McCoy, Thomas M; Liu, Amelia C Y; Tabor, Rico F

    2016-04-07

    The aqueous dispersibility of carbon-based nanomaterials, namely graphene oxide (GO), reduced graphene oxide (rGO) and carbon nanotubes (CNTs), can be controlled by light via the photoisomerisation of a photoswitchable surfactant molecule adsorbed to the surface of these materials. By incorporating a cationic azobenzene photosurfactant into these systems, GO, rGO and CNT dispersions can be separated and redispersed on command utilising UV radiation at 365 nm, whereby the surfactant molecules change from the trans to the cis isomer. This increases their aqueous solubility and in turn, alters their adsorption affinity for the GO and rGO sheets such that the ratio of free to adsorbed surfactant molecules changes significantly, allowing for reversible phase separation of the colloids. These effects present a unique method for controlling the dispersion behaviour of two-dimensional nanomaterials using light as a clean and low energy external stimulus.

  12. Light-controllable dispersion and recovery of graphenes and carbon nanotubes using a photo-switchable surfactant

    NASA Astrophysics Data System (ADS)

    McCoy, Thomas M.; Liu, Amelia C. Y.; Tabor, Rico F.

    2016-03-01

    The aqueous dispersibility of carbon-based nanomaterials, namely graphene oxide (GO), reduced graphene oxide (rGO) and carbon nanotubes (CNTs), can be controlled by light via the photoisomerisation of a photoswitchable surfactant molecule adsorbed to the surface of these materials. By incorporating a cationic azobenzene photosurfactant into these systems, GO, rGO and CNT dispersions can be separated and redispersed on command utilising UV radiation at 365 nm, whereby the surfactant molecules change from the trans to the cis isomer. This increases their aqueous solubility and in turn, alters their adsorption affinity for the GO and rGO sheets such that the ratio of free to adsorbed surfactant molecules changes significantly, allowing for reversible phase separation of the colloids. These effects present a unique method for controlling the dispersion behaviour of two-dimensional nanomaterials using light as a clean and low energy external stimulus.The aqueous dispersibility of carbon-based nanomaterials, namely graphene oxide (GO), reduced graphene oxide (rGO) and carbon nanotubes (CNTs), can be controlled by light via the photoisomerisation of a photoswitchable surfactant molecule adsorbed to the surface of these materials. By incorporating a cationic azobenzene photosurfactant into these systems, GO, rGO and CNT dispersions can be separated and redispersed on command utilising UV radiation at 365 nm, whereby the surfactant molecules change from the trans to the cis isomer. This increases their aqueous solubility and in turn, alters their adsorption affinity for the GO and rGO sheets such that the ratio of free to adsorbed surfactant molecules changes significantly, allowing for reversible phase separation of the colloids. These effects present a unique method for controlling the dispersion behaviour of two-dimensional nanomaterials using light as a clean and low energy external stimulus. Electronic supplementary information (ESI) available: Includes further details

  13. How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO2 nanoparticles? A quasi-elastic neutron scattering study

    NASA Astrophysics Data System (ADS)

    Vaissier, Valerie; Sakai, Victoria Garcia; Li, Xiaoe; Cabral, João T.; Nelson, Jenny; Barnes, Piers R. F.

    2016-12-01

    Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotinic acid (BINA), attached to TiO2 nanoparticles via carboxylate groups. The scattering data indicate that moieties are immobile and do not rotate around the anchoring groups on timescales between around 10 ps and a few ns (corresponding to the instrumental range). This gives an upper limit for the rate at which conformational fluctuations can assist charge transport between anchored molecules. Our observations suggest that if the conformation of larger dye molecules varies with time, it does so on longer timescales and/or in parts of the molecule which are not directly connected to the anchoring group. The QENS measurements also indicate that several layers of acetonitrile solvent molecules are immobilized at the interface with the TiO2 on the measurement time scale, in reasonable agreement with recent classical molecular dynamics results.

  14. How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO2 nanoparticles? A quasi-elastic neutron scattering study

    PubMed Central

    Vaissier, Valerie; Sakai, Victoria Garcia; Li, Xiaoe; Cabral, João T.; Nelson, Jenny; Barnes, Piers R. F.

    2016-01-01

    Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotinic acid (BINA), attached to TiO2 nanoparticles via carboxylate groups. The scattering data indicate that moieties are immobile and do not rotate around the anchoring groups on timescales between around 10 ps and a few ns (corresponding to the instrumental range). This gives an upper limit for the rate at which conformational fluctuations can assist charge transport between anchored molecules. Our observations suggest that if the conformation of larger dye molecules varies with time, it does so on longer timescales and/or in parts of the molecule which are not directly connected to the anchoring group. The QENS measurements also indicate that several layers of acetonitrile solvent molecules are immobilized at the interface with the TiO2 on the measurement time scale, in reasonable agreement with recent classical molecular dynamics results. PMID:27991538

  15. Gemini ester quat surfactants and their biological activity.

    PubMed

    Łuczyński, Jacek; Frąckowiak, Renata; Włoch, Aleksandra; Kleszczyńska, Halina; Witek, Stanisław

    2013-03-01

    Cationic gemini surfactants are an important class of surface-active compounds that exhibit much higher surface activity than their monomeric counterparts. This type of compound architecture lends itself to the compound being easily adsorbed at interfaces and interacting with the cellular membranes of microorganisms. Conventional cationic surfactants have high chemical stability but poor chemical and biological degradability. One of the main approaches to the design of readily biodegradable and environmentally friendly surfactants involves inserting a bond with limited stability into the surfactant molecule to give a cleavable surfactant. The best-known example of such a compound is the family of ester quats, which are cationic surfactants with a labile ester bond inserted into the molecule. As part of this study, a series of gemini ester quat surfactants were synthesized and assayed for their biological activity. Their hemolytic activity and changes in the fluidity and packing order of the lipid polar heads were used as the measures of their biological activity. A clear correlation between the hemolytic activity of the tested compounds and their alkyl chain length was established. It was found that the compounds with a long hydrocarbon chain showed higher activity. Moreover, the compounds with greater spacing between their alkyl chains were more active. This proves that they incorporate more easily into the lipid bilayer of the erythrocyte membrane and affect its properties to a greater extent. A better understanding of the process of cell lysis by surfactants and of their biological activity may assist in developing surfactants with enhanced selectivity and in widening their range of application.

  16. Surfactants and the Mechanics of Respiration

    NASA Astrophysics Data System (ADS)

    Jbaily, Abdulrahman; Szeri, Andrew J.

    2016-11-01

    Alveoli are small sacs found at the end of terminal bronchioles in human lungs with a mean diameter of 200 μm. A thin layer of fluid (hypophase) coats the inner face of an alveolus and is in contact with the air in the lungs. The thickness of this layer varies among alveoli, but is in the range of 0.1 to 0.5 μm for many portions of the alveolar network. The interfacial tension σ at the air-hypophase interface tends to favor collapse of the alveolus, and resists its expansion during inhalation. Type II alveolar cells synthesize and secrete a mixture of phospholipids and proteins called pulmonary surfactant. These surfactant molecules adsorb to the interface causing σ of water at body temperature is 70 mN/m and falls to an equilibrium value of 25 mN/m when surfactants are present. Also, in a dynamic sense, it is known that σ is reduced to near 0 during exhalation when the surfactant film compresses. In this work, the authors develop a mechanical and transport model of the alveolus to study the effect of surfactants on various aspects of respiration. The model is composed of three principal parts: (i) air movement into and out of the alveolus; (ii) a balance of linear momentum across the two-layered membrane of the alveolus (hypophase and elastic wall); and (iii) a pulmonary surfactant transport problem in the hypophase. The goal is to evaluate the influence of pulmonary surfactant on respiratory mechanics.

  17. 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.

  18. Soap opera : polymer-surfactant interactions on thin film surfaces /

    SciTech Connect

    Ozer, B. H.; Johal, M. S.; Wang, H. L.; Robinson, J. M.

    2001-01-01

    Surfactants are macromolecules with unique properties. They commonly contain a polar head group with a nonpolar hydrocarbon chain. These properties allow surfactants to solubilize greases and other nonpolar molecules. One particular way that this is accomplished is through the formation of micelles. Micelles are formed at the critical micelle concentration (cmc), which varies depending upon the nature of the surfactant and also the media in which the surfactant resides. These micelles can take a variety of shapes, but are generally characterized by surrounding the grease with the nonpolar hydrocarbon chains, exposing only the polarized head groups to the media, usually water. This property of easy solubilization has made surfactants a very attractive industrial agent, They are used most conventionally as industrial cleaning agents and detergents. However, they also have lesser-known applications in conjunction with polymers and other macromolecular mixtures, often creating a system with novel properties, such as increased solubilization and smoother mixture consistency. A recently developed field has investigated the self-assembly of polymers and polyelectrolytes onto thin film surfaces. There are many reasons for studying this process, such as for second harmonic generation purposes and bioassays. In this study, the interaction between the anionic polyelectrolyte poly[1-[4-(3-carboxy-4-hydroxyphenylazo)benzenesulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) and two surfactants of opposite charge, Sodium Dodecyl Sulfate (SDS) and Dodecyl Trimethyl Ammonium Bromide (DTAB), in their assembly onto thin film surfaces was investigated. The kinetics of adsorbance onto the thin films was examined, followed by construction of 10-bilayer films using an alternating layer of the cationic polyelectrolyte poly(ethylenimine) (PEI) to provide the electrostatic means for the PAZO/surfactant combination to assemble onto the thin film. The kinetics of adsorption is being

  19. Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials.

    PubMed

    Qi, Xuejun; Song, Wenwu; Shi, Jianwei

    2017-01-01

    Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite's chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface.

  20. Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials

    PubMed Central

    Song, Wenwu; Shi, Jianwei

    2017-01-01

    Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite’s chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface. PMID:28301544

  1. Temperature-dependent adsorption of surfactant molecules and associated crystallization kinetics of noncentrosymmetric Fe(IO{sub 3}){sub 3} nanorods in microemulsions

    SciTech Connect

    El-Kass, Moustafa; Ladj, Rachid; Mugnier, Yannick; Le Dantec, Ronan; Hadji, Rachid; Marty, Jean-Christophe; Rouxel, Didier; Durand, Christiane; Fontvieille, Dominique; Rogalska, Ewa; and others

    2013-11-15

    Graphical abstract: - Highlights: • Crystallization of Fe(IO{sub 3}){sub 3} in microemulsions probed by hyper-Rayleigh scattering. • A faster growth and a better shape control of nanorods are obtained at 80 °C. • Different persistent cell deformations are related to the crystallization kinetics. • A temperature-dependent adsorption of surfactants on nanorods is suggested. - Abstract: Aggregation-induced crystallization of iron iodate nanorods within organic–inorganic aggregates of primary amorphous precursors is probed by time-dependent hyper-Rayleigh scattering measurements in Triton X-100 based-microemulsions. In the context of a growing interest of noncentrosymmetric oxide nanomaterials in multi-photon bioimaging, we demonstrate by a combination of X-ray diffraction and electron microscopy that an increase in the synthesis of temperature results in faster crystallization kinetics and in a better shape-control of the final Fe(IO{sub 3}){sub 3} nanorods. For initial microemulsions of fixed composition, room-temperature synthesis leads to bundles of 1–3 μm long nanorods, whereas shorter individual nanorods are obtained when the temperature is increased. Results are interpreted in terms of kinetically unfavorable mesoscale transformations due to the strong binding interactions with Triton molecules. The interplay between the nanorod crystallization kinetics and their corresponding unit cell deformation, evidenced by lattice parameter refinements, is attributed to a temperature-dependent adsorption of surfactants molecules at the organic–inorganic interface.

  2. Collective degrees of freedom involved in absorption and desorption of surfactant molecules in spherical non-ionic micelles

    NASA Astrophysics Data System (ADS)

    Ahn, Yong Nam; Mohan, Gunjan; Kopelevich, Dmitry I.

    2012-10-01

    Dynamics of absorption and desorption of a surfactant monomer into and out of a spherical non-ionic micelle is investigated by coarse-grained molecular dynamics (MD) simulations. It is shown that these processes involve a complex interplay between the micellar structure and the monomer configuration. A quantitative model for collective dynamics of these degrees of freedom is developed. This is accomplished by reconstructing a multi-dimensional free energy landscape of the surfactant-micelle system using constrained MD simulations in which the distance between the micellar and monomer centers of mass is held constant. Results of this analysis are verified by direct (unconstrained) MD simulations of surfactant absorption in the micelle. It is demonstrated that the system dynamics is likely to deviate from the minimum energy path on the energy landscape. These deviations create an energy barrier for the monomer absorption and increase an existing barrier for the monomer desorption. A reduced Fokker-Planck equation is proposed to model these effects.

  3. Metal-free phthalocyanine (H2Pc) molecule adsorbed on the Au(111) surface: formation of a wide domain along a single lattice direction

    PubMed Central

    Komeda, Tadahiro; Isshiki, Hironari; Liu, Jie

    2010-01-01

    Using low-temperature scanning tunneling microscopy (STM), we observed the bonding configuration of the metal-free phthalocyanine (H2Pc) molecule adsorbed on the Au(111) surface. A local lattice formation started from a quasi-square lattice aligned to the close-packed directions of the Au(111) surface. Although we expected the lattice alignment to be equally distributed along the three crystallographically equivalent directions, the domain aligned normal to the ridge of the herringbone structure was missing in the STM images. We attribute this effect to the uniaxial contraction of the reconstructed Au(111) surface that can account for the formation of a large lattice domain along a single crystallographical direction. PMID:27877365

  4. 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.

  5. 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.

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

    PubMed

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

    2015-10-01

    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.

  7. Excited-state potential-energy surfaces of metal-adsorbed organic molecules from linear expansion Δ-self-consistent field density-functional theory (ΔSCF-DFT)

    NASA Astrophysics Data System (ADS)

    Maurer, Reinhard J.; Reuter, Karsten

    2013-07-01

    Accurate and efficient simulation of excited state properties is an important and much aspired cornerstone in the study of adsorbate dynamics on metal surfaces. To this end, the recently proposed linear expansion Δ-self-consistent field method by Gavnholt et al. [Phys. Rev. B 78, 075441 (2008)], 10.1103/PhysRevB.78.075441 presents an efficient alternative to time consuming quasi-particle calculations. In this method, the standard Kohn-Sham equations of density-functional theory are solved with the constraint of a non-equilibrium occupation in a region of Hilbert-space resembling gas-phase orbitals of the adsorbate. In this work, we discuss the applicability of this method for the excited-state dynamics of metal-surface mounted organic adsorbates, specifically in the context of molecular switching. We present necessary advancements to allow for a consistent quality description of excited-state potential-energy surfaces (PESs), and illustrate the concept with the application to Azobenzene adsorbed on Ag(111) and Au(111) surfaces. We find that the explicit inclusion of substrate electronic states modifies the topologies of intra-molecular excited-state PESs of the molecule due to image charge and hybridization effects. While the molecule in gas phase shows a clear energetic separation of resonances that induce isomerization and backreaction, the surface-adsorbed molecule does not. The concomitant possibly simultaneous induction of both processes would lead to a significantly reduced switching efficiency of such a mechanism.

  8. Surfactant-assisted coal liquefaction

    NASA Technical Reports Server (NTRS)

    Hsu, G. C.

    1977-01-01

    Improved process of coal liquefaction utilizing nonaqueous surfactant has increased oil yield from 50 to about 80%. Asphaltene molecule formation of colloid particles is prevented by surfactant. Separated molecules present more surface area for hydrogenation reaction. Lower requirements for temperature, pressure, and hydrogen lead to reduction in capital and operation costs.

  9. A theoretical study of the XP and NEXAFS spectra of alanine: gas phase molecule, crystal, and adsorbate at the ZnO(10 ̅10) surface.

    PubMed

    Gao, You Kun; Traeger, Franziska; Kotsis, Konstantinos; Staemmler, Volker

    2011-06-14

    The adsorption of alanine on the mixed-terminated ZnO(10 ̅10) surface is studied by means of quantum-chemical ab initio calculations. Using a finite cluster model and the adsorption geometry as obtained both by periodic CPMD and embedded cluster calculations, the C1s, N1s and O1s X-ray photoelectron spectra (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectra are calculated for single alanine molecules on ZnO(10 ̅10). These spectra are compared with the spectra calculated for alanine in the gas phase and in its crystalline form and with experimental XPS and NEXAFS data for the isolated alanine molecule and for alanine adsorbed on ZnO(10 ̅10) at multilayer and monolayer coverage. The excellent agreement between the experimental and calculated XP and NEXAFS spectra confirms the calculated adsorption geometry: A single alanine molecule is bound to ZnO(10 ̅10) in a dissociated bidentate form with the two O atoms of the acid group bound to two Zn atoms of the surface and the proton transferred to one O atom of the surface. Other possible structures, such as adsorption of alanine in one of its neutral or zwitterionic forms in which the proton of the -COOH group remains at this group or is transferred to the amino group, can be excluded since they would give rise to quite different XP spectra. In the multilayer coverage regime, on the other hand, alanine is in its crystalline form as is also shown by the analysis of the XP spectra.

  10. Droplet Deformation in an Extensional Flow: The Role of Surfactant Physical Chemistry

    NASA Technical Reports Server (NTRS)

    Stebe, Kathleen J.

    1996-01-01

    Surfactant-induced Marangoni effects strongly alter the stresses exerted along fluid particle interfaces. In low gravity processes, these stresses can dictate the system behavior. The dependence of Marangoni effects on surfactant physical chemistry is not understood, severely impacting our ability to predict and control fluid particle flows. A droplet in an extensional flow allows the controlled study of stretching and deforming interfaces. The deformations of the drop allow both Marangoni stresses, which resist tangential shear, and Marangoni elasticities, which resist surface dilatation, to develop. This flow presents an ideal model system for studying these effects. Prior surfactant-related work in this flow considered a linear dependence of the surface tension on the surface concentration, valid only at dilute surface concentrations, or a non-linear framework at concentrations sufficiently dilute that the linear approximation was valid. The linear framework becomes inadequate for several reasons. The finite dimensions of surfactant molecules must be taken into account with a model that includes surfaces saturation. Nonideal interactions between adsorbed surfactant molecules alter the partitioning of surfactant between the bulk and the interface, the dynamics of surfactant adsorptive/desorptive exchange, and the sensitivity of the surface tension to adsorbed surfactant. For example, cohesion between hydrocarbon chains favors strong adsorption. Cohesion also slows the rate of desorption from interfaces, and decreases the sensitivity of the surface tension to adsorbed surfactant. Strong cohesive interactions result in first order surface phase changes with a plateau in the surface tension vs surface concentration. Within this surface concentration range, the surface tension is decoupled from surface concentration gradients. We are engaged in the study of the role of surfactant physical chemistry in determining the Marangoni stresses on a drop in an extensional

  11. Molecular mobility in the monolayers of foam films stabilized by porcine lung surfactant.

    PubMed Central

    Lalchev, Z I; Todorov, R K; Christova, Y T; Wilde, P J; Mackie, A R; Clark, D C

    1996-01-01

    Certain physical properties of a range of foam film types that are believed to exist in vivo in the lung have been investigated. The contribution of different lung surfactant components found in porcine lung surfactant to molecular surface diffusion in the plane of foam films has been investigated for the first time. The influence of the type and thickness of black foam films, temperature, electrolyte concentration, and extract composition on surface diffusion has been studied using the fluorescence recovery after photobleaching technique. Fluorescent phospholipid probe molecules in foam films stabilized by porcine lung surfactant samples or their hydrophobic extracts consisting of surfactant lipids and hydrophobic lung surfactant proteins, SP-B and SP-C, exhibited more rapid diffusion than observed in films of its principal lipid component alone, L-alpha-phosphatidylcholine dipalmitoyl. This effect appears to be due to contributions from minor lipid components present in the total surfactant lipid extracts. The minor lipid components influence the surface diffusion in foam films both by their negative charge and by lowering the phase transition temperature of lung surfactant samples. In contrast, the presence of high concentrations of the hydrophillic surfactant protein A (SP-A) and non-lung-surfactant proteins in the sample reduced the diffusion coefficient (D) of the lipid analog in the adsorbed layer of the films. Hysteresis behavior of D was observed during temperature cycling, with the cooling curve lying above the heating curve. However, in cases where some surface molecular aggregation and surface heterogeneity were observed during cooling, the films became more rigid and molecules at the interfaces became immobilized. The thickness, size, capillary pressure, configuration, and composition of foam films of lung surfactant prepared in vitro support their investigation as realistic structural analogs of the surface films that exist in vivo in the lung

  12. Modeling adsorption: Investigating adsorbate and adsorbent properties

    NASA Astrophysics Data System (ADS)

    Webster, Charles Edwin

    1999-12-01

    Surface catalyzed reactions play a major role in current chemical production technology. Currently, 90% of all chemicals are produced by heterogeneously catalyzed reactions. Most of these catalyzed reactions involve adsorption, concentrating the substrate(s) (the adsorbate) on the surface of the solid (the adsorbent). Pore volumes, accessible surface areas, and the thermodynamics of adsorption are essential in the understanding of solid surface characteristics fundamental to catalyst and adsorbent screening and selection. Molecular properties such as molecular volumes and projected molecular areas are needed in order to convert moles adsorbed to surface volumes and areas. Generally, these molecular properties have been estimated from bulk properties, but many assumptions are required. As a result, different literature values are employed for these essential molecular properties. Calculated molar volumes and excluded molecular areas are determined and tabulated for a variety of molecules. Molecular dimensions of molecules are important in the understanding of molecular exclusion as well as size and shape selectivity, diffusion, and adsorbent selection. Molecular dimensions can also be used in the determination of the effective catalytic pore size of a catalyst. Adsorption isotherms, on zeolites, (crystalline mineral oxides) and amorphous solids, can be analyzed with the Multiple Equilibrium Analysis (MEA) description of adsorption. The MEA produces equilibrium constants (Ki), capacities (ni), and thermodynamic parameters (enthalpies, ΔHi, and entropies, ΔSi) of adsorption for each process. Pore volumes and accessible surface areas are calculated from the process capacities. Adsorption isotherms can also be predicted for existing and new adsorbate-adsorbent systems with the MEA. The results show that MEA has the potential of becoming a standard characterization method for microporous solids that will lead to an increased understanding of their behavior in gas

  13. Structural Studies of Protein-Surfactant Complexes

    SciTech Connect

    Chodankar, S. N.; Aswal, V. K.; Wagh, A. G.

    2008-03-17

    The structure of protein-surfactant complexes of two proteins bovine serum albumin (BSA) and lysozyme in presence of anionic surfactant sodium dodecyl sulfate (SDS) has been studied using small-angle neutron scattering (SANS). It is observed that these two proteins form different complex structures with the surfactant. While BSA protein undergoes unfolding on addition of surfactant, lysozyme does not show any unfolding even up to very high surfactant concentrations. The unfolding of BSA protein is caused by micelle-like aggregation of surfactant molecules in the complex. On the other hand, for lysozyme protein there is only binding of individual surfactant molecules to protein. Lysozyme in presence of higher surfactant concentrations has protein-surfactant complex structure coexisting with pure surfactant micelles.

  14. 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.

  15. 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.

  16. Measurement of laser activated electron tunneling from semiconductor zinc oxide to adsorbed organic molecules by a matrix assisted laser desorption ionization mass spectrometer.

    PubMed

    Zhong, Hongying; Fu, Jieying; Wang, Xiaoli; Zheng, Shi

    2012-06-04

    Measurement of light induced heterogeneous electron transfer is important for understanding of fundamental processes involved in chemistry, physics and biology, which is still challenging by current techniques. Laser activated electron tunneling (LAET) from semiconductor metal oxides was observed and characterized by a MALDI (matrix assisted laser desorption ionization) mass spectrometer in this work. Nanoparticles of ZnO were placed on a MALDI sample plate. Free fatty acids and derivatives were used as models of organic compounds and directly deposited on the surface of ZnO nanoparticles. Irradiation of UV laser (λ=355 nm) with energy more than the band gap of ZnO produces ions that can be detected in negative mode. When TiO(2) nanoparticles with similar band gap but much lower electron mobility were used, these ions were not observed unless the voltage on the sample plate was increased. The experimental results indicate that laser induced electron tunneling is dependent on the electron mobility and the strength of the electric field. Capture of low energy electrons by charge-deficient atoms of adsorbed organic molecules causes unpaired electron-directed cleavages of chemical bonds in a nonergodic pathway. In positive detection mode, electron tunneling cannot be observed due to the reverse moving direction of electrons. It should be able to expect that laser desorption ionization mass spectrometry is a new technique capable of probing the dynamics of electron tunneling. LAET offers advantages as a new ionization dissociation method for mass spectrometry.

  17. Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

    NASA Technical Reports Server (NTRS)

    Kumar, Nitin; Couzis, Alex; Maldarelli, Charles; Singh, Bhim S. (Technical Monitor)

    2000-01-01

    Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid/surfaces. At a hydrophobic surface, the air/hydrophobic solid tension is low, and the solid/aqueous tension is high. A large contact angle forms as the aqueous/air tension acts together with the solid/air tension to balance the large solid/aqueous tension. The aqueous phase, instead of spreading, is held in a meniscus by the large angle. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants (i.e. amphiphiles with a hydrophobic chain of methylene groups attached to a large polar group to give aqueous solubility) do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm or polyethylene. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3)) and an extended ethoxylate (-(OCH2CH2)n-) polar group in the form of a chain with seven or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (lermed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread and can be used in microgravity. We propose that the trisiloxane surfactants superspread when the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross sectional area of the disk is larger than that of the extended ethoxylate chain, the

  18. 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.

  19. Bio-inspired surfactants capable of generating plant volatiles.

    PubMed

    Bhadani, Avinash; Rane, Jayant; Veresmortean, Cristina; Banerjee, Sanjoy; John, George

    2015-04-21

    Plants are able to synthesize, store and release lipophilic organic molecules known as plant volatiles (PVs) utilizing specific biological pathways and different enzymes which play vital roles in the plant's defence and in dealing with biotic and abiotic stress situations. The process of generation, storage and release of PVs by plants acquired during the course of evolution is a very complex phenomenon. Bio-inspired molecular design of farnesol-based surfactants facilitates similar production, storage and release of PVs. The designed molecules adsorb at air-water interface and self-aggregate into micelles in aqueous system. The structural design of the molecules allows them to self-activate in water via intramolecular cation-π interactions. The activated molecules undergo molecular rearrangements generating volatile organic molecules both at interface and inside the micelle core. The molecules adsorbed at the interface initially release the formed volatile molecules creating vacant space at interface, thus thermodynamically directing the micelle to release the manufactured volatile products.

  20. Effect of an electric field on a methane molecule. I. Infrared analysis of methane (CH4-CD4) adsorbed in NaA zeolite in the temperature range 150-20 K

    NASA Astrophysics Data System (ADS)

    De Lara, E. Cohen; Kahn, R.; Seloudoux, R.

    1985-09-01

    The spectra of methane adsorbed at low temperature in NaA zeolite show two strong effects of the field existing in the cavities: (i) the appearance of the ν1 forbidden band which increases when decreasing the temperature and (ii) the splitting of the ν3 degenerate band. The variation with T of its components lead to the conclusion that the molecule progressively is oriented in a C3V configuration with respect to the field.

  1. Vibrational frequency shifts of diatomic molecules in interaction with a Na + cation by ab initio calculations. Comparison with experiment on H 2 and N 2 adsorbed in NaA zeolite

    NASA Astrophysics Data System (ADS)

    Koubi, Laure; Blain, Monique; de Lara, Evelyne Cohen; Leclerq, Jean-Marie

    1994-01-01

    Ab initio calculations on H 2 and N 2 and on the same molecules in the presence of a Na + cation are presented. The equilibrium configuration and the vibrational frequency shift due to the interaction are calculated. The potential energy surfaces are obtained by local osculatory interpolations and extrapolations. The vibrational frequencies are calculated by the Numerov—Cooley method. The direction of the frequency shift is found to be related to the orientation of the diatomic molecule with respect to the cation. The results are compared with experimental data on induced infrared bands of H 2 and N 2 adsorbed in NaA zeolite.

  2. 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.

  3. Controlled Clustering in Binary Charged Colloids by Adsorption of Ionic Surfactants.

    PubMed

    Nakamura, Yuki; Okachi, Manami; Toyotama, Akiko; Okuzono, Tohru; Yamanaka, Junpei

    2015-12-15

    We report on the controlled clustering of oppositely charged colloidal particles by the adsorption of ionic surfactants, which tunes charge numbers Z of particles. In particular, we studied the heteroclustering of submicron-sized polystyrene (PS) and silica particles, both of which are negatively charged, in the presence of cetylpyridinium chloride (CPC), a cationic surfactant. The surfactant concentration Csurf was selected below the critical micelle concentration. As CPC molecules were adsorbed, Z values of the PS and silica particles decreased, inverting to positive when Csurf exceeded the isoelectric point Ciep. Hydrophobic PS particles exhibited much lower Ciep than hydrophilic silica particles. At Csurf valuess between their Ciep values, the particles were oppositely charged, and clustering was enabled. To explain the clustering behavior, we investigated adsorption isotherms of the CPC and screened-Coulomb-type pair potential. Expected applications of the present findings are the control of colloidal associations and construction of various particle types into heterogeneous colloidal clusters.

  4. Electrokinetic investigation of surfactant adsorption.

    PubMed

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

    2007-05-15

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

  5. 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.

  6. Surfactants at the Design Limit.

    PubMed

    Czajka, Adam; Hazell, Gavin; Eastoe, Julian

    2015-08-04

    This article analyzes how the individual structural elements of surfactant molecules affect surface properties, in particular, the point of reference defined by the limiting surface tension at the aqueous cmc, γcmc. Particular emphasis is given to how the chemical nature and structure of the hydrophobic tails influence γcmc. By comparing the three different classes of surfactants, fluorocarbon, silicone, and hydrocarbon, a generalized surface packing index is introduced which is independent of the chemical nature of the surfactants. This parameter ϕcmc represents the volume fraction of surfactant chain fragments in a surface film at the aqueous cmc. It is shown that ϕcmc is a useful index for understanding the limiting surface tension of surfactants and can be useful for designing new superefficient surfactants.

  7. Tensiometry and dilational rheology of mixed β-lactoglobulin/ionic surfactant adsorption layers at water/air and water/hexane interfaces.

    PubMed

    Dan, Abhijit; Gochev, Georgi; Miller, Reinhard

    2015-07-01

    Oscillating drop tensiometry was applied to study adsorbed interfacial layers at water/air and water/hexane interfaces formed from mixed solutions of β-lactoglobulin (BLG, 1 μM in 10 mM buffer, pH 7 - negative net charge) and the anionic surfactant SDS or the cationic DoTAB. The interfacial pressure Π and the dilational viscoelasticity modulus |E| of the mixed layers were measured for mixtures of varying surfactant concentrations. The double capillary technique was employed which enables exchange of the protein solution in the drop bulk by surfactant solution (sequential adsorption) or by pure buffer (washing out). The first protocol allows probing the influence of the surfactant on a pre-adsorbed protein layer thus studying the protein/surfactant interactions at the interface. The second protocol gives access to the residual values of Π and |E| measured after the washing out procedure thus bringing information about the process of protein desorption. The DoTAB/BLG complexes exhibit higher surface activity and higher resistance to desorption in comparison with those for the SDS/BLG complexes due to hydrophobization via electrostatic binding of surfactant molecules. The neutral DoTAB/BLG complexes achieve maximum elastic response of the mixed layer. Mixed BLG/surfactant layers at the water/oil interface are found to reach higher surface pressure and lower maximum dilational elasticity than those at the water/air surface. The sequential adsorption mode experiments and the desorption study reveal that binding of DoTAB to pre-adsorbed BLG globules is somehow restricted at the water/air surface in comparison with the case of complex formation in the solution bulk and subsequently adsorbed at the water/air surface. Maximum elasticity is achieved with washed out layers obtained after simultaneous adsorption, i.e. isolation of the most surface active DoTAB/BLG complex. These specific effects are much less pronounced at the W/H interface.

  8. Effect of surfactant on temperature stability of solid lipid nanoparticles studied by dynamic light scattering

    NASA Astrophysics Data System (ADS)

    Kumar, Sacheen; Kaur, Jaspreet

    2013-06-01

    Solid lipid nanoparticles are new paradigm of drug delivery system of water insoluble active pharmaceutical ingredient. Paliperidone, an antipsychotic used in treatment of schizophrenia is a water insoluble molecule with low bioavailability was studied. Macrogol glyceride surfactant, bile salt based surfactant and sodium dodecyl sulphate were used to stabilize the solid lipid as dispersed nanoparticles form by adsorbing on the surface of the nanoparticles. Anionic surfactants bile salt and sodium dodecyl sulphate were found to stabilize forming a monomolecular layer of surfactants on the surface of nanoparticles; whereas macrogol glyceride based surfactant have intrusion in the matrix of lipid nanoparticles. So intrusion of macrogol glyceride in matrix was observed by studying the change in size of nanoparticles with respect to temperature with the help of dynamic light scattering. In case of macrogol glyceride size decrease start form 50°C, for bile salt and sodium dodecyl sulphate size deacrease start at 60°C. So that structural disturbance of nanoparticles by the macrogol glyceride on the surface was found maximum as compared to anionic surfactant.

  9. Lung surfactant.

    PubMed Central

    Rooney, S A

    1984-01-01

    Aspects of pulmonary surfactant are reviewed from a biochemical perspective. The major emphasis is on the lipid components of surfactant. Topics reviewed include surfactant composition, cellular and subcellular sites as well as pathways of biosynthesis of phosphatidylcholine, disaturated phosphatidylcholine and phosphatidylglycerol. The surfactant system in the developing fetus and neonate is considered in terms of phospholipid content and composition, rates of precursor incorporation, activities of individual enzymes of phospholipid synthesis and glycogen content and metabolism. The influence of the following hormones and other factors on lung maturation and surfactant production is discussed: glucocorticoids, thyroid hormone, estrogen, prolactin, cyclic AMP, beta-adrenergic and cholinergic agonists, prostaglandins and growth factors. The influence of maternal diabetes, fetal sex, stress and labor are also considered. Nonphysiologic and toxic agents which influence surfactant in the fetus, newborn and adult are reviewed. PMID:6145585

  10. Preparation and Thermal Properties of Fatty Alcohol/Surfactant/Oil/Water Nanoemulsions and Their Cosmetic Applications.

    PubMed

    Okamoto, Toru; Tomomasa, Satoshi; Nakajima, Hideo

    2016-01-01

    Physicochemical properties of oil-in-water (O/W) emulsions containing fatty alcohols and surfactants have been investigated with the aim of developing new formulations that are less viscous and more transparent than conventional milky lotions, as well as for providing greater skin-improving effects. O/W-based creams can be converted to low viscosity milky lotions following their emulsification with a homogenizer at temperatures greater than the transition temperatures of their molecular assemblies (α-gel). The stability of the O/W emulsions evaluated in the current study increased as the transition temperatures of the molecular assemblies formed from their fatty alcohol and surfactant constituents increased. A decrease in the emulsion droplet size led to the formation of a new formulation, which was transparent in appearance and showed a very low viscosity. The absence of a molecular assembly (α-gel) formed by the fatty alcohol and surfactant molecules in the aqueous phase allowed for the formation of a stable transparent and low viscosity nanoemulsion. Furthermore, this decrease in droplet size led to an increase in the interfacial area of the emulsion droplets, with almost all of the fatty alcohol and surfactant molecules being adsorbed on the surfaces of the emulsion droplets. This was found to be important for preparing a stable transparent formulation. Notably, this new formulation exhibited high occlusivity, which was equivalent to that of an ordinary cosmetic milky lotion, and consequently provided high skin hydration. The nanoemulsion was destroyed following its application to the skin, which led to the release of the fatty alcohol and surfactant molecules from the surface of the nanoemulsion into the aqueous phase. These results therefore suggest that the fatty alcohol and surfactant molecules organized the molecular assembly (α-gel) and allowed for the reconstruction of the network structure.

  11. Correlation between surface free energy of quartz and its wettability by aqueous solutions of nonionic, anionic and cationic surfactants.

    PubMed

    Zdziennicka, Anna; Szymczyk, Katarzyna; Jańczuk, Bronisław

    2009-12-15

    The measurements of the advancing contact angle for water, glycerol, diiodomethane and aqueous solutions of Triton X-100 (TX-100), Triton X-165 (TX-165), sodium dodecyl sulfate (SDDS), sodium hexadecyl sulfonate (SHDS), cetyltrimethylammonium bromide (CTAB) and cetylpyridinium bromide (CPyB) on quartz surface were carried out. On the basis of the contact angles values obtained for water, glycerol and diiodomethane the values of the Lifshitz-van der Waals component and electron-acceptor and electron-donor parameters of the acid-base component of the surface free energy of quartz were determined. The determined components and parameters of the quartz surface free energy were used for interpretation of the influence of nonionic, anionic and cationic surfactants on the wettability of the quartz. From obtained results it was appeared that the wettability of quartz by nonionic and anionic surfactants practically does not depend on the surfactants concentration in the range corresponding to their unsaturated monolayer at water-air interface and that there is linear dependence between adhesional and surface tension of aqueous solution of these surfactants. This dependence for TX-100, TX-165, SDDS and SHDS can be expressed by lines which slopes are positive. This slope and components of quartz surface free energy indicate that the interaction between the water molecules and quartz surface might be stronger than those between the quartz and surfactants molecules. So, the surface excess of surfactants concentration at the quartz-water interface is probably negative, and the possibility of surfactants to adsorb at the quartz/water film-water interface is higher than at the quartz-water interface. This conclusion is confirmed by the values of the adhesion work of "pure" surfactants, aqueous solutions of surfactants and water to quartz surface. In the case of the cationic surfactants the relationship between adhesional and surface tension is more complicated than that for

  12. Affinity transformation from hydrophilicity to hydrophobicity of water molecules on the basis of adsorption of water in graphitic nanopores.

    PubMed

    Ohba, Tomonori; Kanoh, Hirofumi; Kaneko, Katsumi

    2004-02-11

    The interaction of water with hydrophobic surfaces is quite important in a variety of chemical and biochemical phenomena. The coexistence of water and oil can be realized by introduction of surfactants. In the case of water vapor adsorption on graphitic nanopores, plenty of water can be adsorbed in graphitic nanopores without surfactants, although the graphitic surface is not hydrophilic. Why are water molecules adsorbed in hydrophobic nanopores remarkably? This work can give an explicit insight to water adsorption in hydrophobic graphite nanopores using experimental and theoretical approaches. Water molecules are associated with each other to form the cluster of 1 nm in size, leading to a significant stabilization of the cluster in the graphitic nanopores. This mechanism can be widely applied to interfacial phenomena relating to coexistence of water and nanostructural materials of hydrophobicity.

  13. Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

    NASA Technical Reports Server (NTRS)

    Kumar, Nitin; Couzis, Alex; Maldareili, Charles; Singh, Bhim (Technical Monitor)

    2001-01-01

    Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid surfaces. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants; (i.e., amphiphiles with a hydrophobic moiety consisting of an extended chain of (aliphatic) methylene -CH2- groups attached to a large polar group to give aqueous solubility) are capable of reducing the contact angles on surfaces which are not very hydrophobic, but do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm, polyethylene or self assembled monolayers. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3) and an extended ethoxylate (-(OCH2CH2)a-) polar group in the form of a chain with four or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (termed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread. We propose that the trisiloxane surfactants superspread because their structure allows them to strongly lower the high hydrophobic solid/aqueous tension when they adsorb to the solid surface. When the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross-sectional area of the disk is larger than that of the extended ethoxylate chain, the disks can form a space-filling mat on the surface which

  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.

  15. Incorporation and thermal evolution of rhodamine 6G dye molecules adsorbed in porous columnar optical SiO2 thin films.

    PubMed

    Sánchez-Valencia, Juan R; Blaszczyk-Lezak, Iwona; Espinós, Juan P; Hamad, Said; González-Elipe, Agustín R; Barranco, Angel

    2009-08-18

    Rhodamine 6G (Rh6G) dye molecules have been incorporated into transparent and porous SiO2 thin films prepared by evaporation at glancing angles. The porosity of these films has been assessed by analyzing their water adsorption isotherms measured for the films deposited on a quartz crystal monitor. Composite Rh6G/SiO2 thin films were prepared by immersion of a SiO2 thin film into a solution of the dye at a given pH. It is found that the amount of Rh6G molecules incorporated into the film is directly dependent on the pH of the solution and can be accounted for by a model based on the point of zero charge (PZC) concepts originally developed for colloidal oxides. At low pHs, the dye molecules incorporate in the form of monomers, while dimers or higher aggregates are formed if the pH increases. Depending on the actual preparation and treatment conditions, they also exhibit high relative fluorescence efficiency. The thermal stability of the composite films has been also investigated by characterizing their optical behavior after heating in an Ar atmosphere at increasing temperatures up to 275 degrees C. Heating induces a progressive loss of active dye molecules, a change in their agglomeration state, and an increment in their relative fluorescence efficiency. The obtained Rh6G/SiO2 composite thin films did not disperse the light and therefore can be used for integration into optical and photonic devices.

  16. Adsorbate Diffusion on Transition Metal Nanoparticles

    DTIC Science & Technology

    2015-01-01

    systematically studied adsorption and diffusion of atomic and diatomic species (H, C, N, O, CO, and NO) on nanometer-sized Pt and Cu nanoparticles with...species and two diatomic molecules (H, C, N, O, CO, and NO) as adsorbates and study the adsorption and diffusion of these adsorbates across the edges

  17. Adsorption Kinetics in Micellar Solutions of Nonionic Surfactants

    NASA Astrophysics Data System (ADS)

    Colegate, Daniel M.; Bain, Colin D.

    2005-11-01

    Standard models of the adsorption kinetics of surfactants at the air-water surface assume that micelles break down into monomers in the bulk solution and that only monomers adsorb. We show here that micelles of the nonionic surfactant C14E8 adsorb to the surface of a liquid jet at a diffusion-controlled rate. Micellar adsorption can be switched off by incorporation of a small amount of ionic surfactant into the micelle and switched on again by addition of salt. More sophisticated models of adsorption processes in micellar solutions are required that permit a kinetic flux of micelles to the air-water interface.

  18. Proteomic and Lipidomic Analysis of Nanoparticle Corona upon Contact with Lung Surfactant Reveals Differences in Protein, but Not Lipid Composition.

    PubMed

    Raesch, Simon Sebastian; Tenzer, Stefan; Storck, Wiebke; Rurainski, Alexander; Selzer, Dominik; Ruge, Christian Arnold; Perez-Gil, Jesus; Schaefer, Ulrich Friedrich; Lehr, Claus-Michael

    2015-12-22

    Pulmonary surfactant (PS) constitutes the first line of host defense in the deep lung. Because of its high content of phospholipids and surfactant specific proteins, the interaction of inhaled nanoparticles (NPs) with the pulmonary surfactant layer is likely to form a corona that is different to the one formed in plasma. Here we present a detailed lipidomic and proteomic analysis of NP corona formation using native porcine surfactant as a model. We analyzed the adsorbed biomolecules in the corona of three NP with different surface properties (PEG-, PLGA-, and Lipid-NP) after incubation with native porcine surfactant. Using label-free shotgun analysis for protein and LC-MS for lipid analysis, we quantitatively determined the corona composition. Our results show a conserved lipid composition in the coronas of all investigated NPs regardless of their surface properties, with only hydrophilic PEG-NPs adsorbing fewer lipids in total. In contrast, the analyzed NP displayed a marked difference in the protein corona, consisting of up to 417 different proteins. Among the proteins showing significant differences between the NP coronas, there was a striking prevalence of molecules with a notoriously high lipid and surface binding, such as, e.g., SP-A, SP-D, DMBT1. Our data indicate that the selective adsorption of proteins mediates the relatively similar lipid pattern in the coronas of different NPs. On the basis of our lipidomic and proteomic analysis, we provide a detailed set of quantitative data on the composition of the surfactant corona formed upon NP inhalation, which is unique and markedly different to the plasma corona.

  19. Use of surfactants to reduce the driving voltage of switchable optical elements based on electrowetting.

    PubMed

    Roques-Carmes, Thibault; Gigante, Alexandra; Commenge, Jean-Marc; Corbel, Serge

    2009-11-03

    The advantage of using electrowetting as a novel principle for a reflective display has been previously demonstrated. The principle is based on the controlled two-dimensional movement of an oil/water interface across a hydrophobic fluoropolymer insulator. The main objective of this paper is to show experimentally the influence of surfactants on the electro-optic behavior of a single electrowetting pixel. The concentration and type of nonionic surfactant (Tween 80 and Span 20) have been varied. The experimental data are compared with calculations from the electro-optic model developed previously. The electro-optic performance is significantly affected by the nature and the concentration of surfactant. In the presence of Tween, at concentrations lower than the critical micelle concentration (CMC), and mixtures of Tween and Span the electro-optic behavior can be related to the interfacial tension. When decreasing the oil/water interfacial tension, the amplitude of the driving voltage required for obtaining a given oil displacement decreases and the switching curve becomes steeper. These effects can be accurately reproduced by means of the previously developed electro-optic model. Mixtures of Tween and Span produce a significant synergetic reduction of the driving voltage. For Tween concentrations higher than the CMC and Span, a strong disagreement is observed between the previously developed model and experimental data. Here a new physical model is reported that describes the electro-optic behavior of electrowetting-based optical elements in the presence of surfactants. The model takes into account the actual voltage used to control the liquid movement in electrowetting (lower than the applied voltage), the amount of surfactant adsorbed at the decane/water interface, and the dipole moment of the surfactant molecules. The calculated results are in very good agreement with experimental data without employing fitting parameters. The dipoles interact with the applied

  20. Benchmarking the Self-Assembly of Surfactin Biosurfactant at the Liquid-Air Interface to those of Synthetic Surfactants.

    PubMed

    Onaizi, Sagheer A; Nasser, M S; Al-Lagtah, Nasir M A

    The adsorption of surfactin, a lipopeptide biosurfactant, at the liquid-air interface has been investigated in this work. The maximum adsorption density and the nature and the extent of lateral interaction between the adsorbed surfactin molecules at the interface were estimated from surface tension data using the Frumkin model. The quantitative information obtained using the Frumkin model was also compared to those obtained using the Gibbs equation and the Langmuir-Szyszkowski model. Error analysis showed a better agreement between the experimental and the calculated values using the Frumkin model relative to the other two models. The adsorption of surfactin at the liquid-air interface was also compared to those of synthetic anionic, sodium dodecylbenzenesulphonate (SDBS), and nonionic, octaethylene glycol monotetradecyl ether (C14E8), surfactants. It has been estimated that the area occupied by a surfactin molecule at the interface is about 3- and 2.5-fold higher than those occupied by SDBS and C14E8 molecules, respectively. The interaction between the adsorbed molecules of the anionic biosurfactant (surfactin) was estimated to be attractive, unlike the mild repulsive interaction between the adsorbed SDBS molecules.

  1. Molecularly Imprinted Filtering Adsorbents for Odor Sensing

    PubMed Central

    Shinohara, Sho; Chiyomaru, You; Sassa, Fumihiro; Liu, Chuanjun; Hayashi, Kenshi

    2016-01-01

    Versatile odor sensors that can discriminate among huge numbers of environmental odorants are desired in many fields, including robotics, environmental monitoring, and food production. However, odor sensors comparable to an animal’s nose have not yet been developed. An animal’s olfactory system recognizes odor clusters with specific molecular properties and uses this combinatorial information in odor discrimination. This suggests that measurement and clustering of odor molecular properties (e.g., polarity, size) using an artificial sensor is a promising approach to odor sensing. Here, adsorbents composed of composite materials with molecular recognition properties were developed for odor sensing. The selectivity of the sensor depends on the adsorbent materials, so specific polymeric materials with particular solubility parameters were chosen to adsorb odorants with various properties. The adsorption properties of the adsorbents could be modified by mixing adsorbent materials. Moreover, a novel molecularly imprinted filtering adsorbent (MIFA), composed of an adsorbent substrate covered with a molecularly imprinted polymer (MIP) layer, was developed to improve the odor molecular recognition ability. The combination of the adsorbent and MIP layer provided a higher specificity toward target molecules. The MIFA thus provides a useful technique for the design and control of adsorbents with adsorption properties specific to particular odor molecules. PMID:27886070

  2. 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.

  3. Surfactant compositions

    SciTech Connect

    Novakovic, M.; Abend, P.G.

    1987-09-29

    A surfactant composition is described for subsequent addition to a soap slurring comprising an acyloxy alkane sulfonate salt. The sulfonate salt is present in an amount by weight of about 44 percent of about 56 percent. The polyol is present in an amount by weight of about 2 percent to about 6 percent, and water is present in an amount by weight of 26 to 36 percent. The composition constituting a solid reversible solution at ambient temperature and having a solids content of about 58 to 72 percent, whereby subsequent addition of the surfactant composition to a soap slurry results in formation of a soap/detergent bar having a smooth texture, uniform wear properties and a lack of grittiness.

  4. Application of near infrared spectroscopy for the determination of adsorbed p-nitrophenol on HDTMA organoclay--implications for the removal of organic pollutants from water.

    PubMed

    Zhou, Qin; Xi, Yunfei; He, Hongping; Frost, Ray L

    2008-03-01

    NIR spectroscopy has been used to measure the adsorption of p-nitrophenol on untreated montmorillonite and surfactant exchanged montmorillonite. p-Nitrophenol is characterised by an intense NIR band at 8890 cm(-1) which shifts to 8840 cm(-1) upon adsorption on organoclay. The band was not observed for p-nitrophenol adsorbed on untreated montmorillonite. Both the montmorillonite and the surfactant modified montmorillonite are characterised by NIR bands at 7061 and 6791 cm(-1). The organoclay is characterised by two prominent bands at 5871 and 5667 cm(-1) assigned to the fundamental overtones of the mid-IR bands at 2916 and 2850 cm(-1). A band at 6017 cm(-1) is attributed to the p-nitrophenol adsorbed on the organoclay. The band is not observed for the montmorillonite with adsorbed p-nitrophenol. It is concluded that p-nitrophenol is adsorbed to significantly greater amounts on the organoclay compared with the untreated montmorillonite. The implication is that organoclays are most useful for removing organic molecules from water through adsorption.

  5. Adsorbed Tween 80 is unique in its ability to improve the stability of gold nanoparticles in solutions of biomolecules.

    PubMed

    Zhao, Yuyun; Wang, Zhuo; Zhang, Wei; Jiang, Xingyu

    2010-10-01

    This report shows that, of the Tween series (Tween 20, Tween 40, Tween 60 and Tween 80) of nonionic surfactants adsorbed on gold nanoparticles (NPs), Tween 80 makes the NPs most stably dispersed in aqueous solutions with or without the presence of representative biological molecules, such as nucleic acids or proteins of different sizes, isoelectric points (pIs) and shapes. In addition, the stability of gold NPs already modified with poly(L-lysine)-graft-poly(ethylene glycol) (PLL-PEG) or hexa(ethylene glycol)-terminated undecanylthiol (HS(CH(2))(11)EG(6)OH) is further improved in solutions of proteins when Tween 80 is co-adsorbed on the gold NPs. This strategy is the most effective when adsorption of Tween 80 on gold NPs precedes the coating of PLL-PEG or HS(CH(2))(11)EG(6)OH on the NPs.

  6. Wettability of a glass surface in the presence of two nonionic surfactant mixtures.

    PubMed

    Szymczyk, Katarzyna; Jańczuk, Bronisław

    2008-08-05

    Measurements of the advancing contact angle (theta) were carried out for aqueous solution of p-(1,1,3,3-tetramethylbutyl)phenoxypoly(ethylene glycol), Triton X-100 (TX100), and Triton X-165 (TX165) mixtures on glass. The obtained results indicate that the wettability of glass depends on the concentration and composition of the surfactant mixture. The relationship between the contact angle and concentration suggests that the lowest wettability corresponds to the concentration of TX100 and TX165 and their mixture near the critical micelle concentration (CMC). The minimum of the dependence between the contact angle and composition of the mixtures for each concentration at a monomer mole fraction of TX100, alpha, equals 0.2 and 0.4 points to synergism in the wettability of the glass surface. In contrast to the results of Zisman ( Zisman, W. A. In Contact Angle, Wettability and Adhesion; Gould, R. F., Ed.; Advances in Chemistry Series 43; American Chemical Society Washington, DC, 1964; p 1 ) there was no linear dependence between cos theta and the surface tension of aqueous solutions of TX100 and TX165 mixtures for all studied systems, but a linear dependence exists between the adhesional tension and surface tension for glass, practically, in the whole concentration range of surfactants studied, the slopes of which are positive in the range of 0.43-0.67. These positive slopes indicate that the interactions between the water molecules and glass surface might be stronger than those between the surface and surfactant molecules. So, the surface excess of surfactant concentration at the glass-water interface is probably negative, and the possibility for surfactant to adsorb at the glass/water film-water interface is higher than that at the glass-water interface. This conclusion is confirmed by the values of the work of adhesion of "pure" surfactants, aqueous solutions of surfactants, and aqueous solutions of their mixtures to the glass surface and by the negative values of

  7. Surfactant Effects on Particle Generation in Antibody Formulations in Pre-filled Syringes

    PubMed Central

    Gerhardt, Alana; McUmber, Aaron C.; Nguyen, Bao H.; Lewus, Rachael; Schwartz, Daniel K.; Carpenter, John F.; Randolph, Theodore W.

    2016-01-01

    Protein aggregation and particle formation have been observed when protein solutions contact hydrophobic interfaces, and it has been suggested that this undesirable phenomenon may be initiated by interfacial adsorption and subsequent gelation of the protein. The addition of surfactants, such as polysorbate 20, to protein formulations has been proposed as a way to reduce protein adsorption at silicone oil-water interfaces and mitigate the production of aggregates and particles. In an accelerated stability study, monoclonal antibody formulations containing varying concentrations of polysorbate 20 were incubated and agitated in pre-filled glass syringes (PFS), exposing the protein to silicone oil-water interfaces at the siliconized syringe walls, air-water interfaces, and agitation stress. Following agitation in siliconized syringes that contained an air bubble, lower particle concentrations were measured in the surfactant-containing antibody formulations than in surfactant-free formulations. Polysorbate 20 reduced particle formation when added at concentrations above or below the critical micelle concentration (CMC). The ability of polysorbate 20 to decrease particle generation in PFS corresponded with its ability to inhibit gelation of the adsorbed protein layer, which was assessed by measuring the interfacial diffusion of individual antibody molecules at the silicone oil-water interface using total internal reflectance fluorescence (TIRF) microscopy with single-molecule tracking. PMID:26413998

  8. Kinetic multi-layer model of the epithelial lining fluid (KM-ELF): Reactions of ozone and OH with antioxidants and surfactant molecules

    NASA Astrophysics Data System (ADS)

    Lakey, Pascale; Pöschl, Ulrich; Shiraiwa, Manabu

    2015-04-01

    Oxidants cause damage to biosurfaces such as the lung epithelium unless they are effectively scavenged. The respiratory tract is covered in a thin layer of fluid which extends from the nasal cavity to the alveoli and contain species that scavenge ozone and other incoming oxidants. The kinetic multi-layer model of the epithelial lining fluid (KM-ELF) has been developed in order to investigate the reactions of ozone and OH with antioxidants (ascorbate, uric acid, glutathione and α-tocopherol) and surfactant lipids and proteins within the epithelial lining fluid (ELF). The model incorporates different processes: gas phase diffusion, adsorption and desorption from the surface, bulk phase diffusion and known reactions at the surface and in the bulk. The ELF is split into many layers: a sorption layer, a surfactant layer, a near surface bulk layer and several bulk layers. Initial results using KM-ELF indicate that at ELF thicknesses of 80 nm and 1 × 10-4cm the ELF would become rapidly saturated with ozone with saturation occurring in less than a second. However, at an ELF thickness of 1 × 10-3cm concentration gradients were observed throughout the ELF and the presence of antioxidants reduced the O3 reaching the lung cells and tissues by 40% after 1 hour of exposure. In contrast, the antioxidants were efficient scavengers of OH radicals, although the large rate constants of OH reacting with the antioxidants resulted in the antioxidants decaying away rapidly. The chemical half-lives of the antioxidants and surface species were also calculated using KM-ELF as a function of O3 and OH concentration and ELF thickness. Finally, the pH dependence of the products of reactions between antioxidants and O3 were investigated. The KM-ELF model predicted that a harmful ascorbate ozonide product would increase from 1.4 × 1011cm-3at pH 7.4 to 1.1 × 1014 cm-3 at pH 4after 1 hour although a uric acid ozonide product would decrease from 2.0 × 1015cm-3to 5.9 × 1012cm-3.

  9. Preparation of nanocrystalline MgO by surfactant assisted precipitation method

    SciTech Connect

    Rezaei, Mehran; Khajenoori, Majid; Nematollahi, Behzad

    2011-10-15

    Highlights: {yields} Nanocrystalline magnesium oxide with high surface area. {yields} MgO prepared with surfactant showed different morphologies compared with the sample prepared without surfactant. {yields} MgO prepared with surfactant showed a plate-like shape. {yields} Refluxing temperature and time and the surfactant to metal molar ratio affect the textural properties of MgO. -- Abstract: Nanocrystalline magnesium oxide with high surface area was prepared by a simple precipitation method using pluronic P123 triblock copolymer (Poly (ethylene glycol)-block, Poly (propylene glycol)-block, Poly (ethylene glycol)) as surfactant and under refluxing conditions. The prepared samples were characterized by X-ray diffraction (XRD), N{sub 2} adsorption (BET) and scanning and transmission electron microscopies (SEM and TEM). The obtained results revealed that the refluxing time and temperature and the molar ratio of surfactant to metal affect the structural properties of MgO, because of the changes in the rate and extent of P123 adsorption on the prepared samples. The results showed that the addition of surfactant is effective to prepare magnesium oxide with high surface area and affects the morphology of the prepared samples. With increasing the P123/MgO molar ratio to 0.05 the pore size distribution was shifted to larger size. The sample prepared with addition of surfactant showed a plate-like shape which was completely different with the morphology of the sample prepared without surfactant. The formation of nanoplate-like MgO was related to higher surface density of Mg ions on the (0 0 1) plane than that on the other planes of the Mg(OH){sub 2} crystal. The (0 0 1) plane would be blocked preferentially by the adsorbed P123 molecules during the growing process of Mg(OH){sub 2} nanoentities and the growth on the (0 0 1) plane would be markedly restricted, and the consequence is the generation of nanoplate-like MgO. In addition, increase in refluxing temperature and time

  10. Equilibrium and non-equilibrium kinetics of self-assembled surfactant monolayers: a vibrational sum-frequency study of dodecanoate at the fluorite-water interface.

    PubMed

    Schrödle, Simon; Richmond, Geraldine L

    2008-04-16

    The adsorption, desorption, and equilibrium monomer exchange processes of sodium dodecanoate at the fluorite(CaF 2)-water interface have been studied. For the first time, we use in situ vibrational sum-frequency spectroscopy (VSFS) to gain insights into the mechanism and kinetics of monolayer self-assembly at the mineral-water interface. By exploiting the nonlinear optical response of the adsorbate, the temporal correlation of headgroup adsorption and alignment of the surfactant's alkyl chain was monitored. Because of the unique surface-specificity of VSFS, changes in the interfacial water structure were also tracked experimentally. The spectra clearly reveal that the structure of interfacial water molecules is severely disturbed at the start of the adsorption process. With the formation of a well-ordered adsorbate layer, it is partially reestablished; however, the molecular orientation and state of coordination is significantly altered. Even at very low surfactant concentrations, overcharging of the mineral surface (i.e., the adsorption of adsorbates past the point of electrostatic equilibrium) was observed. This points out the importance of effects other than electrostatic interactions and it is proposed that cooperative effects of both water structure and surfactant hemimicelle formation at the interface are key factors. The present study also investigates desorption kinetics of partially and fully established monolayers and a statistical model for data analysis is proposed. Additional experiments were performed in the presence of electrolytes and showed that uni- and divalent anions affect the nonequilibrium kinetics of self-assembled monolayers in strikingly different ways.

  11. The Dispersion Properties of Precipitated Calcium Carbonate Suspensions Adsorbed with Alkyl Polyglycoside in Aqueous Medium.

    PubMed

    Song, Myung-Geun; Kim, Jong-Yun; Kim, Jong-Duk

    2000-06-01

    The zeta potentials and dispersion properties of precipitated calcium carbonate suspensions adsorbed with alkyl polyglycosides in aqueous medium were investigated. Within the investigated pH ranges, the adsorption curves of alkyl polyglycosides on calcium carbonates show sigmoidal shapes, and the zeta potential decreases as the amount of adsorption increases. At positively charged surfaces of low pH, the adsorption amounts were greater than those at negatively charged surfaces, indicating that alkyl polyglycosides were negatively charged in aqueous solutions. At low concentrations of alkyl polyglycosides, the dispersion stabilities of suspensions were very poor and showed no linearity with zeta potentials over the entire range of pHs, which may be attributed to the onset of hydrophobic interaction between particles due to the adsorption of surfactant molecules. This destabilization continued until monolayer coverage by the surfactant layer was complete. Based on the classical DLVO theory, there may be a strong hydrophobic interaction between particles. Beyond monolayer adsorption, the dispersion stability increases, probably by the formation of hemimicelle or admicelle. Therefore, it is believed that ionization of alkyl polyglycosides and admicelles of surfactants on particle surface plays a key role in the stability of dispersions and the abrupt increase in adsorption. Copyright 2000 Academic Press.

  12. Drops in Space: Super Oscillations and Surfactant Studies

    NASA Technical Reports Server (NTRS)

    Apfel, Robert E.; Tian, Yuren; Jankovsky, Joseph; Shi, Tao; Chen, X.; Holt, R. Glynn; Trinh, Eugene; Croonquist, Arvid; Thornton, Kathyrn C.; Sacco, Albert, Jr.; Coleman, Catherine; Leslie, Fred W.; Matthiesen, David H.

    1996-01-01

    An unprecedented microgravity observation of maximal shape oscillations of a surfactant-bearing water drop the size of a ping pong ball was observed during a mission of Space Shuttle Columbia as part of the second United States Microgravity Laboratory-USML-2 (STS-73, October 20-November 5, 1995). The observation was precipitated by the action of an intense sound field which produced a deforming force on the drop. When this deforming force was suddenly reduced, the drop executed nearly free and axisymmetric oscillations for several cycles, demonstrating a remarkable amplitude of nonlinear motion. Whether arising from the discussion of modes of oscillation of the atomic nucleus, or the explosion of stars, or how rain forms, the complex processes influencing the motion, fission, and coalescence of drops have fascinated scientists for centuries. Therefore, the axisymmetric oscillations of a maximally deformed liquid drop are noteworthy, not only for their scientific value but also for their aesthetic character. Scientists from Yale University, the Jet Propulsion Laboratory (JPL) and Vanderbilt University conducted liquid drop experiments in microgravity using the acoustic positioning/manipulation environment of the Drop Physics Module (DPM). The Yale/JPL group's objectives were to study the rheological properties of liquid drop surfaces on which are adsorbed surfactant molecules, and to infer surface properties such as surface tension, Gibb's elasticity, and surface dilatational viscosity by using a theory which relies on spherical symmetry to solve the momentum and mass transport equations.

  13. Synergistic adsorption of mixtures of cationic gemini and nonionic sugar-based surfactant on silica.

    PubMed

    Zhou, Qiong; Somasundaran, P

    2009-03-15

    Adsorption behavior of cationic C(12)-C(4)-C(12) gemini surfactant on silica has been investigated, along with that of nonionic surfactant n-dodecyl-beta-D-maltoside (DM). While DM alone shows meager adsorption on silica, because of the lack of any electrostatic adsorption, cationic gemini adsorbs significantly on the oppositely charged silica surface. Due to the electrostatic nature of cationic gemini adsorption on silica, solution pH affects adsorption of C(12)-C(4)-C(12) gemini dramatically. Meanwhile, C(12)-C(4)-C(12) gemini hemimicelle size at silica/water interface does not seem to change with solution pH. For the mixtures of DM and cationic C(12)-C(4)-C(12) gemini, there is a sharp increase of DM adsorption at silica/water interface, up to 100 times more than DM alone. After mixing with DM, saturation adsorption of cationic C(12)-C(4)-C(12) gemini decreases, due to competition for adsorption sites from DM. At the same time, in its mixture with DM, there is an increased adsorption of C(12)-C(4)-C(12) gemini in the rising part of the adsorption isotherm. Hydrophobic chain-chain interactions, especially with two hydrophobic chains in one C(12)-C(4)-C(12) gemini molecule, and adsorbed C(12)-C(4)-C(12) gemini molecule acting as an anchor or nucleation sites for forming mixed aggregates with DM on silica surface, are attributed to the marked adsorption synergy between DM and cationic C(12)-C(4)-C(12) gemini. The adsorption of surfactants and their mixtures has a marked effect on silica surface charge and silica's wettability.

  14. Remobilizing the Interfaces of Thermocapillary Driven Bubbles Retarded by the Adsorption of a Surfactant Impurity on the Bubble Surface

    NASA Technical Reports Server (NTRS)

    Palaparthi, Ravi; Maldarelli, Charles; Papageorgiou, Dimitri; Singh, Bhim S. (Technical Monitor)

    2000-01-01

    Thermocapillary migration is a method for moving bubbles in space in the absence of buoyancy. A temperature gradient is applied to the continuous phase in which a bubble is situated, and the applied gradient impressed on the bubble surface causes one pole of the drop to be cooler than the opposite pole. As the surface tension is a decreasing function of temperature, the cooler pole pulls at the warmer pole, creating a flow which propels the bubble in the direction of the warmer fluid. A major impediment to the practical use of thermocapillarity to direct the movement of bubbles in space is the fact that surfactant impurities which are unavoidably present in the continuous phase can significantly reduce the migration velocity. A surfactant impurity adsorbed onto the bubble interface is swept to the trailing end of the bubble. When bulk concentrations are low (which is the case with an impurity), diffusion of surfactant to the front end is slow relative to convection, and surfactant collects at the back end of the bubble. Collection at the back lowers the surface tension relative to the front end setting up a reverse tension gradient. For buoyancy driven bubble motions in the absence of a thermocapillarity, the tension gradient opposes the surface flow, and reduces the surface and terminal velocities (the interface becomes more solid-like). When thermocapillary forces are present, the reverse tension gradient set up by the surfactant accumulation reduces the temperature tension gradient, and decreases to near zero the thermocapillary velocity. The objective of our research is to develop a method for enhancing the thermocapillary migration of bubbles which have been retarded by the adsorption onto the bubble surface of a surfactant impurity, Our remobilization theory proposes to use surfactant molecules which kinetically rapidly exchange between the bulk and the surface and are at high bulk concentrations. Because the remobilizing surfactant is present at much higher

  15. 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.

  16. Picosecond adsorbate dynamics at condensed phase interfaces

    SciTech Connect

    Scott, T.W.; Chang, Y.J.; Martorell, J.

    1993-12-31

    Picosecond surface second harmonic generation has been used to probe a variety of elementary adsorbate reactions at liquid-solid interfaces. Electron transfer reactions at semiconductor-liquid junctions, geminate recombination of photogenerated free radical pairs and the orientational dynamics of dipolar adsorbates have all been explored in varying degrees of detail. These kinetic studies have led to a detailed analysis of adsorbate detection on the surface of non-centrosymmetric substrates as well as the use of total internal reflection geometries for signal enhancement from optically absorbing liquids. Particular emphasis has been placed on the static and dynamic characterization of adsorbate orientational distribution functions and how these are determined from the torque exerted on adsorbates by the angular part of the molecule-surface interaction potential.

  17. 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.

  18. Nonionic surfactants enhancing bactericidal activity at their critical micelle concentrations.

    PubMed

    Tobe, Seiichi; Majima, Toshiaki; Tadenuma, Hirohiko; Suekuni, Tomonari; Sakai, Kenichi; Sakai, Hideki; Abe, Masahiko

    2015-01-01

    Bactericidal activities of benzalkonium chloride [also known as alkyldimethylbenzylammonium chloride (ADBAC)] containing nonionic surfactants such as methyl ester ethoxylates (MEE) with the alkyl group C8-C14 and oxyethylene (EO) group of average adduct number 3-15 were measured against Escherichia coli and Staphylococcus aureus. Sample solutions containing MEE in the vicinity of the critical micelle concentration exhibited a dramatic decrease in viable bacterial counts. MEE with an alkyl group of C12 and an oxyethylene group of lower adduct number exhibited little viable bacterial counts than those having higher EO adduct numbers. MEE with reduced EO adduct numbers increased fluorescence intensity in E. coli using the viability stain SYTO 9. Our results show that MEE molecules with low EO adduct numbers exhibited bactericidal activity by increasing the permeability of the E. coli cell membrane. Sample solution containing ADBAC and MEE molecules with lower EO adduct numbers also displayed higher zeta potentials. Moreover, ADBAC molecules incorporated into micelles of MEE with lower EO adduct numbers were adsorbed onto the surface of E. coli, which augmented bactericidal activity.

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

    DOE PAGES

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

    2016-07-23

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

  20. Droplet impact on liquid films in the presence of surfactants

    NASA Astrophysics Data System (ADS)

    Jais, Khadijah; Yip, Natalie; Che, Zhizhao; Matar, Omar

    2016-11-01

    In this study of droplet impact on liquid films, surfactants are added to the droplet, the liquid film or both, and the effects of different surfactant concentrations are investigated using high-speed imaging. The results show that surfactants suppress partial coalescence, due to damping of the capillary waves. Rebounding occurs more frequently when surfactants are added, as the surfactant molecules resist the drainage of the intervening air layer. When the droplet deforms the surfactant film, there is an uneven distribution of surfactant molecules along the interface, resulting in a surface tension gradient and a Marangoni stress. The Marangoni stress acts to even out the surface tension gradient and to aid rebounding. Surfactant droplet ruptures the film with a much lower surfactant concentration, leaving an apparent dry region on the substrate at the impact point. This is likely due to Marangoni stresses where the film pulls the droplet apart. As the film thickness is increased, a Worthington jet is formed, with secondary droplet(s) ejected from the jet only when surfactants are present. This study reveals that the presence of surfactants can significantly alter the impact process of droplets on liquid films. EPSRC UK Programme Grant MEMPHIS (EP/K003976/1).

  1. Structure and Conformational Dynamics of DMPC/Dicationic Surfactant and DMPC/Dicationic Surfactant/DNA Systems

    PubMed Central

    Pietralik, Zuzanna; Krzysztoń, Rafał; Kida, Wojciech; Andrzejewska, Weronika; Kozak, Maciej

    2013-01-01

    Amphiphilic dicationic surfactants, known as gemini surfactants, are currently studied for gene delivery purposes. The gemini surfactant molecule is composed of two hydrophilic “head” groups attached to hydrophobic chains and connected via molecular linker between them. The influence of different concentrations of 1,5-bis (1-imidazolilo-3- decyloxymethyl) pentane chloride (gemini surfactant) on the thermotropic phase behaviour of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) bilayers with and without the presence of DNA was investigated using Fourier transformed infrared (FTIR) and circular dichroism (CD) spectroscopies, small angle scattering of synchrotron radiation and differential scanning calorimetry. With increasing concentration of surfactant in DMPC/DNA systems, a disappearance of pretransition and a decrease in the main phase transition enthalpy and temperature were observed. The increasing intensity of diffraction peaks as a function of surfactant concentration also clearly shows the ability of the surfactant to promote the organisation of lipid bilayers in the multilayer lamellar phase. PMID:23571492

  2. Adsorption of mixed cationic-nonionic surfactant and its effect on bentonite structure.

    PubMed

    Zhang, Yaxin; Zhao, Yan; Zhu, Yong; Wu, Huayong; Wang, Hongtao; Lu, Wenjing

    2012-01-01

    The adsorption of cationic-nonionic mixed surfactant onto bentonite and its effect on bentonite structure were investigated. The objective was to improve the understanding of surfactant behavior on clay mineral for its possible use in remediation technologies of soil and groundwater contaminated by toxic organic compounds. The cationic surfactant used was hexadecylpyridinium bromide (HDPB), and the nonionic surfactant was Triton X-100 (TX100). Adsorption of TX100 was enhanced significantly by the addition of HDPB, but this enhancement decreased with an increase in the fraction of the cationic surfactant. Part of HDPB was replaced by TX100 which decreased the adsorption of HDPB. However, the total adsorbed amount of the mixed surfactant was still increased substantially, indicating the synergistic effect between the cationic and nonionic surfactants. The surfactant-modified bentonite was characterized by Brunauer-Emmett-Teller specific surface area measurement, Fourier transform infrared spectroscopy, and thermogravimetric-derivative thermogravimetric/differential thermal analyses. Surfactant intercalation was found to decrease the bentonite specific surface area, pore volume, and surface roughness and irregularities, as calculated by nitrogen adsorption-desorption isotherms. The co-adsorption of the cationic and nonionic surfactants increased the ordering conformation of the adsorbed surfactants on bentonite, but decreased the thermal stability of the organobentonite system.

  3. The effects of surfactants on the desorption of organic contaminants from aquifer materials

    SciTech Connect

    Brickell, J.L.

    1989-01-01

    The efficiency of removing organic contaminants from groundwater aquifers by the pump and treat process is adversely affected by the retardation of the contaminant's mobility due to adsorption onto aquifer material. The use of surfactants in conjunction with the pump and treat process has the potential for improving contaminant mobility by solubilizing the adsorbed contaminant. An experimental program was conducted to screen various types of commercially available nonionic and anionic surfactants for solubilizing adsorbed naphthalene from one type of aquifer material. Two additional types of aquifer materials were obtained, and the surfactant mixture, Tween 20 and Aerosol AY-65, selected during the screening process was used at various concentrations for equilibrium desorption studies to quantify surfactant effects on naphthalene desorption. Column studies subsequently were conducted to determine surfactant effects in a flow through system. Equilibrium desorption studies showed that a 0.125% surfactant solution decreased the partition coefficient 65% compared with water alone for one soil type, while greater surfactant concentrations resulted in less effective mobilization. However, the same surfactant mixture markedly increased the partition coefficient when used with another soil type, and had negligible effects for the third soil type. It was shown that the clay mineralogy significantly influenced the effect of the surfactant solution. Column studies showed that mass removal efficiencies were increased by approximately 40 to 60% using the surfactant solution as compared with water alone. Varying flow rates did not influence the effectiveness of either the surfactant or water solutions.

  4. Adsorbed Tween 80 is unique in its ability to improve the stability of gold nanoparticles in solutions of biomolecules

    NASA Astrophysics Data System (ADS)

    Zhao, Yuyun; Wang, Zhuo; Zhang, Wei; Jiang, Xingyu

    2010-10-01

    This report shows that, of the Tween series (Tween 20, Tween 40, Tween 60 and Tween 80) of nonionic surfactants adsorbed on gold nanoparticles (NPs), Tween 80 makes the NPs most stably dispersed in aqueous solutions with or without the presence of representative biological molecules, such as nucleic acids or proteins of different sizes, isoelectric points (pIs) and shapes. In addition, the stability of gold NPs already modified with poly(L-lysine)-graft-poly(ethylene glycol) (PLL-PEG) or hexa(ethylene glycol)-terminated undecanylthiol (HS(CH2)11EG6OH) is further improved in solutions of proteins when Tween 80 is co-adsorbed on the gold NPs. This strategy is the most effective when adsorption of Tween 80 on gold NPs precedes the coating of PLL-PEG or HS(CH2)11EG6OH on the NPs.This report shows that, of the Tween series (Tween 20, Tween 40, Tween 60 and Tween 80) of nonionic surfactants adsorbed on gold nanoparticles (NPs), Tween 80 makes the NPs most stably dispersed in aqueous solutions with or without the presence of representative biological molecules, such as nucleic acids or proteins of different sizes, isoelectric points (pIs) and shapes. In addition, the stability of gold NPs already modified with poly(L-lysine)-graft-poly(ethylene glycol) (PLL-PEG) or hexa(ethylene glycol)-terminated undecanylthiol (HS(CH2)11EG6OH) is further improved in solutions of proteins when Tween 80 is co-adsorbed on the gold NPs. This strategy is the most effective when adsorption of Tween 80 on gold NPs precedes the coating of PLL-PEG or HS(CH2)11EG6OH on the NPs. Electronic supplementary information (ESI) available: Chemical structures and physicochemical properties of nonionic surfactants of Tween series, transmission electron microscopy of gold NPs stabilized by citrate and size distribution. See DOI: 10.1039/c0nr00309c

  5. Two-dimensional photonic crystal surfactant detection.

    PubMed

    Zhang, Jian-Tao; Smith, Natasha; Asher, Sanford A

    2012-08-07

    We developed a novel two-dimensional (2-D) crystalline colloidal array photonic crystal sensing material for the visual detection of amphiphilic molecules in water. A close-packed polystyrene 2-D array monolayer was embedded in a poly(N-isopropylacrylamide) (PNIPAAm)-based hydrogel film. These 2-D photonic crystals placed on a mirror show intense diffraction that enables them to be used for visual determination of analytes. Binding of surfactant molecules attaches ions to the sensor that swells the PNIPAAm-based hydrogel. The resulting increase in particle spacing red shifts the 2-D diffracted light. Incorporation of more hydrophobic monomers increases the sensitivity to surfactants.

  6. Tween surfactants: Adsorption, self-organization, and protein resistance

    NASA Astrophysics Data System (ADS)

    Shen, Lei; Guo, Athena; Zhu, Xiaoyang

    2011-03-01

    Tween surfactants, each containing hydrophilic ethylene glycol head groups and a hydrophobic alkyl tail, are being actively explored as protein-resistant surface coatings, but little is known about how they adsorb on surfaces. We carry out a comparative study of the adsorption of two Tween molecules (same hydrophilic head group, but a shorter dodecyl tail for Tween 20 and a longer octadecyl tail for Tween 40) on Au and polystyrene surfaces. Despite the similarity between these two molecules, there is a drastic difference in their protein resistance: a monolayer of Tween 20 on a hydrophobic surface is repulsive against protein adsorption but that of Tween 40 is not. The difference in protein resistance can be attributed to two distinctly different adsorption mechanisms. While the adsorption of Tween 40 is described by a simple first-order mechanism, that of Tween 20 consists of a fast adsorption step and a slower reorganization process at a high surface coverage. The latter leads to the formation of a high-density and self-organized monolayer, which is responsible for the enhanced stability and resistance against non-specific protein adsorption.

  7. DNA compaction by azobenzene-containing surfactant

    SciTech Connect

    Zakrevskyy, Yuriy; Kopyshev, Alexey; Lomadze, Nino; Santer, Svetlana

    2011-08-15

    We report on the interaction of cationic azobenzene-containing surfactant with DNA investigated by absorption and fluorescence spectroscopy, dynamic light scattering, and atomic force microscopy. The properties of the surfactant can be controlled with light by reversible switching of the azobenzene unit, incorporated into the surfactant tail, between a hydrophobic trans (visible irradiation) and a hydrophilic cis (UV irradiation) configuration. The influence of the trans-cis isomerization of the azobenzene on the compaction process of DNA molecules and the role of both isomers in the formation and colloidal stability of DNA-surfactant complexes is discussed. It is shown that the trans isomer plays a major role in the DNA compaction process. The influence of the cis isomer on the DNA coil configuration is rather small. The construction of a phase diagram of the DNA concentration versus surfactant/DNA charge ratio allows distancing between three major phases: colloidally stable and unstable compacted globules, and extended coil conformation. There is a critical concentration of DNA above which the compacted globules can be hindered from aggregation and precipitation by adding an appropriate amount of the surfactant in the trans configuration. This is because of the compensation of hydrophobicity of the globules with an increasing amount of the surfactant. Below the critical DNA concentration, the compacted globules are colloidally stable and can be reversibly transferred with light to an extended coil state.

  8. Adsorption of dimeric surfactants in lamellar silicates

    NASA Astrophysics Data System (ADS)

    Balcerzak, Mateusz; Pietralik, Zuzanna; Domka, Ludwik; Skrzypczak, Andrzej; Kozak, Maciej

    2015-12-01

    The adsorption of different types of cationic surfactants in lamellar silicates changes their surface character from hydrophilic to hydrophobic. This study was undertaken to obtain lamellar silicates modified by a series of novel dimeric (gemini) surfactants of different length alkyl chains and to characterise these organophilised materials. Synthetic sodium montmorillonite SOMASIF® ME 100 (M) and enriched bentonite of natural origin (Nanoclay - hydrophilic bentonite®) were organophilised with dimeric (gemini) surfactants (1,1‧-(1,4-butanediyl)bis(alkoxymethyl)imidazolium dichlorides). As a result of surfactant molecule adsorption in interlamellar space, the d-spacing (d001) increased from 0.97 nm (for the anhydrous structure) to 2.04 nm. A Fourier transform infrared spectroscopy (FTIR) analysis of the modified systems reveals bands assigned to the stretching vibrations of the CH2 and CH3 groups and the scissoring vibrations of the NH group from the structure of the dimeric surfactants. Thermogravimetric (TG) and derivative thermogravimetric (DTG) studies imply a four-stage process of surfactant decomposition. Scanning electron microscopy (SEM) images provide information on the influence of dimeric surfactant intercalation into the silicate structures. Particles of the modified systems show a tendency toward the formation of irregularly shaped agglomerates.

  9. Rheology of Natural Lung Surfactant Films

    NASA Astrophysics Data System (ADS)

    Alonso, Coralie; Waring, Alan; Zsadzinski, Joseph

    2004-03-01

    The lung surfactant (LS) is a lipoprotein mixture lining the inside of the pulmonary alveoli which has the ability to lower the surface tension of the air-liquid hypophase interface to value near zero thus reducing the work of breathing and which also prevents the alveolar collapse. A lack or malfunction of lung surfactant, as it is often the case for premature infants, leads to respiratory distress syndrome. RDS can be treated by supplying replacement LS to the infants and several medications derived from natural sources, are now widely used. The lung surfactant is adsorbed at the air-liquid interface and is subjected to incessant compression expansion cycles therefore Langmuir monolayers provide a suitable model to investigate the physical properties of lung surfactant films. Using a magnetic needle rheometer, we measured the shear viscosity of natural lung surfactant spread at the air-liquid interface upon compression and expansion cycles for three different formulations. The shear viscosity of Survanta changes by orders of magnitude along one cycle while for Curosurf samples it changes only slightly and for Infasurf films it remains constant. These different behaviors can be explained by differences in composition between the three formulations leading to different organizations on the molecular scale.

  10. Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

    NASA Technical Reports Server (NTRS)

    Kumar, Nitin; Couzis, Alex; Maldareili, Charles; Singh, Bhim (Technical Monitor)

    2001-01-01

    Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid surfaces. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants; (i.e., amphiphiles with a hydrophobic moiety consisting of an extended chain of (aliphatic) methylene -CH2- groups attached to a large polar group to give aqueous solubility) are capable of reducing the contact angles on surfaces which are not very hydrophobic, but do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm, polyethylene or self assembled monolayers. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3) and an extended ethoxylate (-(OCH2CH2)a-) polar group in the form of a chain with four or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (termed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread. We propose that the trisiloxane surfactants superspread because their structure allows them to strongly lower the high hydrophobic solid/aqueous tension when they adsorb to the solid surface. When the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross-sectional area of the disk is larger than that of the extended ethoxylate chain, the disks can form a space-filling mat on the surface which

  11. Microbial surfactants and their potential applications: an overview.

    PubMed

    Mukherjee, Ashis K; Das, Kishore

    2010-01-01

    Biosurfactant or microbial surfactants produced by microbes are structurally diverse and heterogeneous groups of surface-active amphipathic molecules. They are capable of reducing surface and interfacial tension and have a wide range of industrial and environmental applications. The present chapter reviews the biochemical properties of different classes of microbial surfactants and their potential application in different industrial sectors.

  12. Surfactant Activated Dip-Pen Nanolithography

    NASA Astrophysics Data System (ADS)

    Collier, C. Patrick

    2005-03-01

    Direct nanoscale patterning of maleimide-linked biotin on mercaptosilane-functionalized glass substrates using dip-pen nanolithography (DPN) is facilitated by the addition of a small amount of the biocompatible nonionic surfactant Tween-20. A correlation was found between activated ink transfer from the AFM tip when surfactant was included in the ink and an increase in the wettability of the partially hydrophobic silanized substrate. Surfactant concentration represents a new control variable for DPN that complements relative humidity, tip-substrate contact force, scan speed, and temperature. Using surfactants systematically as ink additives expands the possible ink-substrate combinations that can be used for patterning biotin and other molecules. For example, we are currently exploring the possibility of developing nickel/nitrilotriacetic acid (NTA)-maleimide based inks that will bind to mercaptosilanized glass surfaces for the reversible immobilization of biomolecules containing polyhistidine tags.

  13. Vibrational sum frequency spectroscopy of surfactants and phospholipid monolayers at liquid-liquid interfaces

    NASA Astrophysics Data System (ADS)

    Smiley, Beth L.; Walker, R. A.; Gragson, D. E.; Hannon, T. E.; Richmond, Geraldine L.

    1998-04-01

    Work from our laboratory on vibrational sum frequency spectroscopic investigations of molecular ordering at the carbon tetrachloride-water interface is reviewed. Simple charged surfactants adsorbed at the liquid-liquid interface are seen to induce alignment of interfacial water molecules to a degree which is dependent on the induced surface potential. Saturation of water molecule alignment occurs at a surfactant surface concentration corresponding to a calculated surface potential of approximately 160 mV. In complementary studies, the relative degree of hydrocarbon chain ordering within monolayers of symmetric phosphatidylcholines of different chain lengths is inferred by the relative signal contributions of the methyl and methylene symmetric stretch modes. The degree of hydrocarbon chain disorder observed depends strongly on the method of monolayer preparation. By one method, a decrease in hydrocarbon chain order is seen with increasing chain length. Another method of monolayer formation yielded very well ordered hydrocarbon chains for the longest chain phosphatidylcholine studied, and showed much greater disorder in shorter chain species which was comparable to the other preparation method. These studies are a foundation for further work with this technique geared towards understanding molecular-level structural features in membrane-like assemblies and surface biochemical interactions of relevance to biomedical research.

  14. Adsorption of phenanthrene on multilayer graphene as affected by surfactant and exfoliation.

    PubMed

    Zhao, Jian; Wang, Zhenyu; Zhao, Qing; Xing, Baoshan

    2014-01-01

    Surfactant mediated exfoliation of multilayer graphene and its effects on phenanthrene adsorption were investigated using a passive dosing technique. In the absence of surfactant (sodium cholate, NaC), multilayer graphene had higher adsorption capacity for phenanthrene than carbon nanotube and graphite due to the higher surface area and micropore volume. The observed desorption hysteresis is likely caused by the formation of closed interstitial spaces through folding and rearrangement of graphene sheets. In the presence of NaC (both 100 and 8000 mg/L), phenanthrene adsorption on graphene was decreased due to the direct competition of NaC molecules on the graphene surface. With the aid of sonication, multilayer graphene sheets were exfoliated by NaC, leading to better dispersion. The degree of dispersion depended on the graphene-NaC ratio in aqueous solution rather than critical micelle concentration of NaC, and the good dispersion occurred after reaching adsorption saturation of NaC molecules on graphene sheets. In addition, exfoliation weakened the competition between phenanthrene and NaC and enhanced the adsorption capacity of graphene for phenanthrene due to exposed new sites. The findings on exfoliation of graphene sheets and related adsorption properties highlight not only the potential applications of multilayer graphene as efficient adsorbent but also its possible environmental risk.

  15. Surfactant-enhanced remediation of organic contaminated soil and water.

    PubMed

    Paria, Santanu

    2008-04-21

    Surfactant based remediation technologies for organic contaminated soil and water (groundwater or surface water) is of increasing importance recently. Surfactants are used to dramatically expedite the process, which in turn, may reduce the treatment time of a site compared to use of water alone. In fact, among the various available remediation technologies for organic contaminated sites, surfactant based process is one of the most innovative technologies. To enhance the application of surfactant based technologies for remediation of organic contaminated sites, it is very important to have a better understanding of the mechanisms involved in this process. This paper will provide an overview of the recent developments in the area of surfactant enhanced soil and groundwater remediation processes, focusing on (i) surfactant adsorption on soil, (ii) micellar solubilization of organic hydrocarbons, (iii) supersolubilization, (iv) density modified displacement, (v) degradation of organic hydrocarbon in presence surfactants, (vi) partitioning of surfactants onto soil and liquid organic phase, (vii) partitioning of contaminants onto soil, and (viii) removal of organics from soil in presence of surfactants. Surfactant adsorption on soil and/or sediment is an important step in this process as it results in surfactant loss reduced the availability of the surfactants for solubilization. At the same time, adsorbed surfactants will retained in the soil matrix, and may create other environmental problem. The biosurfactants are become promising in this application due to their environmentally friendly nature, nontoxic, low adsorption on to soil, and good solubilization efficiency. Effects of different parameters like the effect of electrolyte, pH, soil mineral and organic content, soil composition etc. on surfactant adsorption are discussed here. Micellar solubilization is also an important step for removal of organic contaminants from the soil matrix, especially for low aqueous

  16. Competitive adsorption of surfactants and hydrophilic silica particles at the oil-water interface: interfacial tension and contact angle studies.

    PubMed

    Pichot, R; Spyropoulos, F; Norton, I T

    2012-07-01

    The effect of surfactants' type and concentration on the interfacial tension and contact angle in the presence of hydrophilic silica particles was investigated. Silica particles have been shown to have an antagonistic effect on interfacial tension and contact angle in the presence of both W/O and O/W surfactants. Silica particles, combined with W/O surfactant, have no effect on interfacial tension, which is only dictated by the surfactant concentration, while they strongly affect interfacial tension when combined with O/W surfactants. At low O/W surfactant, both particles and surfactant are adsorbed at the interface, modifying the interface structure. At higher concentration, interfacial tension is only dictated by the surfactant. By increasing the surfactant concentration, the contact angle that a drop of aqueous phase assumes on a glass substrate placed in oil media decreases or increases depending on whether the surfactant is of W/O or O/W type, respectively. This is due to the modification of the wettability of the glass by the oil or water induced by the surfactants. Regardless of the surfactant's type, the contact angle profile was dictated by both particles and surfactant at low surfactant concentration, whereas it is dictated by the surfactant only at high concentration.

  17. The binding and insertion of imidazolium-based ionic surfactants into lipid bilayers: the effects of the surfactant size and salt concentration.

    PubMed

    Lee, Hwankyu; Jeon, Tae-Joon

    2015-02-28

    Imidazolium-based ionic surfactants with hydrocarbon tails of different sizes were simulated with lipid bilayers at different salt concentrations. Starting with the random position of ionic surfactants outside the bilayer, surfactants with long tails mostly insert into the bilayer, while those with short tails show the insertion of fewer surfactant molecules, indicating the effect of the tail length. In particular, surfactants with a tail of two or four hydrocarbons insert and reversibly detach from the bilayer, while the inserted longer surfactants cannot be reversibly detached because of the strong hydrophobic interaction with lipid tails, in quantitative agreement with experiments. Longer surfactants insert more deeply and irreversibly into the bilayer and thus increase lateral diffusivities of the bilayer, indicating that longer surfactants more significantly disorder lipid bilayers, which also agrees with experiments regarding the effect of the tail length of ionic surfactants on membrane permeability and toxicity. Addition of NaCl ions weakens the electrostatic interactions between headgroups of surfactants and lipids, leading to the binding of fewer surfactants into the bilayer. In particular, our simulation findings indicate that insertion of ionic surfactants can be initiated by either the hydrophobic interaction between tails of surfactants and lipids or the electrostatic binding between imidazolium heads and lipid heads, and the strength of hydrophobic and electrostatic interactions depends on the tail length of surfactants.

  18. Biodegradation of phenanthrene in soils in the presence of surfactants

    SciTech Connect

    Jahan, K.

    1993-01-01

    This research addresses the effect of low surfactant concentrations on the biodegradation of slightly soluble organic compounds in the presence and absence of soil. Biodegradation of phenanthrene in excess of its aqueous solubility by an acclimated mixed culture was studied in the presence of nonionic surfactants. Nonionic surfactants were selected over other types of surfactants because of their higher hydrocarbon solubilizing power, weaker adsorption to charged sites, less toxicity to bacteria, and poor foaming properties. Surfactants were tested to measure their effectiveness for increasing the solubility of phenanthrene, their adsorption on the soil matrix, their biodegradability, their effect on the adsorption of phenanthrene and on the rates of biodegradation of phenanthrene. Solubility enhancement studies of phenanthrene by the surfactants indicated relatively small effects at sub-micellar surfactant concentrations. Batch biodegradation studies in which phenanthrene was available as particulates and as a surface coating on sand were carried out in closed BOD bottles in the Hach manometric system. Addition of surfactants at 25 mg/L enhanced biodegradation rates as measured by oxygen uptake, protein production and disappearance of phenanthrene. A dynamic model which couples dissolution and biodegradation processes could adequately represent the experimental batch data. Modelling studies suggest that biodegradation was accelerated because the dissolution rates of phenanthrene increased in presence of the surfactants. Continuous flow column studies with phenanthrene coated Jordan sand was carried out to simulate groundwater flow conditions. Sorption studies on Jordan aquifer sand indicated that this low-carbon aquifer material adsorbs small amounts of phenanthrene as well as surfactants. The tests show that low surfactant concentrations were marginally beneficial in washing phenanthrene from precoated sand.

  19. [Removal of nitrate from aqueous solution using cetylpyridinium chloride (CPC)-modified activated carbon as the adsorbent].

    PubMed

    Zheng, Wen-Jing; Lin, Jian-Wei; Zhan, Yan-Hui; Fang, Qiao; Yang, Meng-Juan; Wang, Hong

    2013-11-01

    Surfactant-modified activated carbon (SMAC) was prepared by loading cetylpyridinium chloride (CPC) onto activated carbon and used as adsorbents to remove nitrate from aqueous solution. The SMAC was effective for removing nitrate from aqueous solution. The SMAC exhibited much higher nitrate adsorption capacity than that of the unmodified activated carbon. The nitrate adsorption capacity for SMAC increased with increasing the CPC loading. The adsorption kinetics of nitrate on SMAC followed a pseudo-second-order kinetic model. The equilibrium adsorption data of nitrate on SMAC could be described by the Langmuir isotherm model. Based on the Langmuir isotherm model, the maximum nitrate adsorption capacity for SMAC with CPC loading amount of444 mmol per 1 kg activated carbon was determined to be 16.1 mg x g(-1). The nitrate adsorption capacity for SMAC decreased with the increasing solution pH. The presence of competing anions such as chloride, sulfate and bicarbonate reduced the nitrate adsorption capacity. The nitrate adsorption capacity for SMAC slightly decreased with the increasing reaction temperature. Almost 95% of nitrate molecules adsorbed on SMAC could be desorbed in 1 mol x L(-1) NaCl solution. The main mechanisms for the adsorption of nitrate on SMAC are anionic exchange and electrostatic attraction. The results of this work indicate that SMAC is a promising adsorbent for removing nitrate from aqueous solution.

  20. Impact of a surfactant on the electroactivity of proteins at an aqueous-organogel microinterface array.

    PubMed

    O'Sullivan, Shane; Arrigan, Damien W M

    2013-02-05

    The impact of surfactant addition to the organic phase on the electroactivity of proteins at the aqueous-organogel interface was examined by voltammetry. The presence of bis(2-ethylhexyl)sulfosuccinate (AOT) in the organogel phase, as the sodium salt, caused marked changes in the peak currents for myoglobin detection. The protein desorption voltammetric peak exhibited a 6-fold increase in the current compared to the corresponding experiment without surfactant. Interfacial coverage showed a 17-fold increase in the adsorbed protein at the interface, from 50 pmol cm(-2), in the absence of surfactant, to 850 pmol cm(-2), in the presence of 10 mM surfactant. Additionally, the presence of the surfactant resulted in a second pair of adsorption/desorption peaks at lower potentials and in a change in the capacitance of the system. The formation of surfactant-protein and surfactant-protein-organic anion deposits is proposed on the basis of these features, leading to increased voltammetric signals for myoglobin, hemoglobin, and cytochrome c. The mechanism of protein-surfactant interaction was probed by using the surfactant as the anion in the organic phase electrolyte salt. Repetitive cyclic voltammetry of cytochrome c showed that in the presence of surfactant there was an enhancement of the signal, caused by a buildup of the protein-surfactant-electrolyte anion assembly at the interface. These findings provide the basis for surfactant-modified interfaces to enhance the electroanalytical performance for protein detection.

  1. 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.

  2. [Study of novel artificial lung surfactants incorporating partially fluorinated amphiphiles].

    PubMed

    Nakahara, Hiromichi

    2012-01-01

    Lung surfactants (LS), a complex of ∼90 wt% lipids (mainly dipalmitoylphosphatidylcholine or DPPC) and ∼10 wt% surfactant proteins (SP-A, -B, -C, and -D), adsorb to an air-alveolar fluid interface and then lower its surface tension down to near zero during expiration. Intratracheal instillation of exogenous LS preparations can effectively compensate for surfactant deficiency in premature infants with respiratory distress syndrome (RDS). Surfacten® (Mitsubishi Tanabe Pharma Corporation, Osaka, Japan), a modified bovine lung extract and an effective surfactant replacement in treatment for RDS patients, is supplemented with DPPC, palmitic acid, and tripalmitin. For the premature infants suffering from RDS, instillation of Surfacten® leads to a dramatic improvement in lung function and compliance. Herein, the author reviews potential use of newly designed preparations containing a mimicking peptide of SP-B and also introduces the current research on the preparations incorporated with partially fluorinated amphiphiles to improve their efficacy.

  3. The role of surfactants in drop formation and thread breakup

    NASA Astrophysics Data System (ADS)

    Kamat, Pritish; Wagoner, Brayden; Thete, Sumeet; Basaran, Osman

    2016-11-01

    The ability of surfactants to adsorb onto and lower the surface tension of water-air and water-oil interfaces is exploited in industrial applications, nature, and everyday life. An important example is provided by drop formation where a thinning liquid thread connects an about-to-form globular, primary drop to the rest of the liquid that remains on the nozzle when the primary drop falls from it. Surfactants can affect pinch-off in two ways: first, by lowering surface tension they lower capillary pressure (which equals, to highest order, surface tension divided by thread radius), and second, as surfactant concentration along the interface can be non-uniform, they cause the interface to be subjected to a gradient of surface tension, or Marangoni stress. By means of high-accuracy simulations and supporting experiments, we clarify the role played by surfactants on drop formation and thread breakup.

  4. Molecular simulation of surfactant-assisted protein refolding

    NASA Astrophysics Data System (ADS)

    Lu, Diannan; Liu, Zheng; Liu, Zhixia; Zhang, Minlian; Ouyang, Pingkai

    2005-04-01

    Protein refolding to its native state in vitro is a challenging problem in biotechnology, i.e., in the biomedical, pharmaceutical, and food industry. Protein aggregation and misfolding usually inhibit the recovery of proteins with their native states. These problems can be partially solved by adding a surfactant into a suitable solution environment. However, the process of this surfactant-assisted protein refolding is not well understood. In this paper, we wish to report on the first-ever simulations of surfactant-assisted protein refolding. For these studies, we defined a simple model for the protein and the surfactant and investigated how a surfactant affected the folding behavior of a two-dimensional lattice protein molecule. The model protein and model surfactant were chosen such that we could capture the important features of the folding process and the interaction between the protein and the surfactant, namely, the hydrophobic interaction. It was shown that, in the absence of surfactants, a protein in an "energy trap" conformation, i.e., a local energy minima, could not fold into the native form, which was characterized by a global energy minimum. The addition of surfactants created folding pathways via the formation of protein-surfactant complexes and thus enabled the conformations that fell into energy trap states to escape from these traps and to form the native proteins. The simulation results also showed that it was necessary to match the hydrophobicity of surfactant to the concentration of denaturant, which was added to control the folding or unfolding of a protein. The surfactants with different hydrophobicity had their own concentration range on assisting protein refolding. All of these simulations agreed well with experimental results reported elsewhere, indicating both the validity of the simulations presented here and the potential application of the simulations for the design of a surfactant on assisting protein refolding.

  5. Surfactant Enhanced DNAPL Removal

    DTIC Science & Technology

    2001-08-01

    or the permeability contrast (i.e., degree of heterogeneity) that is present in the DNAPL zone. To solubilize DNAPL with surfactants, a sufficient...with respect to the effects of permeability and heterogeneity upon the costs of SEAR: as permeability decreases and/or the degree of heterogeneity...not be an issue for surfactant recovery at all sites. The degree to which MEUF will concentrate the calcium is a function of the surfactant itself

  6. Towards unravelling surfactant transport

    NASA Astrophysics Data System (ADS)

    Sellier, Mathieu; Panda, Satyananda

    2015-11-01

    Surfactant transport arises in many natural or industrial settings. Examples include lipid tear layers in the eye, pulmonary surfactant replacement therapy, or industrial coating flows. Flows driven by the surface tension gradient which arises as a consequence of surfactant concentration inhomogeneity, also known as Marangoni-driven flows, have attracted the attention of fluid dynamists for several decades and has led to the development of sophisticated models and the undeniable advancement of the understanding of such flows. Yet, experimental confirmation of these models has been hampered by the difficulty in reliably and accurately measuring the surfactant concentration and its temporal evolution. In this contribution, we propose a methodology which may help shed some light on surfactant transport at the surface of thin liquid films. The surface stress induced by surfactant concentration induces a flow at the free surface which is visible and measurable. In the context of thin film flows for which the lubrication approximation hold, we demonstrate how the knowledge of this free surface flow field provides sufficient information to reconstruct the surfactant tension field. From the surface tension and an assumed equation of state, the local surfactant concentration can also be calculated and other transport parameters such as the surfactant surface diffusivity indirectly inferred. In this contribution, the proposed methodology is tested with synthetic data generated by the forward solution of the governing partial differential equations in order to illustrate the feasibility of the algorithm and highlight numerical challenges.

  7. Surfactant phospholipid metabolism

    PubMed Central

    Agassandian, Marianna; Mallampalli, Rama K.

    2012-01-01

    Pulmonary surfactant is essential for life and is comprised of a complex lipoprotein-like mixture that lines the inner surface of the lung to prevent alveolar collapse at the end of expiration. The molecular composition of surfactant depends on highly integrated and regulated processes involving its biosynthesis, remodeling, degradation, and intracellular trafficking. Despite its multicomponent composition, the study of surfactant phospholipid metabolism has focused on two predominant components, disaturated phosphatidylcholine that confers surface-tension lowering activities, and phosphatidylglycerol, recently implicated in innate immune defense. Future studies providing a better understanding of the molecular control and physiological relevance of minor surfactant lipid components are needed. PMID:23026158

  8. Mixtures of latex particles and the surfactant of opposite charge used as interface stabilizers--influence of particle contact angle, zeta potential, flocculation and shear energy.

    PubMed

    Deleurence, Rémi; Parneix, Caroline; Monteux, Cécile

    2014-09-28

    We investigate the stabilization of air-water interfaces by mixtures of negatively charged latex particles (sulfate polystyrene) and cationic surfactants (alkyl trimethylammonium bromides). First we report results concerning the binding of surfactant molecules to the latex particles. As the surfactant concentration increases, the charge of the particles reverses, from negative to positive, because CnTAB first binds electrostatically to the latex particles and then through hydrophobic interaction with the monolayer already adsorbed on the particles as well as directly with the hydrophobic surface of the latex. Over a large range of surfactant concentrations around the charge inversion, a strong flocculation is observed and 100 μm large aggregates form in the suspension. Unlike previous studies published on mixtures of inorganic particles with oppositely charged surfactants, we show that we can vary the sign of the zeta potential of the particles without changing the contact angle of the particles over a large range of surfactant concentrations. Indeed, the latex particles that we study are more hydrophobic than inorganic particles, hence adding moderate concentrations of the surfactant results in a weak variation of the contact angle while the charge of the particles can be reversed. This enables decoupling of the effect of zeta potential and contact angle on the interfacial properties of the mixtures. Our study shows that the contact angle and the charge of the particles are not sufficient parameters to control the foam properties, and the key-parameters are the flocculation state and the shear energy applied to produce the foam. Indeed, flocculated samples, whatever the sign of the zeta potential, enable production of a stable armour at the interface. The large aggregates do not adsorb spontaneously at the interface because of their large size, however when a large shear energy is used to produce the foam very stable foam is obtained, where particles are trapped

  9. Characterization on the precipitate sample of cetyltrimethylammonium bromide adsorbed onto nanocube CaCO3 particles from aqueous-ammonia-rich solution

    NASA Astrophysics Data System (ADS)

    Virtudazo, Raymond V. Rivera; Fuji, Masayoshi; Takai, Chika; Shirai, Takashi

    2012-12-01

    Physicochemical analysis on the precipitate samples of the cationic cetyltrimethylammonium bromide (CTAB) adsorbed onto nanocube CaCO3 particles (NcCP) in aqueous ammonia rich (NH4 +) solution was initially examined. The amount of CTAB added to the (<100 nm) NcCP ranging from 0.04 to 88.5 mM was prepared under room temperature aqueous alkaline condition and characterized by thermogravimetry/differential thermogravimetric analysis (TGA/DTA), Raman spectroscopy (RS), scanning electron microscopy, transmission electron microscopy (TEM), gas chromatograph combined with mass spectrometer analysis (GC-MS), and powder X-ray diffraction pattern. RS, GC-MS, and TGA/DTA analyses indicate that only layer of CTAB molecules were present on the surface of the NcCP. Moreover, this thin sheet layer was morphologically observed by the TEM image (particularly at 88 mM concentration of CTAB). In general, adsorption of CTAB molecules onto NcCP under aqueous alkaline medium had no effect on the cubic crystal structure and particle morphology. The present study confirms the adsorption mechanism of cationic surfactant onto NcCP colloids model and contributes to the better understanding of the possible structural arrangement of the sorbed surfactant molecules onto the NcCP-aqueous alkaline interface by simple characterization method. This investigation is expected to create new, low-cost route to produce promising nanopowders and conversion to hollow particles with multi-component porous surface shell wall.

  10. Surfactant loss control in chemical flooding spectroscopic and calorimetric study of adsorption and precipitation on reservoir minerals. Annual report, September 30, 1992--September 30 1995

    SciTech Connect

    Casteel, J.

    1996-07-01

    The aim of this research project was to investigate mechanisms governing adsorption and surface precipitation of flooding surfactants on reservoir minerals. Effects of surfactant structure, surfactant combinations, various inorganic and polymeric species, and solids mineralogy have been determined. A multi-pronged approach consisting of micro & nano spectroscopy, electrokinetics, surface tension and wettability is used in this study. The results obtained should help in controlling surfactant loss in chemical flooding and in developing optimum structures and conditions for efficient chemical flooding processes. During the three years contract period, adsorption of single surfactants and select surfactant mixtures was studied at the solid-liquid and gas-liquid interfaces. Alkyl xylene sulfonates, polyethoxylated alkyl phenols, octaethylene glycol mono n-decyl ether, and tetradecyl trimethyl ammonium chloride were the surfactants studied. Adsorption of surfactant mixtures of varying composition was also investigated. The microstructure of the adsorbed layer was characterized using fluorescence spectroscopy. Changes in interfacial properties such as wettability, electrokinetics and stability of reservoir minerals were correlated with the amounts of reagent adsorbed. Strong effects of the structure of the surfactant and position of functional groups were revealed. Changes of microstructure upon dilution (desorption) were also studied. Presence of the nonionic surfactants in mixed aggregate leads to shielding of the charge of ionic surfactants which in turn promotes aggregation but reduced electrostatic attraction between the charged surfactant and the mineral surface. Strong consequences of surfactant interactions in solution on adsorption as well as correlations between monomer concentration in mixtures and adsorption were revealed.

  11. CHARACTERIZATION OF PHASE AND EMULSION BEHAVIOR, SURFACTANT RETENTION, AND OIL RECOVERY FOR NOVEL ALCOHOL ETHOXYCARBOXYLATE SURFACTANTS

    SciTech Connect

    Lebone T. Moeti; Ramanathan Sampath

    2001-09-28

    this project. The M/B and B/M morphologies and their inversion hysteresis lines conformed to the previously postulated dispersion morphology diagram; that is, within experimental uncertainties, the two emulsion inversion lines in phase volume-temperature space met at a critical point that coincided with the upper critical end point for the phases. Coreflooding measurements were performed by our industrial partner in this project, Surtek, Golden, CO which showed poor hydrocarbon recovery (38.1%) for NEODOX 23-4. It was also found that NEODOX 23-4 surfactant adsorbed too much to the rock (97.1% surfactant loss to the core), a characteristic of the non-ionic part of the surfactant.

  12. Dewetting transition induced by surfactants in sessile droplets at the early evaporation stage.

    PubMed

    Zhong, Xin; Duan, Fei

    2016-01-14

    As surfactants are employed to control the wettability of solutions, we observe that the sessile droplet dewetting induced by autophobing exhibits a unique relation with the surfactant concentration. Below the critical micelle concentration (cmc) of the surfactant, the autophobic effect makes the droplet go through a rapid depinning at first (Phase 1) and then a relatively slower shrinkage (Phase 2). Unexpectedly, the rapid velocity of the three-phase contact line in Phase 1 shows a transition as the surfactant concentration increases above 0.043 cmc, while such a transition is absent for the velocity in Phase 2. The spreading of the sessile droplets as they form before retraction, the maximum contact angle led by dewetting, and the droplet lifetime are regularly sensitive to the surfactant concentration as well. These phenomena are correlated with the assembling structure and the adsorbed amount at different interfaces with the loading of surfactant inventory.

  13. NMR study of the dynamics of cationic gemini surfactant 14-2-14 in mixed solutions with conventional surfactants.

    PubMed

    Jiang, Yan; Lu, Xing-Yu; Chen, Hong; Mao, Shi-Zhen; Liu, Mai-Li; Luo, Ping-Ya; Du, You-Ru

    2009-06-18

    Three kinds of conventional surfactants, namely, two nonionic surfactants [polyethylene glycol (23) lauryl ether (Brij-35) and Triton X-100 (TX-100)], one cationic surfactant [n-tetradecyltrimethyl ammonium bromide (TTAB)], and an anionic surfactant [sodium n-dodecyl sulfate (SDS)}, were mixed into the quaternary ammonium gemini surfactant [C(14)H(29)N(+)(CH(3))(2)](2)(CH(2))(2).2Br(-) (14-2-14) in aqueous solution. The exchange rate constants between 14-2-14 molecules in the mixed micelles and those in the bulk solution were detected using two nuclear magnetic resonance (NMR) methods: one-dimensional (1D) line shape analysis and two-dimensional (2D) exchange spectroscopy (EXSY). The results obtained from these two methods were consistent. Both showed that mixing a nonionic conventional surfactant, either Brij-35 or TX-100, enhanced the exchange process between the 14-2-14 molecules in the mixed micelles and those in the bulk solution. In contrast, the anionic surfactant SDS and the cationic surfactant TTAB slowed the process slightly.

  14. Remobilizing the Interface of Thermocapillary Driven Bubbles Retarded By the Adsorption of a Surfactant Impurity on the Bubble Surface

    NASA Technical Reports Server (NTRS)

    Palaparthi, Ravi; Maldarelli, Charles; Papageorgiou, Dimitri; Singh, Bhim (Technical Monitor)

    2001-01-01

    molecules which kinetically rapidly exchange between the bulk and the surface and are at high bulk concentrations. Because the remobilizing surfactant is present at much higher concentrations than the impurity, it adsorbs to the bubble surface much faster than the impurity when the bubble is formed, and thereby prevents the impurity from adsorbing onto the surface. In addition, the rapid kinetic exchange and high bulk concentration maintain a saturated surface with uniform surface concentrations. This prevents retarding surface tension gradients and keeps the thermocapillary velocity high. In our reports over the first 2 years, we presented numerical simulations of the bubble motion and surfactant transport which verified theoretically the concept of remobilization, and the development of an apparatus to track and measure the velocity of rising bubbles in a glycerol/water surfactant solution. This year, we detail experimental observations of remobilization. Two polyethylene oxide surfactants were studied, C12E6 (CH3(CH2)11(OCH2)6OH) and C10E8 (CH3(CH2)4(OCH2CH2)8OH). Measurements of the kinetic exchange for these surfactants show that the one with the longer hydrophobe chain C12E6 has a lower rate of kinetic exchange. In addition, this surfactant is much less soluble in the glycerol/water mixture because of the shorter ethoxylate chain. As a result, we found that C12E6 had only a very limited ability to remobilize rising bubbles because of the limited kinetic exchange and reduced solubility. However, C10E8, with its higher solubility and more rapid exchange was found to dramatically remobilize rising bubbles. We also compared our theoretical calculations to the experimental measurements of velocity for both the non-remobilizing and remobilizing surfactants and found excellent agreement. We further observed that for C10E8 at high concentrations, which exceeded the critical micelle concentrations, additional remobilization was measured. In this case the rapid exchange of

  15. Remobilizing the Interface of Thermocapillary Driven Bubbles Retarded By the Adsorption of a Surfactant Impurity on the Bubble Surface

    NASA Technical Reports Server (NTRS)

    Palaparthi, Ravi; Maldarelli, Charles; Papageorgiou, Dimitri; Singh, Bhim (Technical Monitor)

    2001-01-01

    molecules which kinetically rapidly exchange between the bulk and the surface and are at high bulk concentrations. Because the remobilizing surfactant is present at much higher concentrations than the impurity, it adsorbs to the bubble surface much faster than the impurity when the bubble is formed, and thereby prevents the impurity from adsorbing onto the surface. In addition, the rapid kinetic exchange and high bulk concentration maintain a saturated surface with uniform surface concentrations. This prevents retarding surface tension gradients and keeps the thermocapillary velocity high. In our reports over the first 2 years, we presented numerical simulations of the bubble motion and surfactant transport which verified theoretically the concept of remobilization, and the development of an apparatus to track and measure the velocity of rising bubbles in a glycerol/water surfactant solution. This year, we detail experimental observations of remobilization. Two polyethylene oxide surfactants were studied, C12E6 (CH3(CH2)11(OCH2)6OH) and C10E8 (CH3(CH2)4(OCH2CH2)8OH). Measurements of the kinetic exchange for these surfactants show that the one with the longer hydrophobe chain C12E6 has a lower rate of kinetic exchange. In addition, this surfactant is much less soluble in the glycerol/water mixture because of the shorter ethoxylate chain. As a result, we found that C12E6 had only a very limited ability to remobilize rising bubbles because of the limited kinetic exchange and reduced solubility. However, C10E8, with its higher solubility and more rapid exchange was found to dramatically remobilize rising bubbles. We also compared our theoretical calculations to the experimental measurements of velocity for both the non-remobilizing and remobilizing surfactants and found excellent agreement. We further observed that for C10E8 at high concentrations, which exceeded the critical micelle concentrations, additional remobilization was measured. In this case the rapid exchange of

  16. 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.

  17. SURFACTANTS IN LUBRICATION

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Surfactants are one of the most widely applied materials by consumers and industry. The application areas for surfactants span from everyday mundane tasks such as cleaning, to highly complex processes involving the formulation of pharmaceuticals, foods, pesticides, lubricants, etc. Even though sur...

  18. SURFACTANTS AND SUBSURFACE REMEDIATION

    EPA Science Inventory

    Because of the limitations of pump-and-trat technology, attention is now focused on the feasibility of surfactant use to increase its efficiency. Surfactants have been studied for use in soil washing and enhanced oil recovery. Although similarities exist between the application...

  19. 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.

  20. Effects of the conjugation of whey proteins with gellan polysaccharides on surfactant-induced competitive displacement from the air-water interface.

    PubMed

    Cai, B; Ikeda, S

    2016-08-01

    Whey proteins can be used to stabilize foams and emulsions against coalescence because of their ability to form viscoelastic films at the interface that resist film rupture on collision between colloidal particles. However, whey proteins are competitively displaced from the interface if small-molecule surfactants are added, leading to destabilization of the entire system. This is because surfactants are more effective in molecular packing at the interface, and they lower interfacial tension to a greater degree than whey proteins do, but their interfacial films are poor in viscoelasticity. We hypothesized that whey proteins would become more resistant to surfactant-induced competitive displacement if they were conjugated with network-forming polysaccharides. The protein moiety of the conjugate would be expected to enable its adsorption to the interface, and the polysaccharide moiety would be expected to form self-assembled networks, strengthening the interfacial film as a whole. In this study, whey proteins were conjugated with gellan polysaccharides using the Maillard reaction. Atomic force microscopy images of interfacial films formed by the whey protein-gellan conjugate at the air-water interface and transferred onto mica sheets using the Langmuir-Blodgett method revealed that gellan did form self-assembled networks at the interface and that interfacial films also contained a large number of unconjugated whey protein molecules. Following the addition of a small-molecule surfactant (Tween 20) to the sub-phase, surface pressure increased, indicating spontaneous adsorption of surfactants to the interface. Atomic force microscopy images showed decreases in interfacial area coverage by whey proteins as surface pressure increased. At a given surface pressure, the interfacial area coverage by whey protein-gellan conjugates was greater than coverage by unconjugated whey proteins, confirming that whey proteins became more resistant to surfactant-induced displacement after

  1. Self-assembled surfactants on patterned surfaces: confinement and cooperative effects on aggregate morphology.

    PubMed

    Suttipong, Manaswee; Grady, Brian P; Striolo, Alberto

    2014-08-21

    The adsorption and self-assembly of surfactants are ubiquitous processes in several technological applications, including the manufacture of nano-structured materials using bottom-up strategies. Although much is known about the adsorption of surfactants on homogeneous flat surfaces from experiments, theory, and simulations, limited information is available, in quantifiable terms, regarding the adsorption of surfactants on surfaces with chemical and/or morphological heterogeneity. In an effort to fill this knowledge gap, we report here results obtained using equilibrium dissipative particle dynamics (DPD) simulations for the adsorption of model surfactants onto patterned flat surfaces (i.e., flat surfaces with chemical heterogeneity). The patterns consist of one or two stripes of variable width on which the surfactants could adsorb. The adsorbing stripes are surrounded by a surface that effectively repels the surfactants. This repelling surface, perhaps not realistic, allows us to quantify the effect of lateral confinement on the morphology of surfactant aggregates. When the stripe width is large (effectively providing a homogeneous flat surface), the surfactants yield a flat monolayer. Our simulations suggest that the flat monolayers become hemi-cylinders, hemi-spheres, and individual surfactants as the stripe width decreases, a consequence of lateral confinement. In some cases our simulations show evidence of cooperative effects when two adsorbing stripes are present on the surface. If the distance between the stripes and the widths of the stripes are both less than about one surfactant length, hemi-cylindrical shells and irregular structures are observed because of cooperativity; otherwise the results match those found for a single isolated stripe. Our predictions could be useful for the design of new nano-structured materials and coatings, for applications ranging from nano-fluidic devices to nano-reactors.

  2. Self Assembly of Biogenic Surfactants at Mineral Surfaces and Their Effect on Biological Iron Acquisition

    NASA Astrophysics Data System (ADS)

    Kraemer, S. M.

    2005-12-01

    Microorganisms exude biogenic surfactants to modify the physical and chemical properties of mineral-water interfaces. Surfactants with negatively charged hydrophilic head groups interact strongly with oppositely charged mineral surfaces such as iron or aluminum oxides. Surfactant self assembly at mineral surfaces can result in the formation of admicelles that have a significant effect on the surface charge and hydrophobicity. These effects are exploited by microorganisms to facilitate attachment to mineral surfaces. Similarly, plants exude surfactants into the rhizosphere and change the surface tension and flow of soil water. Other surface active compounds that are typically found in soils and surface waters are humic substances and fatty acids that are produced by degradation of biomass. In general, surface active compounds are ubiquitous in natural systems. In this study we investigated how surfactants influence bio-mineral interactions using the example of siderophore promoted iron acquisition. Siderophore promoted iron acquisition involves the adsorption of a biogenic iron specific ligand (i.e. the siderophore) to iron oxides and the subsequent siderophore promoted iron oxide dissolution. The hypothesis of this project is that the modification of the iron oxide surface charge and hydrophobicity by adsorbed surfactants will have an important effect on siderophore adsorption and dissolution kinetics. We approached this subject by investigating the adsorption of a natural surfactant (rhamnolipids: RhL) and the synthetic surfactant (sodium dodecyl sulfate: SDS) on goethite (α-FeOOH, a common pedogenic iron oxide) and observing the effect of surfactant self assembly on the properties of the mineral water interface. We observed fast adsorption kinetics at pH 3 and slow adsorption at pH 6. The adsorbed surfactants reversed the surface potential of goethite (as evidenced by electrophoretic mobility measurements) at soluble surfactant concentrations below 10 μM (SDS

  3. Surface shear inviscidity of soluble surfactants

    PubMed Central

    Zell, Zachary A.; Nowbahar, Arash; Mansard, Vincent; Leal, L. Gary; Deshmukh, Suraj S.; Mecca, Jodi M.; Tucker, Christopher J.; Squires, Todd M.

    2014-01-01

    Foam and emulsion stability has long been believed to correlate with the surface shear viscosity of the surfactant used to stabilize them. Many subtleties arise in interpreting surface shear viscosity measurements, however, and correlations do not necessarily indicate causation. Using a sensitive technique designed to excite purely surface shear deformations, we make the most sensitive and precise measurements to date of the surface shear viscosity of a variety of soluble surfactants, focusing on SDS in particular. Our measurements reveal the surface shear viscosity of SDS to be below the sensitivity limit of our technique, giving an upper bound of order 0.01 μN·s/m. This conflicts directly with almost all previous studies, which reported values up to 103–104 times higher. Multiple control and complementary measurements confirm this result, including direct visualization of monolayer deformation, for SDS and a wide variety of soluble polymeric, ionic, and nonionic surfactants of high- and low-foaming character. No soluble, small-molecule surfactant was found to have a measurable surface shear viscosity, which seriously undermines most support for any correlation between foam stability and surface shear rheology of soluble surfactants. PMID:24563383

  4. Coacervation with surfactants: From single-chain surfactants to gemini surfactants.

    PubMed

    Zhao, Weiwei; Wang, Yilin

    2017-01-01

    Coacervation is a spontaneous process during which a colloidal dispersion separates into two immiscible liquid phases: a colloid-rich liquid phase in equilibrium with a diluted phase. Coacervation is usually divided into simple coacervation and complex coacervation according to the number of components. Surfactant-based coacervation normally contains traditional single-chain surfactants. With the development of surfactants, gemini surfactants with two amphiphilic moieties have been applied to form coacervation. This review summarizes the development of simple coacervation and complex coacervation in the systems of single-chain surfactants and gemini surfactants. Simple coacervation in surfactant solutions with additives or at elevated temperature and complex coacervation in surfactant/polymer mixtures by changing charge densities, molecular weight, ionic strength, pH, or temperature are reviewed. The comparison between gemini surfactants and corresponding monomeric single-chain surfactants reveals that the unique structures of gemini surfactants endow them with higher propensity to generate coacervation.

  5. Adsorbent and adsorbent bed for materials capture and separation processes

    DOEpatents

    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.

  6. Surfactant effect on functionalized carbon nanotube coated snowman-like particles and their electro-responsive characteristics

    SciTech Connect

    Zhang, Ke; Liu, Ying Dan; Choi, Hyoung Jin

    2012-10-15

    The core–shell structured snowman-like (SL) microparticles coated by functionalized multi-walled carbon nanotube (MWNT) were prepared in the presence of different surfactants including cationic surfactant-cetyl trimethylammonium bromide (CTAB) and anionic surfactant-sodium lauryl sulfate (SDS). The effect of surfactants on adsorption onto SL particles was characterized by scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and conductivity. The cationic surfactant is found to be more effective than anionic surfactant for helping nanotube adsorbed onto microparticle due to the presence of electrostatic interaction between the functionalized MWNT and the surfactant. Furthermore, the MWNT/SL particles dispersed in silicone oil exhibited a typical fibril structure of the electrorheological characteristics under an applied electric field observed by an optical microscope (OM), in which the state of nanotubes wrapped on the particles strongly affects their electro-responsive characteristics.

  7. Hydrogen-bonding molecular ruler surfactants as probes of specific solvation at liquid/liquid interfaces.

    PubMed

    Siler, A Renee; Brindza, Michael R; Walker, Robert A

    2009-10-01

    Resonance-enhanced, second harmonic generation (SHG) is used to measure the electronic structure of solutes sensitive to specific solvation adsorbed to liquid/liquid and liquid/solid interfaces. Here, specific solvation refers to solvent-solute interactions that are directional and localized. N-methyl-p-methoxyaniline (NMMA) is a solute whose first allowed electronic transition wavelength remains almost constant (approximately 315 nm) in non-hydrogen-bonding solvents regardless of solvent polarity. However, in hydrogen-bond-accepting solvents such as dimethylsulfoxide, NMMA's absorbance shifts to longer wavelengths (320 nm), whereas in hydrogen-bond-donating solvents (e.g., water), the absorbance shifts to shorter wavelengths (approximately 300 nm). SHG experiments show that at alkane/silica interfaces, surface silanol groups serve as moderately strong hydrogen-bond donors as evidenced by NMMA's absorbance of 307 nm. At the carbon tetrachloride/water interface, NMMA absorbance also shifts to slightly shorter wavelengths (298 nm) implying that water molecules at this liquid/liquid interface are donating strong hydrogen bonds to the adsorbed NMMA solutes. In contrast, experiments using newly developed molecular ruler surfactants with NMMA as a model hydrophobic solute and a hydrophilic, cationic headgroup imply that, as NMMA migrates across an aqueous/alkane interface, it carries with it water that functions as a hydrogen-bond-accepting partner.

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

    SciTech Connect

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

    2016-07-23

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

  9. Surfactants in the environment.

    PubMed

    Ivanković, Tomislav; Hrenović, Jasna

    2010-03-01

    Surfactants are a diverse group of chemicals that are best known for their wide use in detergents and other cleaning products. After use, residual surfactants are discharged into sewage systems or directly into surface waters, and most of them end up dispersed in different environmental compartments such as soil, water or sediment. The toxic effects of surfactants on various aquatic organisms are well known. In general, surfactants are present in the environment at levels below toxicity and in Croatia below the national limit. Most surfactants are readily biodegradable and their amount is greatly reduced with secondary treatment in wastewater treatment plants. The highest concern is the release of untreated wastewater or wastewater that has undergone primary treatment alone. The discharge of wastewater polluted with massive quantities of surfactants could have serious effects on the ecosystem. Future studies of surfactant toxicities and biodegradation are necessary to withdraw highly toxic and non-biodegradable compounds from commercial use and replace them with more environmentally friendly ones.

  10. Ionic Nature of a Gemini Surfactant at the Air/Water Interface.

    PubMed

    Phan, Chi M; Nguyen, Cuong V; Nakahara, Hiromichi; Shibata, Osamu; Nguyen, Thanh V

    2016-12-06

    The ionic state of an adsorbed gemini surfactant at the air/water interface was investigated using a combination of surface potential and surface tension data. The combined model was developed and successfully described the experimental data. The results verified the existence of three ionic states of the gemini surfactant in the interfacial zone. Furthermore, the model can quantify the adsorbed concentrations of these species. At low concentrations, the fully dissociated state dominates the adsorption. At high concentrations, the fully associated state dominates, accounting for up to 80% of the total adsorption. In the middle range, the adsorption is dominated by the partially associated state, which has a maximum percentage of 80% at a critical micelle concentration of 0.5. The variation in the ionic state is a unique characteristic of gemini surfactants, which can be the underlying mechanism for their advantages over conventional surfactants.

  11. Enhanced photodegradation of pentachlorophenol by single and mixed nonionic and anionic surfactants using graphene-TiO₂ as catalyst.

    PubMed

    Zhang, Yaxin; He, Xin; Zeng, Guangming; Chen, Tan; Zhou, Zeyu; Wang, Hongtao; Lu, Wenjing

    2015-11-01

    The photodegradation of pentachlorophenol (PCP) in a surfactant-containing (single and mixed) complex system using graphene-TiO2 (GT) as catalyst was investigated. The objective was to better understand the behavior of surfactants in a GT catalysis system for its possible use in remediation technology of soil contaminated by hydrophobic organic compounds (HOCs). In a single-surfactant system, surfactant molecules aggregated on GT via hydrogen bonding and electrostatic force; nonideal mixing between nonionic and anionic surfactants rendered GT surface with mixed admicelles in a mixed surfactant system. Both effects helped incorporating PCP molecules into surfactant aggregates on catalyst surface. Hence, the targeted pollutants were rendered easily available to photo-yielded oxidative radicals, and photodegradation efficiency was significantly enhanced. Finally, real soil washing-photocatalysis trials proved that anionic-nonionic mixed surfactant soil washing coupled with graphene-TiO2 photocatalysis can be one promising technology for HOC-polluted soil remediation.

  12. Adsorption of the natural protein surfactant Rsn-2 onto liquid interfaces.

    PubMed

    Brandani, Giovanni B; Vance, Steven J; Schor, Marieke; Cooper, Alan; Kennedy, Malcolm W; Smith, Brian O; MacPhee, Cait E; Cheung, David L

    2017-03-22

    To stabilize foams, droplets and films at liquid interfaces a range of protein biosurfactants have evolved in nature. Compared to synthetic surfactants, these combine surface activity with biocompatibility and low solution aggregation. One recently studied example is Rsn-2, a component of the foam nest of the frog Engystomops pustulosus, which has been predicted to undergo a clamshell-like opening transition at the air-water interface. Using atomistic molecular dynamics simulations and surface tension measurements we study the adsorption of Rsn-2 onto air-water and cyclohexane-water interfaces. The protein adsorbs readily at both interfaces, with adsorption mediated by the hydrophobic N-terminus. At the cyclohexane-water interface the clamshell opens, due to the favourable interaction between hydrophobic residues and cyclohexane molecules and the penetration of cyclohexane molecules into the protein core. Simulations of deletion mutants showed that removal of the N-terminus inhibits interfacial adsorption, which is consistent with the surface tension measurements. Deletion of the hydrophilic C-terminus also affects adsorption, suggesting that this plays a role in orienting the protein at the interface. The characterisation of the interfacial behaviour gives insight into the factors that control the interfacial adsorption of proteins, which may inform new applications of this and similar proteins in areas including drug delivery and food technology and may also be used in the design of synthetic molecules showing similar changes in conformation at interfaces.

  13. β-Cristobalite (001) surface as 4-formaminoantipyrine adsorbent: First principle study of the effect on adsorption of surface modification.

    PubMed

    Simonetti, S; Compañy, A Díaz; Brizuela, G; Juan, A

    2016-12-01

    Silica based materials find applications as excipients and particularly as drug delivery agents for pharmaceutical drugs. Their performance can be crucially affected by surface treatments, as it can modify the adsorption (and release) of these formulations. The role of surface modification on the features of 4-formaminoantipyrine (FAA) adsorbed on β-cristobalite (001) surface is studied by means of simulations based on the Density Functional Theory (DFT). Starting from the results of FAA in interaction with a dehydroxylated surface; a fully hydroxylated surface and a functionalized surface with benzalkonium chloride (BC) surfactant have been added to study the configurational landscape. Calculations suggest that the trend for FAA preferential adsorption on silica surfaces is: dehydroxylated>hydroxylated>BC-functionalized. The potential for hydrogen bonding causes the main contribution to the bonding while dispersion forces present an additional contribution independently of whether the drug is hydrogen-bonded or BC-bonded to the surface. Adsorption takes mainly place through nitrogen atoms in the heterocyclic ring, the carbonyl and amine functional groups. Associated mode's shifts and concurrent changes in bond length are also observed showing accordance between electronic and geometrical structure results. BC surfactant reduces the number of formed H-bonds and lowers the attractive molecule-surface interaction being it useful to prevent particle agglomeration and could favor drug release in therapies that requires faster but controlled delivery.

  14. Electronic structure of benzene adsorbed on Ni and Cu surfaces

    SciTech Connect

    Weinelt, M.; Nilsson, A.; Wassdahl, N.

    1997-04-01

    Benzene has for a long time served as a prototype adsorption system of large molecules. It adsorbs with the molecular plane parallel to the surface. The bonding of benzene to a transition metal is typically viewed to involve the {pi} system. Benzene adsorbs weakly on Cu and strongly on Ni. It is interesting to study how the adsorption strength is reflected in the electronic structure of the adsorbate-substrate complex. The authors have used X-ray Emission (XE) and X-ray Absorption (XA) spectroscopies to selectively study the electronic states localized on the adsorbed benzene molecule. Using XES the occupied states can be studies and with XAS the unoccupied states. The authors have used beamline 8.0 and the Swedish endstation equipped with a grazing incidence x-ray spectrometer and a partial yield absorption detector. The resolution in the XES and XAS were 0.5 eV and 0.05 eV, respectively.

  15. Recent advances in gemini surfactants: oleic Acid-based gemini surfactants and polymerizable gemini surfactants.

    PubMed

    Sakai, Kenichi; Sakai, Hideki; Abe, Masahiko

    2011-01-01

    Gemini surfactants recently developed by our research group are introduced from the standpoints of their syntheses, aqueous solution properties, and potential applications. Two series of gemini surfactants are introduced in this short review, the first of which is the oleic acid-based gemini surfactants, and the second is the polymerizable gemini surfactants. These gemini surfactants have been developed not only as environmentally friendly materials (the use of gemini surfactants enables the reduction of the total consumption of surfactants in chemical products owing to their excellent adsorption and micellization capabilities at low concentrations) but also as functional organic materials.

  16. Phosphine oxide surfactants revisited.

    PubMed

    Stubenrauch, Cosima; Preisig, Natalie; Laughlin, Robert G

    2016-04-01

    This review summarizes everything we currently know about the nonionic surfactants alkyl dimethyl (C(n)DMPO) and alkyl diethyl (C(n)DEPO) phosphine oxide (PO surfactants). The review starts with the synthesis and the general properties (Section 2) of these compounds and continues with their interfacial properties (Section 3) such as surface tension, surface rheology, interfacial tension and adsorption at solid surfaces. We discuss studies on thin liquid films and foams stabilized by PO surfactants (Section 4) as well as studies on their self-assembly into lyotropic liquid crystals and microemulsions, respectively (Section 5). We aim at encouraging colleagues from both academia and industry to take on board PO surfactants whenever possible and feasible because of their broad variety of excellent properties.

  17. Dynamic surface tension of polyelectrolyte/surfactant systems with opposite charges: two states for the surfactant at the interface.

    PubMed

    Ritacco, Hernán A; Busch, Jorge

    2004-04-27

    The molecular reorientation model of Fainerman et al. is conceptually adapted to explain the dynamic surface tension behavior in polyelectrolyte/surfactant systems with opposite charges. The equilibrium surface tension curves and the adsorption dynamics may be explained by assuming that there are two different states for surfactant molecules at the interface. One of these states corresponds to the adsorption of the surfactant as monomers, and the other to the formation of a mixed complex at the surface. The model also explains the plateaus that appear in the dynamic surface tension curves and gives a picture of the adsorption process.

  18. Adsorption behavior of hydrophobin and hydrophobin/surfactant mixtures at the solid-solution interface.

    PubMed

    Zhang, Xiaoli L; Penfold, Jeffrey; Thomas, Robert K; Tucker, Ian M; Petkov, Jordan T; Bent, Julian; Cox, Andrew

    2011-09-06

    The adsorption of surface-active protein hydrophobin, HFBII, and HFBII/surfactant mixtures at the solid-solution interface has been studied by neutron reflectivity, NR. At the hydrophilic silicon surface, HFBII adsorbs reversibly in the form of a bilayer at the interface. HFBII adsorption dominates the coadsorption of HFBII with cationic and anionic surfactants hexadecyltrimethyl ammonium bromide, CTAB, and sodium dodecyl sulfate, SDS, at concentrations below the critical micellar concentration, cmc, of conventional cosurfactants. For surfactant concentrations above the cmc, HFBII/surfactant solution complex formation dominates and there is little HFBII adsorption. Above the cmc, CTAB replaces HFBII at the interface, but for SDS, there is no affinity for the anionic silicon surface hence there is no resultant adsorption. HFBII adsorbs onto a hydrophobic surface (established by an octadecyl trimethyl silane, OTS, layer on silicon) irreversibly as a monolayer, similar to what is observed at the air-water interface but with a different orientation at the interface. Below the cmc, SDS and CTAB have little impact upon the adsorbed layer of HFBII. For concentrations above the cmc, conventional surfactants (CTAB and SDS) displace most of the HFBII at the interface. For nonionic surfactant C(12)E(6), the pattern of adsorption is slightly different, and although some coadsorption at the interface takes place, C(12)E(6) has little impact on the HFBII adsorption.

  19. Rhamnolipid surfactants: alternative substrates, new strategies.

    PubMed

    Benincasa, Maria; Marqués, AnaM; Pinazo, Aurora; Manresa, Angels

    2010-01-01

    This chapter concentrates on the various possibilities of using alternative substrates and new strategies. Such strategies include an integrated production system to reduce the environmental impact and an attempt to minimize residues, which reinforces socio-economic and region-structural development. Additionally, we offer an overview of the physicochemical and biological properties of rhamnolipid surfactants associated with the applications of these molecules in different circumstances.

  20. Controlling the Mobility of the Fluid Interface of Moving Gas Bubbles or Liquid Drops by Using Micellar Solutions of Surfactants

    NASA Technical Reports Server (NTRS)

    Maldarelli, Charles; Papageorgiou, Demetrios

    1998-01-01

    Microgravity processes must rely on mechanisms other than buoyancy to move bubbles or droplets from one region to another in a continuous liquid phase. One suggested method is thermocapillary migration in which a temperature gradient is applied to the continuous phase. A significant and as yet unresolved impediment to the use of thermocapillary migration to direct bubble or drop motion is that these migrations can be significantly retarded by the adsorption onto the fluid particle surface of surface active impurities unavoidably present in the continuous or (if the particle is a liquid) droplet phases. The focus of our research was to develop a theory for remobilizing fluid particle interfaces retarded by a surfactant impurity in an effort to make more viable the use of thermocapillary migrations for the management of bubbles and drops in microgravity. We postulated that a surfactant at high bulk concentration which kinetically exchanges rapidly with the surface can restore interface mobility. The scaling arguments along with a discussion of the previous literature is reviewed in the context of the scaling framework. The specific objectives of the research were twofold. The first was to prove the remobilization theory by studying a model problem. As the mechanism for remobilization is independent of the force which drives the particle, the fluid particle shape and the presence of fluid inertia, we chose the simplest model consisting of a spherical bubble rising steadily by buoyancy in creeping flow. We solved the hydrodynamic and surfactant transport equations for rapid kinetic exchange to demonstrate that as the concentration increases, the Marangoni retardation at first increases (the low k behavior) and then decreases (the high k behavior). The second objective was to develop a method to determine the kinetic rate constants of a surfactant molecule, since this information is necessary to select surfactants which will exchange rapidly enough relative to the

  1. Probing dynamics and mechanism of exchange process of quaternary ammonium dimeric surfactants, 14-s-14, in the presence of conventional surfactants.

    PubMed

    Liu, Jun; Jiang, Yan; Chen, Hong; Mao, Shi Zhen; Du, You Ru; Liu, Mai Li

    2012-12-27

    In this Article, we investigated effects of different types of conventional surfactants on exchange dynamics of quaternary ammonium dimeric surfactants, with chemical formula C(14)H(29)N(+)(CH(3))(2)- (CH(2))(s)-N(+)(CH(3))(2)C(14)H(29)·2Br(-), or 14-s-14 for short. Two nonionic surfactants, TritonX-100 (TX-100) and polyethylene glycol (23) laurylether (Brij-35), and one cationic surfactant, n-tetradecyltrimethyl ammonium bromide (TTAB), and one ionic surfactant, sodium dodecyl sulfate (SDS) were chosen as typical conventional surfactants. Exchange rates of 14-s-14 (s = 2, 3, and 4) between the micelle form and monomer in solution were detected by two NMR methods: one-dimensional (1D) line shape analysis and two-dimensional (2D) exchange spectroscopy (EXSY). Results show that the nonionic surfactants (TX-100 and Brij-35), the cationic surfactant (TTAB), and the ionic surfactant (SDS) respectively accelerated, barely influenced, and slowed the exchange rate of 14-s-14. The effect mechanism was investigated by the self-diffusion experiment, relaxation time measurements (T(2)/T(1)), the fluorescence experiment (I(1)/I(3)) and observed chemical shift variations. Results reveal that, nonionic conventional surfactants (TX-100 and Brij-35) loosened the molecule arrangement and decreased hydrophobic interactions in the micelle, and thus accelerated the exchange rate of 14-s-14. The cationic conventional surfactant (TTAB) barely changed the molecule arrangement and thus barely influenced the exchange rate of 14-s-14. The ionic conventional surfactant (SDS) introduced the electrostatic attraction effect, tightened the molecule arrangement, and increased hydrophobic interactions in the micelle, and thus slowed down the exchange rate of 14-s-14. Additionally, the two-step exchange mechanism of 14-s-14 in the mixed solution was revealed through interesting variation tendencies of exchange rates of 14-s-14.

  2. Probing Nanoscale Thermal Transport in Surfactant Solutions

    PubMed Central

    Cao, Fangyu; Liu, Ying; Xu, Jiajun; He, Yadong; Hammouda, B.; Qiao, Rui; Yang, Bao

    2015-01-01

    Surfactant solutions typically feature tunable nanoscale, internal structures. Although rarely utilized, they can be a powerful platform for probing thermal transport in nanoscale domains and across interfaces with nanometer-size radius. Here, we examine the structure and thermal transport in solution of AOT (Dioctyl sodium sulfosuccinate) in n-octane liquids using small-angle neutron scattering, thermal conductivity measurements, and molecular dynamics simulations. We report the first experimental observation of a minimum thermal conductivity occurring at the critical micelle concentration (CMC): the thermal conductivity of the surfactant solution decreases as AOT is added till the onset of micellization but increases as more AOT is added. The decrease of thermal conductivity with AOT loading in solutions in which AOT molecules are dispersed as monomers suggests that even the interfaces between individual oleophobic headgroup of AOT molecules and their surrounding non-polar octane molecules can hinder heat transfer. The increase of thermal conductivity with AOT loading after the onset of micellization indicates that the thermal transport in the core of AOT micelles and across the surfactant-oil interfaces, both of which span only a few nanometers, are efficient. PMID:26534840

  3. Mobility and surfactant migration in EA/MAA latex films; ATR FT-IR spectroscopic study

    SciTech Connect

    Thorstenson, T.A.; Tebelius, L.K.; Urban, M.W.

    1993-12-31

    Although numerous factors such as compatibility, mechanical deformation, and the nature of the substrate have been addressed with respect to surfactant migration and distribution within latex films, latex suspension stability and the effects of particle flocculation are also key issues. In this paper, surfactant behavior in an ethyl acrylate/methacrylic acid/sodium dioctyl sulfosuccinate (EA/MAA/SDOSS) latex system is monitored as a function of stability of the liquid latex suspensions. Particle size data obtained using light scattering reveals an appreciable degree of flocculation over the period of study. It is found that flocculation is paralleled by a significantly increased degree of interfacial surfactant enrichment, a monitored by attenuated total reflectance Fourier transform infrared spectroscopy (ATR FT-IR). It is concluded that the enhanced surfactant exudation observed for flocculated latexes is due to displacement of adsorbed surfactant during the course of flocculation.

  4. Emulsification at the Liquid/Liquid Interface: Effects of Potential, Electrolytes and Surfactants.

    PubMed

    Chowdhury, Mehrin; Kataky, Ritu

    2016-01-04

    Emulsification of oils at liquid/liquid interfaces is of fundamental importance across a range of applications, including detergency. Adsorption and partitioning of the anionic surface active ions at the interface between two immiscible solutions is known to cause predictable chaos at the transfer potential region of the surfactant. In this work, the phenomenon that leads to the chaotic behaviour shown by sodium dodecylbenzene sulfonate (SDBS) at the water/1,2-dichloroethane interface is applied to commercial surfactants and aqueous/glyceryl trioleate interface. Electrochemical methods, electrocapillary curves, optical microscopy and conductivity measurements demonstrated that at 1.5 mm of SDBS, surfactants are adsorbed at the interface and assemble into micelles, leading to interfacial instability. As the concentration of the anionic surfactant was enhanced to 8 and 13.4 mm, the Marangoni effect and the interfacial emulsification became more prominent. The chaotic behaviour was found to be dependent on the surfactant concentration and the electrolytes present.

  5. Interactions of structurally modified surfactants with reservoir minerals: Calorimetric, spectroscopic and electrokinetic study

    SciTech Connect

    Somasundaran, P.; Sivakumar, A.; Xu, Q.

    1991-03-01

    The objective of this project is to elucidate mechanisms of adsorption of structurally modified surfactants on reservoir minerals and to develop a full understanding of the effect of the surfactant structure on the nature of the adsorbed layers at the molecular level. An additional aim is to study the adsorption of surfactant mixtures on simple well-characterized minerals and on complex minerals representing real conditions. The practical goal of these studies is the identification of the optimum surfactant structures and their combinations for micellar flooding. In this work, the experiments on adsorption were focussed on the position of sulfonate and methyl groups on the aromatic ring of alkyl xylene sulfonates. A multi-pronged approach consisting of calorimetry, electrokinetics, wettability and spectroscopy is planned to elucidate the adsorption mechanism of surfactants and their mixtures on minerals such as alumina and kaolinite. 32 refs., 15 figs., 7 tabs.

  6. An embedded boundary method for soluble surfactants with interface tracking for two-phase flows

    NASA Astrophysics Data System (ADS)

    Khatri, Shilpa; Tornberg, Anna-Karin

    2014-01-01

    Surfactants, surface reacting agents, lower the surface tension of the interface between fluids in multiphase flow. This capability of surfactants makes them ideal for many applications, including wetting, foaming, and dispersing. Due to their molecular composition, surfactants are adsorbed from the bulk fluid to the interface between the fluids, leading to different concentrations on the interface and in the fluid. In a previous paper [21], we introduced a new second order method using uniform grids to simulate insoluble surfactants in multiphase flow. This method used Strang splitting allowing for a fully second order treatment in time. Here, we use the same numerical methods to explicitly represent the singular interface, treat the interfacial surfactant concentration, and couple with the Navier-Stokes equations. Now, we introduce a second order method for the surfactants in the bulk that continues to allow the use of regular grids for the full problem. Difficulties arise since the boundary condition for the bulk concentration, which handles the flux of surfactant between the interface and bulk fluid, is applied at the interface which cuts arbitrarily through the regular grid. We extend the embedded boundary method, introduced in [22], to handle this challenge. Through our results, we present the effect of the solubility of the surfactants. We show results of drop dynamics due to resulting Marangoni stresses and of drop deformations in shear flow in the presence of soluble surfactants. There is a large nondimensional parameter space over which we try to understand the drop dynamics.

  7. Chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism

    PubMed Central

    Dolamic, Igor; Varnholt, Birte; Bürgi, Thomas

    2015-01-01

    The transfer of chirality from one set of molecules to another is fundamental for applications in chiral technology and has likely played a crucial role for establishing homochirality on earth. Here we show that an intrinsically chiral gold cluster can transfer its handedness to an achiral molecule adsorbed on its surface. Solutions of chiral Au38(2-PET)24 (2-PET=2-phenylethylthiolate) cluster enantiomers show strong vibrational circular dichroism (VCD) signals in vibrations of the achiral adsorbate. Density functional theory (DFT) calculations reveal that 2-PET molecules adopt a chiral conformation. Chirality transfer from the cluster to the achiral adsorbate is responsible for the preference of one of the two mirror images. Intermolecular interactions between the adsorbed molecules on the crowded cluster surface seem to play a dominant role for the phenomena. Such chirality transfer from metals to adsorbates likely plays an important role in heterogeneous enantioselective catalysis. PMID:25960309

  8. Chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism

    NASA Astrophysics Data System (ADS)

    Dolamic, Igor; Varnholt, Birte; Bürgi, Thomas

    2015-05-01

    The transfer of chirality from one set of molecules to another is fundamental for applications in chiral technology and has likely played a crucial role for establishing homochirality on earth. Here we show that an intrinsically chiral gold cluster can transfer its handedness to an achiral molecule adsorbed on its surface. Solutions of chiral Au38(2-PET)24 (2-PET=2-phenylethylthiolate) cluster enantiomers show strong vibrational circular dichroism (VCD) signals in vibrations of the achiral adsorbate. Density functional theory (DFT) calculations reveal that 2-PET molecules adopt a chiral conformation. Chirality transfer from the cluster to the achiral adsorbate is responsible for the preference of one of the two mirror images. Intermolecular interactions between the adsorbed molecules on the crowded cluster surface seem to play a dominant role for the phenomena. Such chirality transfer from metals to adsorbates likely plays an important role in heterogeneous enantioselective catalysis.

  9. Hyperbranched hydrocarbon surfactants give fluorocarbon-like low surface energies.

    PubMed

    Sagisaka, Masanobu; Narumi, Tsuyoshi; Niwase, Misaki; Narita, Shioki; Ohata, Atsushi; James, Craig; Yoshizawa, Atsushi; Taffin de Givenchy, Elisabeth; Guittard, Frédéric; Alexander, Shirin; Eastoe, Julian

    2014-06-03

    Two series of Aerosol-OT-analogue surfactants (sulfosuccinate-type di-BCnSS and sulfoglutarate-type di-BCnSG) with hyperbranched alkyl double tails (so-called "hedgehog" groups, carbon number n = 6, 9, 12, and 18) have been synthesized and shown to demonstrate interfacial properties comparable to those seen for related fluorocarbon (FC) systems. Critical micelle concentration (CMC), surface tension at the CMC (γCMC), and minimum area per molecule (Amin) were obtained from surface tension measurements of aqueous surfactant solutions. The results were examined for relationships between the structure of the hedgehog group and packing density at the interface. To evaluate A and B values in the Klevens equation for these hedgehog surfactants, log(CMC) was plotted as a function of the total carbon number in the surfactant double tail. A linear relationship was observed, producing B values of 0.20-0.25 for di-BCnSS and di-BCnSG, compared to a value of 0.31 for standard double-straight-tail sulfosuccinate surfactants. The lower B values of these hedgehog surfactants highlight their lower hydrophobicity compared to double-straight-tail surfactants. To clarify how hydrocarbon density in the surfactant-tail layer (ρ(layer)) affects γCMC, the ρ(layer) of each double-tail surfactant was calculated and the relationship between γCMC and ρ(layer) examined. As expected for the design of low surface energy surfactant layers, ρ(layer) was identified as an important property for controlling γCMC with higher ρ(layer), leading to a lower γCMC. Interestingly, surfactants with BC9 and BC12 tails achieved much lower γCMC, even at low ρ(layer) values of <0.55 g cm(-3). The lowest surface energy surfactant studied here was di-BC6SS, which had a γCMC of only 23.8 mN m(-1). Such a low γCMC is comparable to those obtained with short FC-tail surfactants (e.g., 22.0 mN m(-1) for the sulfosuccinate-type FC-surfactant with R = F(CF2)6CH2CH2-).

  10. Ionic liquids as surfactants

    NASA Astrophysics Data System (ADS)

    Smirnova, N. A.; Safonova, E. A.

    2010-10-01

    Problems of self-assembling in systems containing ionic liquids (ILs) are discussed. Main attention is paid to micellization in aqueous solutions of dialkylimidazolium ILs and their mixtures with classical surfactants. Literature data are reviewed, the results obtained by the authors and co-workers are presented. Thermodynamic aspects of the studies and problems of molecular-thermodynamic modeling receive special emphasis. It is shown that the aggregation behavior of dialkylimidazolium ILs is close to that of alkyltrimethylammonium salts (cationic surfactants) though ILs have a higher ability to self-organize, especially as it concerns long-range ordering. Some aspects of ILs applications are outlined where their common features with classical surfactants and definite specificity are of value.

  11. The effect of surfactant on pollutant biosorption of Trametes versicolor

    NASA Astrophysics Data System (ADS)

    Gül, Ülküye Dudu; Silah, Hülya; Akbaş, Halide; Has, Merve

    2016-04-01

    The major problem concerning industrial wastewater is treatment of dye and heavy metal containing effluents. Industrial effluents are also contained surfactants that are used as levelling, dispersing and wetting agents. The purpose of this study was to investigate the effect of surfactant on textile dye biosorption properties of a white rot fungus named Trametes versicolor. Reactive dyes are commonly used in textile industry because of their advantages such as brightness and excellent color fastness. A recative textile dye, called Everzol Black, was used in this study. The low-cost mollasses medium is used for fungal growth. The usage of mollases, the sugar refinery effluent as a source of energy and nutrients, gained importance because of reducing the cost and also reusing another waste. In biosorption process the effect of surfactant on dye removal properties of T. versicolor was examined as a function of pH, dye consentration and surfactant concentration. The results of this study showed that the surfactant enhanced the dye removal capacity of Trametes versicolor. The dye and surfactant molecules were interacted electrostatically and these electrostatic interactions improved dye removal properties of filamentous fungus T. versicolor. The results of this study recommended the use of surfactants as an inducer in textile wastewater treatment technologies.

  12. Molecular dynamics for surfactant-assisted protein refolding

    NASA Astrophysics Data System (ADS)

    Lu, Diannan; Liu, Zheng; Wu, Jianzhong

    2007-02-01

    Surfactants are widely used to refold recombinant proteins that are produced as inclusion bodies in E. Coli. However, the microscopic details of the surfactant-assisted protein refolding processes are yet to be uncovered. In the present work, the authors aim to provide insights into the effect of hydrophobic interactions of a denatured protein with surfactant molecules on the refolding kinetics and equilibrium by using the Langevin dynamics for coarse-grained models. The authors have investigated the folding behavior of a β-barrel protein in the presence of surfactants of different hydrophobicities and concentrations. It is shown that the protein folding process follows a "collapse-rearrangement" mechanism, i.e., the denatured protein first falls into a collapsed state before acquiring the native conformation. In comparison with the protein folding without surfactants, the protein-surfactant hydrophobic interactions promote the collapse of a denatured protein and, consequently, the formation of a hydrophobic core. However, the surfactants must be released from the hydrophobic core during the rearrangement step, in which the native conformation is formed. The simulation results can be qualitatively reproduced by experiments.

  13. Surfactants in microbiology and biotechnology: Part 2. Application aspects.

    PubMed

    Singh, Ajay; Van Hamme, Jonathan D; Ward, Owen P

    2007-01-01

    Surfactants are amphiphilic compounds which can reduce surface and interfacial tensions by accumulating at the interface of immiscible fluids and increase the solubility, mobility, bioavailability and subsequent biodegradation of hydrophobic or insoluble organic compounds. Chemically synthesized surfactants are commonly used in the petroleum, food and pharmaceutical industries as emulsifiers and wetting agents. Biosurfactants produced by some microorganisms are becoming important biotechnology products for industrial and medical applications due to their specific modes of action, low toxicity, relative ease of preparation and widespread applicability. They can be used as emulsifiers, de-emulsifiers, wetting and foaming agents, functional food ingredients and as detergents in petroleum, petrochemicals, environmental management, agrochemicals, foods and beverages, cosmetics and pharmaceuticals, and in the mining and metallurgical industries. Addition of a surfactant of chemical or biological origin accelerates or sometimes inhibits the bioremediation of pollutants. Surfactants also play an important role in enhanced oil recovery by increasing the apparent solubility of petroleum components and effectively reducing the interfacial tensions of oil and water in situ. However, the effects of surfactants on bioremediation cannot be predicted in the absence of empirical evidence because surfactants sometimes stimulate bioremediation and sometimes inhibit it. For medical applications, biosurfactants are useful as antimicrobial agents and immunomodulatory molecules. Beneficial applications of chemical surfactants and biosurfactants in various industries are discussed in this review.

  14. The effect of surfactants on drop deformation, collisions and breakup

    NASA Astrophysics Data System (ADS)

    Cristini, Vittorio; Zhou, Hua; Lowengrub, John; Macosko, Chris

    2001-11-01

    The dynamics of deformable drops in viscous flows are investigated via numerical simulations. A novel finite-element/sharp-interface algorithm based on adaptive tetrahedra (Hooper et al. 2001) for simulations is used. Three-dimensional drop deformation is studied in the presence of a surfactant coating of the drop interface. Under these conditions, flow-driven surfactant redistribution induces Marangoni stresses at the interface that modify the hydrodynamics and thus affect the rheology of emulsions and polymer blends. The effects of the equation of state that relates the concentration of surfactant on the interface to the surface tension, and of diffusion and solubility of surfactant molecules are included in our model. Results of simulations under strong-flow conditions are presented that describe the effect of surfactants on the development of lamellar microstructures in emulsions (Wetzel and Tucker 2001; Cristini et al. 2001). More stable drop lamellae with larger interfacial area are predicted in the presence of surfactants, in agreement with recent experimental observations (Jeon and Macosko 2000). In addition, the feasibility of accurate simulations of drop collisions and breakup is demonstrated using our model, and preliminary results on the effects of surfactants on these phenomena are presented.

  15. Solubilization of herbicides by single and mixed commercial surfactants.

    PubMed

    Galán-Jiménez, M C; Gómez-Pantoja, E; Morillo, E; Undabeytia, T

    2015-12-15

    The solubilization capabilities of micellar solutions of three single surfactants, two alcohol alkoxylates B048 and B266, and the tallow alkyl ethoxylated amine ET15, and their equimolar mixed solutions toward the herbicides flurtamone (FL), metribuzin (MTZ) and mesotrione (MST) were investigated. The solubilization capacity was quantified in terms of the molar solubilization ratio (MSR), critical micellar concentration (CMC), micelle-water partition coefficient (Kmc), binding constant (K1), number of aggregation (Nagg) and Stern-Volmer constant (Ksv). The herbicides were greatly solubilized into different loci of the micelles: FL within the inner hydrophobic core, MST at the micelle/water interface and MTZ in the palisade region. Equimolar binary surfactant mixtures did not improve the solubilization of herbicides over those of single components, with the exception of MTZ by the B266/ET15 system which enhanced solubilization by 10-20%. This enhanced solubilization of MTZ was due to an increased number of micelles that arise from both the intermediate Nagg relative to that of the single surfactants and the lower CMC. The use of Ksv values was a better predictor of the solubilization of polar molecules within binary mixtures of these surfactants than the interaction parameter β(M) from regular solution theory (RST). The results herein suggest that the use of mixed surfactant systems for the solubilization of polar molecules in environmental remediation technologies may be very limited in scope, without clear advantages over the use of single surfactant systems.

  16. General hydrophobic interaction potential for surfactant/lipid bilayers from direct force measurements between light-modulated bilayers

    PubMed Central

    Donaldson, Stephen H.; Lee, C. Ted; Chmelka, Bradley F.; Israelachvili, Jacob N.

    2011-01-01

    We establish and quantify correlations among the molecular structures, interaction forces, and physical processes associated with light-responsive self-assembled surfactant monolayers or bilayers at interfaces. Using the surface forces apparatus (SFA), the interaction forces between adsorbed monolayers and bilayers of an azobenzene-functionalized surfactant can be drastically and controllably altered by light-induced conversion of trans and cis molecular conformations. These reversible conformation changes affect significantly the shape of the molecules, especially in the hydrophobic region, which induces dramatic transformations of molecular packing in self-assembled structures, causing corresponding modulation of electrostatic double layer, steric hydration, and hydrophobic interactions. For bilayers, the isomerization from trans to cis exposes more hydrophobic groups, making the cis bilayers more hydrophobic, which lowers the activation energy barrier for (hemi)fusion. A quantitative and general model is derived for the interaction potential of charged bilayers that includes the electrostatic double-layer force of the Derjaguin–Landau–Verwey–Overbeek theory, attractive hydrophobic interactions, and repulsive steric-hydration forces. The model quantitatively accounts for the elastic strains, deformations, long-range forces, energy maxima, adhesion minima, as well as the instability (when it exists) as two bilayers breakthrough and (hemi)fuse. These results have several important implications, including quantitative and qualitative understanding of the hydrophobic interaction, which is furthermore shown to be a nonadditive interaction. PMID:21896718

  17. Arsenic retention and transport behavior in the presence of typical anionic and nonionic surfactants.

    PubMed

    Liang, Chuan; Wang, Xianliang; Peng, Xianjia

    2016-01-01

    The massive production and wide use of surfactants have resulted in a large amount of surfactant residuals being discharged into the environment, which could have an impact on arsenic behavior. In the present study, the influence of the anionic surfactant sodium dodecyl benzene sulfonate (SDBS) and nonionic surfactant polyethylene glycol octylphenyl ether (Triton X-100) on arsenic behavior was investigated in batch and column tests. The presence of SDBS and Triton X-100 reduced arsenic retention onto ferrihydrite (FH), enhanced arsenic transport through FH coated sand (FH-sand) columns and promoted arsenic release from the FH surface. With coexisting surfactants in solution, the equilibrium adsorbed amount of arsenic on FH decreased by up to 29.7% and the adsorption rate decreased by up to 52.3%. Pre-coating with surfactants caused a decrease in the adsorbed amount and adsorption rate of arsenic by up to 15.1% and 58.3%, respectively. Because of the adsorption attenuation caused by surfactants, breakthrough of As(V) and As(III) with SDBS in columns packed with FH-sand was 23.8% and 14.3% faster than that in those without SDBS, respectively. In columns packed with SDBS-coated FH-sand, transport of arsenic was enhanced to a greater extent. Breakthrough of As(V) and As(III) was 52.4% and 43.8% faster and the cumulative retention amount was 44.5% and 57.3% less than that in pure FH-sand column systems, respectively. Mobilization of arsenic by surfactants increased with the increase of the initial adsorbed amount of arsenic. The cumulative release amount of As(V) and As(III) from the packed column reached 10.8% and 36.0%, respectively.

  18. Solubilization capacity of nonionic surfactant micelles exhibiting strong influence on export of intracellular pigments in Monascus fermentation.

    PubMed

    Kang, Biyu; Zhang, Xuehong; Wu, Zhenqiang; Qi, Hanshi; Wang, Zhilong

    2013-09-01

    In this study, perstractive fermentation of intracellular Monascus pigments in nonionic surfactant micelle aqueous solution had been studied. The permeability of cell membrane modified by nonionic surfactant might have influence on the rate of export of intracellular pigments into its extracellular broth while nearly no effect on the final extracellular pigment concentration. However, the solubilization of pigments in nonionic surfactant micelles strongly affected the final extracellular pigment concentration. The solubilization capacity of micelles depended on the kind of nonionic surfactant, the super-molecule assembly structure of nonionic surfactant in an aqueous solution, and the nonionic surfactant concentration. Elimination of pigment degradation by export of intracellular Monascus pigments and solubilizing them into nonionic surfactant micelles was also confirmed experimentally. Thus, nonionic surfactant micelle aqueous solution is potential for replacement of organic solvent for perstractive fermentation of intracellular product.

  19. Solubilization capacity of nonionic surfactant micelles exhibiting strong influence on export of intracellular pigments in Monascus fermentation

    PubMed Central

    Kang, Biyu; Zhang, Xuehong; Wu, Zhenqiang; Qi, Hanshi; Wang, Zhilong

    2013-01-01

    Summary In this study, perstractive fermentation of intracellular Monascus pigments in nonionic surfactant micelle aqueous solution had been studied. The permeability of cell membrane modified by nonionic surfactant might have influence on the rate of export of intracellular pigments into its extracellular broth while nearly no effect on the final extracellular pigment concentration. However, the solubilization of pigments in nonionic surfactant micelles strongly affected the final extracellular pigment concentration. The solubilization capacity of micelles depended on the kind of nonionic surfactant, the super-molecule assembly structure of nonionic surfactant in an aqueous solution, and the nonionic surfactant concentration. Elimination of pigment degradation by export of intracellular Monascus pigments and solubilizing them into nonionic surfactant micelles was also confirmed experimentally. Thus, nonionic surfactant micelle aqueous solution is potential for replacement of organic solvent for perstractive fermentation of intracellular product. PMID:23425092

  20. Fabrication of Annealed Gold Nanostructures on Pre-Treated Glow-Discharge Cleaned Glasses and Their Used for Localized Surface Plasmon Resonance (LSPR) and Surface Enhanced Raman Spectroscopy (SERS) Detection of Adsorbed (Bio)molecules

    PubMed Central

    Ionescu, Rodica Elena; Aybeke, Ece Neslihan; Bourillot, Eric; Lacroute, Yvon; Lesniewska, Eric; Adam, Pierre-Michel; Bijeon, Jean-Louis

    2017-01-01

    Metallic nanoparticles are considered as active supports in the development of specific chemical or biological biosensors. Well-organized nanoparticles can be prepared either through expensive (e.g., electron beam lithography) or inexpensive (e.g., thermal synthesis) approaches where different shapes of nanoparticles are easily obtained over large solid surfaces. Herein, the authors propose a low-cost thermal synthesis of active plasmonic nanostructures on thin gold layers modified glass supports after 1 h holding on a hot plate (~350 °C). The resulted annealed nanoparticles proved a good reproducibility of localized surface plasmon resonance (LSPR) and surface enhanced Raman spectroscopy (SERS) optical responses and where used for the detection of low concentrations of two model (bio)chemical molecules, namely the human cytochrome b5 (Cyt-b5) and trans-1,2-bis(4-pyridyl)ethylene (BPE). PMID:28134754

  1. Direct suppression of phagocytosis by amphipathic polymeric surfactants.

    PubMed

    Watrous-Peltier, N; Uhl, J; Steel, V; Brophy, L; Merisko-Liversidge, E

    1992-09-01

    Recent studies have demonstrated that phagocytosis of colloidal particles by the mononuclear phagocytes of the liver and spleen can be controlled by either coating or stabilizing particulate carriers with the amphipathic polymeric surfactants, F108 and T908. These surfactants consist of copolymers of polypropylene oxide (PPO) and polyethylene oxide (PEO) and, when adsorbed to particulate surfaces, significantly decrease sequestration of particulates by the mononuclear phagocytes (MPS) of the liver. To evaluate these observations further, murine peritoneal macrophages were incubated for varying periods with surfactant-coated and noncoated polystyrene particles (PSPs). Phagocytosis was monitored using gamma counting and quantitative fluorescence microscopy. The data show that phagocytosis is decreased when PSPs are coated with F108 and T908. In addition, suppression of phagocytic activity was observed when cells were pretreated with the surfactant and then challenged with noncoated particles. The data confirm previous observations that polymeric surfactants consisting of PEO and PPO protect particulate carriers from rapid uptake by the MPS of the liver. Further, F108 and T908 suppress phagocytosis directly without affecting the integrity, viability, or functional state of the cell.

  2. Self-Probing of Micellization within Phenyl-Containing Surfactant Solutions

    SciTech Connect

    Om, Hari; Behera, Kamalakanta; Kumar, Vinod; Verma, Krishan; Pandey, Siddharth

    2010-01-01

    The propensity of amphiphilic molecules to accumulate at the interface between the solution and adjacent gaseous, liquid, or solid phases is responsible for many remarkable physicochemical properties of aqueous surfactant systems such as wetting, foaming, emulsification, dispersion, adsorption, micellization, detergency, synergistic interactions with other surfactants, solubility, and solubilization, among others.

  3. Colloidal stability of iron oxide nanoparticles with multivalent polymer surfactants.

    PubMed

    Choi, Young-Wook; Lee, Hoik; Song, Youngjun; Sohn, Daewon

    2015-04-01

    This paper introduces a new approach for preparing magnetic colloidal suspensions with electrostatic repulsion between particles and polyelectrolyte surfactants. The surface charge of the iron oxide particles was positive in acidic aqueous conditions; however the surface charge of the colloid was negative in basic aqueous conditions due to the amphoteric property of Fe2O3. The long-term colloidal stability and particle distribution of the multivalent charged polymers, Poly(4-vinylbenzenesulfonate sodium salt) (PSS), Poly(acrylic acid) (PAA), and Poly(allylamine hydrochloride) (PAH) were compared with the monovalent surfactant sodium dodecyl sulfate (SDS). Both mono- and multivalent surfactant molecules showed good colloidal stability for extended periods of time. However, the particle distribution was dependent on the hydrophobicity of the surfactants' functional groups. Polyelectrolytes with a negatively charged functional group showed good long-term stability of particles and a narrow particle distribution regardless of the acid dissociation constant (pKa) of the polymer.

  4. Development of glucose sensor using two-photon adsorbed photopolymerization.

    PubMed

    Kim, Jong Min; Park, Jung-Jin; Lee, Haeng-Ja; Kim, Woo-Sik; Muramatsu, Hiroshi; Chang, Sang-Mok

    2010-01-01

    A novel glucose sensor was constructed, and its analytical potential examined. A chip-type three-electrode system for use in a flow-type electrochemical glucose sensor was fabricated using a UV lithography technique on a glass slide. An Ag/AgCl reference electrode was made by electroplating silver onto a Pt electrode and dipping in a saturated KCl solution for 30 min. In addition, a glucose-sensing electrode was fabricated using a two-photon adsorbed photopolymerization technique with a photo-reactive resin containing a glucose oxidase enzyme, ferrocene mediator, non-ionic surfactant, and carbon nanotubes. The cyclic voltammetry of the potassium ferrocyanide in the Pt sensor system showed a stable electrode condition. The response of the modified Pt sensor confirms the feasibility of using a two-photon adsorbed photopolymerization technique for the easy fabrication of functional biosensors.

  5. Effect of surfactants on shear-induced gelation and gel morphology of soft strawberry-like particles.

    PubMed

    Xie, Delong; Arosio, Paolo; Wu, Hua; Morbidelli, Massimo

    2011-06-07

    The role of surfactant type in the aggregation and gelation of strawberry-like particles induced by intense shear without any electrolyte addition is investigated. The particles are composed of a rubbery core, partially covered by a plastic shell, and well stabilized by fixed (sulfate) charges in the end group of the polymer chains originating from the initiator. In the absence of any surfactant, after the system passes through a microchannel at a Peclet number equal to 220 and a particle volume fraction equal to 0.15, not only shear-induced gelation but also partial coalescence among the particles occurs. The same shear-induced aggregation/gelation process has been carried out in the presence of an ionic (sulfonate) surfactant or a nonionic (Tween 20) steric surfactant. It is found that for both surfactants shear-induced gelation does occur at low surfactant surface density but the conversion of the primary particles to the clusters constituting the gel decreases as the surfactant surface density increases. When the surfactant surface density increases above certain critical values, shear-induced gelation and eventually even aggregation do not occur any longer. For the sulfonate surfactant, this was explained in the literature by the non-DLVO, short-range repulsive hydration forces generated by the adsorbed surfactant layer. In this work, it is shown that the steric repulsion generated by the adsorbed Tween 20 layer can also protect particles from aggregation under intense shear. Moreover, the nonionic steric surfactant can also protect the strawberry-like particles from coalescence. This implies a decrease in the fractal dimension of the clusters constituting the gel from 2.76 to 2.45, which cannot be achieved using the ionic sulfonate surfactant.

  6. Surfactant mixing rules applied to surfactant enhanced alkaline flooding

    SciTech Connect

    Taylor, K.C. )

    1992-01-01

    This paper discusses surfactant mixing rules which have been used to describe crude oil/alkali/surfactant phase behavior, using David Lloydminster crude oil and the surfactant Neodol 25-3S. It was found that at a fixed salinity and alkali concentration, a specific mole fraction of synthetic surfactant to petroleum soap was required to produce optimal phase behavior as the water-to-oil ratio varied. This methodology is useful in understanding the relationship between the variables of water-to-oil ratio and synthetic surfactant concentration in phase behavior systems that produce a petroleum soap.

  7. Remobilizing the Interfaces of Thermocapillary Driven Bubbles Retarded by the Adsorption of a Surfactant Impurity on the Bubble Surface

    NASA Technical Reports Server (NTRS)

    Palaparthi, Ravi; Maldarelli, Charles; Papageorgiou, Dimitri; Singh, Bhim S. (Technical Monitor)

    2000-01-01

    Thermocapillary migration is a method for moving bubbles in space in the absence of buoyancy. A temperature gradient is applied to the continuous phase in which a bubble is situated, and the applied gradient impressed on the bubble surface causes one pole of the drop to be cooler than the opposite pole. As the surface tension is a decreasing function of temperature, the cooler pole pulls at the warmer pole, creating a flow which propels the bubble in the direction of the warmer fluid. A major impediment to the practical use of thermocapillarity to direct the movement of bubbles in space is the fact that surfactant impurities which are unavoidably present in the continuous phase can significantly reduce the migration velocity. A surfactant impurity adsorbed onto the bubble interface is swept to the trailing end of the bubble. When bulk concentrations are low (which is the case with an impurity), diffusion of surfactant to the front end is slow relative to convection, and surfactant collects at the back end of the bubble. Collection at the back lowers the surface tension relative to the front end setting up a reverse tension gradient. For buoyancy driven bubble motions in the absence of a thermocapillarity, the tension gradient opposes the surface flow, and reduces the surface and terminal velocities (the interface becomes more solid-like). When thermocapillary forces are present, the reverse tension gradient set up by the surfactant accumulation reduces the temperature tension gradient, and decreases to near zero the thermocapillary velocity. The objective of our research is to develop a method for enhancing the thermocapillary migration of bubbles which have been retarded by the adsorption onto the bubble surface of a surfactant impurity, Our remobilization theory proposes to use surfactant molecules which kinetically rapidly exchange between the bulk and the surface and are at high bulk concentrations. Because the remobilizing surfactant is present at much higher

  8. 1H NMR relaxation of water: a probe for surfactant adsorption on kaolin.

    PubMed

    Totland, Christian; Lewis, Rhiannon T; Nerdal, Willy

    2011-11-01

    In this study, (1)H NMR is used to investigate properties of sodium dodecyl sulfate (SDS), tetradecyl trimethyl ammonium bromide (TTAB), and dodecyl trimethyl ammonium bromide (DTAB) adsorbed on kaolin by NMR T(1) and T(2) measurements of the water proton resonance. The results show that adsorbed surfactants form a barrier between sample water and the paramagnetic species present on the clay surface, thus significantly increasing the proton T(1) values of water. This effect is attributed to the amount of adsorbed surfactants and the arrangement of the surfactant aggregates. The total surface area covered by the cationic (DTAB and TTAB) and anionic (SDS) surfactants could be estimated from the water T(1) data and found to correspond to the fractions of negatively and positively charged surface area, respectively. For selected samples, the amount of paramagnetic species on the clay surface was reduced by treatment with hydrofluoric (HF) acid. For these samples, T(1) and T(2) measurements were taken in the temperature range 278-338 K, revealing detailed information on molecular mobility and nuclear exchange for the sample water that is related to surfactant behavior both on the surface and in the aqueous phase.

  9. Effects of surfactants on the desorption of organic contaminants from aquifer materials. Doctoral thesis

    SciTech Connect

    Brickell, J.L.

    1989-08-01

    The efficiency of removing organic contaminants from groundwater aquifers by the pump and treat process is adversely affected by the retardation of the contaminant's mobility due to adsorption onto aquifer material. The use of surfactants in conjunction with the pump and treat process has the potential for improving contaminant mobility by solubilizing the adsorbed contaminant.

  10. Surfactant-enhanced bioremediation

    SciTech Connect

    Churchill, P.F.; Dudley, R.J.; Churchill, S.A.

    1995-12-31

    This study was undertaken to examine the effect of three structurally related, non-ionic surfactants, Triton X-45, Triton X-100 and Triton X-165, as well as the oleophilic fertilizer, Inipol EAP 22, on the rate of biodegradation of phenanthrene by pure bacterial cultures. Each surfactant dramatically increased the apparent aqueous solubility of phenanthrene. Model studies were conducted to investigate the ability of these surfactants to enhance the rate of transport and uptake of polycyclic aromatic hydrocarbons into bacterial cells, and to assess the impact that increasing the aqueous solubility of hydrocarbons has on their rate of biodegradation. The results indicate that increasing the apparent aqueous solubility of hydrocarbons can lead to enhanced biodegradation rates by two Pseudomonas saccharophila strains. However, the experiments also suggest that some surfactants can inhibit aromatic hydrocarbon biodegradation by certain bacteria. The data also support the hypothesis that surface-active components present in the oleophilic fertilizer formulation, Inipol EAP 22, may have significantly contributed to the positive results reported in tests of remedial agent impact on bioremediation, which was used as a supplemental clean-up technology on Exxon Valdez crude oil-contaminated Alaskan beaches.

  11. Enhanced photocatalytic degradation of norfloxacin in aqueous Bi2WO6 dispersions containing nonionic surfactant under visible light irradiation.

    PubMed

    Tang, Lin; Wang, Jiajia; Zeng, Guangming; Liu, Yani; Deng, Yaocheng; Zhou, Yaoyu; Tang, Jing; Wang, Jingjing; Guo, Zhi

    2016-04-05

    Photocatalytic degradation is an alternative method to remove pharmaceutical compounds in water, however it is hard to achieve efficient rate because of the poor solubility of pharmaceutical compounds in water. This study investigated the photodegradation of norfloxacin in a nonionic surfactant Triton-X100 (TX100)/Bi2WO6 dispersion under visible light irradiation (400-750nm). It was found that the degradation of poorly soluble NOF can be strongly enhanced with the addition of TX100. TX100 was adsorbed strongly on Bi2WO6 surface and accelerated NOF photodegradation at the critical micelle concentration (CMC=0.25mM). Higher TX100 concentration (>0.25mM) lowered the degradation rate. In the presence of TX100, the degradation rate reached the maximum value when the pH value was 8.06. FTIR analyses demonstrated that the adsorbed NOF on the catalyst was completely degraded after 2h irradiation. According to the intermediates identified by HPLC/MS/MS, three possible degradation pathways were proposed to include addition of hydroxyl radical to quinolone ring, elimination of piperazynilic ring in fluoroquinolone molecules, and replacement of F atoms on the aromatic ring by hydroxyl radicals.

  12. Adsorption of the anionic surfactant sodium dodecyl sulfate on a C18 column under micellar and high submicellar conditions in reversed-phase liquid chromatography.

    PubMed

    Ortiz-Bolsico, C; Ruiz-Angel, M J; García-Alvarez-Coque, M C

    2015-02-01

    Micellar liquid chromatography makes use of aqueous solutions or aqueous-organic solutions containing a surfactant, at a concentration above its critical micelle concentration. In the mobile phase, the surfactant monomers aggregate to form micelles, whereas on the surface of the nonpolar alkyl-bonded stationary phases they are significantly adsorbed. If the mobile phase contains a high concentration of organic solvent, micelles break down, and the amount of surfactant adsorbed on the stationary phase is reduced, giving rise to another chromatographic mode named high submicellar liquid chromatography. The presence of a thinner coating of surfactant enhances the selectivity and peak shape, especially for basic compounds. However, the risk of full desorption of surfactant is the main limitation in the high submicellar mode. This study examines the adsorption of the anionic surfactant sodium dodecyl sulfate under micellar and high submicellar conditions on a C18 column, applying two methods. One of them uses a refractive index detector to obtain direct measurements of the adsorbed amount of sodium dodecyl sulfate, whereas the second method is based on the retention and peak shape for a set of cationic basic compounds that indirectly reveal the presence of adsorbed monomers of surfactant on the stationary phase.

  13. Marangoni Effects of a Drop in an Extensional Flow: The Role of Surfactant Physical Chemistry

    NASA Technical Reports Server (NTRS)

    Stebe, Kathleen J.; Balasubramaniam, R. (Technical Monitor)

    2002-01-01

    While the changes in stresses caused by surfactant adsorption on non-deforming interfaces have been fairly well established, prior to this work, there were few studies addressing how surfactants alter stresses on strongly deforming interfaces. We chose the model problem of a drop in a uniaxial extensional flow to study these stress conditions To model surfactant effects at fluid interfaces, a proper description of the dependence of the surface tension on surface concentration, the surface equation of state, is required. We have adopted a surface equation of state that accounts for the maximum coverage limit; that is, because surfactants have a finite cross sectional area, there is an upper bound to the amount of surfactant that can adsorb in a monolayer. The surface tension reduces strongly only when this maximum coverage is approached. Since the Marangoni stresses go as the derivative of the surface equation of state times the surface concentration gradient, the non-linear equation of state determines both the effect of surfactants in the normal stress jump, (which is balanced by the product of the mean curvature of the interface times the surface tension), and the tangential stress jump, which is balanced by Marangoni stresses. First, the effects of surface coverage and intermolecular interactions among surfactants which drive aggregation of surfactants in the interface were studied. (see Pawar and Stebe, Physics of Fluids).

  14. Diseases of Pulmonary Surfactant Homeostasis

    PubMed Central

    Whitsett, Jeffrey A.; Wert, Susan E.; Weaver, Timothy E.

    2015-01-01

    Advances in physiology and biochemistry have provided fundamental insights into the role of pulmonary surfactant in the pathogenesis and treatment of preterm infants with respiratory distress syndrome. Identification of the surfactant proteins, lipid transporters, and transcriptional networks regulating their expression has provided the tools and insights needed to discern the molecular and cellular processes regulating the production and function of pulmonary surfactant prior to and after birth. Mutations in genes regulating surfactant homeostasis have been associated with severe lung disease in neonates and older infants. Biophysical and transgenic mouse models have provided insight into the mechanisms underlying surfactant protein and alveolar homeostasis. These studies have provided the framework for understanding the structure and function of pulmonary surfactant, which has informed understanding of the pathogenesis of diverse pulmonary disorders previously considered idiopathic. This review considers the pulmonary surfactant system and the genetic causes of acute and chronic lung disease caused by disruption of alveolar homeostasis. PMID:25621661

  15. Non-covalent bonding interaction of surfactants with functionalized carbon nanotubes in proton exchange membranes for fuel cell applications.

    PubMed

    Sayeed, M Abu; Kim, Young Ho; Park, Younjin; Gopalan, A I; Lee, Kwang-Pill; Choi, Sang-June

    2013-11-01

    Dispersion of functionalized multiwalled carbon nanotubes (MWCNTs) in proton exchange membranes (PEMs) was conducted via non-covalent bonding between benzene rings of various surfactants and functionalized MWCNTs. In the solution casting method, dispersion of functionalized MWCNTs in PEMs such as Nafion membranes is a critical issue. In this study, 1 wt.% pristine MWCNTs (p-MWCNTs) and oxidized MWCNTs (ox-MWCNTs) were reinforced in Nafion membranes by adding 0.1-0.5 wt.% of a surfactant such as benzalkonium chloride (BKC) as a cationic surfactant with a benzene ring, Tween-80 as a nonanionic surfactant without a benzene ring, sodium dodecylsulfonate (SDS) as an anionic surfactant without a benzene ring, or sodium dodecylben-zenesulfonate (SDBS) as an anionic surfactant with a benzene ring and their effects on the dispersion of nanocomposites were then observed. Among these surfactants, those with benzene rings such as BKC and SDBS produced enhanced dispersion via non-covalent bonding interaction between CNTs and surfactants. Specifically, the surfactants were adsorbed onto the surface of functionalized MWCNTs, where they prevented re-aggregation of MWCNTs in the nanocomposites. Furthermore, the prepared CNTs reinforced nanocomposite membranes showed reduced methanol uptake values while the ion exchange capacity values were maintained. The enhanced properties, including thermal property of the CNTs reinforced PEMs with surfactants, could be applicable to fuel cell applications.

  16. Theoretical analysis of coverage-dependent rotational hindrance of PF 3 adsorbed on Ru(001)

    NASA Astrophysics Data System (ADS)

    Kaji, H.; Kakitani, K.; Yagi, Y.; Yoshimori, A.

    1996-08-01

    Distribution of the azimuthal orientation of PF 3 molecules adsorbed on Ru(001) measured by ESDIAD shows interesting temperature and coverage dependences. It is interpreted in this analysis as due to the short range order in the locative distribution of the PF 3 molecules. Monte Carlo simulations are performed to obtain the temperature and coverage-dependent distribution of the adsorbed molecules. The distribution of the azimuthal orientation of the molecule is discussed on the basis of the obtained locative distribution of the molecules by using simple models for rotational hindrance to be compared with the experimental results.

  17. Mixing Effect of Polyoxyethylene-Type Nonionic Surfactants on the Liquid Crystalline Structures.

    PubMed

    Kunieda; Umizu; Yamaguchi

    1999-10-01

    An effective cross-sectional area per surfactant molecule at hydrophobic interfaces of aggregates, a(S), in hexagonal (H(1)) and lamellar (L(alpha)) liquid crystals was calculated in homogeneous and mixed polyoxyethylene dodecyl ether systems as a function of polyoxyethylene (EO) chain length by means of small-angle X-ray scattering. The a(S) increases with increasing the EO chain length. The a(S) in the mixed surfactant system is considerably smaller than that in the single surfactant system, even if the average EO chain length is the same. The reduction of a(S) is larger than that predicted by ideal mixing of the surfactants. Moreover, if the EO chain lengths of the surfactants are more separated, the a(S) is smaller. The shapes of surfactant self-organizing structures may be governed by the balance of the attractive and the repulsive forces acting at the hydrophobic interfaces of the aggregates. According to this consideration, the mixing effect of surfactants with the different EO chain lengths on the a(S) in the L(alpha) phase was discussed. It is considered that the surfactant molecules are tightly packed in the aggregates since the reduction in repulsion force takes place in the excess EO chain part of the hydrophilic surfactant longer than the short EO chain of the lipophilic one. The lower surface tensions and the better stability of macroemulsions and the large solubilizing capacity of microemulsions result from the mixing effect. Copyright 1999 Academic Press.

  18. Surfactant treatments alter endogenous surfactant metabolism in rabbit lungs

    SciTech Connect

    Oetomo, S.B.; Lewis, J.; Ikegami, M.; Jobe, A.H. )

    1990-04-01

    The effect of exogenous surfactant on endogenous surfactant metabolism was evaluated using a single-lobe treatment strategy to compare effects of treated with untreated lung within the same rabbit. Natural rabbit surfactant, Survanta, or 0.45% NaCl was injected into the left main stem bronchus by use of a Swan-Ganz catheter. Radiolabeled palmitic acid was then given by intravascular injection at two times after surfactant treatment, and the ratios of label incorporation and secretion in the left lower lobe to label incorporation and secretion in the right lung were compared. The treatment procedure resulted in a reasonably uniform surfactant distribution and did not disrupt lobar pulmonary blood flow. Natural rabbit surfactant increased incorporation of palmitate into saturated phosphatidylcholine (Sat PC) approximately 2-fold (P less than 0.01), and secretion of labeled Sat PC increased approximately 2.5-fold in the surfactant-treated left lower lobe relative to the right lung (P less than 0.01). Although Survanta did not alter incorporation, it did increase secretion but not to the same extent as rabbit surfactant (P less than 0.01). Alteration of endogenous surfactant Sat PC metabolism in vivo by surfactant treatments was different from that which would have been predicted by previous in vitro studies.

  19. Surfactants for Bubble Removal against Buoyancy.

    PubMed

    Raza, Md Qaisar; Kumar, Nirbhay; Raj, Rishi

    2016-01-08

    The common phenomenon of buoyancy-induced vapor bubble lift-off from a heated surface is of importance to many areas of science and technology. In the absence of buoyancy in zero gravity of space, non-departing bubbles coalesce to form a big dry patch on the heated surface and heat transfer deteriorates despite the high latent heat of vaporization of water. The situation is worse on an inverted heater in earth gravity where both buoyancy and surface tension act upwards to oppose bubble removal. Here we report a robust passive technique which uses surfactants found in common soaps and detergents to avoid coalescence and remove bubbles downwards, away from an inverted heater. A force balance model is developed to demonstrate that the force of repulsion resulting from the interaction of surfactants adsorbed at the neighboring liquid-vapor interfaces of the thin liquid film contained between bubbles is strong enough to overcome buoyancy and surface tension. Bubble removal frequencies in excess of ten Hz resulted in more than twofold enhancement in heat transfer in comparison to pure water. We believe that this novel bubble removal mechanism opens up opportunities for designing boiling-based systems for space applications.

  20. Surfactants for Bubble Removal against Buoyancy

    PubMed Central

    Raza, Md. Qaisar; Kumar, Nirbhay; Raj, Rishi

    2016-01-01

    The common phenomenon of buoyancy-induced vapor bubble lift-off from a heated surface is of importance to many areas of science and technology. In the absence of buoyancy in zero gravity of space, non-departing bubbles coalesce to form a big dry patch on the heated surface and heat transfer deteriorates despite the high latent heat of vaporization of water. The situation is worse on an inverted heater in earth gravity where both buoyancy and surface tension act upwards to oppose bubble removal. Here we report a robust passive technique which uses surfactants found in common soaps and detergents to avoid coalescence and remove bubbles downwards, away from an inverted heater. A force balance model is developed to demonstrate that the force of repulsion resulting from the interaction of surfactants adsorbed at the neighboring liquid-vapor interfaces of the thin liquid film contained between bubbles is strong enough to overcome buoyancy and surface tension. Bubble removal frequencies in excess of ten Hz resulted in more than twofold enhancement in heat transfer in comparison to pure water. We believe that this novel bubble removal mechanism opens up opportunities for designing boiling-based systems for space applications. PMID:26743179

  1. Surfactants for Bubble Removal against Buoyancy

    NASA Astrophysics Data System (ADS)

    Raza, Md. Qaisar; Kumar, Nirbhay; Raj, Rishi

    2016-01-01

    The common phenomenon of buoyancy-induced vapor bubble lift-off from a heated surface is of importance to many areas of science and technology. In the absence of buoyancy in zero gravity of space, non-departing bubbles coalesce to form a big dry patch on the heated surface and heat transfer deteriorates despite the high latent heat of vaporization of water. The situation is worse on an inverted heater in earth gravity where both buoyancy and surface tension act upwards to oppose bubble removal. Here we report a robust passive technique which uses surfactants found in common soaps and detergents to avoid coalescence and remove bubbles downwards, away from an inverted heater. A force balance model is developed to demonstrate that the force of repulsion resulting from the interaction of surfactants adsorbed at the neighboring liquid-vapor interfaces of the thin liquid film contained between bubbles is strong enough to overcome buoyancy and surface tension. Bubble removal frequencies in excess of ten Hz resulted in more than twofold enhancement in heat transfer in comparison to pure water. We believe that this novel bubble removal mechanism opens up opportunities for designing boiling-based systems for space applications.

  2. Sorption of nonionic organic compounds in soil-water systems containing a micelle-forming surfactant

    SciTech Connect

    Sun, S.; Inskeep, W.P.; Boyd, S.A. |

    1994-12-31

    The solubility enhancement of nonionic organic compounds (NOCs) by surfactants may represent an important tool in chemical and biological remediation of contaminated soils. In aqueous systems, the presence of dissolved surfactant emulsions or micelles may enhance the solubility of NOCs by acting as a hydrophobic partitioning phase for the NOCs. However, most environmental remediation efforts involve soil-water or sediment-water systems, where surfactant molecules may also interact with the solid phase. An understanding of the effect of surfactants on the sorption and distribution of NOCs in soil or sediment environments will provide an essential basis for utilizing surfactants in environmental remediation. In this study, the authors examined the effect of a micelle-forming surfactant (Triton X-100) on the sorption of 2,2{prime},4,4{prime},5,5{prime}-PCB, 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethane (p,p{prime}-DDT) and 1,2,4-trichlorobenzene (1,2,4-TCB). A conceptual model, which accurately describes the functional dependence of K* on Triton X-100 concentration, was developed based on the partition coefficients of these NOCs by soil, soil-surfactant, surfactant monomer and surfactant micelle phases. This model can be further modified to provide quantitative prediction of K* of a given NOC at different surfactant concentrations.

  3. Mixed surfactant systems for enhanced oil recovery

    SciTech Connect

    Llave, F.M.; Gall, B.L.; Noll, L.A.

    1990-12-01

    The results of an evaluation of mixed surfactant systems for enhanced oil recovery are described. Several surfactant combinations have been studied. These include alkyl aryl sulfonates as primary surfactants and carboxymethylated ethoxylated (CME) surfactants and ethoxylated sulfonates (ES) as secondary surfactants. The ethoxylated surfactants increase the salinity tolerance of the primary surfactants and, in theory, allow tailoring of the surfactant system to match selected reservoir conditions. The experiments conducted included interfacial tension (IFT) measurements, phase behavior measurements, adsorption and/or chromatographic separation of mixed surfactant systems, measurements of solution properties such as the critical micelle concentration (CMC) of surfactant mixtures, and crude oil displacement experiments. The effects of temperature, surfactant concentration, salinity, presence of divalent ions, hydrocarbon type, and component proportions in the mixed surfactant combinations, and injection strategies on the performance potential of the targeted surfactant/hydrocarbon systems were studied. 40 refs., 37 figs., 8 tabs.

  4. Dynamic surface tension of surfactant TA: experiments and theory.

    PubMed

    Otis, D R; Ingenito, E P; Kamm, R D; Johnson, M

    1994-12-01

    A bubble surfactometer was used to measure the surface tension of an aqueous suspension of surfactant TA as a function of bubble area over a range of cycling rates and surfactant bulk concentrations. Results of the surface tension-interfacial area loops exhibited a rich variety of phenomena, the character of which varied systematically with frequency and bulk concentration. A model was developed to interpret and explain these data and for use in describing the dynamics of surface layers under more general circumstances. Surfactant was modeled as a single component with surface tension taken to depend on only the interfacial surfactant concentration. Two distinct mechanisms were considered for the exchange of surfactant between the bulk phase and interface. The first is described by a simple kinetic relationship for adsorption and desorption that pertains only when the interfacial concentration is below its maximum equilibrium value. The second mechanism is "squeeze-out" by which surfactant molecules are expelled from an interface compressed past a maximum packing state. The model provided good agreement with experimental measurements for cycling rates from 1 to 100 cycles/min and for bulk concentrations between 0.0073 and 7.3 mg/ml.

  5. Bacterial Lipopolysaccharide Promotes Destabilization of Lung Surfactant-Like Films

    PubMed Central

    Cañadas, Olga; Keough, Kevin M.W.; Casals, Cristina

    2011-01-01

    The airspaces are lined with a dipalmitoylphosphatidylcholine (DPPC)-rich film called pulmonary surfactant, which is named for its ability to maintain normal respiratory mechanics by reducing surface tension at the air-liquid interface. Inhaled airborne particles containing bacterial lipopolysaccharide (LPS) may incorporate into the surfactant monolayer. In this study, we evaluated the effect of smooth LPS (S-LPS), containing the entire core oligosaccharide region and the O-antigen, on the biophysical properties of lung surfactant-like films composed of either DPPC or DPPC/palmitoyloleoylphosphatidylglycerol (POPG)/palmitic acid (PA) (28:9:5.6, w/w/w). Our results show that low amounts of S-LPS fluidized DPPC monolayers, as demonstrated by fluorescence microscopy and changes in the compressibility modulus. This promoted early collapse and prevented the attainment of high surface pressures. These destabilizing effects could not be relieved by repeated compression-expansion cycles. Similar effects were observed with surfactant-like films composed of DPPC/POPG/PA. On the other hand, the interaction of SP-A, a surfactant membrane-associated alveolar protein that also binds to LPS, with surfactant-like films containing S-LPS increased monolayer destabilization due to the extraction of lipid molecules from the monolayer, leading to the dissolution of monolayer material in the aqueous subphase. This suggests that SP-A may act as an LPS scavenger. PMID:21190662

  6. Highly stable surfactant assisted polyaniline nanostructures with enhanced electroactivity

    NASA Astrophysics Data System (ADS)

    Jamdegni, Monika; Kaur, Amarjeet

    2016-05-01

    Different nanostructures of Polyaniline(PANI) i.e. nanospheres, nanorods, nanofibers and layered structures have been successfully synthesized using varied concentration of anionic sodium dodecyl sulphate(SDS) and cationic Hexamethyltriammonium bromide (HTAB) by electrochemical method. Surfactant assisted morphology has been studied using FESEM. Incorporation of surfactants to the polymer matrix has been confirmed using FTIR spectroscopy. Electro activity and stability towards reversible redox activity was studied using cyclic voltammatry and chronoamperometry.The anionic surfactant severely enhances electroactivity and areal capacitance (3 Fcm-2) which was found to be two order higher than PANI film prepared without surfactant (0.039 Fcm-2), attributable to its additional doping effect. Immobilization of large surfactant molecule to polymer matrix inhibits its degradation due to nuleophilic attack ascribed to hydrophobic effect of surfactant. For PANI-SDS redox behavior remained almost same after 1000 reverse redox cycles while for PANI-HTAB we got only marginal changes.Our PANI-SDS samples are promising candidates for electro chromic applications.

  7. Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry

    NASA Astrophysics Data System (ADS)

    Silber, David; Kowalski, Piotr M.; Traeger, Franziska; Buchholz, Maria; Bebensee, Fabian; Meyer, Bernd; Wöll, Christof

    2016-09-01

    Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO2(110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a significant substrate-mediated interaction between adsorbates. The result is a complex superstructure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not deprotonate on the defect-free terraces of the rutile TiO2(110) surface.

  8. Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry.

    PubMed

    Silber, David; Kowalski, Piotr M; Traeger, Franziska; Buchholz, Maria; Bebensee, Fabian; Meyer, Bernd; Wöll, Christof

    2016-09-30

    Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO2(110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a significant substrate-mediated interaction between adsorbates. The result is a complex superstructure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not deprotonate on the defect-free terraces of the rutile TiO2(110) surface.

  9. Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry

    PubMed Central

    Silber, David; Kowalski, Piotr M.; Traeger, Franziska; Buchholz, Maria; Bebensee, Fabian; Meyer, Bernd; Wöll, Christof

    2016-01-01

    Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO2(110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a significant substrate-mediated interaction between adsorbates. The result is a complex superstructure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not deprotonate on the defect-free terraces of the rutile TiO2(110) surface. PMID:27686286

  10. Contact interaction of double-chained surfactant layers on silica: bilayer rupture and capillary bridge formation.

    PubMed

    Barthel, Etienne; Roquigny, Renaud; Serreau, Laurence; Denoyel, Renaud; Clerc-Imperor, Marianne; Drummond, Carlos

    2013-11-26

    The contact between two layers of double-chained C18 surfactants adsorbed on silica has been investigated. Using a custom-made surface forces apparatus with high stiffness, we have studied the process of (1) compression and collapse of the layers and (2) surface separation after layer collapse. A continuum mechanics model accounts for the compression and collapse of the surfactant layers. The layer compressibility and molecular energy of rupture can be inferred directly. When the surfaces are rinsed in deionized water, an intriguing structural force is observed: the resulting attractive interaction induces the diffusion of surfactant to the contact area, with the gradual buildup of a capillary bridge of the pure smectic phase of the surfactant. Models are proposed to analyze the force profile.

  11. Separation of surfactant functionalized single-walled carbon nanotubes via free solution electrophoresis method

    NASA Astrophysics Data System (ADS)

    Scheibe, Blazej; Rümmeli, Mark; Borowiak-Palen, Ewa; Kalenczuk, Ryszard

    2011-04-01

    This work presents the application of the free solution electrophoresis method (FSE) in the metallic / semiconductive (M/S) separation process of the surfactant functionalized single-walled carbon nanotubes (SWCNTs). The SWCNTs synthesized via laser ablation were purified through high vacuum annealing and subsequent refluxing processes in aqua regia solution. The purified and annealed material was divided into six batches. First three batches were dispersed in anionic surfactants: sodium dodecyl sulfate (SDS), sodium cholate (SC) and sodium deoxycholate (DOC). The next three batches were dispersed in cationic surfactants: cetrimonium bromide (CTAB), benzalkonium chloride (BKC) and cetylpyridinium chloride (CPC). All the prepared SWCNTs samples were subjected to FSE separation process. The fractionated samples were recovered from control and electrode areas and annealed in order to remove the adsorbed surfactants on carbon nanotubes (CNTs) surface. The changes of the van Hove singularities (vHS) present in SWCNTs spectra were investigated via UV-Vis-NIR optical absorption spectroscopy (OAS).

  12. MTBE adsorption on alternative adsorbents and packed bed adsorber performance.

    PubMed

    Rossner, Alfred; Knappe, Detlef R U

    2008-04-01

    Widespread use of the fuel additive methyl tertiary-butyl ether (MTBE) has led to frequent MTBE detections in North American and European drinking water sources. The overall objective of this research was to evaluate the effectiveness of a silicalite zeolite, a carbonaceous resin, and a coconut-shell-based granular activated carbon (GAC) for the removal of MTBE from water. Isotherm and short bed adsorber tests were conducted in ultrapure water and river water to obtain parameters describing MTBE adsorption equilibria and kinetics and to quantify the effect of natural organic matter (NOM) on MTBE adsorption. Both the silicalite zeolite and the carbonaceous resin exhibited larger MTBE adsorption uptakes than the tested GAC. Surface diffusion coefficients describing intraparticle MTBE mass transfer rates were largest for the GAC and smallest for the carbonaceous resin. Pilot tests were conducted to verify MTBE breakthrough curve predictions obtained with the homogeneous surface diffusion model and to evaluate the effect of NOM preloading on packed bed adsorber performance. Results showed that GAC was the most cost-competitive adsorbent when considering adsorbent usage rate only; however, the useful life of an adsorber containing silicalite zeolite was predicted to be approximately 5-6 times longer than that of an equally sized adsorber containing GAC. Pilot column results also showed that NOM preloading did not impair the MTBE removal efficiency of the silicalite zeolite. Thus, it may be possible to regenerate spent silicalite with less energy-intensive methods than those required to regenerate GAC.

  13. Evaporation of Sessile Droplets Laden with Particles and Insoluble Surfactants.

    PubMed

    Karapetsas, George; Chandra Sahu, Kirti; Matar, Omar K

    2016-07-12

    We consider the flow dynamics of a thin evaporating droplet in the presence of an insoluble surfactant and noninteracting particles in the bulk. On the basis of lubrication theory, we derive a set of evolution equations for the film height, the interfacial surfactant, and bulk particle concentrations, taking into account the dependence of liquid viscosity on the local particle concentration. An important ingredient of our model is that it takes into account the fact that the surfactant adsorbed at the interface hinders evaporation. We perform a parametric study to investigate how the presence of surfactants affects the evaporation process as well as the flow dynamics with and without the presence of particles in the bulk. Our numerical calculations show that the droplet lifetime is affected significantly by the balance between the ability of the surfactant to enhance spreading, suppressing the effect of thermal Marangoni stresses-induced motion, and to hinder the evaporation flux through the reduction of the effective interfacial area of evaporation, which tend to accelerate and decelerate the evaporation process, respectively. For particle-laden droplets and in the case of dilute solutions, the droplet lifetime is found to be weakly dependent on the initial particle concentration. We also show that the particle deposition patterns are influenced strongly by the direct effect of the surfactant on the evaporative flux; in certain cases, the "coffee-stain" effect is enhanced significantly. A discussion of the delicate interplay between the effects of capillary pressure and solutal and thermal Marangoni stresses, which drive the liquid flow inside of the evaporating droplet giving rise to the observed results, is provided herein.

  14. Drag reduction efficiency for polymer-surfactant mixtures

    SciTech Connect

    Kim, C.A.; Kim, J.T.; Choi, H.J.

    1996-12-31

    In a high Reynolds number fluid flow, significant energy loss occurs due to friction. However, by the addition of a minute amount of additives into this turbulent flow, frictional drag can be drastically reduced. This drag reduction phenomenon provides considerable motivation for diverse research to investigate its origin and application. Drag reduction has been reported for several solvent/additive systems, including dilute solution of high molecular weight polymers, surfactants, and micellar systems. Polymer systems as drag reducers have been extensively investigated. Recently, Choi and Jhon investigated the concentration dependence of drag reduction for PEO in water and PIB in kerosene systems using the rotating disk apparatus (RDA). However, due to the thermal instability and molecular degradation of drag reducing polymers, it is necessary to select alternative drag reducers. The possible formation of a polymer-surfactant complex takes on the character of a polyelectrolyte and it is shown that such polymer-surfactant complexes may have enhanced drag reduction properties based on the investigation of the turbulent pipe flow properties of high molecular weight PEO in SDS solution. In this study, we discuss details of conformation transitions of PEO molecules depending on external conditions such as pH, SDS and shear rate by adding the surfactant (Sodium dodecyl sulfate SDS, C{sub 12}H{sub 25}O{sub 4}SNa, (Fw:288.4) from Sigma Co. was used as a surfactant) and the PAA molecules. We also investigate modes of intermolecular interactions of both non-ionic and ionic polymers with surfactant and, finally, the polymer-surfactant complex under turbulent flow in an RDA.

  15. Nanoparticle decoration with surfactants: Molecular interactions, assembly, and applications

    NASA Astrophysics Data System (ADS)

    Heinz, Hendrik; Pramanik, Chandrani; Heinz, Ozge; Ding, Yifu; Mishra, Ratan K.; Marchon, Delphine; Flatt, Robert J.; Estrela-Lopis, Irina; Llop, Jordi; Moya, Sergio; Ziolo, Ronald F.

    2017-02-01

    Nanostructures of diverse chemical nature are used as biomarkers, therapeutics, catalysts, and structural reinforcements. The decoration with surfactants has a long history and is essential to introduce specific functions. The definition of surfactants in this review is very broad, following its lexical meaning ;surface active agents;, and therefore includes traditional alkyl modifiers, biological ligands, polymers, and other surface active molecules. The review systematically covers covalent and non-covalent interactions of such surfactants with various types of nanomaterials, including metals, oxides, layered materials, and polymers as well as their applications. The major themes are (i) molecular recognition and noncovalent assembly mechanisms of surfactants on the nanoparticle and nanocrystal surfaces, (ii) covalent grafting techniques and multi-step surface modification, (iii) dispersion properties and surface reactions, (iv) the use of surfactants to influence crystal growth, as well as (v) the incorporation of biorecognition and other material-targeting functionality. For the diverse materials classes, similarities and differences in surfactant assembly, function, as well as materials performance in specific applications are described in a comparative way. Major factors that lead to differentiation are the surface energy, surface chemistry and pH sensitivity, as well as the degree of surface regularity and defects in the nanoparticle cores and in the surfactant shell. The review covers a broad range of surface modifications and applications in biological recognition and therapeutics, sensors, nanomaterials for catalysis, energy conversion and storage, the dispersion properties of nanoparticles in structural composites and cement, as well as purification systems and classical detergents. Design principles for surfactants to optimize the performance of specific nanostructures are discussed. The review concludes with challenges and opportunities.

  16. Therapeutic surfactant-stripped frozen micelles

    NASA Astrophysics Data System (ADS)

    Zhang, Yumiao; Song, Wentao; Geng, Jumin; Chitgupi, Upendra; Unsal, Hande; Federizon, Jasmin; Rzayev, Javid; Sukumaran, Dinesh K.; Alexandridis, Paschalis; Lovell, Jonathan F.

    2016-05-01

    Injectable hydrophobic drugs are typically dissolved in surfactants and non-aqueous solvents which can induce negative side-effects. Alternatives like `top-down' fine milling of excipient-free injectable drug suspensions are not yet clinically viable and `bottom-up' self-assembled delivery systems usually substitute one solubilizing excipient for another, bringing new issues to consider. Here, we show that Pluronic (Poloxamer) block copolymers are amenable to low-temperature processing to strip away all free and loosely bound surfactant, leaving behind concentrated, kinetically frozen drug micelles containing minimal solubilizing excipient. This approach was validated for phylloquinone, cyclosporine, testosterone undecanoate, cabazitaxel and seven other bioactive molecules, achieving sizes between 45 and 160 nm and drug to solubilizer molar ratios 2-3 orders of magnitude higher than current formulations. Hypertonic saline or co-loaded cargo was found to prevent aggregation in some cases. Use of surfactant-stripped micelles avoided potential risks associated with other injectable formulations. Mechanistic insights are elucidated and therapeutic dose responses are demonstrated.

  17. Therapeutic surfactant-stripped frozen micelles

    PubMed Central

    Zhang, Yumiao; Song, Wentao; Geng, Jumin; Chitgupi, Upendra; Unsal, Hande; Federizon, Jasmin; Rzayev, Javid; Sukumaran, Dinesh K.; Alexandridis, Paschalis; Lovell, Jonathan F.

    2016-01-01

    Injectable hydrophobic drugs are typically dissolved in surfactants and non-aqueous solvents which can induce negative side-effects. Alternatives like ‘top-down' fine milling of excipient-free injectable drug suspensions are not yet clinically viable and ‘bottom-up' self-assembled delivery systems usually substitute one solubilizing excipient for another, bringing new issues to consider. Here, we show that Pluronic (Poloxamer) block copolymers are amenable to low-temperature processing to strip away all free and loosely bound surfactant, leaving behind concentrated, kinetically frozen drug micelles containing minimal solubilizing excipient. This approach was validated for phylloquinone, cyclosporine, testosterone undecanoate, cabazitaxel and seven other bioactive molecules, achieving sizes between 45 and 160 nm and drug to solubilizer molar ratios 2–3 orders of magnitude higher than current formulations. Hypertonic saline or co-loaded cargo was found to prevent aggregation in some cases. Use of surfactant-stripped micelles avoided potential risks associated with other injectable formulations. Mechanistic insights are elucidated and therapeutic dose responses are demonstrated. PMID:27193558

  18. Competitive surfactant adsorption of AOT and Tween 20 on gold measured using a quartz crystal microbalance with dissipation.

    PubMed

    Thavorn, Jakkrit; Hamon, Joshua J; Kitiyanan, Boonyarach; Striolo, Alberto; Grady, Brian P

    2014-09-23

    Competitive surfactant adsorption of anionic surfactant AOT and nonionic surfactant Tween 20 on gold was investigated by using a quartz crystal microbalance with dissipation (QCM-D) at 25 °C. The adsorption isotherm of pure AOT did not reach a plateau at the CMC, but rather adsorption continued to increase gradually at concentrations higher than the CMC before reaching a plateau. This behavior is evidence of competitive adsorption between AOT and impurities. The adsorbed layer of AOT on gold became more viscoelastic as the concentration of AOT increased. Tween 20 reached the plateau adsorption on gold before its concentration reached the CMC, suggesting that the attraction between Tween 20 and gold is very strong. The Tween 20 adsorbed layer was rigid when compared to the AOT adsorbed layer, as indicated by low dissipation. The addition of Tween 20 to a surface covered by AOT resulted in an increase in adsorbed mass, suggestive of the insertion of Tween 20 into the AOT adsorbed layer as expected because Tween 20 is able to separate the repulsive headgroups of AOT. When AOT was added to a preformed Tween 20 layer, a drop in the adsorbed amount was found between 0 and 0.1 CMC, and then no change was observed until the CMC of AOT was reached; the adsorbed amount then increased, reaching a final adsorption greater than that of pure AOT. All data support the formation of mixed surfactant layers on the surface. Although a two-step model fit both AOT and Tween 20 adsorption kinetic data well, AOT was found to adsorb much more slowly than Tween 20.

  19. Mineral-Surfactant Interactions for Minimum Reagents Precipitation and Adsorption for Improved Oil Recovery

    SciTech Connect

    P. Somasundaran

    2008-09-20

    /conformation of the adsorbed layers), as well as precipitation/abstraction characteristics. (3) Investigation of the role of dissolved species, especially multivalent ions, on interactions between reservoir minerals and surfactants and/or polymers leading to surfactant precipitation or activated adsorption. (4) Solution behavior tests--surface tension, interaction, ultra filtration, and other tests. (5) Surfactant-mineral interactions relative to adsorption, wettability, and electrophoresis. (6) Work on the effects of multivalent ions, pH, temperature, salinity, and mixing ratio on the adsorption. Developments of adsorption models to explain interactions between surfactants/polymers/minerals. (7) General guidelines for the use of certain surfactants, polymers and their mixtures in micelle flooding processes.

  20. Control of stain geometry by drop evaporation of surfactant containing dispersions.

    PubMed

    Erbil, H Yildirim

    2015-08-01

    Control of stain geometry by drop evaporation of surfactant containing dispersions is an important topic of interest because it plays a crucial role in many applications such as forming templates on solid surfaces, in ink-jet printing, spraying of pesticides, micro/nano material fabrication, thin film coatings, biochemical assays, deposition of DNA/RNA micro-arrays, and manufacture of novel optical and electronic materials. This paper presents a review of the published articles on the diffusive drop evaporation of pure liquids (water), the surfactant stains obtained from evaporating drops that do not contain dispersed particles and deposits obtained from drops containing polymer colloids and carbon based particles such as carbon nanotubes, graphite and fullerenes. Experimental results of specific systems and modeling attempts are discussed. This review also has some special subtopics such as suppression of coffee-rings by surfactant addition and "stick-slip" behavior of evaporating nanosuspension drops. In general, the drop evaporation process of a surfactant/particle/substrate system is very complex since dissolved surfactants adsorb on both the insoluble organic/inorganic micro/nanoparticles in the drop, on the air/solution interface and on the substrate surface in different extends. Meanwhile, surfactant adsorbed particles interact with the substrate giving a specific contact angle, and free surfactants create a solutal Marangoni flow in the drop which controls the location of the particle deposition together with the rate of evaporation. In some cases, the presence of a surfactant monolayer at the air/solution interface alters the rate of evaporation. At present, the magnitude of each effect cannot be predicted adequately in advance and consequently they should be carefully studied for any system in order to control the shape and size of the final deposit.

  1. Surfactant loss control in chemical flooding: Spectroscopic and calorimetric study of adsorption and precipitation on reservoir minerals. Annual report, September 30, 1992--September 30, 1993

    SciTech Connect

    Somasundaran, P.

    1994-07-01

    The aim of this research project is to investigate mechanisms underlying adsorption and surface precipitation of flooding surfactants on reservoir minerals. Effects of surfactant structure, surfactant combinations, various inorganic and polymeric species, and solids mineralogy will be determined. A multi-pronged approach consisting of micro & nano spectroscopy, microcalorimetry, electrokinetics, surface tension and wettability; is used in this study. The results obtained should help in controlling surfactant loss in chemical flooding and in developing optimum structures and conditions for efficient chemical flooding processes. During the first year of this three year contract, adsorption of single surfactants and select surfactant mixtures was studied at the solid-liquid and gas-liquid interfaces. Surfactants studied include alkyl xylene sulfonates, polyethoxylated alkyl phenols, octaethylene glycol mono n-decyl ether, and tetradecyl trimethyl ammonium chloride. Adsorption of surfactant mixtures of varying composition was also investigated. The microstructure of the adsorbed layer was characterized using fluorescence spectroscopy. Changes interfacial properties such as wettability, electrokinetics and stability of reservoir minerals were correlated with the amount of reagent adsorbed. Strong effects of the structure of the surfactant and position of functional groups were revealed.

  2. Surfactant adsorption and interfacial tension investigations on cyclopentane hydrate.

    PubMed

    Aman, Zachary M; Olcott, Kyle; Pfeiffer, Kristopher; Sloan, E Dendy; Sum, Amadeu K; Koh, Carolyn A

    2013-02-26

    Gas hydrates represent an unconventional methane resource and a production/safety risk to traditional oil and gas flowlines. In both systems, hydrate may share interfaces with both aqueous and hydrocarbon fluids. To accurately model macroscopic properties, such as relative permeability in unconventional systems or dispersion viscosity in traditional systems, knowledge of hydrate interfacial properties is required. This work presents hydrate cohesive force results measured on a micromechanical force apparatus, and complementary water-hydrocarbon interfacial tension data. By combining a revised cohesive force model with experimental data, two interfacial properties of cyclopentane hydrate were estimated: hydrate-water and hydrate-cyclopentane interfacial tension values at 0.32 ± 0.05 mN/m and 47 ± 5 mN/m, respectively. These fundamental physiochemical properties have not been estimated or measured for cyclopentane hydrate to date. The addition of surfactants in the cyclopentane phase significantly reduced the cyclopentane hydrate cohesive force; we hypothesize this behavior to be the result of surfactant adsorption on the hydrate-oil interface. Surface excess quantities were estimated for hydrate-oil and water-oil interfaces using four carboxylic and sulfonic acids. The results suggest the density of adsorbed surfactant may be 2× larger for the hydrate-oil interface than the water-oil interface. Additionally, hydrate-oil interfacial tension was observed to begin decreasing from the baseline value at significantly lower surfactant concentrations (1-3 orders of magnitude) than those for the water-oil interfacial tension.

  3. Structure of adsorbed organometallic rhodium: model single atom catalysts.

    PubMed

    Bennett, R A; McCavish, N D; Basham, M; Dhanak, V R; Newton, M A

    2007-02-02

    We have determined the structure of a complex rhodium carbonyl chloride [Rh(CO)2Cl] molecule adsorbed on the TiO2(110) surface by the normal incidence x-ray standing wave technique. The data show that the technique is applicable to reducible oxide systems and that the dominant adsorbed species is undissociated with Rh binding atop bridging oxygen and to the Cl found close to the fivefold coordinated Ti ions in the surface. A minority geminal dicarbonyl species, where Rh-Cl bond scission has occurred, is found bridging the bridging oxygen ions forming a high-symmetry site.

  4. Wettability of quartz in presence of nonionic surfactants and short chain alcohols mixtures.

    PubMed

    Zdziennicka, Anna; Jańczuk, Bronisław

    2010-03-15

    Measurements of advancing contact angles for aqueous solution of Triton X-100 (TX-100) with methanol, ethanol and propanol mixtures and Triton X-165 (TX-165) with the same alcohols on quartz surface were carried out. From the obtained results it appeared that the wettability of quartz depends on Triton's and alcohol concentrations and that there is a linear dependence between the adhesional and surface tension of aqueous solution of Triton's and alcohols mixtures. This dependence can be described by linear equations which constants depend somewhat on the Triton's and alchohols concentration. The slope of all linear dependencies between the adhesional and surface tension is positive. The critical surface tension of quartz wetting determined from these dependencies by extrapolating the adhesional tension to a value equal to the surface tension (for contact angle equal zero) depends on the assumption whether the concentration of Triton or alcohols was constant. The average value at constant Triton's concentration was equal to 27.1 mN/m and was lower than that evaluated at constant alcohol concentration (29.5 mN/m). The critical surface tension of quartz wetting at constant alcohol concentration was nearly the same as the apolar component of the surface tension of quartz covered with water monolayer film. The positive slope of the adhesional-surface tension curves and the work of water adhesion, Triton's and alcohols to quartz surface indicates that the interaction between water molecules and quartz surface might be stronger than that between quartz and surface active agents molecules. So, the concentration excess of surfactants at quartz-water interface is probably negative, and the possibility of the surface active agents to adsorb at quartz/water film-water interface is higher than that at the quartz-water. However, at alcohol concentration above that of its aggregation the molecules of the surface active agents probably destroy the strongly ordered film of water.

  5. A Computational Study of the Rheology and Structure of Surfactant Covered Droplets

    NASA Astrophysics Data System (ADS)

    Maia, Joao; Boromand, Arman

    Using different types of surface-active agents are ubiquitous in different industrial applications ranging from cosmetic and food industries to polymeric nano-composite and blends. This allows to produce stable multiphasic systems like foams and emulsions whose stability and shelf-life are directly determined by the efficiency and the type of the surfactant molecules. Moreover, presence and self-assembly of these species on an interface will display complex dynamics and structural evolution under different processing conditions. Analogous to bulk rheology of complex systems, surfactant covered interfaces will response to an external mechanical forces or deformation differently depends on the molecular configuration and topology of the system constituents. Although the effect of molecular configuration of the surface-active molecules on the planar interfaces has been studied both experimentally and computationally, it remains challenging from both experimental and computational aspects to track efficiency and effectiveness of different surfactant molecules with different molecular geometries on curved interfaces. Using Dissipative Particle Dynamics, we have studies effectiveness and efficiency of different surfactant molecules on a curved interface in equilibrium and far from equilibrium. Interfacial tension is calculated for linear and branched surfactant with different hydrophobic and hydrophilic tail and head groups with different branching densities. Deformation parameter and Taylor plots are obtained for individual surfactant molecules under shear flow.

  6. Molecular-scale interface engineering of nanocrystalline titania by co-adsorbents for solar energy conversion.

    PubMed

    Wang, Mingkui; Plogmaker, Stefan; Humphry-Baker, Robin; Pechy, Peter; Rensmo, Håkan; Zakeeruddin, Shaik M; Grätzel, Michael

    2012-01-09

    The use of mixed self-assembled monolayers, combining hydrophobic co-adsorbents with the sensitizer, has been demonstrated to enhance the efficiency of dye-sensitized solar cells (DSCs). Herein, the influence of the anchoring groups of the co-adsorbents on the performance of the DSCs is carefully examined by selecting two model molecules: neohexyl phosphonic acid (NHOOP) and bis-(3,3-dimethyl-butyl)-phosphinic acid (DINHOP). The effect of these co-adsorbents on the photovoltaic performance (J-V curves, incident photon-to-electron conversion efficiency) is investigated. Photoelectron spectroscopy and electrochemical impedance spectroscopy are performed to assess the spatial configuration of adsorbed dye and co-adsorbent molecules. The photoelectron spectroscopy studies indicate that the ligands of the ruthenium complex, containing thiophene groups, point out away from the surface of TiO(2) in comparison with the NCS group.

  7. Surfactant loss control in chemical flooding spectroscopic and calorimetric study of adsorption and precipitation on reservoir minerals. Annual report, September 30, 1993--September 30, 1994

    SciTech Connect

    Somasundaran, P.

    1995-06-01

    The aim of this project is to elucidate the mechanisms underlying adsorption and surface precipitation of flooding surfactants on reservoir minerals. Effect of surfactant structure, surfactant combinations, other inorganic and polymeric species is being studied. A multi-pronged approach consisting of micro and nano spectroscopy, microcalorimetry, electrokinetics, surface tension and wettability is used to achieve the goals. The results of this study should help in controlling surfactant loss in chemical flooding and also in developing optimum structures and conditions for efficient chemical flooding processes. During the second year of this three year contract, adsorption/desorption of single surfactants and select surfactant mixtures on alumina and silica was studied. Surfactants studied include the anionic sodium dodecyl sulfate (SDS), cationic tetradecyl trimethyl ammonium chloride (TTAC), nonionic pentadecylethoxylated nonyl phenol (NP-15) and the nonionic octaethylene glycol n-dodecyl ether (C{sub 12}EO{sub 8}) of varying hydrocarbon chain length. The microstructure of the adsorbed layer in terms of micropolarity and aggregation numbers was probed using fluorescence spectroscopy. Changes of microstructure upon dilution (desorption) were also studied. Presence of the nonionic surfactant in the mixed aggregate led to shielding of the charge of the ionic surfactant which in-turn promoted aggregation but reduced electrostatic attraction between the charged surfactant and the mineral surface. Strong consequences of surfactant interactions in solution upon adsorption as well as correlations between monomer concentrations in mixtures and adsorption were revealed.

  8. Surfactant loss control in chemical flooding: Spectroscopic and calorimetric study of adsorption and precipitation on reservoir minerals. Quarterly technical progress report. October 1, 1994--December 31, 1994

    SciTech Connect

    Somasundaran, P.

    1995-03-01

    The aim of this research is to elucidate the mechanisms underling adsorption and surface precipitation of flooding surfactants on reservoir minerals. The adsorption and desorption behaviors of tetradecyltrimethyl ammonium chloride (TTAC) and pentadecylethoxylated nonylphenol (NP-15) mixtures as reported earlier were rather complex and to better understand the interactions involved fluorescence spectroscopy and ultrafiltration were used during this report period to probe the microstructure of the adsorbed layer and to determine individual surfactant monomer concentration respectively. It was observed that pyrene was solubilized in mixed aggregates (hemimicelles) of a 1:1 TTAC:NP-15 mixture at the alumina-water interface over a wider concentration range than for TTAC alone. It was also observed that the adsorbed aggregate of a 1:1 TTAC:NP-15 mixture is as hydrophobic as the mixed micelle in solution. This is contrary to what was observed for the adsorption of TTAC alone: pyrene was preferentially solubilized in the TTAC micelles rather than the adsorbed aggregate. The preference of pyrene for the mixed adsorbed aggregates over individual aggregates is relevant to the application of surfactant mixtures in enhanced oil recovery and solubilization. The adsorption/desorption behavior of surfactants is directly related to the monomer concentration of the surfactant, hence it is important to monitor changes in monomer concentration during the adsorption and desorption processes. Ultrafiltration techniques were used to monitor the monomer concentration in solution and at the interface to determine the partitioning of the surfactants to the solid-liquid interface.

  9. R&D for graft adsorbents by radiation processing

    NASA Astrophysics Data System (ADS)

    Seko, Noriaki; Tamada, Masao

    Fibrous adsorbent for removal and recovery of metal ions have been synthesized by graft polymerization. In the grafting, the functional groups which have high selectivity against for target metal ions such as Fe, Sc, As, and U are introduced onto nonwoven fabric. When the monomer has a chelate group which makes selective coordination bond to specific these ions, it was directly grafted on the trunk polymer. In the case of precursor monomer having functional groups such as epoxy ring, the grafted trunk fabric is chemically modified. The resultant fibrous adsorbent leads the swift adsorption of metal ions. This property by using fibrous material can reduce the column size of adsorbent in the purification of waste water. The size of purification equipment becomes quite compact and that implies total volume of equipment can reduce. Instead of organic solvent, emulsion system which disperses monomer micelles in water with assistance of surfactant was found to accelerate the graft polymerization. This means the air pollution from organic solvent can be avoided by water system grafting. Furthermore, since the emulsion grafting was highly efficient, the required irradiation dose was considerably lower compared to general organic solvent system. As a result, the emulsion grafting has enormous potential for natural polymer to use as a trunk material for grafting. If a natural polymer such as cellulose can be used, the dependence on petroleum resources, the amount of industrial waste and the generation of carbon dioxide will be reduced to some extent.

  10. Chemisorption on surfaces — an historical look at a representative adsorbate: carbon monoxide

    NASA Astrophysics Data System (ADS)

    Yates, John T.

    1994-01-01

    The study of the interaction of molecules with clean surfaces extends back to the work of Irving Langmuir. In this historical account, the development of selected experimental methods for the study of molecular adsorption will be discussed. This will be done by historically reviewing research on one of the most well-studied adsorbate molecules, carbon monoxide. Many of the modern surface science techniques have first been used to study chemisorbed carbon monoxide, and the CO molecule is employed even today as a test molecule for currently developing surface measurement instruments such as the low temperature STM. In addition to being a good test molecule for new surface measurement techniques, adsorbed carbon monoxide is one of the centrally important molecules in the field of heterogeneous catalysis where the production of synthetic fuels and useful organic molecules often depends on the catalytic behavior of the adsorbed CO molecule. Interestingly, the carbon monoxide molecule also serves as a bridge between surface chemistry on the transition metals and the field of organometallic chemistry. Concepts about the chemical bonding and the reactive behavior of CO chemisorbed on transition metal surfaces and CO bound in transition metal carbonyls link these two fields together in a significant manner. The carbon monoxide molecule has been the historical focal point of many endeavors in surface chemistry and surface physics, and research on adsorbed carbon monoxide well represents many of the key advances which characterize the first thirty years of the development of surface science.

  11. Surfactant adsorption kinetics in microfluidics

    PubMed Central

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

    2016-01-01

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

  12. Surfactant monitoring by foam generation

    DOEpatents

    Mullen, Ken I.

    1997-01-01

    A device for monitoring the presence or absence of active surfactant or other surface active agents in a solution or flowing stream based on the formation of foam or bubbles is presented. The device detects the formation of foam with a light beam or conductivity measurement. The height or density of the foam can be correlated to the concentration of the active surfactant present.

  13. ADSORPTION OF SURFACTANT ON CLAYS

    EPA Science Inventory

    Surfactants used to enhance remediation of soils by soil washing are often lost in the process. Neither the amount nor the cause of this loss is known. It is assumed that clays present in the soil are responsible for the loss of the surfactant. In this papere, adsorption prope...

  14. Surfactant adsorption kinetics in microfluidics

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  15. New multifunctional surfactants from natural phenolic acids.

    PubMed

    Centini, Marisanna; Rossato, Maria Sole; Sega, Alessandro; Buonocore, Anna; Stefanoni, Sara; Anselmi, Cecilia

    2012-01-11

    Several new multifunctional molecules derived from natural sources such as amino acids and hydroxycinnamic acids were synthesized. They exhibit various activities such as emulsifying, UV-protecting, and radical scavenging, thereby conforming to the latest requirements for cosmetic ingredients. The synthesis comprises only a few steps: (i) the amino acid, the acid groups of which are protected by esterification, is coupled with ferulic or caffeic acid; (ii) the p-hydroxyl group of the cinnamic derivative reacts with dodecyl bromide in the presence of potassium carbonate (the resulting compounds are highly lipophilic and tested as water/oil (W/O) emulsifiers); (iii) these molecules, by deprotonating the acid groups of the amino acids, with successive salification, are more hydrophilic, with stronger O/W emulsifying properties. The new multifunctional surfactants might prove useful for the treatment of multiple skin conditions, including loss of cellular antioxidants, damage from free radicals, damage from UV, and others.

  16. Random bilayer phases of dilute surfactant solutions

    NASA Astrophysics Data System (ADS)

    Cates, M. E.; Roux, D.

    1990-12-01

    Surfactant molecules in dilute solution may aggregate reversibly into extended structures. For suitably chosen molecules, the preferred packing involves a locally flat bilayer which tends to wander entropically at large distances. At low temperatures (and/or high concentrations) the system forms a stack of flat sheets with one-dimensional quasi-long range order (a smectic liquid crystal), but at high temperatures or low concentrations, the stack can melt into a random surface structure that resembles a multiply connected labyrinth or 'sponge' of bilayer in a sea of solvent. Recent theoretical and experimental progress in understanding the properties of the sponge is reviewed. The authors argue that the sponge phase may provide a good system for the study of various liquid-state critical phenomena.

  17. Rotary adsorbers for continuous bulk separations

    DOEpatents

    Baker, Frederick S [Oak Ridge, TN

    2011-11-08

    A rotary adsorber for continuous bulk separations is disclosed. The rotary adsorber includes an adsorption zone in fluid communication with an influent adsorption fluid stream, and a desorption zone in fluid communication with a desorption fluid stream. The fluid streams may be gas streams or liquid streams. The rotary adsorber includes one or more adsorption blocks including adsorbent structure(s). The adsorbent structure adsorbs the target species that is to be separated from the influent fluid stream. The apparatus includes a rotary wheel for moving each adsorption block through the adsorption zone and the desorption zone. A desorption circuit passes an electrical current through the adsorbent structure in the desorption zone to desorb the species from the adsorbent structure. The adsorbent structure may include porous activated carbon fibers aligned with their longitudinal axis essentially parallel to the flow direction of the desorption fluid stream. The adsorbent structure may be an inherently electrically-conductive honeycomb structure.

  18. Effect of surfactants on preformed fibrils of human serum albumin.

    PubMed

    Pandey, Nitin Kumar; Ghosh, Sudeshna; Dasgupta, Swagata

    2013-08-01

    The central reason behind pathogenesis of various neurological disorders is usually attributed to the accumulation of aggregated proteins particularly in fibrillar morphology in vivo. One of the plausible remedial treatments for such disorders may be to identify molecules which are capable of either preventing formation of fibrils or disintegrating formed fibrils. The effect of cationic surfactants cetyl trimethylammonium bromide (CTAB), dodecyl trimethylammonium bromide (DTAB) and the anionic surfactant sodium dodecyl sulfate (SDS) in vitro toward mature HSA fibrils has been investigated. The process has been monitored using ThT fluorescence, FTIR, circular dichroism, fluorescence microscopy and HRTEM. It was observed that the micelles of cationic surfactants were able to effectively disrupt the HSA fibrils, among which CTAB was found to be the most potent.

  19. Modification of Deeply Buried Hydrophobic Interfaces by Ionic Surfactants

    SciTech Connect

    Ocko, B.M.; Tamam, L.; Pontoni, D.; Sapir, Z.; Yefet, S.; Sloutskin, E.; Reichert, H.; Deutsch, M.

    2011-04-05

    Hydrophobicity, the spontaneous segregation of oil and water, can be modified by surfactants. The way this modification occurs is studied at the oil-water interface for a range of alkanes and two ionic surfactants. A liquid interfacial monolayer, consisting of a mixture of alkane molecules and surfactant tails, is found. Upon cooling, it freezes at T{sub s}, well above the alkane's bulk freezing temperature, T{sub b}. The monolayer's phase diagram, derived by surface tensiometry, is accounted for by a mixtures-based theory. The monolayer's structure is measured by high-energy X-ray reflectivity above and below T{sub s}. A solid-solid transition in the frozen monolayer, occurring approximately 3 C below T{sub s}, is discovered and tentatively suggested to be a rotator-to-crystal transition.

  20. Modification of Deeply Buried Hydrophobic Interfaces by Ionic Surfactants

    SciTech Connect

    L Tamam; D Pontoni Z Sapir; S Yefet; S Sloutskin; B Ocko; H Reichert; M Deutsch

    2011-12-31

    Hydrophobicity, the spontaneous segregation of oil and water, can be modified by surfactants. The way this modification occurs is studied at the oil-water interface for a range of alkanes and two ionic surfactants. A liquid interfacial monolayer, consisting of a mixture of alkane molecules and surfactant tails, is found. Upon cooling, it freezes at T{sub s}, well above the alkane's bulk freezing temperature, T{sub b}. The monolayer's phase diagram, derived by surface tensiometry, is accounted for by a mixtures-based theory. The monolayer's structure is measured by high-energy X-ray reflectivity above and below T{sub s}. A solid-solid transition in the frozen monolayer, occurring approximately 3 C below T{sub s}, is discovered and tentatively suggested to be a rotator-to-crystal transition.

  1. Whey protein coating efficiency on surfactant-modified hydrophobic surfaces.

    PubMed

    Lin, Shih-Yu D; Krochta, John M

    2005-06-15

    Whey protein oxygen-barrier coatings on peanuts are not effective, due to incomplete peanut-surface coverage, as well as some cracking and flaking of the coating. Addition of sorbitan laurate (Span 20) in the whey protein coating solution up to the critical micelle concentration (cmc) of 0.05% (w/w) significantly improved coating coverage to 88% of the peanut surface. Increasing the Span 20 concentration in the coating solution to 3 times the cmc (0.15% w/w) produced a substantial increase in peanut surface energy (>70 dyn/cm), indicating adsorption of the surfactant to the peanut surface. With this level of Span 20, the whey protein coating coverage on peanuts increased to 95%. These results suggest that a concentration of surfactant above the cmc in the coating solution is required for formation of self-assembled structures of surfactant molecules on peanut surfaces, which significantly increases the hydrophilicity, and thus coatability, of peanut surfaces.

  2. On-line surfactant monitoring

    SciTech Connect

    Mullen, K.I.; Neal, E.E.; Soran, P.D.; Smith, B.

    1995-04-01

    This group has developed a process to extract metal ions from dilute aqueous solutions. The process uses water soluble polymers to complex metal ions. The metal/polymer complex is concentrated by ultrafiltration and the metals are recovered by a pH adjustment that frees the metal ions. The metal ions pass through the ultrafiltration membrane and are recovered in a concentrated form suitable for reuse. Surfactants are present in one of the target waste streams. Surfactants foul the costly ultrafiltration membranes. It was necessary to remove the surfactants before processing the waste stream. This paper discusses an on-line device the authors fabricated to monitor the process stream to assure that all the surfactant had been removed. The device is inexpensive and sensitive to very low levels of surfactants.

  3. Spreading, evaporation, and contact line dynamics of surfactant-laden microdrops.

    PubMed

    Gokhale, Shripad J; Plawsky, Joel L; Wayner, Peter C

    2005-08-30

    An optical technique based on the reflectivity measurements of a thin film was used to experimentally study the spreading, evaporation, contact line motion, and thin film characteristics of drops consisting of a water-surfactant (polyalkyleneoxide-modified heptamethyltrisiloxane, called superspreader) solution on a fused silica surface. On the basis of the experimental observations, we concluded that the surfactant adsorbs primarily at the solid-liquid and liquid-vapor interfaces near the contact line region. At equilibrium, the completely wetting corner meniscus was associated with a flat adsorbed film having a thickness of approximately 31 nm. The calculated Hamaker constant, A = -4.47 x 10(-)(20) J, shows that this thin film was stable under equilibrium conditions. During a subsequent evaporation/condensation phase-change process, the thin film of the surfactant solution was unstable, and it broke into microdrops having a finite contact angle. The thickness of the adsorbed film associated with the drops was lower than that of the equilibrium meniscus. The drop profiles were experimentally measured and analyzed during the phase-change process as the contact line advanced and receded. The apparent contact angle, the maximum concave curvature near the contact line region, and the convex curvature of the drop increased as the drop grew during condensation, whereas these quantities decreased during evaporation. The position of the maximum concave curvature of the drop moved toward the center of the drop during condensation, whereas it moved away from the center during evaporation. The contact line velocity was correlated to the observed experimental results and was compared with the results of the drops of a pure alcohol. The experimentally obtained thickness profiles, contact angle profiles, and curvature profiles of the drops explain how the surfactant adsorption affects the contact line motion. We found that there was an abrupt change in the velocity of the

  4. Production And Artile Of Iron/Surfactant-Modified Zeolite Pellets To Retain And Destroy Water Pollutants

    DOEpatents

    BOWMAN, ROBERT S.; [et al

    2001-07-17

    A method of producing a pollutant adsorption and degradation article, and such article, are provided. At least one adsorbent is mixed with at least one pollutant transforming agent to form a mixture. This mixture is compacted to form a porous, highly permeable article. If necessary, the article can be modified with surfactant either after the compacting step or by adding the surfactant to the mixture prior to the compacting step. In addition, if necessary, a binding agent can be added to the mixture prior to the compacting step.

  5. Surfactant Assemblies and their Various Possible Roles for the Origin(S) of Life

    NASA Astrophysics Data System (ADS)

    Walde, Peter

    2006-04-01

    A large number of surfactants (surface active molecules) are chemically simple compounds that can be obtained by simple chemical reactions, in some cases even under presumably prebiotic conditions. Surfactant assemblies are self-organized polymolecular aggregates of surfactants, in the simplest case micelles, vesicles, hexagonal and cubic phases. It may be that these different types of surfactant assemblies have played various, so-far underestimated important roles in the processes that led to the formation of the first living systems. Although nucleic acids are key players in the formation of cells as we know them today (RNA world hypothesis), it is still unclear how RNA could have been formed under prebiotic conditions. Surfactants with their self-organizing properties may have assisted, controlled and compartimentalized some of the chemical reactions that eventually led to the formation of molecules like RNA. Therefore, surfactants were possibly very important in prebiotic times in the sense that they may have been involved in different physical and chemical processes that finally led to a transformation of non-living matter to the first cellular form(s) of life. This hypothesis is based on four main experimental observations: (i) Surfactant aggregation can lead to cell-like compartimentation (vesicles). (ii) Surfactant assemblies can provide local reaction conditions that are very different from the bulk medium, which may lead to a dramatic change in the rate of chemical reactions and to a change in reaction product distributions. (iii) The surface properties of surfactant assemblies that may be liquid- or solid-like, charged or neutral, and the elasticity and packing density of surfactant assemblies depend on the chemical structure of the surfactants, on the presence of other molecules, and on the overall environmental conditions (e. g. temperature). This wide range of surface characteristics of surfactant assemblies may allow a control of surface

  6. Surfactant assemblies and their various possible roles for the origin(s) of life.

    PubMed

    Walde, Peter

    2006-04-01

    A large number of surfactants (surface active molecules) are chemically simple compounds that can be obtained by simple chemical reactions, in some cases even under presumably prebiotic conditions. Surfactant assemblies are self-organized polymolecular aggregates of surfactants, in the simplest case micelles, vesicles, hexagonal and cubic phases. It may be that these different types of surfactant assemblies have played various, so-far underestimated important roles in the processes that led to the formation of the first living systems. Although nucleic acids are key players in the formation of cells as we know them today (RNA world hypothesis), it is still unclear how RNA could have been formed under prebiotic conditions. Surfactants with their self-organizing properties may have assisted, controlled and compartimentalized some of the chemical reactions that eventually led to the formation of molecules like RNA. Therefore, surfactants were possibly very important in prebiotic times in the sense that they may have been involved in different physical and chemical processes that finally led to a transformation of non-living matter to the first cellular form(s) of life. This hypothesis is based on four main experimental observations: (i) Surfactant aggregation can lead to cell-like compartimentation (vesicles). (ii) Surfactant assemblies can provide local reaction conditions that are very different from the bulk medium, which may lead to a dramatic change in the rate of chemical reactions and to a change in reaction product distributions. (iii) The surface properties of surfactant assemblies that may be liquid- or solid-like, charged or neutral, and the elasticity and packing density of surfactant assemblies depend on the chemical structure of the surfactants, on the presence of other molecules, and on the overall environmental conditions (e. g. temperature). This wide range of surface characteristics of surfactant assemblies may allow a control of surface

  7. Feasibility of fullerene waste as carbonaceous adsorbent

    SciTech Connect

    Cleveland, T.G.; Garg, S.; Rixey, W.G.

    1996-03-01

    This note investigates using the waste soot generated in fullerene manufacture as an adsorbent. Both oven-dried and air-activated samples of waste soot are compared with three commercially available powdered activated carbons (PACs): Nuchar-SA, HDH, and Calgon-RC. Three model compounds were chosen for adsorption tests--TCE, Benzene, and Phenol--representing a small branched molecule, a small nonpolar ring molecule, and relatively polar ring molecule. Additionally, the effectiveness of total organic carbon (TOC) removal from wastewater was evaluated. Oven-dried soot performed poorly as compared to the commercial carbons, but activation of the waste soot for 60 min at 450 C in air resulted in an activated carbon (aFWS) with properties similar to those of commercially available PACs. The aFWS performed better than one would predict from the typical characterization measures of iodine number, molasses number, and methylene blue number. The data for phenol suggest some functional groups are created during the activation of the waste soot. These results show that large-scale fullerene manufacturing can be a zero-waste industry, because its primary waste product can be converted into a useful material.

  8. Tuning cellulose nanocrystal gelation with polysaccharides and surfactants.

    PubMed

    Hu, Zhen; Cranston, Emily D; Ng, Robin; Pelton, Robert

    2014-03-18

    Gelation of cellulose nanocrystal (CNC) dispersions was measured as a function of the presence of four nonionic polysaccharides. Addition of hydroxyethyl cellulose (HEC), hydroxypropyl guar (HPG), or locust bean gum (LBG) to CNC dispersions induced the gelation of dilute CNC dispersions, whereas dextran (DEX) did not. These behaviors correlated with adsorption tendencies; HEC, HPG, and LBG adsorbed onto CNC-coated quartz crystal microbalance sensors, whereas DEX did not adsorb. We propose that the adsorbing polysaccharides greatly increased the effective volume fraction of dilute CNC dispersions, driving more of the nanocrystals into anisotropic domains. SDS and Triton X-100 addition disrupted HEC-CNC gels whereas CTAB did not. Surface plasmon resonance measurements with CNC-coated sensors showed that SDS and Triton X-100 partially removed adsorbed HEC, whereas CTAB did not. These behaviors illustrate the complexities associated with including CNC dispersions in formulated products: low CNC contents can induce spectacular changes in rheology; however, surfactants and soluble polymers may promote gel formation or induce CNC coagulation.

  9. Uremic toxins and oral adsorbents.

    PubMed

    Goto, Shunsuke; Yoshiya, Kunihiko; Kita, Tomoyuki; Fujii, Hideki; Fukagawa, Masafumi

    2011-04-01

    Uremic toxins are associated with various disorders in patients with end-stage renal disease and it is difficult to remove some of these toxins by dialysis. Since some uremic toxins are generated by bacterial metabolites in the colon, oral adsorbents that interfere with the absorption of uremic toxins or their precursors are believed to prevent their accumulation in the body. AST-120 adsorbs various uremic retention solutes in the gastrointestinal system and has potential for providing clinical benefit. Sevelamer hydrochloride binds some harmful compounds in addition to phosphate and seems to have pleiotropic effects that include lowering serum LDL cholesterol levels and reduction of inflammation. The effect of sevelamer hydrochloride on indoxyl sulfate and p-cresol has been shown in an in vitro study; however, in vivo studies in mice or humans did not demonstrate this effect on protein-binding uremic toxins. Oral adsorbents are thus one of the important modalities in the treatment of uremic syndrome.

  10. The condensation of water on adsorbed viruses.

    PubMed

    Alonso, José María; Tatti, Francesco; Chuvilin, Andrey; Mam, Keriya; Ondarçuhu, Thierry; Bittner, Alexander M

    2013-11-26

    The wetting and dewetting behavior of biological nanostructures and to a greater degree single molecules is not well-known even though their contact with water is the basis for all biology. Here, we show that environmental electron microscopy (EM) can be applied as a means of imaging the condensation of water onto viruses. We captured the formation of submicrometer water droplets and filaments on single viral particles by environmental EM and by environmental transmission EM. The condensate structures are compatible with capillary condensation between adsorbed virus particles and with known droplet shapes on patterned surfaces. Our results confirm that such droplets exist down to <50 nm. The viruses preserved their shape after a condensation/evaporation cycle as expected from their stability in air and water. Moreover we developed procedures that overcome problems of beam damage and of resolving structures with a low atomic number.

  11. Chemical speciation of adsorbed glycine on metal surfaces

    NASA Astrophysics Data System (ADS)

    Han, Jeong Woo; James, Joanna N.; Sholl, David S.

    2011-07-01

    Experimental studies have reported that glycine is adsorbed on the Cu(110) and Cu(100) surfaces in its deprotonated form at room temperature, but in its zwitterionic form on Pd(111) and Pt(111). In contrast, recent density functional theory (DFT) calculations indicated that the deprotonated molecules are thermodynamically favored on Cu(110), Cu(100), and Pd(111). To explore the source of this disagreement, we have tested three possible hypotheses. Using DFT calculations, we first show that the kinetic barrier for the deprotonation reaction of glycine on Pd(111) is larger than on Cu(110) or Cu(100). We then report that the presence of excess hydrogen would have little influence on the experimentally observed results, especially for Pd(111). Lastly, we perform Monte Carlo simulations to demonstrate that the aggregates of zwitterionic species on Pt(111) are energetically preferred to those of neutral species. Our results strongly suggest that the formation of aggregates with relatively large numbers of adsorbed molecules is favored under experimentally relevant conditions and that the adsorbate-adsorbate interactions in these aggregates stabilize the zwitterionic species.

  12. High-capacity hydrogen storage in Al-adsorbed graphene

    NASA Astrophysics Data System (ADS)

    Ao, Z. M.; Peeters, F. M.

    2010-05-01

    A high-capacity hydrogen storage medium—Al-adsorbed graphene—is proposed based on density-functional theory calculations. We find that a graphene layer with Al adsorbed on both sides can store hydrogen up to 13.79wt% with average adsorption energy -0.193eV/H2 . Its hydrogen storage capacity is in excess of 6wt% , surpassing U. S. Department of Energy (DOE’s) target. Based on the binding-energy criterion and molecular-dynamics calculations, we find that hydrogen storage can be recycled at near ambient conditions. This high-capacity hydrogen storage is due to the adsorbed Al atoms that act as bridges to link the electron clouds of the H2 molecules and the graphene layer. As a consequence, a two-layer arrangement of H2 molecules is formed on each side of the Al-adsorbed graphene layer. The H2 concentration in the hydrogen storage medium can be measured by the change in the conductivity of the graphene layer.

  13. Conformational changes of adsorbed proteins

    NASA Astrophysics Data System (ADS)

    Allen, Scott

    2005-03-01

    The adsorption of bovine serum albumin (BSA) and pepsin to gold surfaces has been studied using surface plasmon resonance (SPR). Proteins are adsorbed from solution onto a gold surface and changes in the conformation of the adsorbed proteins are induced by changing the buffer solution. We selected pH and ionic strength values for the buffer solutions that are known from our circular dichroism measurements to cause conformational changes of the proteins in bulk solution. We find that for both BSA and pepsin the changes in conformation are impeded by the interaction of the protein with the gold surface.

  14. Effect of Surfactant Hydrophobicity on the Pathway for Unfolding of Ubiquitin

    PubMed Central

    Shaw, Bryan F.; Schneider, Grégory F.; Whitesides, George M.

    2012-01-01

    This paper describes the interaction between ubiquitin (UBI) and three sodium n-alkyl sulfates (SCnS) that have the same charge (Z = −1), but different hydrophobicity (n = 10, 12 and 14). Increasing the hydrophobicity of the n-alkyl sulfate resulted in: (i) an increase in the number of distinct intermediates (that is, complexes of UBI and surfactant) that form along the pathway of unfolding; (ii) a decrease in the minimum concentrations of surfactant at which intermediates begin to form (i.e., a more negative ΔGbinding of surfactant for UBI), and (iii) an increase in the number of surfactant molecules (p) bound to UBI in each intermediate or complex. These results demonstrate that small changes in the hydrophobicity of a surfactant can significantly alter the binding interactions with a folded or unfolded cytosolic protein. PMID:23095057

  15. A double injection ADSA-CSD methodology for lung surfactant inhibition and reversal studies.

    PubMed

    Saad, Sameh M I; Policova, Zdenka; Dang, Andrew; Acosta, Edgar J; Hair, Michael L; Neumann, A Wilhelm

    2009-10-15

    This paper presents a continuation of the development of a drop shape method for film studies, ADSA-CSD (Axisymmetric Drop Shape Analysis-Constrained Sessile Drop). ADSA-CSD has certain advantages over conventional methods. The development presented here allows complete exchange of the subphase of a spread or adsorbed film. This feature allows certain studies relevant to lung surfactant research that cannot be readily performed by other means. The key feature of the design is a second capillary into the bulk of the drop to facilitate addition or removal of a secondary liquid. The development will be illustrated through studies concerning lung surfactant inhibition. After forming a sessile drop of a basic lung surfactant preparation, the bulk phase can be removed and exchanged for one containing different inhibitors. Such studies mimic the leakage of plasma and blood proteins into the alveolar spaces altering the surface activity of lung surfactant in a phenomenon called surfactant inhibition. The resistance of the lung surfactant to specific inhibitors can be readily evaluated using the method. The new method is also useful for surfactant reversal studies, i.e. the ability to restore the normal surface activity of an inhibited lung surfactant film by using special additives. Results show a distinctive difference between the inhibition when an inhibitor is mixed with and when it is injected under a preformed surfactant film. None of the inhibitors studied (serum, albumin, fibrinogen, and cholesterol) were able to penetrate a preexisting film formed by the basic preparation (BLES and protasan), while all of them can alter the surface activity of such preparation when mixed with the preparation. Preliminary results show that reversal of serum inhibition can be easily achieved and evaluated using the modified methodology.

  16. Ecotoxicological characterization of polyoxyethylene glycerol ester non-ionic surfactants and their mixtures with anionic and non-ionic surfactants.

    PubMed

    Ríos, Francisco; Fernández-Arteaga, Alejandro; Lechuga, Manuela; Fernández-Serrano, Mercedes

    2017-03-03

    This paper reports on a study that investigated the aquatic toxicity of new non-ionic surfactants derived from renewable raw materials, polyoxyethylene glycerol ester (PGE), and their binary mixtures with anionic and non-ionic surfactants. Toxicity of pure PGEs was determined using representative organisms from different trophic levels: luminescent bacteria (Vibrio fischeri), microalgae (Pseudokirchneriella subcapitata), and freshwater crustaceans (Daphnia magna). Relationships between toxicity and the structural parameters such as unit of ethylene oxide (EO) and hydrophilic-lipophilic balance (HLB) were evaluated. Critical micellar concentration (CMC) in the conditions of the toxicity test was also determined. It was found that the toxicity of the aqueous solutions of PGE decreased when the number of EO units in the molecule, HLB, and CMC increased. PGEs showed lower CMC in marine medium, and the toxicity to V. ficheri is lower when the CMC was higher. Given their non-polar nature, narcosis was expected to be the primary mode of toxic action of PGEs. For the mixture of surfactants, we observed that the mixtures with PGE that had the higher numbers of EO units were more toxic than the aqueous solutions of pure surfactants. Moreover, we found that concentration addition was the type of action more likely to occur for mixtures of PGE with lower numbers of EO units with non-ionic surfactants (alkylpolyglucoside and fatty alcohol ethoxylate), whereas for the mixture of PGE with lower EO units and anionic surfactant (ether carboxylic derivative), the most common response type was response addition. In case of mixtures involving amphoteric surfactants and PGEs with the higher numbers of EO units, no clear pattern with regard to the mixture toxicity response type could be observed.

  17. Highly dealuminated Y zeolite as efficient adsorbent for the hydrophobic fraction from wastewater treatment plants effluents.

    PubMed

    Navalon, Sergio; Alvaro, Mercedes; Garcia, Hermenegildo

    2009-07-15

    In this work we report that highly dealuminated zeolite Y is a hydrophobic material that is able to remove selectively fatty acids and hydrocarbon compounds from the effluent of an urban wastewater treatment plant (UWTP). This adsorbent capability of zeolite Y could lead to an improved quality of UWTP effluents. Typical domestic wastewaters contain detergents, soaps and surfactants that are only partially removed in conventional UWTP. In the present work using an effluent from a UWTP located at Ribarroja del Turia (Valencia, Spain) containing 10 ppm of total organic carbon, we have been able to retain by adsorption on the dealuminated Y zeolite up to 16 and 60% of the organic matter of the effluent at pH values 7.2 and 4, respectively. Characterization of the adsorbed organic matter by Fourier transformed infrared (FT-IR), (1)H NMR and GC-MS after derivatization has shown that the zeolite adsorbs selectively the hydrophobic compounds of the effluent.

  18. On-chip controlled surfactant-DNA coil-globule transition by rapid solvent exchange using hydrodynamic flow focusing.

    PubMed

    Iliescu, Ciprian; Mărculescu, Cătălin; Venkataraman, Shrinivas; Languille, Baptiste; Yu, Hanry; Tresset, Guillaume

    2014-11-11

    This paper presents a microfluidic method for precise control of the size and polydispersity of surfactant-DNA nanoparticles. A mixture of surfactant and DNA dispersed in 35% ethanol is focused between two streams of pure water in a microfluidic channel. As a result, a rapid change of solvent quality takes place in the central stream, and the surfactant-bound DNA molecules undergo a fast coil-globule transition. By adjusting the concentrations of DNA and surfactant, fine-tuning of the nanoparticle size, down to a hydrodynamic diameter of 70 nm with a polydispersity index below 0.2, can be achieved with a good reproducibility.

  19. Surfactant damping of water waves

    NASA Astrophysics Data System (ADS)

    Lapham, Gary S.; Dowling, David R.; Schultz, William W.

    1997-11-01

    The most well known and perhaps most important distinguishing characteristic of a water surface laden with surfactant is the profound increase in small-wave damping with the addition of even small amounts of surfactant material. It would seem to follow that damping increases with increasing surfactant concentration. This is undoubtedly true for some surfactants, however our experiments with a soluble surfactant show that it is possible to increase surfactant concentration and measure a decrease in damping. While the increased concentration is accompanied by a dramatic decrease in measured static surface tension, some of the capillary-wave frequency regime is less damped. Experimental measurements of the real and imaginary parts of the wave speed are compared with existing theory where at least one other physical quantity besides surface tension is needed to properly model the interface. Our on-going work with insoluble surfactants may also provide an example of this type of behavior for materials that do not readily transfer to and from the bulk water. [Supported by the Office of Naval Research

  20. Theoretical and Simulations-Based Modeling of Micellization in Linear and Branched Surfactant Systems

    NASA Astrophysics Data System (ADS)

    Mendenhall, Jonathan D.

    Surfactants are chemically-heterogeneous molecules possessing hydrophilic (head) and hydrophobic (tail) moieties. This dual nature of surfactants leads to interesting phase behavior in aqueous solution as a function of surfactant concentration, including: (i) formation of surfactant monolayers at surfaces and interfaces, and (ii) self-assembly into finite aggregates (micelles) in the bulk solution beyond the critical micelle concentration (cmc). This concentration-dependent phase behavior induces changes in solution properties. For example, the surface activity of surfactants can decrease the surface tension, and self-assembly in bulk solution can lead to changes in viscosity, equivalent conductivity, solubilization capacity, and other bulk properties. These effects make surfactants quite attractive and unique for use in product formulations, where they are utilized as detergents, dispersants, emulsifiers, solubilizers, surface and interfacial tension modifiers, and in other contexts. The specific chemical structure of the surfactant head and tail is essential in determining the overall performance properties of a surfactant in aqueous media. The surfactant tail drives the self-assembly process through the hydrophobic effect, while the surfactant head imparts a certain extent of solubility to the surfactant in aqueous solution through preferential interactions with the hydrogen-bonding network of water. The interplay between these two effects gives rise to the particular phase diagram of a surfactant, including the specific cmc at which micelles begin to form. In addition to serving as a quantitative indicator of micelle formation, the cmc represents a limit to surface monolayer formation, and hence to surface and interfacial tension reduction, because surfactant adsorption at interfaces remains approximately constant beyond the cmc. In addition, the cmc represents the onset of changes in bulk solution properties. This Thesis is concerned with the prediction of cmc

  1. Radiolysis of alanine adsorbed in a clay mineral

    SciTech Connect

    Aguilar-Ovando, Ellen Y.; Negron-Mendoza, Alicia

    2013-07-03

    Optical activity in molecules is a chemical characteristic of living beings. In this work, we examine the hypothesis of the influence of different mineral surfaces on the development of a specific chirality in organic molecules when subjected to conditions simulating the primitive Earth during the period of chemical evolution. By using X-ray diffraction techniques and HPLC/ELSD to analyze aqueous suspensions of amino acids adsorbed on minerals irradiated in different doses with a cobalt-60 gamma source, the experiments attempt to prove the hypothesis that some solid surfaces (like clays and meteorite rocks) may have a concentration capacity and protective role against external sources of ionizing radiation (specifically {gamma}-ray) for some organic compounds (like some amino acids) adsorbed on them. Preliminary results show a slight difference in the adsorption and radiolysis of the D-and L-alanine.

  2. Nanoscience: Single-molecule instant replay

    NASA Astrophysics Data System (ADS)

    Camillone, Nicholas

    2016-11-01

    A nanoscale imaging method that uses ultrashort light pulses to initiate and follow the motion of a single molecule adsorbed on a solid surface opens a window onto the physical and chemical dynamics of molecules on surfaces. See Letter p.263

  3. Sorption of phenol and 4-chlorophenol onto pumice treated with cationic surfactant.

    PubMed

    Akbal, Feryal

    2005-02-01

    In this study the sorption of phenol and 4-chlorophenol on pumice modified with the cationic surfactants hexadecyltrimethyl ammonium bromide (HDTMA) and benzyldimethyl tetradecylammonium chloride (BDTDA) was investigated. Experimental studies indicate that HDTMA-pumice and BDTDA-pumice have the capability to remove phenol and 4-chlorophenol from aqueous solution. The influence of initial concentration and adsorbent dosage was studied. The adsorption of phenol and 4-chlorophenol increased with increasing initial concentration and decreased with increasing amount of adsorbent used. The Freundlich adsorption isotherm was found to describe well the equilibrium adsorption data. The parameters of the Freundlich model have been determined using the adsorption data.

  4. Development of Targeted Nonionic Surfactant Vesicles for Treatment of Vascular Injury

    DTIC Science & Technology

    2008-12-01

    Inflammatory processes play a crucial role in cardiovascular injury and disease . Inflamed endothelial cells express adhesion molecules which are...typically composed of synthetic surfactants, cholesterol and dicetyl phosphate (DCP, an electrostatic stabilizer). Niosomes can encapsulate aqueous...of leukocytes from the blood stream to the site of injury or disease . This is mediated by cellular adhesion molecules (CAMs) expressed on the cell

  5. Pulmonary surfactant for neonatal respiratory disorders.

    PubMed

    Merrill, Jeffrey D; Ballard, Roberta A

    2003-04-01

    Surfactant therapy has revolutionized neonatal care and is used routinely for preterm infants with respiratory distress syndrome. Recent investigation has further elucidated the function of surfactant-associated proteins and their contribution toward surfactant and lung immune defense functions. As the field of neonatology moves away from intubation and mechanical ventilation of preterm infants at birth toward more aggressive use of nasal continuous positive airway pressure, the optimal timing of exogenous surfactant therapy remains unclear. Evidence suggests that preterm neonates with bronchopulmonary dysplasia and prolonged mechanical ventilation also experience surfactant dysfunction; however, exogenous surfactant therapy beyond the first week of life has not been well studied. Surfactant replacement therapy has been studied for use in other respiratory disorders, including meconium aspiration syndrome and pneumonia. Commercial surfactant preparations currently available are not optimal, given the variability of surfactant protein content and their susceptibility to inhibition. Further progress in the treatment of neonatal respiratory disorders may include the development of "designer" surfactant preparations.

  6. Interaction of bovine serum albumin with N-acyl amino acid based anionic surfactants: Effect of head-group hydrophobicity.

    PubMed

    Ghosh, Subhajit; Dey, Joykrishna

    2015-11-15

    The function of a protein depends upon its structure and surfactant molecules are known to alter protein structure. For this reason protein-surfactant interaction is important in biological, pharmaceutical, and cosmetic industries. In the present work, interactions of a series of anionic surfactants having the same hydrocarbon chain length, but different amino acid head group, such as l-alanine, l-valine, l-leucine, and l-phenylalanine with the transport protein, bovine serum albumin (BSA), were studied at low surfactant concentrations using fluorescence and circular dichroism (CD) spectroscopy, and isothermal titration calorimetry (ITC). The results of fluorescence measurements suggest that the surfactant molecules bind simultaneously to the drug binding site I and II of the protein subdomain IIA and IIIA, respectively. The fluorescence as well as CD spectra suggest that the conformation of BSA goes to a more structured state upon surfactant binding at low concentrations. The binding constants of the surfactants were determined by the use of fluorescence as well as ITC measurements and were compared with that of the corresponding glycine-derived surfactant. The binding constant values clearly indicate a significant head-group effect on the BSA-surfactant interaction and the interaction is mainly hydrophobic in nature.

  7. Adsorption of atrazine by natural organic matter and surfactant dispersed carbon nanotubes.

    PubMed

    Shi, Baoyou; Zhuang, Xiaoyan; Yan, Xiaomin; Lu, Jiajuan; Tang, Hongxiao

    2010-01-01

    The aggregation and dispersion behaviors of carbon nanotubes (CNTs) can regulate the environmental spread and fate of CNTs, as well as the organic pollutants adsorbed onto them. In this study, multi-walled carbon nanotubes (MWNTs) and single-walled carbon nanotubes (SWNTs) were surface modified with humic acids from different sources and with surfactants of different ionic types. The dispersion stability of surface modified CNTs was observed by UV-Vis spectrophotometry. The effect of humic acid and surfactant dispersion on the adsorption of atrazine by CNTs was investigated by batch equilibrium experiments. Both humic acid and surfactant could effectively disperse MWNTs, but not SWNTs, into stable suspensions under the studied conditions. Surface modified CNTs had a greatly reduced capacity for adsorption of atrazine. The inhibitory effect of peat humic acid was relatively stronger than that of soil humic acid, but the two surfactants had a similar inhibitory effect on atrazine adsorption by the two CNT types. Increases in surfactant concentration resulted in rapid decreases in the adsorption of atrazine by CNTs when the surfactant concentration was less than 0.5 critical micelle concentration.

  8. Surfactant-enhanced solubility and mobility of polycyclic aromatic hydrocarbons in soil

    SciTech Connect

    Sun, X.; Puri, R.K.

    1997-12-31

    The role of some selected nonionic, anionic and cationic surfactants was investigated in solubilizing and mobilizing polycyclic aromatic hydrocarbons (PAHs) from soil. The data from the batch experiment showed that Brij 30 (a nonionic surfactant) started transporting the PAHs from soil to water at concentrations well below its apparent critical micelle concentration (ACMC). At its high concentrations, however, Brij 30 transported more PAHs to the aqueous phase. Thus, it showed a great potential in remediation of PAH-contaminated soils. The tested anionic and cationic surfactants did not show the solubilization effect until the concentrations reached their ACMCs. The experiment showed that the decomposition of the surfactants was more significant than tat of the PAHs with the passage of time. A considerable portion of the solubilized PAHs was either re-adsorbed by the soil particles or was hanging in the mobile phase after 170 days, depending on the nature and concentration of the individual surfactants. The data showed that the solubilized portion of the PAHs became more persistent in the soil-water system, and its transport is proportional to the concentration and nature of the surfactants studied.

  9. Minimally invasive approaches for surfactant administration.

    PubMed

    Trevisanuto, D; Marchetto, L

    2013-01-01

    Respiratory distress syndrome (RDS) is the most common respiratory morbidity in preterm infants. In addition to respiratory support, the current clinical treatment includes endotracheal intubation and rapid instillation of exogenous surfactant. However, this approach needs skilled operators and has been associated with complications such as hemodynamic instability and electroencephalogram abnormalities. New, less invasive methods for surfactant administration are needed. In this article, we reviewed the available noninvasive procedures for surfactant administration. In particular, we focused on aerosolized surfactant and surfactant administration through LMA.

  10. Factors influencing the mechanism of surfactant catalyzed reaction of vitamin C-ferric chloride hexahydrate system

    NASA Astrophysics Data System (ADS)

    Farrukh, Muhammad Akhyar; Kauser, Robina; Adnan, Rohana

    2013-09-01

    The kinetics of vitamin C by ferric chloride hexahydrate has been investigated in the aqueous ethanol solution of basic surfactant viz. octadecylamine (ODA) under pseudo-first order conditions. The critical micelle concentration (CMC) of surfactant was determined by surface tension measurement. The effect of pH (2.5-4.5) and temperature (15-35°C) in the presence and absence of surfactant were investigated. Activation parameters, Δ E a, Δ H #, Δ S #, Δ G ≠, for the reaction were calculated by using Arrhenius and Eyring plot. Surface excess concentration (Γmax), minimum area per surfactant molecule ( A min), average area occupied by each molecule of surfactant ( a), surface pressure at the CMC (Πmax), Gibb's energy of micellization (Δ G M°), Gibb's energy of adsorption (Δ G ad°), were calculated. It was found that the reaction in the presence of surfactant showed faster oxidation rate than the aqueous ethanol solution. Reaction mechanism has been deduced in the presence and absence of surfactant.

  11. Binding of 12-s-12 dimeric surfactants to calf thymus DNA: Evaluation of the spacer length influence.

    PubMed

    Sarrión, Beatriz; Bernal, Eva; Martín, Victoria Isabel; López-López, Manuel; López-Cornejo, Pilar; García-Calderón, Margarita; Moyá, María Luisa

    2016-08-01

    Several cationic dimeric surfactants have shown high affinity towards DNA. Bis-quaternary ammonium salts (m-s-m) have been the most common type of dimeric surfactants investigated and it is generally admitted that those that posses a short spacer (s≤3) show better efficiency to bind or compact DNA. However, experimental results in this work show that 12-s-12 surfactants with long spacers make the surfactant/ctDNA complexation more favorable than those with short spacers. A larger contribution of the hydrophobic interactions, which control the binding Gibbs energy, as well as a higher average charge of the surfactant molecules bound to the nucleic acid, which favors the electrostatic attractions, could explain the experimental observations. Dimeric surfactants with intermediate spacer length seem to be the less efficient for DNA binding.

  12. Cationic surfactants derived from lysine: effects of their structure and charge type on antimicrobial and hemolytic activities.

    PubMed

    Colomer, A; Pinazo, A; Manresa, M A; Vinardell, M P; Mitjans, M; Infante, M R; Pérez, L

    2011-02-24

    Three different sets of cationic surfactants from lysine have been synthesized. The first group consists of three monocatenary surfactants with one lysine as the cationic polar head with one cationic charge. The second consists of three monocatenary surfactants with two amino acids as cationic polar head with two positive charges. Finally, four gemini surfactants were synthesized in which the spacer chain and the number and type of cationic charges have been regulated. The micellization process, antimicrobial activity, and hemolytic activity were evaluated. The critical micelle concentration was dependent only on the hydrophobic character of the molecules. Nevertheless, the antimicrobial and hemolytic activities were related to the structure of the compounds as well as the type of cationic charges. The most active surfactants against the bacteria were those with a cationic charge on the trimethylated amino group, whereas all of these surfactants showed low hemolytic character.

  13. Hydration level dependence of the microscopic dynamics of water adsorbed in ultramicroporous carbon

    SciTech Connect

    Mamontov, Eugene; Yue, Yanfeng; Bahadur, Jitendra; Guo, Junjie; Contescu, Cristian I.; Gallego, Nidia C.; Melnichenko, Yuri B.

    2016-10-20

    Even when not functionalized intentionally, most carbon materials are not hydrophobic and readily adsorb water molecules from atmospheric water vapor. We have equilibrated an ultramicroporous carbon at several levels of relative humidity, thereby attaining various hydration levels. The water molecules were adsorbed on the pore walls (but did not fill completely the pore volume) and thus could be better described as hydration, or surface, rather than confined, water. We used quasielastic neutron scattering to perform a detailed investigation of the dependence of microscopic dynamics of these adsorbed water species on the hydration level and temperature. The behavior of hydration water in ultramicroporous carbon clearly demonstrates the same universal traits that characterize surface (hydration) water in other materials that are surface-hydrated. In addition, unless special treatment is intentionally applied to ultramicroporous carbon, the species filling its pores in various applications, ranging from hydrogen molecules to electrolytes, likely find themselves in contact with non-freezing water molecules characterized by rich microscopic dynamics.

  14. Understanding the structure of hydrophobic surfactants at the air/water interface from molecular level.

    PubMed

    Zhang, Li; Liu, Zhipei; Ren, Tao; Wu, Pan; Shen, Jia-Wei; Zhang, Wei; Wang, Xinping

    2014-11-25

    Understanding the behavior of fluorocarbon surfactants at the air/water interface is crucial for many applications, such as lubricants, paints, cosmetics, and fire-fighting foams. In this study, molecular dynamics (MD) simulations were employed to investigate the microscopic properties of non-ionic fluorocarbon surfactants at the air/water interface. Several properties, including the distribution of head groups, the distribution probability of the tilt angle between hydrophobic tails with respect to the xy plane, and the order parameter of surfactants, were computed to probe the structure of hydrophobic surfactants at the air/water interface. The effects of the monomer structure on interfacial phenomena of non-ionic surfactants were investigated as well. It is observed that the structure of fluorocarbon surfactants at the air/water interface is more ordered than that of hydrocarbons, which is dominated by the van der Waals interaction between surfactants and water molecules. However, replacing one or two CF2 with one or two CH2 group does not significantly influence the interfacial structure, suggesting that hydrocarbons may be promising alternatives to perfluorinated surfactants.

  15. Remediation of soil-bound polynuclear aromatic hydrocarbons using nonionic surfactants

    SciTech Connect

    Yeom, IckTae; Ghosh, Mriganka; Cox, C.

    1996-12-31

    The solubilization and biodegradation of soil-bound PAHs from a manufactured gas plant (MGP) site soil was investigated using surfactants. Three nonionic polyoxyethylene (POE) surfactants, Triton X-100, Tween 80, and Brij 35, were used. The fate of four PAHs, phenanthrene, anthracene, pyrene, and benzo(a)pyrene were monitored during the remediation process. The measured concentrations of solubilized PAHs agreed well with those estimated using micelle-water partitioning coefficient, K{sub m}, and Raoult`s law. The solubilization of soil-bound PAHs by surfactants is a slow, nonequilibrium process. Diffusion of PAH molecules within the weathered soil-tar matrix is proposed as the rate-limiting step in solubilizing PAHs from such soils. A radial diffusion model is used to describe solubilization of PAHs by surfactant washing. The model predicts experimental results fairly well at low surfactant dosages while at high dosages it somewhat overestimates the extent of solubilization. Biodegradation studies were performed using a natural consortium of microorganisms enriched from PAH-contaminated soils. Surfactants enhanced biodegradation of PAHs except for Tween 80. However, biodegradation of surfactants themselves appear to attenuate the beneficial effects of surfactant-mediated bioremediation.

  16. A study of corrosion inhibition of steel AISI-SAE 1020 in CO2-brine using surfactant Tween 80

    NASA Astrophysics Data System (ADS)

    Cedeño, M. L.; L, E. Vera; Pineda T, Y.

    2017-01-01

    Surfactant inhibitors also called active surface agents are molecules composed of a polar hydrophilic group and a non-polar hydrophobic group, with characteristics of adsorption on metal surfaces, high efficiency of inhibiting, low price, low toxicity and easy production. In this work, the corrosion inhibition was study by CO2 steel AISI-SAE 1020 with the addition of 0.01M Tween 80 surfactant to a brine solution (3% NaCl). Electrochemical Impedance Spectroscopy and potentiodynamic polarization testing investigated the phenomenon. The results revealed that the surfactant studied acts as an excellent corrosion inhibitor and inhibition efficiency (E%) increases with increasing fluid velocity. The morphology of the steel surface after exposure to the solution of 3% NaCl with and without surfactant indicates the inhibition phenomenon is due to the adsorption of the surfactant molecules, which insulate the surface of the corrosive medium and reduces the attack surficial.

  17. Molecular switches from benzene derivatives adsorbed on metal surfaces

    PubMed Central

    Liu, Wei; Filimonov, Sergey N.; Carrasco, Javier; Tkatchenko, Alexandre

    2013-01-01

    Transient precursor states are often experimentally observed for molecules adsorbing on surfaces. However, such precursor states are typically rather short-lived, quickly yielding to more stable adsorption configurations. Here we employ first-principles calculations to systematically explore the interaction mechanism for benzene derivatives on metal surfaces, enabling us to selectively tune the stability and the barrier between two metastable adsorption states. In particular, in the case of the tetrachloropyrazine molecule, two equally stable adsorption states are identified with a moderate and conceivably reversible barrier between them. We address the feasibility of experimentally detecting the predicted bistable behaviour and discuss its potential usefulness in a molecular switch. PMID:24157660

  18. Temperature programmed desorption of weakly bound adsorbates on Au(111)

    NASA Astrophysics Data System (ADS)

    Engelhart, Daniel P.; Wagner, Roman J. V.; Meling, Artur; Wodtke, Alec M.; Schäfer, Tim

    2016-08-01

    We have performed temperature programmed desorption (TPD) experiments to analyze the desorption kinetics of Ar, Kr, Xe, C2H2, SF6, N2, NO and CO on Au(111). We report desorption activation energies (Edes), which are an excellent proxy for the binding energies. The derived binding energies scale with the polarizability of the molecules, consistent with the conclusion that the surface-adsorbate bonds arise due to dispersion forces. The reported results serve as a benchmark for theories of dispersion force interactions of molecules at metal surfaces.

  19. Do methanethiol adsorbates on the Au(111) surface dissociate?

    PubMed

    Zhou, Jian-Ge; Hagelberg, Frank

    2006-07-28

    The interaction of methanethiol molecules CH3SH with the Au(111) surface is investigated, and it is found for the first time that the S-H bond remains intact when the methanethiol molecules are adsorbed on the regular Au(111) surface. However, it breaks if defects are present in the Au(111) surface. At low coverage, the fcc region is favored for S atom adsorption, but at saturated coverage the adsorption energies at various sites are almost isoenergetic. The presented calculations show that a methanethiol layer on the regular Au(111) surface does not dimerize.

  20. Do Methanethiol Adsorbates on the Au(111) Surface Dissociate?

    NASA Astrophysics Data System (ADS)

    Zhou, Jian-Ge; Hagelberg, Frank

    2006-07-01

    The interaction of methanethiol molecules CH3SH with the Au(111) surface is investigated, and it is found for the first time that the S-H bond remains intact when the methanethiol molecules are adsorbed on the regular Au(111) surface. However, it breaks if defects are present in the Au(111) surface. At low coverage, the fcc region is favored for S atom adsorption, but at saturated coverage the adsorption energies at various sites are almost isoenergetic. The presented calculations show that a methanethiol layer on the regular Au(111) surface does not dimerize.

  1. Interactions between polymers and surfactants

    SciTech Connect

    de Gennes, P.G. )

    1990-11-01

    A surfactant film (at the water/air interface, or in a bilayer) is exposed to a solution of a neutral, flexible, polymer. Depending on the interactions, and on the Langmuir pressure II of the pure surfactant film, the authors expected to find three types of behavior: (I) the polymer does not absorb; (II) the polymer absorbs and mixes with the surfactant; (III) the polymer absorbs but segregates from the surfactant. Their interest here is in case II. They predict that (a) bilayers become rigid; (b) bilayers, exposed to polymer on one side only, tend to bend strongly; (c) the surface viscosity of monolayers or bilayers is considerably increased; soap films or foams, which usually drain by turbulent (two-dimensional) flows, may be stabilized in case II.

  2. Genetics Home Reference: surfactant dysfunction

    MedlinePlus

    ... easy. Without normal surfactant, the tissue surrounding the air sacs in the lungs (the alveoli ) sticks together (because of a force called surface tension) after exhalation, causing the alveoli ...

  3. Factors Affecting the Design of Slow Release Formulations of Herbicides Based on Clay-Surfactant Systems. A Methodological Approach

    PubMed Central

    Galán-Jiménez, María del Carmen; Mishael, Yael-Golda; Nir, Shlomo; Morillo, Esmeralda; Undabeytia, Tomás

    2013-01-01

    A search for clay-surfactant based formulations with high percentage of the active ingredient, which can yield slow release of active molecules is described. The active ingredients were the herbicides metribuzin (MZ), mesotrione (MS) and flurtamone (FL), whose solubilities were examined in the presence of four commercial surfactants; (i) neutral: two berols (B048, B266) and an alkylpolyglucoside (AG6202); (ii) cationic: an ethoxylated amine (ET/15). Significant percent of active ingredient (a.i.) in the clay/surfactant/herbicide formulations could be achieved only when most of the surfactant was added as micelles. MZ and FL were well solubilized by berols, whereas MS by ET/15. Sorption of surfactants on the clay mineral sepiolite occurred mostly by sorption of micelles, and the loadings exceeded the CEC. Higher loadings were determined for B266 and ET/15. The sorption of surfactants was modeled by using the Langmuir-Scatchard equation which permitted the determination of binding coefficients that could be used for further predictions of the sorbed amounts of surfactants under a wide range of clay/surfactant ratios. A possibility was tested of designing clay-surfactant based formulations of certain herbicides by assuming the same ratio between herbicides and surfactants in the formulations as for herbicides incorporated in micelles in solution. Calculations indicated that satisfactory FL formulations could not be synthesized. The experimental fractions of herbicides in the formulations were in agreement with the predicted ones for MS and MZ. The validity of this approach was confirmed in in vitro release tests that showed a slowing down of the release of a.i. from the designed formulations relative to the technical products. Soil dissipation studies with MS formulations also showed improved bioactivity of the clay-surfactant formulation relative to the commercial one. This methodological approach can be extended to other clay-surfactant systems for encapsulation and

  4. Factors affecting the design of slow release formulations of herbicides based on clay-surfactant systems. A methodological approach.

    PubMed

    Galán-Jiménez, María Del Carmen; Mishael, Yael-Golda; Nir, Shlomo; Morillo, Esmeralda; Undabeytia, Tomás

    2013-01-01

    A search for clay-surfactant based formulations with high percentage of the active ingredient, which can yield slow release of active molecules is described. The active ingredients were the herbicides metribuzin (MZ), mesotrione (MS) and flurtamone (FL), whose solubilities were examined in the presence of four commercial surfactants; (i) neutral: two berols (B048, B266) and an alkylpolyglucoside (AG6202); (ii) cationic: an ethoxylated amine (ET/15). Significant percent of active ingredient (a.i.) in the clay/surfactant/herbicide formulations could be achieved only when most of the surfactant was added as micelles. MZ and FL were well solubilized by berols, whereas MS by ET/15. Sorption of surfactants on the clay mineral sepiolite occurred mostly by sorption of micelles, and the loadings exceeded the CEC. Higher loadings were determined for B266 and ET/15. The sorption of surfactants was modeled by using the Langmuir-Scatchard equation which permitted the determination of binding coefficients that could be used for further predictions of the sorbed amounts of surfactants under a wide range of clay/surfactant ratios. A possibility was tested of designing clay-surfactant based formulations of certain herbicides by assuming the same ratio between herbicides and surfactants in the formulations as for herbicides incorporated in micelles in solution. Calculations indicated that satisfactory FL formulations could not be synthesized. The experimental fractions of herbicides in the formulations were in agreement with the predicted ones for MS and MZ. The validity of this approach was confirmed in in vitro release tests that showed a slowing down of the release of a.i. from the designed formulations relative to the technical products. Soil dissipation studies with MS formulations also showed improved bioactivity of the clay-surfactant formulation relative to the commercial one. This methodological approach can be extended to other clay-surfactant systems for encapsulation and

  5. Interactions in water of alkyl and perfluoroalkyl surfactants with fluorocarbon- and hydrocarbon-modified poly(N-isopropylacrylamides).

    PubMed

    Kujawa, Piotr; Raju, B Bangar; Winnik, Francoise M

    2005-10-25

    Fluorescence spectroscopy and isothermal titration calorimetry (ITC) have been used to study the interactions in water at 25 degrees C of two anionic surfactants--sodium dodecyl sulfate (SDS) and sodium perfluorononanoate (SPFN)--with various pyrene-labeled hydrophobically modified poly(N-isopropylacrylamides) (HM-PNIPAM) grafted at random with small amounts of fluorocarbon chains (1H,1H-perfluorooctyl, CH2C7F15); (PNIPAM-F), or (n-octadecyl, C18H37) (PNIPAM-HPy) or both (PNIPAM-F/HPy). In aqueous solution, the copolymers form micellar structures consisting of a loose corona of hydrated poly(N-isopropylacrylamide) chains and a hydrophobic core rich in hydrocarbon or fluorocarbon groups. From fluorescence studies based on changes in the ratio of pyrene excimer to monomer emission intensity, it has been established (1) that mixed SDS/C18H37 clusters form along the polymer chain upon addition of SDS to either PNIPAM-HPy or PNIPAM-F/HPy and (2) that SPFN does not interact with the hydrocarbon-rich microdomains of the polymeric micelles. The conclusions were corroborated by ITC experiments, which yield the overall enthalpy change associated with polymer/surfactant interactions. They provided strong evidence (1) that SDS molecules adsorb along the PNIPAM main chain but do not mix with the fluorocarbon-rich microdomains of PNIPAM-F or PNIPAM-F/HPy and (2) that SPFN associates with the perfluorocarbon substituents of PNIPAM-F and PNIPAM-F/HPy but has a poor affinity for the polymer chain.

  6. Application of 1H NMR spectroscopy method for determination of characteristics of thin layers of water adsorbed on the surface of dispersed and porous adsorbents.

    PubMed

    Turov, V V; Leboda, R

    1999-02-01

    The paper presents 1H NMR spectroscopy as a perspective method of the studies of the characteristics of water boundary layers in the hydrated powders and aqueous dispergated suspensions of the adsorbents. The method involves measurements of temperature dependence proton signals intensity in the adsorbed water at temperatures lower than 273 K. Free energy of water molecules at the adsorbent/water interface is diminished due to the adsorption interactions causing the water dosed to the adsorbent surface freezes at T < 273 K. Thickness of a non-freezing layer of water can be determined from the intensity of the water signal of 1H NMR during the freezing-thawing process. Due to a disturbing action of the adsorbent surface, water occurs in the quasi-liquid state. As a result, it is observed in the 1H NMR spectra as a relatively narrow signal. The signal of ice is not registered due to great differences in the transverse relaxation times of the adsorbed water and ice. The method of measuring the free surface energy of the adsorbents from the temperature dependence of the signal intensity of non-freezing water is based on the fact that the temperature of water freezing decreases by the quantity which depends on the surface energy and the distance of the adsorbed molecules from the solid surface. The water at the interface freezes when the free energies of the adsorbed water and ice are equal. To illustrate the applicability of the method under consideration the series of adsorption systems in which the absorbents used differed in the surface chemistry and porous structure. In particular, the behaviour of water on the surface of the following adsorbents is discussed: non-porous and porous silica (aerosils, silica gels); chemically and physically modified non-porous and porous silica (silanization, carbonization, biopolymer deposition); and pyrogeneous Al2O3 and aluminasilicas. The effect of preliminary treatment of the adsorbent (thermal, high pressure, wetting with polar

  7. Role of interaction energies in the behavior of mixed surfactant systems: a lattice Monte Carlo simulation.

    PubMed

    Poorgholami-Bejarpasi, Niaz; Hashemianzadeh, Majid; Mousavi-Khoshdel, S Morteza; Sohrabi, Beheshteh

    2010-09-07

    We have investigated micellization in systems containing two surfactant molecules with the same structure using a lattice Monte Carlo simulation method. For the binary systems containing two surfactants, we have varied the head-head interactions or tail-tail repulsions in order to mimic the nonideal behavior of mixed surfactant systems and to manipulate the net interactions between surfactant molecules. The simulation results indicate that interactions between headgroups or tailgroups have an effect on thermodynamic properties such as the mixed critical micelle concentration (cmc), distribution of aggregates, shape of the aggregates, and composition of the micelles formed. Moreover, we have compared the simulation results with estimates based on regular solution theory, a mean-field theory, to determine the applicability of this theory to the nonideal mixed surfactant systems. We have found that the simulation results agree reasonable well with regular solution theory for the systems with attractions between headgroups and repulsions between tailgroups. However, the large discrepancies observed for the systems with head-head repulsions could be attributed to the disregarding of the correlation effect on the interaction among surfactant molecules and the nonrandom mixing effect in the theory.

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

    NASA Astrophysics Data System (ADS)

    Sun, Baichuan; Chakraborty, Anutosh

    2014-05-01

    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.

  9. First-principles calculations of surfactant-assisted growth of polar CaO(111) oxide film: The case of water-based surfactant

    NASA Astrophysics Data System (ADS)

    Tan, Xin; Zapol, Peter

    2012-07-01

    Surfactant-assisted growth of polar CaO(111) oxide film in the presence of water-based surfactant is studied by first-principles calculations both from thermodynamic and kinetic points of view. We show that the water molecules not only supply a surfactant by depositing hydrogen on the surface throughout the growth process, but also supply oxygen atoms as an elemental constituent in the film growth with rather small energy barriers, i.e. water oxygen atoms are easily inserted in the top surface layer of the growth film during the wet oxidation process. Adding the water surfactants to conventional synthesis techniques leads to the continuous presence of hydrogen atoms in the surface region during the growth process, which efficiently quenches polarity and dynamically stabilizes the growth of the polar surface, and thus facilitates the growth of defect-free CaO(111) films with arbitrary thickness.

  10. A theoretical study of the interaction of hydrogen and oxygen with palladium or gold adsorbed on pyridine-like nitrogen-doped graphene.

    PubMed

    Rangel, Eduardo; Magana, Luis Fernando; Sansores, Luis Enrique

    2014-12-15

    The interaction of H2 and O2 molecules in the presence of nitrogen-doped graphene decorated with either a palladium or gold atom was investigated by using density functional theory. It was found that two hydrogen molecules were adsorbed on the palladium atom. The interaction of these adsorbed hydrogen molecules with two oxygen molecules generates two hydrogen peroxide molecules first through a Eley-Rideal mechanism and then through a Langmuir-Hinshelwood mechanism. The barrier energies for this reaction were small; therefore, we expect that this process may occur spontaneously at room temperature. In the case of gold, a single hydrogen molecule is adsorbed and dissociated on the metal atom. The interaction of the dissociated hydrogen molecule on the surface with one oxygen molecule generates a water molecule. The competitive adsorption between oxygen and hydrogen molecules slightly favors oxygen adsorption.

  11. Enhanced perfume surface delivery to interfaces using surfactant surface multilayer structures.

    PubMed

    Brabury, Robert; Penfold, Jeffrey; Thomas, Robert K; Tucker, Ian M; Petkov, Jordan T; Jones, Craig

    2016-01-01

    Enhanced surface delivery and retention of perfumes at interfaces are the keys to their more effective and efficient deployment in a wide range of home and personal care related formulations. It has been previously demonstrated that the addition of multivalent counterions, notably Ca(2+), induces multilayer adsorption at the air-water interface for the anionic surfactant, sodium dodecyl-6-benzenesulfonate, LAS-6. Neutron reflectivity, NR, measurements are reported here which demonstrate that such surfactant surface multilayer structures are a potentially promising vehicle for enhanced delivery of perfumes to interfaces. The data show that the incorporation of the model perfumes, phenylethanol, PE, and linalool, LL, into the surface multilayer structure formed by LAS-6/Ca(2+) results in the surface structures being retained up to relatively high perfume mole fractions. Furthermore the amount of perfume at the surface is enhanced by at least an order of magnitude, compared to that co-adsorbed with a surfactant monolayer.

  12. MINERAL-SURFACTANT INTERACTIONS FOR MINIMUM REAGENTS PRECIPITATION AND ADSORPTION FOR IMPROVED OIL RECOVERY

    SciTech Connect

    P. Somasundaran

    2004-10-30

    Significant surfactant loss by adsorption or precipitation on reservoir minerals can cause chemical flooding processes to be less than satisfactory for enhanced oil recovery. This project is aimed towards an understanding of the role of reservoir minerals and their dissolved species in chemical loss by precipitation or adsorption of surfactants/polymers in enhanced oil recovery. Emphasis will be on the type and nature of different minerals in the oil reservoirs. Macroscopic adsorption, precipitation, wettability and nanoscopic orientation/conformation studies for aggregates of various surfactant/polymer mixtures on reservoir rocks systems is planned for exploring the cause of chemical loss by means of precipitation or adsorption, and the effect of rock mineralogy on the chemical loss. During this reporting period, the minerals proposed in this study: sandstone, limestone, gypsum, kaolinite and pyrite, have been characterized to obtain their particle size distribution and surface area, which will be used in the analysis of adsorption and wettability data. The effect of surfactant mixing ratio on the adsorption of mixture of C{sub 12}-C{sub 4}-C{sub 12} Gemini surfactant (synthesized during last period) and sugar-based nonionic surfactant n-dodecyl-{beta}-D-maltoside (DM) has been studied. It was discovered that even trace amounts of Gemini in the mixture is sufficient to force significant adsorption of DM. DM adsorption on silica increased from relatively negligible levels to very high levels. It is clear form analysis of the results that desired adsorption of either surfactant component in the mixtures can be obtained by controlling the mixing ratio, the total mixture concentration, pH etc. Along with these adsorption studies, changes in mineral wettability due to the adsorption of Gemini/DM mixtures were determined under relevant conditions to identify the nano-structure of the adsorbed layers. With increasing total surfactant adsorption, the silica mineral

  13. MINERAL-SURFACTANT INTERACTIONS FOR MINIMUM REAGENTS PRECIPITATION AND ADSORPTION FOR IMPROVED OIL RECOVERY

    SciTech Connect

    P. Somasundaran

    2005-04-30

    The aim of this project is to delineate the role of mineralogy of reservoir rocks in determining interactions between reservoir minerals and externally added reagents (surfactants/polymers) and its effect on critical solid-liquid and liquid-liquid interfacial properties such as adsorption, wettability and interfacial tension in systems relevant to reservoir conditions. Previous studies have suggested that significant surfactant loss by precipitation or adsorption on reservoir minerals can cause chemical schemes to be less than satisfactory for enhanced oil recovery. Both macroscopic adsorption, wettability and microscopic orientation and conformation studies for various surfactant/polymer mixtures/reservoir rocks systems were conducted to explore the cause of chemical loss by means of precipitation or adsorption, and the effect of rock mineralogy on the chemical loss. During this period, the adsorption of mixed system of n-dodecyl-{beta}-D-maltoside (DM) and dodecyl sulfonate (C{sub 12}SO{sub 3}Na) has been studied. The effects of solution pH, surfactant mixing ratio and different salts on surfactant adsorption on alumina have been investigated in detail. Along with these adsorption studies, changes in mineral wettability due to the adsorption of the mixtures were determined under relevant conditions to identify the nano-structure of the adsorbed layers. Solution properties of C{sub 12}SO{sub 3}Na/DM mixtures were also studied to identify surfactant interactions that affect the mixed aggregate formation in solution. Adsorption of SDS on gypsum and limestone suggested stronger surfactant/mineral interaction than on alumina, due to the precipitation of surfactant by dissolved calcium ions. The effects of different salts such as sodium nitrate, sodium sulfite and sodium chloride on DM adsorption on alumina have also been determined. As surfactant hemimicelles at interface and micelles in solution have drastic effects on oil recovery processes, their microstructures in

  14. Surfactant-assisted Nanocasting Route for Synthesis of Highly Ordered Mesoporous Graphitic Carbon and Its Application in CO2 Adsorption

    NASA Astrophysics Data System (ADS)

    Wang, Yangang; Bai, Xia; Wang, Fei; Qin, Hengfei; Yin, Chaochuang; Kang, Shifei; Li, Xi; Zuo, Yuanhui; Cui, Lifeng

    2016-05-01

    Highly ordered mesoporous graphitic carbon was synthesized from a simple surfactant-assisted nanocasting route, in which ordered mesoporous silica SBA-15 maintaining its triblock copolymer surfactant was used as a hard template and natural soybean oil (SBO) as a carbon precursor. The hydrophobic domain of the surfactant assisted SBO in infiltration into the template’s mesoporous channels. After the silica template was carbonized and removed, a higher yield of highly-ordered graphitic mesoporous carbon with rod-like morphology was obtained. Because of the improved structural ordering, the mesoporous carbon after amine modification could adsorb more CO2 compared with the amine-functionalized carbon prepared without the assistance of surfactant.

  15. Surfactant-assisted Nanocasting Route for Synthesis of Highly Ordered Mesoporous Graphitic Carbon and Its Application in CO2 Adsorption

    PubMed Central

    Wang, Yangang; Bai, Xia; Wang, Fei; Qin, Hengfei; Yin, Chaochuang; Kang, Shifei; Li, Xi; Zuo, Yuanhui; Cui, Lifeng

    2016-01-01

    Highly ordered mesoporous graphitic carbon was synthesized from a simple surfactant-assisted nanocasting route, in which ordered mesoporous silica SBA-15 maintaining its triblock copolymer surfactant was used as a hard template and natural soybean oil (SBO) as a carbon precursor. The hydrophobic domain of the surfactant assisted SBO in infiltration into the template’s mesoporous channels. After the silica template was carbonized and removed, a higher yield of highly-ordered graphitic mesoporous carbon with rod-like morphology was obtained. Because of the improved structural ordering, the mesoporous carbon after amine modification could adsorb more CO2 compared with the amine-functionalized carbon prepared without the assistance of surfactant. PMID:27220563

  16. Dicationic alkylammonium bromide gemini surfactants. Membrane perturbation and skin irritation.

    PubMed

    Almeida, João A S; Faneca, Henrique; Carvalho, Rui A; Marques, Eduardo F; Pais, Alberto A C C

    2011-01-01

    Dicationic alkylammonium bromide gemini surfactants represent a class of amphiphiles potentially effective as skin permeation enhancers. However, only a limited number of studies has been dedicated to the evaluation of the respective cytotoxicity, and none directed to skin irritation endpoints. Supported on a cell viability study, the cytotoxicity of gemini surfactants of variable tail and spacer length was assessed. For this purpose, keratinocyte cells from human skin (NCTC 2544 cell line), frequently used as a model for skin irritation, were employed. The impact of the different gemini surfactants on the permeability and morphology of model vesicles was additionally investigated by measuring the leakage of calcein fluorescent dye and analyzing the NMR spectra of ³¹P, respectively. Detail on the interaction of gemini molecules with model membranes was also provided by a systematic differential scanning calorimetry (DSC) and molecular dynamics (MD) simulation. An irreversible impact on the viability of the NCTC 2544 cell line was observed for gemini concentrations higher than 25 mM, while no cytotoxicity was found for any of the surfactants in a concentration range up to 10 mM. A higher cytotoxicity was also found for gemini surfactants presenting longer spacer and shorter tails. The same trend was obtained in the calorimetric and permeability studies, with the gemini of longest spacer promoting the highest degree of membrane destabilization. Additional structural and dynamical characterization of the various systems, obtained by ³¹P NMR and MD, provide some insight on the relationship between the architecture of gemini surfactants and the respective perturbation mechanism.

  17. Dicationic Alkylammonium Bromide Gemini Surfactants. Membrane Perturbation and Skin Irritation

    PubMed Central

    Almeida, João A. S.; Faneca, Henrique; Carvalho, Rui A.; Marques, Eduardo F.; Pais, Alberto A. C. C.

    2011-01-01

    Dicationic alkylammonium bromide gemini surfactants represent a class of amphiphiles potentially effective as skin permeation enhancers. However, only a limited number of studies has been dedicated to the evaluation of the respective cytotoxicity, and none directed to skin irritation endpoints. Supported on a cell viability study, the cytotoxicity of gemini surfactants of variable tail and spacer length was assessed. For this purpose, keratinocyte cells from human skin (NCTC 2544 cell line), frequently used as a model for skin irritation, were employed. The impact of the different gemini surfactants on the permeability and morphology of model vesicles was additionally investigated by measuring the leakage of calcein fluorescent dye and analyzing the NMR spectra of 31P, respectively. Detail on the interaction of gemini molecules with model membranes was also provided by a systematic differential scanning calorimetry (DSC) and molecular dynamics (MD) simulation. An irreversible impact on the viability of the NCTC 2544 cell line was observed for gemini concentrations higher than 25 mM, while no cytotoxicity was found for any of the surfactants in a concentration range up to 10 mM. A higher cytotoxicity was also found for gemini surfactants presenting longer spacer and shorter tails. The same trend was obtained in the calorimetric and permeability studies, with the gemini of longest spacer promoting the highest degree of membrane destabilization. Additional structural and dynamical characterization of the various systems, obtained by 31P NMR and MD, provide some insight on the relationship between the architecture of gemini surfactants and the respective perturbation mechanism. PMID:22102870

  18. Protein-nanoparticle interactions evaluation by immunomethods: Surfactants can disturb quantitative determinations.

    PubMed

    Fornaguera, Cristina; Calderó, Gabriela; Solans, Conxita; Vauthier, Christine

    2015-08-01

    The adsorption of proteins on nanoparticle surface is one of the first events that occur when nanoparticles enter in the blood stream, which influences nanoparticles lifetime and further biodistribution. Albumin, which is the most abundant protein in serum and which has been deeply characterized, is an interesting model protein to investigate nanoparticle-protein interactions. Therefore, the interaction of nanoparticles with serum albumin has been widely studied. Immunomethods were suggested for the investigation of adsorption isotherms because of their ease to quantify the non-adsorbed bovine serum albumin without the need of applying separation methods that could modify the balance between the adsorbed and non-adsorbed proteins. The present work revealed that this method should be applied with caution. Artifacts in the determination of free protein can be generated by the presence of surfactants such as polysorbate 80, widely used in the pharmaceutical and biomedical field, that are needed to preserve the stability of nanoparticle dispersions. It was shown that the presence of traces of polysorbate 80 in the dispersion leads to an overestimation of the amount of bovine serum albumin remaining free in the dispersion medium when determined by both radial immunodiffusion and rocket immunoelectrophoresis. However, traces of poloxamer 188 did not result in clear perturbed migrations. These methods are not appropriate to perform adsorption isotherms of proteins on nanoparticle dispersions containing traces of remaining free surfactant. They should only be applied on dispersions that are free of surfactant that is not associated with nanoparticles.

  19. Comparison of positional surfactant isomers for displacement of rubisco protein from the air-water interface.

    PubMed

    He, Lizhong; Onaizi, Sagheer A; Dimitrijev-Dwyer, Mirjana; Malcolm, Andrew S; Shen, Hsin-Hui; Dong, Chuchuan; Holt, Stephen A; Thomas, Robert K; Middelberg, Anton P J

    2011-08-15

    Protein-surfactant interaction, which is a function of the protein and surfactant characteristics, is a common phenomenon in a wide range of industrial applications. In this work, we used rubisco, the most abundant protein in nature, as a model protein and sodium dodecylbenzenesulfonate (SDOBS), one of the most widely used commercial surfactants, with two positional isomers (SDOBS-2 and SDOBS-6), as a model surfactant. We first examined the surface tension and the mechanical properties of interfacial mixed rubisco-SDOBS films adsorbed at the air-water interface. The concentration of rubisco in solution was fixed at 0.1 mg mL(-1) while the SDOBS concentration varied from 0 to 150 μM. Both the surface tension and the mechanical strength of the interfacial film decreased with increasing SDOBS concentration. Overall, the surface tension of a rubisco-SDOBS-6 mixture is lower than that of rubisco-SDOBS-2, while the mechanical strength of both systems is similar. Neutron reflection data suggest that rubisco protein is likely denatured at the interface. The populations of rubisco and SDOBS of the mixed systems at the interface were determined by combining non-deuterated and deuterated SDOBS to provide contrast variation. At a low surfactant concentration, SDOBS-6 has a stronger ability to displace rubisco from the air-water interface than SDOBS-2. However, when surfactant concentration reaches 50 μM, SDOBS-2 has a higher population than SDOBS-6, with more rubisco displaced from the interface. The results presented in this work suggest that the extent of protein displacement from the air-water interface, and hence the nature of the protein-surfactant interactions at the interface, are strongly affected by the position of surfactant isomerisation, which might allow the design of formulations for efficient removal of protein stains.

  20. Extra adsorption and adsorbate superlattice formation in metal-organic frameworks.

    PubMed

    Sung Cho, Hae; Deng, Hexiang; Miyasaka, Keiichi; Dong, Zhiyue; Cho, Minhyung; Neimark, Alexander V; Ku Kang, Jeung; Yaghi, Omar M; Terasaki, Osamu

    2015-11-26

    Metal-organic frameworks (MOFs) have a high internal surface area and widely tunable composition, which make them useful for applications involving adsorption, such as hydrogen, methane or carbon dioxide storage. The selectivity and uptake capacity of the adsorption process are determined by interactions involving the adsorbates and their porous host materials. But, although the interactions of adsorbate molecules with the internal MOF surface and also amongst themselves within individual pores have been extensively studied, adsorbate-adsorbate interactions across pore walls have not been explored. Here we show that local strain in the MOF, induced by pore filling, can give rise to collective and long-range adsorbate-adsorbate interactions and the formation of adsorbate superlattices that extend beyond an original MOF unit cell. Specifically, we use in situ small-angle X-ray scattering to track and map the distribution and ordering of adsorbate molecules in five members of the mesoporous MOF-74 series along entire adsorption-desorption isotherms. We find in all cases that the capillary condensation that fills the pores gives rise to the formation of 'extra adsorption domains'-that is, domains spanning several neighbouring pores, which have a higher adsorbate density than non-domain pores. In the case of one MOF, IRMOF-74-V-hex, these domains form a superlattice structure that is difficult to reconcile with the prevailing view of pore-filling as a stochastic process. The visualization of the adsorption process provided by our data, with clear evidence for initial adsorbate aggregation in distinct domains and ordering before an even distribution is finally reached, should help to improve our understanding of this process and may thereby improve our ability to exploit it practically.

  1. Extra adsorption and adsorbate superlattice formation in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Sung Cho, Hae; Deng, Hexiang; Miyasaka, Keiichi; Dong, Zhiyue; Cho, Minhyung; Neimark, Alexander V.; Ku Kang, Jeung; Yaghi, Omar M.; Terasaki, Osamu

    2015-11-01

    Metal-organic frameworks (MOFs) have a high internal surface area and widely tunable composition, which make them useful for applications involving adsorption, such as hydrogen, methane or carbon dioxide storage. The selectivity and uptake capacity of the adsorption process are determined by interactions involving the adsorbates and their porous host materials. But, although the interactions of adsorbate molecules with the internal MOF surface and also amongst themselves within individual pores have been extensively studied, adsorbate-adsorbate interactions across pore walls have not been explored. Here we show that local strain in the MOF, induced by pore filling, can give rise to collective and long-range adsorbate-adsorbate interactions and the formation of adsorbate superlattices that extend beyond an original MOF unit cell. Specifically, we use in situ small-angle X-ray scattering to track and map the distribution and ordering of adsorbate molecules in five members of the mesoporous MOF-74 series along entire adsorption-desorption isotherms. We find in all cases that the capillary condensation that fills the pores gives rise to the formation of ‘extra adsorption domains’—that is, domains spanning several neighbouring pores, which have a higher adsorbate density than non-domain pores. In the case of one MOF, IRMOF-74-V-hex, these domains form a superlattice structure that is difficult to reconcile with the prevailing view of pore-filling as a stochastic process. The visualization of the adsorption process provided by our data, with clear evidence for initial adsorbate aggregation in distinct domains and ordering before an even distribution is finally reached, should help to improve our understanding of this process and may thereby improve our ability to exploit it practically.

  2. Competitive adsorption of monoclonal antibodies and nonionic surfactants at solid hydrophobic surfaces.

    PubMed

    Kapp, Sebastian J; Larsson, Iben; Van De Weert, Marco; Cárdenas, Marité; Jorgensen, Lene

    2015-02-01

    Two monoclonal antibodies from the IgG subclasses one and two were compared in their adsorption behavior with hydrophobic surfaces upon dilution to 10 mg/mL with 0.9% NaCl. These conditions simulate handling of the compounds at hospital pharmacies and surfaces encountered after preparation, such as infusion bags and i.v. lines. Total internal reflection fluorescence and quartz crystal microbalance with dissipation monitoring were used to follow and quantify this. Furthermore, the influence of the nonionic surfactant polysorbate 80 (PS80) on the adsorption process of these two antibodies was investigated. Despite belonging to two different IgG subclasses, both antibodies displayed comparable adsorption behavior. Both antibodies readily adsorbed in the absence of PS80, whereas adsorption was reduced in the presence of 30 mg/L surfactant. The sequence of exposure of the surfactant and protein to the surface was found to have a major influence on the extent of protein adsorption. Although only a fraction of adsorbed protein could be removed by rinsing with 30 mg/L surfactant solution, adsorption was entirely prevented when surfaces were pre-exposed to PS80.

  3. Biomimicry of surfactant protein C.

    PubMed

    Brown, Nathan J; Johansson, Jan; Barron, Annelise E

    2008-10-01

    Since the widespread use of exogenous lung surfactant to treat neonatal respiratory distress syndrome, premature infant survival and respiratory morbidity have dramatically improved. Despite the effectiveness of the animal-derived surfactant preparations, there still remain some concerns and difficulties associated with their use. This has prompted investigation into the creation of synthetic surfactant preparations. However, to date, no clinically used synthetic formulation is as effective as the natural material. This is largely because the previous synthetic formulations lacked analogues of the hydrophobic proteins of the lung surfactant system, SP-B and SP-C, which are critical functional constituents. As a result, recent investigation has turned toward the development of a new generation of synthetic, biomimetic surfactants that contain synthetic phospholipids along with a mimic of the hydrophobic protein portion of lung surfactant. In this Account, we detail our efforts in creating accurate mimics of SP-C for use in a synthetic surfactant replacement therapy. Despite SP-C's seemingly simple structure, the predominantly helical protein is extraordinarily challenging to work with given its extreme hydrophobicity and structural instability, which greatly complicates the creation of an effective SP-C analogue. Drawing inspiration from Nature, two promising biomimetic approaches have led to the creation of rationally designed biopolymers that recapitulate many of SP-C's molecular features. The first approach utilizes detailed SP-C structure-activity relationships and amino acid folding propensities to create a peptide-based analogue, SP-C33. In SP-C33, the problematic and metastable polyvaline helix is replaced with a structurally stable polyleucine helix and includes a well-placed positive charge to prevent aggregation. SP-C33 is structurally stable and eliminates the association propensity of the native protein. The second approach follows the same design

  4. Activity and biophysical inhibition resistance of a novel synthetic lung surfactant containing Super-Mini-B DATK peptide

    PubMed Central

    Notter, Robert H.; Wang, Zhengdong

    2016-01-01

    Background/objectives. This study examines the surface activity, resistance to biophysical inhibition, and pulmonary efficacy of a synthetic lung surfactant containing glycerophospholipids combined with Super Mini-B (S-MB) DATK, a novel and stable molecular mimic of lung surfactant protein (SP)-B. The objective of the work is to test whether S-MB DATK synthetic surfactant has favorable biophysical and physiological activity for future use in treating surfactant deficiency or dysfunction in lung disease or injury. Methods. The structure of S-MB DATK peptide was analyzed by homology modeling and by FTIR spectroscopy. The in vitro surface activity and inhibition resistance of synthetic S-MB DATK surfactant was assessed in the presence and absence of albumin, lysophosphatidylcholine (lyso-PC), and free fatty acids (palmitoleic and oleic acid). Adsorption and dynamic surface tension lowering were measured with a stirred subphase dish apparatus and a pulsating bubble surfactometer (20 cycles/min, 50% area compression, 37 °C). In vivo pulmonary activity of S-MB DATK surfactant was measured in ventilated rabbits with surfactant deficiency/dysfunction induced by repeated lung lavages that resulted in arterial PO2 values <100 mmHg. Results. S-MB DATK surfactant had very high surface activity in all assessments. The preparation adsorbed rapidly to surface pressures of 46–48 mN/m at 37 °C (low equilibrium surface tensions of 22–24 mN/m), and reduced surface tension to <1 mN/m under dynamic compression on the pulsating bubble surfactometer. S-MB DATK surfactant showed a significant ability to resist inhibition by serum albumin, C16:0 lyso-PC, and free fatty acids, but surfactant inhibition was mitigated by increasing surfactant concentration. S-MB DATK synthetic surfactant quickly improved arterial oxygenation and lung compliance after intratracheal instillation to ventilated rabbits with severe surfactant deficiency. Conclusions. S-MB DATK is an active mimic of native SP

  5. A theoretical study of bubble motion in surfactant solutions

    NASA Astrophysics Data System (ADS)

    Wang, Yanping

    1999-08-01

    We examine the effect of surfactants on a spherical gas bubble rising steadily in an infinite fluid at low and order one Reynolds number with order one and larger Peclet numbers. Our mathematical model is based on the Navier-Stokes equations coupled with a convection- diffusion equation together with appropriate interfacial conditions. The nonlinearity of the equations and boundary conditions, and the coupling between hydrodynamics and surfactant transport make the problem very challenging. When a bubble rises in a fluid containing surface-active agents, surfactant adsorbs onto the bubble surface at the leading edge, convects to the trailing edge by the surface flow and desorbs into the bulk along the interface. This adsorption develops a surface concentration gradient on the interface that makes the surface tension at the back end relatively lower than that at the front end, and thus retards the bubble velocity. Because of surfactant impurities unavoidably present in materials, this retardation can cause a problem in materials processing in space and glass processing when bubbles are created during chemical reactions. Thus the study of how to remobilize (remove the surfactant gradient on the surface) the bubble surface becomes necessary. Many studies have been done on this retarding effects of the surfactant on a moving bubble. However, most were focused on the retarding effect due to a trace amount of surfactant, in which case the bubble velocity monotonically decreases as the bulk concentration increases. The question of how to remobilize the bubble surface remains unanswered. In this work, we will show that the bubble velocity can be controlled by remobilizing the bubble interface using the surfactant concentration. This technique not only can be used to maximize the bubble velocity, but also can be used to maximize mass transfer on purifying materials and extracting materials from mixtures. In the first part of the work, we illustrate numerically that the

  6. Activity of alkaline phosphatase adsorbed and grafted on "polydopamine" films.

    PubMed

    Ball, Vincent

    2014-09-01

    The oxidation of dopamine in slightly basic solutions and in the presence of oxygen as an oxidant allows for the deposition of dopamine-eumelanin ("polydopamine") films on almost all kinds of materials allowing for an easy secondary functionalization. Molecules carrying nucleophilic groups like thiols and amines can be easily grafted on those films. Herein we show that alkaline phosphatase (ALP), as a model enzyme, adsorbs to "polydopamine" films and part of the adsorbed enzyme is rapidly desorbed in contact with Tris buffer. However a significant part of the enzyme remains irreversibly adsorbed and keeps some enzymatic activity for at least 2 weeks whereas ALP adsorbed on quartz slides is rapidly and quantitatively deactivated. In addition we estimated the Michaelis constant Km of the enzyme irreversibly bound to the "polydopamine" film. The Michaelis constant, and hence the affinity constant between paranitrophenol phosphate and ALP are almost identical between the enzyme bound on the film and the free enzyme in solution. Complementarily, it was found that "polydopamine" films display some phosphatase like catalytic activity.

  7. Performance of metal-organic framework MIL-101 after surfactant modification in the extraction of endocrine disrupting chemicals from environmental water samples.

    PubMed

    Huang, Zhenzhen; Lee, Hian Kee

    2015-10-01

    The research presented in this paper explored the modification and application of a metal-organic framework, MIL-101, with nonionic surfactant-Triton X-114 in dispersive solid-phase extraction for the preconcentration of four endocrine disrupting chemicals (estrone, 17α-ethynylestradiol, estriol and diethylstilbestrol) from environmental water samples. Triton X-114 molecules could be adsorbed by the hydrophobic surface of the MIL-101 crystals, and thus improved the dispersibility of MIL-101 in aqueous solution by serving as a hydrophilic coating. Cloud point phase separation from Triton X-114 accelerated the separation of extracts from the aqueous matrix. The proposed method combines the favorable attributes of strong adsorption capacity resulting from the porous structure of MIL-101 and self-assembly of Triton X-114 molecules. Post-extraction derivatization using N-methyl-N-(trimethylsilyl)trifluoroacetamide was employed to facilitate the quantitative determination of the extracts by gas chromatography-mass spectrometry. The main factors affecting the preparation of modified MIL-101, and extraction of the analytes, such as the amount of surfactant, the ultrasonic and vortex durations, solution pH and desorption conditions, were investigated in detail. Under the optimized conditions, the present method yielded low limits of detection (0.006-0.023 ng/mL), good linearity from 0.09 to 45 ng/mL (coefficients of determination higher than 0.9980) and acceptable precision (relative standard deviations of 2.2-13%). The surface modified MIL-101 was demonstrated to be effective for the extraction of the selected estrogens from aqueous samples, giving rise to markedly improved extraction performance compared to the unmodified MIL-101.

  8. 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.

  9. Titration of mixed micelles containing a pH-sensitive surfactant and conventional (pH-Insensitive) surfactants: a regular solution theory modeling approach.

    PubMed

    Goldsipe, Arthur; Blankschtein, Daniel

    2006-11-21

    We present a thermodynamic theory to model the hydrogen-ion titration of mixed micelles containing a pH-sensitive surfactant and any number of conventional (pH-insensitive) surfactants. In particular, a simple expression is derived for the pKm, a parameter analogous to the pKa of simple acids, which describes the deprotonation equilibrium of the micellized pH-sensitive surfactant. The pseudophase approximation and regular solution theory (RST) are used to relate the pKm to (1) the pKa of the surfactant monomers, (2) the critical micelle concentrations (cmc's) of the protonated and deprotonated forms of the pH-sensitive surfactant, (3) the composition of the mixed micelle, and (4) parameters characterizing pairwise interactions between the surfactant molecules in the mixed micelle. Micellar titrations can be used to determine the magnitude of these interaction parameters. Conversely, knowledge of the cmc's and the interaction parameters allows the prediction of the pKm, which can then be used to calculate the micelle composition and surface charge as a function of solution pH. In addition, we have found that, in the context of RST, multicomponent surfactant mixtures are equivalent to a binary surfactant mixture of the pH-sensitive surfactant and a single effective surfactant whose interactions with the pH-sensitive surfactant are an average of those in the multicomponent surfactant mixture. We also discuss the experimental uncertainty in the pKm measurements. To account for the increased uncertainty in the pKm data at extreme micelle compositions, a weighted regression is proposed for the analysis of experimental titration data characterized by widely varying uncertainties. The theory presented here is validated using micellar titration data from the literature for several pH-sensitive surfactants in solutions containing 0.1 M salt. In most cases, the parameters extracted from an analysis of the titration data agree with the cmc and interaction parameters obtained

  10. Determination of the critical micelle concentration in simulations of surfactant systems

    SciTech Connect

    Santos, Andrew P.; Panagiotopoulos, Athanassios Z.

    2016-01-28

    Alternative methods for determining the critical micelle concentration (cmc) are investigated using canonical and grand canonical Monte Carlo simulations of a lattice surfactant model. A common measure of the cmc is the “free” (unassociated) surfactant concentration in the presence of micellar aggregates. Many prior simulations of micellizing systems have observed a decrease in the free surfactant concentration with overall surfactant loading for both ionic and nonionic surfactants, contrary to theoretical expectations from mass-action models of aggregation. In the present study, we investigate a simple lattice nonionic surfactant model in implicit solvent, for which highly reproducible simulations are possible in both the canonical (NVT) and grand canonical (μVT) ensembles. We confirm the previously observed decrease of free surfactant concentration at higher overall loadings and propose an algorithm for the precise calculation of the excluded volume and effective concentration of unassociated surfactant molecules in the accessible volume of the solution. We find that the cmc can be obtained by correcting the free surfactant concentration for volume exclusion effects resulting from the presence of micellar aggregates. We also develop an improved method for determination of the cmc based on the maximum in curvature for the osmotic pressure curve determined from μVT simulations. Excellent agreement in cmc and other micellar properties between NVT and μVT simulations of different system sizes is observed. The methodological developments in this work are broadly applicable to simulations of aggregating systems using any type of surfactant model (atomistic/coarse grained) or solvent description (explicit/implicit)

  11. Adsorption of Polyoxyethylenic Nonionic and Anionic Surfactants from Aqueous Solution: Effects Induced by the Addition of NaCl and CaCl2.

    PubMed

    Nevskaia; Guerrero-Ruíz; de D López-González J

    1998-09-01

    The adsorption processes of two different types of surfactant from aqueous solutions have been studied on several solids. The adsorbates used were a nonionic (TX-100) and a series of anionic (NP4S, NP10S, and NP25S) oxyethylenic surfactants. As adsorbent, five nonporous solids, including three quartz (QA, QB, and QC), a kaolin, and a dolomite, were chosen for this study, since these types of materials are frequently found in oil reservoirs. Great differences have been found in the adsorption plateaus, depending on the nature of the surfactant (anionic or nonionic). The influence of the presence of NaCl and CaCl2 in the solutions has been also studied. NaCl affects the adsorption of anionic surfactants on quartz and kaolin samples in a similar way. When this salt is added, the amount of anionic surfactants adsorbed on the solid surfaces increases. Some differences in the adsorption of the TX-100 surfactant, depending on the nature of the surface and the type of salt added, have been detected. Basically, three different adsorption behaviors have been found when NaCl is added. The amounts of TX-100 adsorbed decrease when NaCl is added to the solution on the QA sample; the amounts increase on the QB and kaolin samples; no alteration is observed on QC and dolomite samples. Changes in adsorption isotherms, depending on whether NaCl or CaCl2 is added, have also been observed. For the same five adsorbents, zeta potential measurements also have been carried out. When the nonionic TX-100 surfactant is adsorbed, a decrease in the negative values of the zeta potential takes place. However, for the adsorption of anionic surfactants, an increase in the negative values of the zeta potential is detected. The surface charge has been also determined by potentiometric titration (in presence and in absence of TX-100), and a decrease in surface charge when TX-100 is adsorbed on the sample surfaces has been detected. Copyright 1998 Academic Press.

  12. Distribution of metal and adsorbed guest species in zeolites

    SciTech Connect

    Chmelka, B.F.

    1989-12-01

    Because of their high internal surface areas and molecular-size cavity dimensions, zeolites are used widely as catalysts, shape- selective supports, or adsorbents in a variety of important chemical processes. For metal-catalyzed reactions, active metal species must be dispersed to sites within the zeolite pores that are accessible to diffusing reactant molecules. The distribution of the metal, together with transport and adsorption of reactant molecules in zeolite powders, are crucial to ultimate catalyst performance. The nature of the metal or adsorbed guest distribution is known, however, to be dramatically dependent upon preparatory conditions. Our objective is to understand, at the molecular level, how preparatory treatments influence the distribution of guest species in zeolites, in order that macroscopic adsorption and reaction properties of these materials may be better understood. The sensitivity of xenon to its adsorption environment makes {sup 129}Xe NMR spectroscopy an important diagnostic probe of metal clustering and adsorbate distribution processes in zeolites. The utility of {sup 129}Xe NMR depends on the mobility of the xenon atoms within the zeolite-guest system, together with the length scale of the sample heterogeneity being studied. In large pore zeolites containing dispersed guest species, such as Pt--NaY, {sup 129}Xe NMR is insensitive to fine structural details at room temperature.

  13. Surfactant therapy and spontaneous diuresis.

    PubMed

    Bhat, R; John, E; Diaz-Blanco, J; Ortega, R; Fornell, L; Vidyasagar, D

    1989-03-01

    The effect of artificial surfactant therapy on renal function and the onset of spontaneous diuresis was prospectively evaluated in 19 infants with hyaline membrane disease in a double-blind, controlled study. Twelve infants were in the surfactant group; seven infants received placebo (0.9% saline solution). There was no difference in the time of onset of spontaneous diuresis (as defined by output greater than or equal to 80% of intake). The glomerular filtration rate, determined by endogenous creatinine clearance, was also similar in the surfactant- and placebo-treated infants during the first 3 days of life. The fractional excretion of sodium was significantly higher in the placebo group at 24 hours and 36 hours. Infants in the placebo group had a higher negative sodium balance than those in the surfactant group. Ventilatory status improved significantly soon after surfactant treatment, as evidenced by improvement in the alveolar/arterial oxygen pressure ratio and by a lower mean airway pressure. These data suggest that ventilatory status can be improved without diuresis; the factors that regulate diuresis are multiple and not fully understood.

  14. Perfluorobutane sulfonic acid hydration and interactions with O2 adsorbed on Pt3.

    PubMed

    Yan, Liuming; Balbuena, Perla B; Seminario, Jorge M

    2006-04-06

    The side chain of NAFION, a proton conductive membrane used as electrolyte in low-temperature fuel cells, is modeled with perfluorobutane sulfonic acid. Density functional theory is used to characterize structures and energetics of hydration of the model system interacting with a proton solvated with up to 24 water molecules and analyze interactions of some of these hydrated complexes with O(2) adsorbed on Pt(3). It is found that at least three water molecules are needed to ionize the sulfonic acid, and higher degrees of hydration induce the formation of cages where the water molecules are held together via complex hydrogen-bond networks. The interaction between the complex formed by the ionized acid and the hydrated proton, in contact with a bridge-adsorbed O(2)-Pt(3), promotes the protonation of the adsorbed O(2). Upon protonation, the O(2)-Pt(3) system evolves from hydrophobic to hydrophilic behavior, which may facilitate further interfacial contact.

  15. Three stage multilayer formation kinetics during adsorption of an anionic fluorinated surfactant onto germanium: solution pH and salt effects.

    PubMed

    Xing, Rong; Rankin, Stephen E

    2013-07-01

    The effects of solution pH, salt type and its concentration on the adsorption kinetics and the structural evolution of an anionic fluorinated surfactant, tetraethylammonium perfluorooctylsulfonate (TEA-FOS), at the hydroxylated Ge/aqueous solution interface are investigated by using Fourier transform infrared spectroscopy in attenuated total reflection mode (ATR-FTIR). The surface excess, the adsorption rate, the durations of three-stage adsorption and the molecular orientation of adsorbed TEA-FOS are all dependent on the pH of the solution. Consistent with the expected effects of solution pH on surface charge of the germanium oxide crystal surface, the most surfactant adsorbs at acidic pH 3.4 although a considerable amount still adsorbs at pH 10.0. Linear dichroism measurements suggest that the adsorbed surfactants prefer to form less-curved (flattened) multilayer admicelles, which pack more closely on the solid surface as the solution pH decreases. Under both acidic (pH 3.4) and basic (pH 10.0) conditions, the equilibrium surface excess first passes through a maximum as NaCl concentration increases, followed by a decrease. This suggests that excessive NaCl concentration is not favorable for multilayer formation due to increased electrostatic shielding which reduces the ion-pairing ability between TEA(+) and FOS(-). In addition, infrared dichroism measurements of CF2 stretching show that salt type and its concentration influence the structural evolution of adsorbed surfactants. A moderate amount of NaCl favors the assembly of adsorbed micelles into ordered flattened aggregates, but an excess of NaCl makes adsorbed surfactants assemble randomly like spherical aggregates. Compared to Na(+) and K(+) ions, Ca(2+) ions cause the adsorbed surfactants to pack more closely on the solid surface into flattened micellar aggregates. All of the effects of solution pH and salt can be rationalized based on Coulombic interactions between the substrate surface, surfactants and

  16. Direct measurement of adsorbed gas redistribution in metal-organic frameworks.

    PubMed

    Chen, Ying-Pin; Liu, Yangyang; Liu, Dahuan; Bosch, Mathieu; Zhou, Hong-Cai

    2015-03-04

    Knowledge about the interactions between gas molecules and adsorption sites is essential to customize metal-organic frameworks (MOFs) as adsorbents. The dynamic interactions occurring during adsorption/desorption working cycles with several states are especially complicated. Even so, the gas dynamics based upon experimental observations and the distribution of guest molecules under various conditions in MOFs have not been extensively studied yet. In this work, a direct time-resolved diffraction structure envelope (TRDSE) method using sequential measurements by in situ synchrotron powder X-ray diffraction has been developed to monitor several gas dynamic processes taking place in MOFs: infusion, desorption, and gas redistribution upon temperature change. The electron density maps indicate that gas molecules prefer to redistribute over heterogeneous types of sites rather than to exclusively occupy the primary binding sites. We found that the gas molecules are entropically driven from open metal sites to larger neighboring spaces during the gas infusion period, matching the localized-to-mobile mechanism. In addition, the partitioning ratio of molecules adsorbed at each site varies with different temperatures, as opposed to an invariant distribution mode. Equally important, the gas adsorption in MOFs is intensely influenced by the gas-gas interactions, which might induce more molecules to be accommodated in an orderly compact arrangement. This sequential TRDSE method is generally applicable to most crystalline adsorbents, yielding information on distribution ratios of adsorbates at each type of site.

  17. Direct Measurement of Adsorbed Gas Redistribution in Metal–Organic Frameworks

    SciTech Connect

    Chen, Ying-Pin; Liu, Yangyang; Liu, Dahuan; Bosch, Mathieu; Zhou, Hong-Cai

    2015-03-04

    Knowledge about the interactions between gas molecules and adsorption sites is essential to customize metal-organic frameworks (MOFs) as adsorbents. The dynamic interactions occurring during adsorption/desorption working cycles with several states are especially complicated. Even so, the gas dynamics based upon experimental observations and the distribution of guest molecules under various conditions in MOFs have not been extensively studied yet. In this work, a direct time-resolved diffraction structure envelope (TRDSE) method using sequential measurements by in situ synchrotron powder X-ray diffraction has been developed to monitor several gas dynamic processes taking place in MOFs: infusion, desorption, and gas redistribution upon temperature change. The electron density maps indicate that gas molecules prefer to redistribute over heterogeneous types of sites rather than to exclusively occupy the primary binding sites. We found that the gas molecules are entropically driven from open metal sites to larger neighboring spaces during the gas infusion period, matching the localized-to-mobile mechanism. In addition, the partitioning ratio of molecules adsorbed at each site varies with different temperatures, as opposed to an invariant distribution mode. Equally important, the gas adsorption in MOFs is intensely influenced by the gas–gas interactions, which might induce more molecules to be accommodated in an orderly compact arrangement. This sequential TRDSE method is generally applicable to most crystalline adsorbents, yielding information on distribution ratios of adsorbates at each type of site.

  18. Wettability of polytetrafluoroethylene by aqueous solutions of two anionic surfactant mixtures.

    PubMed

    Zdziennicka, Anna; Jańczuk, Bronisław; Wójcik, Wiesław

    2003-12-01

    Advancing contact angle (theta) measurements were carried out on mixtures of aqueous solutions of sodium dodecyl sulfate (SDDS) and sodium hexadecyl sulfonate (SHDSs) on polytetrafluoroethylene (PTFE). The obtained results indicate that there were only small contact angle changes over the range of surfactant concentrations in the solution, corresponding to the unsaturated surfactant layer at the aqueous solution-air interface. However, when saturation of the surfactant layer was achieved a considerable decrease in the contact angle (increase in costheta) as a function of concentration was observed. The dependence of costheta on the monomer mole fraction of SHDSs in the mixture of the surfactants (alpha) for aqueous solutions of mixtures at concentrations corresponding to the critical micelle concentration (CMC) had a maximum at alpha=0.2. From the results of these measurements and application of the Gibbs and Young equations the ratio of the excess concentration of surfactants at the solid-aqueous solution interface to the excess of their concentration at the aqueous solution-air interface was calculated. On the basis of the measurements and calculations it was found that there was a straight linear relationship between the adhesion tension and surface tension of aqueous solutions of surfactant mixtures at a given alpha, and that the slope of the obtained straight lines was equal to -1, which suggests that the surface excess of the surfactant concentrations at the PTFE-solution interface is the same as that at the solution-air interface for a given bulk concentration of the surfactant mixtures. The dependence of the surface concentration excess at the PTFE-solution interface on the monomer mole fraction of SHDSs in the mixture of the surfactants for the concentration region of the mixture of aqueous solutions, corresponding to a saturated monolayer, had a maximum at alpha=0.4, probably resulting from increased degree of binding between adsorbed surface-active ions

  19. Biodegradability and aquatic toxicity of quaternary ammonium-based gemini surfactants: Effect of the spacer on their ecological properties.

    PubMed

    Garcia, M Teresa; Kaczerewska, Olga; Ribosa, Isabel; Brycki, Bogumił; Materna, Paulina; Drgas, Małgorzata

    2016-07-01

    Aerobic biodegradability and aquatic toxicity of five types of quaternary ammonium-based gemini surfactants have been examined. The effect of the spacer structure and the head group polarity on the ecological properties of a series of dimeric dodecyl ammonium surfactants has been investigated. Standard tests for ready biodegradability assessment (OECD 310) were conducted for C12 alkyl chain gemini surfactants containing oxygen, nitrogen or a benzene ring in the spacer linkage and/or a hydroxyethyl group attached to the nitrogen atom of the head groups. According to the results obtained, the gemini surfactants examined cannot be considered as readily biodegradable compounds. The negligible biotransformation of the gemini surfactants under the standard biodegradation test conditions was found to be due to their toxic effects on the microbial population responsible for aerobic biodegradation. Aquatic toxicity of gemini surfactants was evaluated against Daphnia magna. The acute toxicity values to Daphnia magna, IC50 at 48 h exposure, ranged from 0.6 to 1 mg/L. On the basis of these values, the gemini surfactants tested should be classified as toxic or very toxic to the aquatic environment. However, the dimeric quaternary ammonium-based surfactants examined result to be less toxic than their corresponding monomeric analogs. Nevertheless the aquatic toxicity of these gemini surfactants can be reduced by increasing the molecule hydrophilicity by adding a heteroatom to the spacer or a hydroxyethyl group to the polar head groups.

  20. Phospholipid bilayer-perturbing properties underlying lysis induced by pH-sensitive cationic lysine-based surfactants in biomembranes.

    PubMed

    Nogueira, Daniele Rubert; Mitjans, Montserrat; Busquets, M Antonia; Pérez, Lourdes; Vinardell, M Pilar

    2012-08-14

    Amino acid-based surfactants constitute an important class of natural surface-active biomolecules with an unpredictable number of industrial applications. To gain a better mechanistic understanding of surfactant-induced membrane destabilization, we assessed the phospholipid bilayer-perturbing properties of new cationic lysine-based surfactants. We used erythrocytes as biomembrane models to study the hemolytic activity of surfactants and their effects on cells' osmotic resistance and morphology, as well as on membrane fluidity and membrane protein profile with varying pH. The antihemolytic capacity of amphiphiles correlated negatively with the length of the alkyl chain. Anisotropy measurements showed that the pH-sensitive surfactants, with the positive charge on the α-amino group of lysine, significantly increased membrane fluidity at acidic conditions. SDS-PAGE analysis revealed that surfactants induced significant degradation of membrane proteins in hypo-osmotic medium and at pH 5.4. By scanning electron microscopy examinations, we corroborated the interaction of surfactants with lipid bilayer. We found that varying the surfactant chemical structure is a way to modulate the positioning of the molecule inside bilayer and, thus, the overall effect on the membrane. Our work showed that pH-sensitive lysine-based surfactants significantly disturb the lipid bilayer of biomembranes especially at acidic conditions, which suggests that these compounds are promising as a new class of multifunctional bioactive excipients for active intracellular drug delivery.

  1. Sand sorption process for the removal of sodium dodecyl sulfate (anionic surfactant) from water.

    PubMed

    Khan, M Nasiruddin; Zareen, Uzma

    2006-05-20

    Granite sand was used to adsorb anionic surfactant, sodium dodecyl sulfate (SDS) from water at natural pH 6.25. The effect of adsorbent size, pH, temperature and amount of adsorbent has been examined. The results indicate that the Langmuir model provides the best correlation of experimental data. Thermodynamic parameters like entropy, enthalpy and free energy of adsorption were evaluated. Decreasing the temperature accelerates the adsorption of SDS onto sand surface. The kinetic data were analyzed by using pseudo-first order Lagergren equation. Adsorption of SDS was exothermic and dominated by physisorption with activation energy (Ea) 33.65 kJ mol(-1). In addition, regeneration of granite sand by washing with Fenton likes reagent was examined. The results suggested that granite sand is suitable as a sorbent material for recovery and adsorption of SDS from aqueous solutions in view of its effectiveness and cheaper cost.

  2. Synthesis of carbohydrate-based surfactants

    DOEpatents

    Pemberton, Jeanne E.; Polt, Robin L.; Maier, Raina M.

    2016-11-22

    The present invention provides carbohydrate-based surfactants and methods for producing the same. Methods for producing carbohydrate-based surfactants include using a glycosylation promoter to link a carbohydrate or its derivative to a hydrophobic compound.

  3. Preparations of organobentonite using nonionic surfactants.

    PubMed

    Shen, Y H

    2001-08-01

    Due to hydrophilic environment at its surface, natural bentonite is an ineffective sorbent for nonpolar nonionic organic compounds in water even though it has high surface area. The surface properties of natural bentonite can be greatly modified by simple ion-exchange reactions with large organic cations (cationic surfactants) and this organobentonite is highly effective in removing nonionic organic compounds from water. Cationic surfactant derived organobentonites have been investigated extensively for a wide variety of environmental applications. In this study, the preparation of organobentonite using nonionic surfactants has been investigated for the first time. Results indicate that nonionic surfactants intercalates into the interlamellar space of bentonite and may demonstrate higher sorption capacity than cationic surfactant. It is possible to create large interlayer spacing and high organic carbon content organobentonite by use of nonionic surfactants with suitable balance between the hydrocarbon and ethylene oxide chain lengths. In addition, nonionic surfactant derived organobentonites are more chemically stable than cationic surfactant derived organobentonites.

  4. Surfactant recovery from water using foam fractionation

    SciTech Connect

    Tharapiwattananon, N.; Osuwan, S.; Scamehorn, J.F.

    1996-05-01

    The purpose of this study was to investigate the use of foam fractionation to recover surfactant from water. A simple continuous mode foam fractionation was used and three surfactants were studied (two anionic and one cationic). The effects of air flow rate, foam height, liquid height, liquid feed surfactant concentration, and sparger porosity were studied. This technique was shown to be effective in either surfactant recovery or the reduction of surfactant concentration in water to acceptable levels. As an example of the effectiveness of this technique, the cetylpyridinium chloride concentration in water can be reduced by 90% in one stage with a liquid residence time of 375 minutes. The surfactant concentration in the collapsed foam is 21.5 times the feed concentration. This cationic surfactant was easier to remove from water by foam fractionation than the anionic surfactants studied.

  5. Investigation on interaction of DNA and several cationic surfactants with different head groups by spectroscopy, gel electrophoresis and viscosity technologies.

    PubMed

    Guo, Qing; Zhang, Zhaohong; Song, Youtao; Liu, Shuo; Gao, Wei; Qiao, Heng; Guo, Lili; Wang, Jun

    2017-02-01

    In this study, the interaction between DNA and several cationic surfactants with different head groups such as ethyl hexadecyl dimethyl ammonium bromide (EHDAB), hexadecyl dimethyl benzyl ammonium chloride (HDBAC), and cetyl pyridinium bromide (CPB) were investigated by UV-vis absorption, fluorescence and circular dichroism (CD) spectroscopy, gel electrophoresis, and viscosity technologies. The results show that these cationic surfactants can interact with DNA and major binding modes are electrostatic and hydrophobic. Also, CPB and HDBAC molecules interact with DNA by partial intercalation, and CPB has slightly stronger intercalation than HDBAC, while EHDAB interacts with DNA by non-intercalation. The different head groups of the surfactant molecules can influence the interaction strength. CPB has the stronger interaction with DNA than the others. Moreover, surfactant concentration, the ratio of DNA and fluorescence probe, ionic strength can influence the interaction. The surfactants may interact with DNA by the competition reactions with BR for DNA-BR. The increase of ionic strength may favor the surface binding between DNA and surfactants to some extent. This work provides deep mechanistic insight on the toxicity of cationic surfactants with different head groups to DNA molecules.

  6. 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.

  7. Biofoams and natural protein surfactants

    PubMed Central

    Cooper, Alan; Kennedy, Malcolm W.

    2010-01-01

    Naturally occurring foam constituent and surfactant proteins with intriguing structures and functions are now being identified from a variety of biological sources. The ranaspumins from tropical frog foam nests comprise a range of proteins with a mixture of surfactant, carbohydrate binding and antimicrobial activities that together provide a stable, biocompatible, protective foam environment for developing eggs and embryos. Ranasmurfin, a blue protein from a different species of frog, displays a novel structure with a unique chromophoric crosslink. Latherin, primarily from horse sweat, but with similarities to salivary, oral and upper respiratory tract proteins, illustrates several potential roles for surfactant proteins in mammalian systems. These proteins, together with the previously discovered hydrophobins of fungi, throw new light on biomolecular processes at air–water and other interfaces. This review provides a perspective on these recent findings, focussing on structure and biophysical properties. PMID:20615601

  8. Stability of purple membranes from Halobacterium salinarum toward surfactants: inkjet printing of a retinal protein.

    PubMed

    Imhof, Martin; Pudewills, Jens; Rhinow, Daniel; Chizhik, Ivan; Hampp, Norbert

    2012-08-16

    Inkjet printing is a versatile technique widely applied in biological microarray technology. Because of its photochemical and photophysical properties, bacteriorhodopsin (BR) from Halobacterium salinarum holds promise for applications in nanotechnology, and inkjet printing would simplify the transfer of BR to suitable substrates. Surfactants are essential parts of inkjet formulations tuning viscosity, rheology, and spreading behavior of the solution. However, many surfactants destabilize the structure of proteins and often cause denaturation accompanied by a complete loss of function. Inkjet printing of membrane proteins is particularly challenging and special care must be taken in the choice of the surfactant. For BR, the situation is complicated by the fact that the structural integrity of BR depends on its native membrane environment, the so-called purple membrane (PM). PM contains 10 lipid molecules per BR monomer and is very sensitive toward surfactants. In this work, we identified surfactants suitable for inkjet formulations containing PM. Initially, we screened a variety of technically relevant surfactants for compatibility with PM using the UV-vis absorption of the retinal chromophore as a natural probe. Promising candidates were selected, and their impact on the structure of PM and BR was analyzed using UV-vis spectroscopy, CD spectroscopy, and small-angle X-ray scattering (SAXS). We identified two surfactants compatible with PM and suitable for inkjet formulations. An inkjet formulation containing PM as dye component was developed. We demonstrate that the photochromic properties of BR are maintained upon inkjet printing.

  9. Highly efficient hyperbranched CNT surfactants: influence of molar mass and functionalization.

    PubMed

    Bertels, Ellen; Bruyninckx, Kevin; Kurttepeli, Mert; Smet, Mario; Bals, Sara; Goderis, Bart

    2014-10-21

    End-group-functionalized hyperbranched polymers were synthesized to act as a carbon nanotube (CNT) surfactant in aqueous solutions. Variation of the percentage of triphenylmethyl (trityl) functionalization and of the molar mass of the hyperbranched polyglycerol (PG) core resulted in the highest measured surfactant efficiency for a 5000 g/mol PG with 5.6% of the available hydroxyl end-groups replaced by trityl functions, as shown by UV-vis measurements. Semiempirical model calculations suggest an even higher efficiency for PG5000 with 2.5% functionalization and maximal molecule specific efficiency in general at low degrees of functionalization. Addition of trityl groups increases the surfactant-nanotube interactions in comparison to unfunctionalized PG because of π-π stacking interactions. However, at higher functionalization degrees mutual interactions between trityl groups come into play, decreasing the surfactant efficiency, while lack of water solubility becomes an issue at very high functionalization degrees. Low molar mass surfactants are less efficient compared to higher molar mass species most likely because the higher bulkiness of the latter allows for a better CNT separation and stabilization. The most efficient surfactant studied allowed dispersing 2.85 mg of CNT in 20 mL with as little as 1 mg of surfactant. These dispersions, remaining stable for at least 2 months, were mainly composed of individual CNTs as revealed by electron microscopy.

  10. Influence of nonionic surfactants on the potentiometric response of hydrogen ion-selective polymeric membrane electrodes.

    PubMed

    Espadas-Torre, C; Bakker, E; Barker, S; Meyerhoff, M E

    1996-05-01

    The influence of poly(ethylene oxide)-based nonionic surfactants (i.e., Triton X-100 and Brij 35) in the sample phase on the response properties of hydrogen ion-selective polymeric membrane electrodes containing mobile (lipophilic amines) or covalently bound (aminated-poly-(vinyl chloride)) hydrogen ion carriers is reported. In the presence of these nonionic surfactants, membrane electrode response toward interfering cation activity (e.g., Na+) in the sample phase is increased substantially and the pH measuring range shortened. The degree of cation interference for pH measurements is shown to correlate with the basicity of the hydrogen ion carrier doped within the membrane phase. The observed deterioration in selectivity arises from the partitioning of the surfactant into the membrane and concomitant extraction of metal cations by the surfactants in the organic phase. The effect of nonionic surfactants on pH electrodes prepared with aminated-PVC membranes is shown to be more complex, with additional large shifts in EMF values apparently arising from multidentate interactions between the surfactant molecules and the polymeric amine in the membrane, leading to a change in the apparent pKa values for the amine sites. The effects induced by nonionic surfactants on the EMF response function of hydrogen ion-selective polymeric membrane electrodes are modeled, and experimental results are shown to correlate well with theoretical predictions.

  11. Investigation of the electrokinetic properties of paraffin suspension. 2. In cationic and anionic surfactant solutions.

    PubMed

    Chibowski, Emil; Wiacek, Agnieszka; Holysz, Lucyna; Terpilowski, Konrad

    2005-08-16

    Electrical phenomena at nonionogenic hydrophobic surfaces (solid or liquid) in water, electrolyte, and/or surfactant solutions still attract research. In part 1 of this paper we described the electrokinetic behavior of paraffin wax suspension in water and electrolyte solutions (NaCl or LaCl3). On the basis of the latest data of water structure near hydrophobic surfaces it was concluded that immobilized water dipoles at the interface can play an essential role in the zeta potential formation. In this paper were investigated the zeta potentials of paraffin wax in cationic surfactants cetyltrimethylammonium bromide, C16H33(CH3)3NBr, and octadecyltrimethylammonium chloride, C18H37(CH3)3NCl, and anionic surfactant sodium dodecyl sulfate, C12H25SO4Na. Also changes in wettability of the paraffin surface due to the surfactant's adsorption were studied via wetting contact angle measurements and calculation of the surface free energy. It was concluded that at a low surfactant concentration (10(-6) M) the water dipole structure still contributes to the zeta potential, but at a higher one the zeta potential is determined by the surfactant molecules' adsorption. A special role of OH- ions is also clearly seen. Moreover, a functional relationship was found between the surface free energy of the surfactant-covered paraffin surface and the zeta potential.

  12. Monte Carlo lattice models for adsorbed polymer conformation

    NASA Technical Reports Server (NTRS)

    Good, B. S.

    1985-01-01

    The adhesion between a polymer film and a metal surface is of great technological interest. However, the prediction of adhesion and wear properties of polymer coated metals is quite difficult because a fundamental understanding of the polymer surface interaction does not yet exist. A computer model for the conformation of a polymer molecule adsorbed on a surface is discussed. The chain conformation is assumed to be described by a partially directed random walk on a three dimensional simple cubic lattice. An attractive surface potential is incorporated into the model through the use of a random walk step probability distribution that is anisotropic in the direction normal to the attractive surface. The effects of variations in potential characteristics are qualitatively included by varying both the degree of anisotropy of the step distribution and the range of the anisotropy. Polymer conformation is characterized by the average end to end distance, average radius of gyration, and average number of chain segments adsorbed on the surface.

  13. Allantoin as a solid phase adsorbent for removing endotoxins.

    PubMed

    Vagenende, Vincent; Ching, Tim-Jang; Chua, Rui-Jing; Gagnon, Pete

    2013-10-04

    In this study we present a simple and robust method for removing endotoxins from protein solutions by using crystals of the small-molecule compound 2,5-dioxo-4-imidazolidinyl urea (allantoin) as a solid phase adsorbent. Allantoin crystalline powder is added to a protein solution at supersaturated concentrations, endotoxins bind and undissolved allantoin crystals with bound endotoxins are removed by filtration or centrifugation. This method removes an average of 99.98% endotoxin for 20 test proteins. The average protein recovery is ∼80%. Endotoxin binding is largely independent of pH, conductivity, reducing agent and various organic solvents. This is consistent with a hydrogen-bond based binding mechanism. Allantoin does not affect protein activity and stability, and the use of allantoin as a solid phase adsorbent provides better endotoxin removal than anion exchange, polymixin affinity and biological affinity methods for endotoxin clearance.

  14. Molecule nanoweaver

    DOEpatents

    Gerald, II; Rex E.; Klingler, Robert J.; Rathke, Jerome W.; Diaz, Rocio; Vukovic, Lela

    2009-03-10

    A method, apparatus, and system for constructing uniform macroscopic films with tailored geometric assemblies of molecules on the nanometer scale. The method, apparatus, and system include providing starting molecules of selected character, applying one or more force fields to the molecules to cause them to order and condense with NMR spectra and images being used to monitor progress in creating the desired geometrical assembly and functionality of molecules that comprise the films.

  15. Adsorption of a cationic surfactant by a magsorbent based on magnetic alginate beads.

    PubMed

    Obeid, Layaly; El Kolli, Nadia; Dali, Noëlle; Talbot, Delphine; Abramson, Sébastien; Welschbillig, Mathias; Cabuil, Valérie; Bée, Agnès

    2014-10-15

    Adsorption of cetylpyridinium chloride (CPC), a cationic surfactant, by magnetic alginate beads (MagAlgbeads) was investigated. The magnetic adsorbent (called magsorbent) was prepared by encapsulation of magnetic functionalized nanoparticles in an alginate gel. The influence on CPC adsorption of several parameters such as contact time, pH and initial surfactant concentration was studied. The equilibrium isotherm shows that adsorption occurs through both electrostatic interactions with charge neutralization of the carboxylate groups of the beads and hydrophobic interactions inducing the formation of surfactant aggregates in the beads. The dosage of calcium ions released in the solution turns out to be a useful tool for understanding the adsorption mechanisms. Adsorption is accompanied by a shrinking of the beads that corresponds to a 45% reduction of the volume. Adsorption kinetic experiments show that equilibrium time is strongly dependent on the surfactant concentration, which monitors the nature of the interactions. On the other hand, since the pH affects the ionization state of adsorption sites, adsorption depends on the pH solution, maximum adsorption being obtained in a large pH range (3.2-12) in agreement with the pKa value of alginate (pKa=3.4-4.2). Finally, due to the formation of micelle-like surfactants aggregates in the magnetic alginate beads, they could be used as a new efficient magsorbent for hydrophobic pollutants.

  16. Dendritic saccharide surfactant polymers as antifouling interface materials to reduce platelet adhesion.

    PubMed

    Zhu, Junmin; Marchant, Roger E

    2006-04-01

    Here, we report on the synthesis of dendritic saccharide surfactant polymers as antifouling interface materials to reduce platelet adhesion. An acetal-protected poly(amidoamine) (PAMAM) dendron (5, G = 2) was first synthesized by using aminoacetaldehyde dimethyl acetal (1) as the starting material to provide a monovalent focal structure with dimethyl acetal-protected aldehyde functionality. Maltose dendron (M4, 6) was obtained by reacting the peripheral amine groups of acetal-dendron (5) with maltonolactone. The dendritic surfactant polymers (9) were then synthesized via a two-step method by sequential addition of maltose dendron and hexanal to react with the amine groups on the poly(vinylamine) (PVAm) backbone. Surface activity of the amphiphilic glycopolymers at the air/water interface was demonstrated by reduction in water surface tension. Adsorption of the amphiphilic glycopolymers at the solid/water interface was examined on octadecyltrichlorosilane (OTS)-coated coverslips by water contact angle measurements. A nanoscale understanding of surface-induced self-assembly of the dendritic surfactant polymer on highly oriented pyrolytic graphite (HOPG) was gained using AFM operated in fluid tapping mode. A lateral ordering of adsorbing surfactant polymer was visualized with a pattern in strands 60 degrees out of alignment. The static platelet adhesion tests show that the hexyl side chains can facilitate adsorption of the surfactant polymers onto hydrophobic substrates, while the maltose dendron side chains can provide a dense canopy of protective glycocalyx-like layer as an antifouling interface to reduce platelet adhesion.

  17. Fiber coating with surfactant solutions

    NASA Astrophysics Data System (ADS)

    Shen, Amy Q.; Gleason, Blake; McKinley, Gareth H.; Stone, Howard A.

    2002-11-01

    When a fiber is withdrawn at low speeds from a pure fluid, the variation in the thickness of the entrained film with imposed fiber velocity is well-predicted by the Landau-Levich-Derjaguin (LLD) equation. However, surfactant additives are known to alter this response. We study the film thickening properties of the protein BSA (bovine serum albumin), the nonionic surfactant Triton X-100, and the anionic surfactant SDS (sodium dodecyl sulfate). For each of these additives, the film thickening factor alpha (the ratio of the measured thickness to the LLD prediction) for a fixed fiber radius varies as a function of the ratio of the surfactant concentration c to the critical micelle concentration (CMC). In the case of BSA, which does not form micelles, the reference value is the concentration at which multilayers form. As a result of Marangoni effects, alpha reaches a maximum as c approaches the CMC from below. However, when the surfactant concentration c exceeds the CMC, the behavior of alpha varies as a consequence of the dynamic surface properties, owing for example to different sorption kinetics of these additives, or possibly surface or bulk rheological effects. For SDS, alpha begins to decrease when c exceeds the CMC and causes the surface to become partially or completely remobilized, which is consistent with the experimental and theoretical results published for studies of slug flows of bubbles and surfactant solutions in a capillary tube and the rise of bubbles in surfactant solutions. However, when the SDS or Triton X-100 surfactant concentration is well above the CMC, we observe that the film thickening parameter alpha increases once again. In the case of SDS we observe a second maximum in the film thickening factor. For all the experiments, transport of monomers to the interface is limited by diffusion and the second maximum in the film thickening factor may be explained as a result of a nonmonotonic change in the stability characteristics of suspended SDS

  18. [Determination of contact angle of pharmaceutical excipients and regulating effect of surfactants on their wettability].

    PubMed

    Hua, Dong-dong; Li, He-ran; Yang, Bai-xue; Song, Li-na; Liu, Tiao-tiao; Cong, Yu-tang; Li, San-ming

    2015-10-01

    To study the effects of surfactants on wettability of excipients, the contact angles of six types of surfactants on the surface of two common excipients and mixture of three surfactants with excipients were measured using hypsometry method. The results demonstrated that contact angle of water on the surface of excipients was associated with hydrophilcity of excipients. Contact angle was lowered with increase in hydrophilic groups of excipient molecules. The sequence of contact angle from small to large was starch < sodium benzoate < polyvinylpyrrolidone < sodium carboxymethylcellulose < sodium alginate < chitosan < hydroxypropyl methyl cellulose surfactants both in droplets and mixed in excipients significantly reduced the contact angle of excipients, and their abilities to lower contact angle varied. The results of the present study offer a guideline in the formulation design of tablets.

  19. Behavior of P85 and P188 Poloxamer Molecules: Computer Simulations Using United Atom Force Field.

    SciTech Connect

    Goliaei, Ardeshir; Lau, Edmond Y.; Adhikari, Upendra; Schwegler, Eric; Berkowitz, Max L.

    2016-05-27

    To study the interaction between poloxamer molecules and lipid bilayers using molecular dynamics simulation technique with the united atom resolution, we augmented the GROMOS force field to include poloxamers. We validated the force field by calculating the radii of gyration of two poloxamers, P85 and P188, solvated in water and by considering the poloxamer density distributions at the air/water interface. The emphasis of our simulations was on the study of the interaction between poloxamers and lipid bilayer. At the water/lipid bilayer interface, we observed that both poloxamers studied, P85 and P188, behaved like surfactants: the hydrophilic blocks of poloxamers became adsorbed at the polar interface, while their hydrophobic block penetrated the interface into the aliphatic tail region of the lipid bilayer. We also observed that when P85 and P188 poloxamers interacted with damaged membranes that contained pores, the hydrophobic blocks of copolymers penetrated into the membrane in the vicinity of the pore and compressed the membrane. Lastly, due to this compression, water molecules were evacuated from the pore.

  20. Behavior of P85 and P188 Poloxamer Molecules: Computer Simulations Using United Atom Force Field.

    DOE PAGES

    Goliaei, Ardeshir; Lau, Edmond Y.; Adhikari, Upendra; ...

    2016-05-27

    To study the interaction between poloxamer molecules and lipid bilayers using molecular dynamics simulation technique with the united atom resolution, we augmented the GROMOS force field to include poloxamers. We validated the force field by calculating the radii of gyration of two poloxamers, P85 and P188, solvated in water and by considering the poloxamer density distributions at the air/water interface. The emphasis of our simulations was on the study of the interaction between poloxamers and lipid bilayer. At the water/lipid bilayer interface, we observed that both poloxamers studied, P85 and P188, behaved like surfactants: the hydrophilic blocks of poloxamers becamemore » adsorbed at the polar interface, while their hydrophobic block penetrated the interface into the aliphatic tail region of the lipid bilayer. We also observed that when P85 and P188 poloxamers interacted with damaged membranes that contained pores, the hydrophobic blocks of copolymers penetrated into the membrane in the vicinity of the pore and compressed the membrane. Lastly, due to this compression, water molecules were evacuated from the pore.« less

  1. SURFACTANT ENHANCED AQUIFER REMEDIATION WITH SURFACTANT REGENERATION/REUSE

    EPA Science Inventory

    A demonstration of surfactant-enhanced aquifer remediation was conducted during the spring of 1999 at Marine Corps Base, Camp LeJeune, NC. A PCE-DNAPL zone was identified and delineated by extensive soil sampling in 1997, and was further characteized by a partitioning interwell t...

  2. Phospholipid surfactant adsorption by respirable quartz and in vitro expression of cytotoxicity and DNA damage.

    PubMed

    Liu, X; Keane, M J; Harrison, J C; Cilento, E V; Ong, T; Wallace, W E

    1998-08-01

    Respirable-sized quartz was treated with a saline dispersion of dipalmitoyl phosphatidylcholine (DPPC), a primary component of pulmonary surfactant, to model the adsorption of phospholipid surfactant onto quartz dust following particle deposition in the bronchoalveolar region of the lung. Control and surfactant-treated dusts were used to challenge lavaged rat pulmonary macrophages in vitro over a 1-week period, to determine the effects of adsorbed surfactant on the expression of quartz cytotoxicity and genotoxicity. DNA damage was determined by the single cell gel electrophoresis 'comet' assay. Untreated quartz induced DNA damage, increasing with dose and with time of incubation of dust with macrophages over a 5 day period. DPPC treatment of quartz suppressed DNA damage through 1 day of macrophage challenge. DNA damage then increased over a 5 day period, to approximately half the positive control (untreated quartz) values. Cytotoxicity was measured by trypan blue dye exclusion and by the Live-Dead fluorescence assay for cell viability. Cytotoxicity of surfactant-treated quartz measured one day after challenge of lavaged macrophages was suppressed to values near those of the negative controls, and then increased over a 1 week incubation period to levels near those expressed by native quartz positive controls. Quartz similarly treated with dioleoyl phosphatidylcholine mixed with DPPC substituted in one acyl group with a boron-containing fluorescent chromophore was used with confocal microscopy to measure particle-associated fluorescent surfactant in cells. Approximately half of the fluorescence intensity was lost over a 1 week period following challenge of lavaged macrophage. Results are discussed in terms of a model of restoration of quartz particle surface toxicity as prophylactic surfactant is removed from particle surface by cellular enzymatic digestion processes.

  3. Solution Properties of Dissymmetric Sulfonate-type Anionic Gemini Surfactants.

    PubMed

    Yoshimura, Tomokazu; Akiba, Kazuki

    2016-01-01

    Dissymmetric and symmetric anionic gemini surfactants, N-alkyl-N'-alkyl-N,N'dipropanesulfonylethylenediamine (CmCnSul, where m and n represent alkyl chain lengths of m-n = 4-16, 6-14, 8-12, 10-10, and 12-12), were synthesized by two- or three-step reactions. Their physicochemical properties were characterized by equilibrium surface tension measurements, steady-state fluorescence spectroscopy of pyrene, and dynamic light scattering. The critical micelle concentration (CMC) of the dissymmetric surfactants C4C16Sul, C6C14Sul, and C8C12Sul was slightly lower than that of the symmetric surfactant C10C10Sul. The occupied area per molecule (A) of C8C12Sul was smaller than that of C10C10Sul, indicating that C8C12Sul has a high surface activity. However, the increase in the degree of dissymmetry from C8C12Sul to C6C14Sul and then to C4C16Sul resulted in high surface tension and large A. Based on the surface tension, the standard free energies of micellization (∆G°mic) and adsorption (∆G°ads), the efficiency of surface adsorption (pC20), and the effectiveness of surface adsorption (CMC/C20) were obtained. These parameters suggested that C8C12Sul formed micelles more readily than the other surfactants. The properties determined from the surface tension indicated that C8C12Sul's ability is intermediate between those of C10C10Sul and C12C12Sul. The pyrene fluorescence and dynamic light scattering results revealed that the micelle size depends on the longer of the two alkyl chains in dissymmetric surfactants.

  4. The interaction of photo-responsive surfactants with biological macromolecules

    NASA Astrophysics Data System (ADS)

    Mazwi, Khiza L.

    The interaction of photo-responsive surfactants with proteins has been considered as a means to exert reversible control over a number of aspects of protein structure and function. The azobenzene trimethylammonium bromide (azoTAB) family of cationic surfactants undergo a photo-reversible cis to trans isomerization upon exposure to light of the appropriate wavelength. The trans form of the molecule has a lower dipole moment across its azo linkage, and is more hydrophobic than the cis isomer. This results in a higher binding affinity with proteins for the trans isomer, inducing a greater degree of unfolding of tertiary and secondary structures. The surfactant has been applied to the study of the amyloid fibrillation pathway in insulin, in which the protein self-associates into long, insoluble, rod-like structures. The fibrillation rate in insulin is enhanced in the presence of the trans- isomer while the formation of fibrils is largely inhibited in the presence of the cis- isomer, where amorphous aggregates are observed instead. Additionally early fibrillar species formed in the trans-azoTAB assays exhibit a greater tendency to lateral aggregation than do structures in the pure protein, resulting in a more truncated, bundled final aggregate morphology. Use of the surfactants as a means to control protein quaternary solution structure has also been explored in the subunit dissociation of tetrameric catalase. In the presence of azoTAB surfactants, catalase dissociates first into a super-active dimer, then at higher concentrations into an aggregation prone monomer. Finally, the structural changes associated with azoTAB-induced unfolding of the two domain protein papain are tracked. The denaturation pathway involves a progressive loss in secondary structure with increasing azoTAB concentration, along with a relaxation of the compact tertiary structure, and a spatial separation of the two domains. A number of complementary experimental techniques are combined to determine

  5. Photocontrolled adsorption of polyelectrolyte molecules on a silicon substrate.

    PubMed

    Malyar, Ivan V; Gorin, Dmitry A; Santer, Svetlana; Stetsyura, Svetlana V

    2013-12-31

    We report on a change in the properties of monomolecular films of polyelectrolyte molecules, induced by illuminating the silicon substrate on which they adsorb. It was found that under illumination the thickness of the adsorbed layer decreases by at least 27% and at the same time the roughness is significantly reduced in comparison to a layer adsorbed without irradiation. Furthermore, the homogeneity of the film topography and the surface potential is shown to be improved by illumination. The effect is explained by a change in surface charge density under irradiation of n- and p-type silicon wafers. The altered charge density in turn induces conformational changes of the adsorbing polyelectrolyte molecules. Their photocontrolled adsorption opens new possibilities for selective manipulation of adsorbed films. This possibility is of potential importance for many applications such as the production of well-defined coatings in biosensors or microelectronics.

  6. 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.

  7. Photoexcitation of adsorbates on metal surfaces: One-step or three-step

    SciTech Connect

    Petek, Hrvoje

    2012-09-07

    In this essay we discuss the light-matter interactions at molecule-covered metal surfaces that initiate surface photochemistry. The hot-electron mechanism for surface photochemistry, whereby the absorption of light by a metal surface creates an electron-hole pair, and the hot electron scatters through an unoccupied resonance of adsorbate to initiate nuclear dynamics leading to photochemistry, has become widely accepted. Yet, ultrafast spectroscopic measurements of molecule-surface electronic structure and photoexcitation dynamics provide scant support for the hot electron mechanism. Instead, in most cases the adsorbate resonances are excited through photoinduced substrate-to-adsorbate charge transfer. Based on recent studies of the role of coherence in adsorbate photoexcitation, as measured by the optical phase and momentum resolved two-photon photoemission measurements, we examine critically the hot electron mechanism, and propose an alternative description based on direct charge transfer of electrons from the substrate to adsorbate. The advantage of this more quantum mechanically rigorous description is that it informs how material properties of the substrate and adsorbate, as well as their interaction, influence the frequency dependent probability of photoexcitation and ultimately how light can be used to probe and control surface femtochemistry.

  8. On the orientational effects in monolayers of diatomic molecules

    NASA Astrophysics Data System (ADS)

    Patrykiejew, A.; Sałamacha, A.; Sokołowski, S.; Zientarski, T.; Binder, K.

    2001-09-01

    The Monte Carlo simulation method is used to study orientational ordering in monolayer films of diatomic molecules on the (100) plane of face centered cubic crystal. Systems of admolecules with different elongation are studied and their orientational and positional ordering discussed. It is shown that in the case of small elongations the adsorbed monolayer orders into a simple (1×1) structure. When the elongation of adsorbed molecules increases, the film orders into more complex structures. In such cases, the adsorbate lattice decomposes into four interpenetrating sublattices.

  9. Polymer gels with associating side chains and their interaction with surfactants

    NASA Astrophysics Data System (ADS)

    Gordievskaya, Yulia D.; Rumyantsev, Artem M.; Kramarenko, Elena Yu.

    2016-05-01

    Conformational behaviour of hydrophobically modified (HM) polymer gels in solutions of nonionic surfactants is studied theoretically. A HM gel contains hydrophobic side chains (stickers) grafted to its subchains. Hydrophobic stickers are capable to aggregate into joint micelles with surfactant molecules. Micelles containing more than one sticker serve as additional physical cross-links of the network, and their formation causes gel shrinking. In the proposed theoretical model, the interior of the gel/surfactant complex is treated as an array of densely packed spherical polymer brushes consisting of gel subchains tethered to the surface of the spherical sticker/surfactant micelles. Effect of stickers length and grafting density, surfactant concentration and hydrophobicity on gel swelling as well as on hydrophobic association inside it is analyzed. It is shown that increasing surfactant concentration can result in a gel collapse, which is caused by surfactant-induced hydrophobic aggregation of stickers, and a successive gel reswelling. The latter should be attributed to a growing fraction of surfactants in joint aggregates and, hence, increasing number of micelles containing only one sticker and not participating in gel physical cross-linking. In polyelectrolyte (PE) gels hydrophobic aggregation is opposed by osmotic pressure of mobile counterions, so that at some critical ionization degree hydrophobic association is completely suppressed. Hydrophobic modification of polymers is shown to open new ways for controlling gel responsiveness. In particular, it is discussed that incorporation of photosensitive groups into gel subchains and/or surfactant tail could give a possibility to vary the gel volume by light. Since hydrophobic aggregation regularities in gels and solutions are common, we hope our findings will be useful for design of polymer based self-healing materials as well.

  10. Surfactant-laden soft contact lenses for extended delivery of ophthalmic drugs.

    PubMed

    Kapoor, Yash; Thomas, Justin C; Tan, Grace; John, Vijay T; Chauhan, Anuj

    2009-02-01

    Eye drops are inefficient means of delivering ophthalmic drugs because of limited bioavailability and these can cause significant side effects due to systemic uptake of the drug. The bioavailability for ophthalmic drugs can be increased significantly by using contact lenses. This study focuses on the development of surfactant-laden poly-hydroxy ethyl methacrylate (p-HEMA) contact lenses that can release Cyclosporine A (CyA) at a controlled rate for extended periods of time. We focus on various Brij surfactants to investigate the effects of chain length and the presence of an unsaturated group on the drug release dynamics and partitioning inside the surfactant domains inside the gel. The gels were imaged by cryogenic scanning electron microscopy (cryo-SEM) to obtain direct evidence of the presence of surfactant aggregates in the gel, and to investigate the detailed microstructure for different surfactants. The images show a distribution of nano pores inside the surfactant-laden hydrogels which we speculate are regions of surfactant aggregates, possibly vesicles that have a high affinity for the hydrophobic drug molecule. The gels are further characterized by studying their mechanical and physical properties such as transparency, surface contact angle and equilibrium water content to determine their suitability as extended wear contact lenses. Results show that Brij surfactant-laden p-HEMA gels provide extended release of CyA, and possess suitable mechanical and optical properties for contact lens applications. The gels are not as effective for extended release of two other hydrophobic ophthalmic drugs, dexamethasone (DMS) and dexamethasone 21 acetate (DMSA) because of insufficient partitioning inside the surfactant aggregates.

  11. Turning bubbles on and off during boiling using charged surfactants

    NASA Astrophysics Data System (ADS)

    Cho, H. Jeremy; Mizerak, Jordan P.; Wang, Evelyn N.

    2015-10-01

    Boiling--a process that has powered industries since the steam age--is governed by bubble formation. State-of-the-art boiling surfaces often increase bubble nucleation via roughness and/or wettability modification to increase performance. However, without active in situ control of bubbles, temperature or steam generation cannot be adjusted for a given heat input. Here we report the ability to turn bubbles `on and off' independent of heat input during boiling both temporally and spatially via molecular manipulation of the boiling surface. As a result, we can rapidly and reversibly alter heat transfer performance up to an order of magnitude. Our experiments show that this active control is achieved by electrostatically adsorbing and desorbing charged surfactants to alter the wettability of the surface, thereby affecting nucleation. This approach can improve performance and flexibility in existing boiling technologies as well as enable emerging or unprecedented energy applications.

  12. Turning bubbles on and off during boiling using charged surfactants

    PubMed Central

    Cho, H. Jeremy; Mizerak, Jordan P.; Wang, Evelyn N.

    2015-01-01

    Boiling—a process that has powered industries since the steam age—is governed by bubble formation. State-of-the-art boiling surfaces often increase bubble nucleation via roughness and/or wettability modification to increase performance. However, without active in situ control of bubbles, temperature or steam generation cannot be adjusted for a given heat input. Here we report the ability to turn bubbles ‘on and off' independent of heat input during boiling both temporally and spatially via molecular manipulation of the boiling surface. As a result, we can rapidly and reversibly alter heat transfer performance up to an order of magnitude. Our experiments show that this active control is achieved by electrostatically adsorbing and desorbing charged surfactants to alter the wettability of the surface, thereby affecting nucleation. This approach can improve performance and flexibility in existing boiling technologies as well as enable emerging or unprecedented energy applications. PMID:26486275

  13. Turning bubbles on and off during boiling using charged surfactants.

    PubMed

    Cho, H Jeremy; Mizerak, Jordan P; Wang, Evelyn N

    2015-10-21

    Boiling--a process that has powered industries since the steam age--is governed by bubble formation. State-of-the-art boiling surfaces often increase bubble nucleation via roughness and/or wettability modification to increase performance. However, without active in situ control of bubbles, temperature or steam generation cannot be adjusted for a given heat input. Here we report the ability to turn bubbles 'on and off' independent of heat input during boiling both temporally and spatially via molecular manipulation of the boiling surface. As a result, we can rapidly and reversibly alter heat transfer performance up to an order of magnitude. Our experiments show that this active control is achieved by electrostatically adsorbing and desorbing charged surfactants to alter the wettability of the surface, thereby affecting nucleation. This approach can improve performance and flexibility in existing boiling technologies as well as enable emerging or unprecedented energy applications.

  14. Stabilization of lamellar oil-water liquid crystals by surfactant/ co-surfactant monolayers

    NASA Astrophysics Data System (ADS)

    Braganza, L. F.; Dubois, M.; Tabony, J.

    1989-03-01

    LIQUID crystals are divided into two main classes, thermotropic and lyotropic. Thermotropic liquid crystals are formed by melting, whereas lyotropic liquid crystals arise from the association of molecules, such as soap and water, that in general are not in themselves liquid crystalline. Thermotropic liquid crystals are used for liquid-crystal displays; lyotropic liquid crystals occur in living cells. Here we report a novel sequence of lyotropic liquid crystals comprising alternate layers of oil and water whose thickness varies linearly with the relative proportions of oil and water, and we have determined their structure using neutron diffraction methods. The oil and water layers are separated and stabilized by a monolayer film of surfactant and co-surfactant. The individual layers are typically a hundred ångströms or more in thickness, and total lamellar spacings of up to 1,000 Å were observed. This behaviour is difficult to describe in terms of the theories of colloid stability currently used to describe lyotropic liquid crystals. An understanding of the self-organization of such systems over such large distances would elucidate how long-range liquid-crystalline ordering arises in living cells. Moreover, thermotropic liquid crystals are expensive and chemically relatively unstable, and lamellar mesophases of the lyotopic type described here could lead to inexpensive, chemically stable liquid-crystalline materials suitable for industrial application.

  15. Molecular adsorbates as probes of the local properties of doped graphene

    PubMed Central

    Pham, Van Dong; Joucken, Frédéric; Repain, Vincent; Chacon, Cyril; Bellec, Amandine; Girard, Yann; Rousset, Sylvie; Sporken, Robert; Santos, Maria Cristina dos; Lagoute, Jérôme

    2016-01-01

    Graphene-based sensors are among the most promising of graphene’s applications. The ability to signal the presence of molecular species adsorbed on this atomically thin substrate has been explored from electric measurements to light scattering. Here we show that the adsorbed molecules can be used to sense graphene properties. The interaction of porphyrin molecules with nitrogen-doped graphene has been investigated using scanning tunneling microscopy and ab initio calculations. Molecular manipulation was used to reveal the surface below the adsorbed molecules allowing to achieve an atomic-scale measure of the interaction of molecules with doped graphene. The adsorbate’s frontier electronic states are downshifted in energy as the molecule approaches the doping site, with largest effect when the molecule sits over the nitrogen dopant. Theoretical calculations showed that, due to graphene’s high polarizability, the adsorption of porphyrin induces a charge rearrangement on the substrate similar to the image charges on a metal. This charge polarization is enhanced around nitrogen site, leading to an increased interaction of molecules with their image charges on graphene. Consequently, the molecular states are stabilized and shift to lower energies. These findings reveal the local variation of polarizability induced by nitrogen dopant opening new routes towards the electronic tuning of graphene. PMID:27097555

  16. Inactivation of surfactant in rat lungs.

    PubMed

    Bruni, R; Fan, B R; David-Cu, R; Taeusch, H W; Walther, F J

    1996-02-01

    Although surfactant replacement therapy has dramatically improved the outcome of premature infants with respiratory distress syndrome, approximately 30% of treated infants show a transient or no response. Nonresponse to surfactant replacement therapy may be due to extreme lung immaturity and possibly surfactant inactivation. Surfactant inactivation involves aspecific biophysical events, such as interference with the formation or activity of an alveolar monolayer, and specific interactions with serum proteins, including antibodies, leaking into the alveolar space. As formulations containing surfactant proteins appear to better tolerate serum inactivation, we used an excised rat lung model to compare the susceptibility to serum inactivation of a mixture of synthetic phospholipids selected from surfactant lipid constituents, Exosurf (a protein-free synthetic surfactant), Survanta [containing surfactant proteins B and C (SP-B and -C)], and a porcine surfactant (containing SP-A, -B, and -C). For each of these preparations, we used pressure/volume determinations as an in situ measure of surfactant activity and retested the same preparations after mixing with human serum, a nonspecific surfactant inactivator. Human serum inactivated porcine surfactant to a lesser extent than Survanta, Exosurf, or synthetic phospholipids. Temperature exerted a significant effect on deflation stability, as shown by a greater lung compliance in untreated, normal lungs and a larger improvement in compliance after treating lavaged lungs with synthetic phospholipids at 37 degrees C than at 22 degrees C. We conclude that surfactant containing SP-A, -B, and -C is only moderately susceptible to inactivation with whole serum and may therefore exert a greater clinical response than protein-free surfactants or those containing only SP-B and -C.

  17. The uranium from seawater program at PNNL: Overview of marine testing, adsorbent characterization, adsorbent durability, adsorbent toxicity, and deployment studies

    DOE PAGES

    Gill, Gary A.; Kuo, Li -Jung; Janke, Christopher James; ...

    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

  18. The uranium from seawater program at PNNL: Overview of marine testing, adsorbent characterization, adsorbent durability, adsorbent toxicity, and deployment studies

    SciTech Connect

    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; Wood, Jordana R.; Warner, Marvin G.; Peterson, Sonja; Abrecht, David G.; Mayes, Richard T.; Tsouris, Costas; Oyola, Yatsandra; Strivens, Jonathan E.; Schlafer, Nicholas J.; Addleman, Shane R.; Chouyyok, Wilaiwan; Das, Sadananda; Kim, Jungseung; Buesseler, Ken; Breier, Crystal; D'Alessandro, Evan

    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 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

  19. Effect of exogenous surfactant on the development of surfactant synthesis in premature rabbit lung.

    PubMed

    Amato, Maurizio; Petit, Kevin; Fiore, Humberto H; Doyle, Cynthia A; Frantz, Ivan D; Nielsen, Heber C

    2003-04-01

    Surfactant replacement is an effective therapy for neonatal respiratory distress syndrome. Full recovery from respiratory distress syndrome requires development of endogenous surfactant synthesis and metabolism. The influence of exogenous surfactant on the development of surfactant synthesis in premature lungs is not known. We hypothesized that different exogenous surfactants have different effects on the development of endogenous surfactant production in the premature lung. We treated organ cultures of d 25 fetal rabbit lung for 3 d with 100 mg/kg body weight of natural rabbit surfactant, Survanta, and Exosurf and measured their effects on the development of surfactant synthesis. Additional experiments tested how these surfactants and Curosurf affected surfactant protein (SP) SP-A, SP-B, and SP-C mRNA expression. Surfactant synthesis was measured as the incorporation of 3H-choline and 14C-glycerol into disaturated phosphatidylcholine recovered from lamellar bodies. Randomized-block ANOVA showed significant differences among treatments for incorporation of both labels (p < 0.01), with natural rabbit surfactant less than control, Survanta greater than control, and Exosurf unchanged. Additional experiments with natural rabbit surfactant alone showed no significant effects in doses up to 1000 mg/kg. Survanta stimulated disaturated phosphatidylcholine synthesis (173 +/- 41% of control; p = 0.01), increased total lamellar body disaturated phosphatidylcholine by 22% (p < 0.05), and increased 14C-disat-PC specific activity by 35% (p < 0.05). The response to Survanta was dose-dependent up to 1000 mg/kg. Survanta did not affect surfactant release. No surfactant altered the expression of mRNA for SP-A, SP-B, or SP-C. We conclude that surfactant replacement therapy can enhance the maturation of surfactant synthesis, but this potential benefit differs with different surfactant preparations.

  20. Modeling effects of pH and counterions on surfactant adsorption at the oxide/water interface

    SciTech Connect

    Hankins, N.P.; O`Haver, J.H.; Harwell, J.H.

    1996-09-01

    The adsorption of surfactants on minerals is important in areas such as enhanced oil recovery, surfactant-enhanced soil remediation, formation of organic thin films, ore flotation, wetting, adhesion, detergency, and dispersion stability. A model is presented that describes the effect of pH on the adsorption of an isomerically pure anionic surfactant species at a mineral oxide/water interface. A site-binding model, to account for effects of pH, surface heterogeneities, and counterions, is incorporated into a patchwise, phase-separation modeling approach, making it possible to predict both the surface charge and the counterion association beneath an adsorbed surfactant aggregate. Parameters for the site binding model on {alpha}-alumina are obtained from experimental surface charge measurements. The formation of both local monolayers (hemimicelles) and bilayers (admicelles) is allowed, although the isotherms studied in this paper are fit by parameter values that predict admicelle formation only. The model is able to predict experimental measurements of the adsorption of an isomerically pure, anionic surfactant species on {alpha}-alumina as a function of pH. It reproduces several previously unexplained experimental observations; in particular, it offers an explanation for the observation of significant adsorption of anionic surfactant above the point of zero charge (pzc) of a mineral oxide surface.

  1. BEHAVIOR OF SURFACTANT MIXTURES AT SOLID/LIQUID AND OIL/LIQUID INTERFACES IN CHEMICAL FLOODING SYSTEMS

    SciTech Connect

    Prof. P. Somasundaran

    2002-09-30

    The aim of the project is to develop and evaluate efficient novel surfactant mixtures for enhanced oil recovery. Surfactant loss by adsorption or precipitation depends to a great extent on the type of surfactant complexes and aggregates formed. Such information as well as techniques to generate the information is lacking currently particularly for surfactant mixtures and surfactant/polymer systems. A novel analytical centrifuge application is explored during the last period to generate information on structures-performance relationship for different surfactant aggregates in solution and, in turn, at interfaces. To use analytical untracentrifuge for surfactant mixtures, information on partial specific volumes of single surfactants and their mixtures is required. Towards this purpose, surface tension and density measurements were performed to determine critical micellar concentrations (cmc), partial specific volumes of n-dodecyl-{beta}-Dmaltoside (DM), nonyl phenol ethoxylated decyl ether (NP-10) and their 1:1 mixtures at 25 C. Durchschlag's theoretical calculation method was adopted to calculate the partial specific volumes. Effects of temperature and mixing, as well as methods used for estimation on micellization and partial specific volumes were studied during the current period. Surface tension results revealed no interaction between the two surfactants in mixed micelles. Partial specific volume measurements also indicated no interaction in mixed micelles. Maximum adsorption density, area per molecule and free energy of micellization were also calculated. Partial specific volumes were estimated by two experimental methods: d{sub {rho}}/dc and V{sub {sigma}}. The difference between the results of using the two methods is within 0.5% deviation. It was found that the partial specific volume is concentration dependent and sensitive to changes in temperature. The information generated in this study will be used for the study of surfactant aggregate mass distribution

  2. Complete braided adsorbent for marine testing to demonstrate 3g-U/kg-adsorbent

    SciTech Connect

    Janke, Chris; Yatsandra, Oyola; Mayes, Richard; none,; Gill, Gary; Li-Jung, Kuo; Wood, Jordana; Sadananda, Das

    2014-04-30

    ORNL has manufactured four braided adsorbents that successfully demonstrated uranium adsorption capacities ranging from 3.0-3.6 g-U/kg-adsorbent in marine testing at PNNL. Four new braided and leno woven fabric adsorbents have also been prepared by ORNL and are currently undergoing marine testing at PNNL.

  3. Comparison of modified montmorillonite adsorbents. Part II: The effects of the type of raw clays and modification conditions on the adsorption performance.

    PubMed

    Jiang, Jia-Qian; Zeng, Zhiqiang

    2003-10-01

    This paper builds on the preceding researches to study the effects of the type of clays (montmorillonites K10, KSF) and modifying conditions on the structure and adsorption behavior of resulting clay adsorbents. The raw clays were modified by polymeric Al/Fe species, hexadecyl-trimethylammonium (HDTMA) surfactant and a complex of polymeric Al/Fe-HDTMA. X-ray diffraction spectra was applied to analyze the structure of the raw and modified clays. After modification, the basal spacing of the clays varied, depending on the types of raw clay and modification conditions. Copper and phenol were selected as adsorbates for evaluating the adsorption performance of various clays, which was affected significantly by the types of raw clay and modification conditions. In general the inorganic contaminant (e.g., Cu) tend to be adsorbed by the polymeric Al/Fe modified clay and the organic impurities (e.g., phenol) will be preferably captured by the surfactant modified clay; both due to the specific surface properties resulting from introducing the modifiers. The complex modified clays possessed the ability of adsorbing both inorganic and organic contaminants. In addition, the d 0 0 1 spacing of modified KSF was greater than that of K10; the adsorption performance with modified KSF was thus greater than that with the modified K10. Finally, the ratio of modifiers to the clay (metal:surfactant:clay) has been observed to affect the adsorption performance; the optimal conditions have been defined.

  4. Effect of binding of an oligomeric cationic fluorosurfactant on the dilational rheological properties of gelatin adsorbed at the air-water interface.

    PubMed

    Rao, Ashwin; Kim, Yongsin; Kausch, Charles M; Thomas, Richard R

    2006-09-12

    The effect of binding of an oligomeric cationic fluorooxetane surfactant on the interfacial properties of adsorbed gelatin-fluorooxetane complexes has been studied using dynamic surface tension and dilational rheological measurements. Adsorption kinetics of gelatin-fluorooxetane complexes are reminiscent of a mixed (barrier/diffusion limited) process, while the dilational rheological properties of the interface exhibit a strong dependence on surfactant concentration. At low surfactant concentrations, dilational surface moduli as well as phase angles are relatively insensitive to the presence of the fluorooxetane. However, at the critical aggregation concentration of the polymer-surfactant system, there is a sharp increase in the complex modulus. Further increase in the fluorooxetane concentration does not significantly affect the complex modulus. The phase angle, however, does increase with increasing fluorooxetane concentration due to the transport of bound fluorooxetane from the subsurface to the solution-air interface. These results indicate that, at fluorooxetane concentrations exceeding the critical aggregation concentration, the polymer-surfactant complexes adsorb to form cross-linked multilayers at the solution-air interface.

  5. Making More-Complex Molecules Using Superthermal Atom/Molecule Collisions

    NASA Technical Reports Server (NTRS)

    Shortt, Brian; Chutjian, Ara; Orient, Otto

    2008-01-01

    A method of making more-complex molecules from simpler ones has emerged as a by-product of an experimental study in outer-space atom/surface collision physics. The subject of the study was the formation of CO2 molecules as a result of impingement of O atoms at controlled kinetic energies upon cold surfaces onto which CO molecules had been adsorbed. In this study, the O/CO system served as a laboratory model, not only for the formation of CO2 but also for the formation of other compounds through impingement of rapidly moving atoms upon molecules adsorbed on such cold interstellar surfaces as those of dust grains or comets. By contributing to the formation of increasingly complex molecules, including organic ones, this study and related other studies may eventually contribute to understanding of the origins of life.

  6. Infrared spectral investigations of UV irradiated nucleobases adsorbed on mineral surfaces

    NASA Astrophysics Data System (ADS)

    Brucato, John Robert; Pace, Emanuele; Pucci, Amaranta; Branciamore, Sergio; Cestelli Guidi, Mariangela; Fornaro, Teresa

    The interaction between electromagnetic radiation and bio-molecules in heterogeneous environments is a prebiotically relevant process. Minerals may have a pivotal role in the prebiotic evolution of complex chemical systems, mediating the effects of electromagnetic radiation, influencing the photostability of bio-molecules, catalyzing important chemical reactions and/or protecting molecules against degradation. In particular, nucleobases are relevant bio-molecules to investigate both in the prebiotic context, because they are coding components of nucleic acids, and from the standpoint of the survival of biological systems in space conditions. In this talk, laboratory results on photostability of nucleobases adsorbed on minerals will be presented.

  7. Nanofiltration and Fenton's process over iron shavings for surfactants removal.

    PubMed

    Martins, Rui C; Nunes, Marta; Gando-Ferreira, Licínio M; Quinta-Ferreira, Rosa M

    2014-01-01

    The presence of surfactants in wastewater composition tends to jeopardize the efficiency of the traditional aerobic treatment processes. In this regard, the application of Fenton's reaction and nanofiltration as single processes and integrated (nanofiltration followed by Fenton's process) was investigated on the abatement of a solution containing two surfactants usually found in effluents coming from detergent industry (dodecylbenzene--DDB and sodium lauryl ether sulphate--SLES). The potential of a solid waste (iron shavings) as catalyst in the Fenton's process was evaluated and the reaction system was optimized regarding the key operating parameters (iron and hydrogen peroxide concentration and pH). The highest chemical oxygen demand (COD) degradation (66%) was attained for pH 3, [H2O2] = 32 mM and 50 g/L of iron shavings. Besides, it was concluded that oxidation was due to hydroxyl radicals adsorbed on the metal surface even if bulk interaction between hydrogen peroxide and dissolved iron cannot be neglected. The main variables ruling nanofiltration were evaluated (pH, temperature and cross-flow rate). Eighty-four percent of COD rejection was determined at pH 7.5, cross-flow 14.4 cm3 s(-1), 20 degrees C and 15 bar of pressure drop. Finally, nanofiltration followed by Fenton's process under the best conditions was integrated; however, no significant improvement was attained with 85% of COD being globally removed.

  8. Pulmonary surfactant: hydrophobic nature of the mucosal surface of the human amnion.

    PubMed

    Cotton, D B; Hills, B A

    1984-04-01

    The contact angle has been measured for a drop of saline placed upon the rinsed mucosal surface of the amnion in eleven human placental membranes obtained from normal births at full term. The contact angle averaged 70 degrees, indicating a hydrophobic surface comparable with graphite (86 degrees), polyethylene (94 degrees) or oxyntic tissue (85 degrees) which is also exposed to endogenous surface-active phospholipids in vivo. By comparison, four pre-term placentas with an average gestation period of 29.5 weeks gave a mean contact angle of 32 degrees, indicating that hydrophobicity of the placenta increases with maturity (41 weeks) and might well be imparted by adsorbed surfactants present in amniotic fluid and known to render other surfaces hydrophobic. Since the mucosal epithelium of the amnion is exposed to the same surfactants in the same physical state as the fetal alveolar wall, the above results imply that this surface may also be hydrophobic, as indicated in the adult lung by other studies. The concept of surfactant directly adsorbed to the pulmonary tissue surfaces is discussed in connexion with its possible functional advantages in 'de-watering' the lung at birth, maintaining homeostasis by water repellency , releasing airway surfaces and lymph ducts glued by protein and lubricating tissue respiratory movement.

  9. Interaction of Moringa oleifera seed protein with a mineral surface and the influence of surfactants.

    PubMed

    Kwaambwa, Habauka M; Hellsing, Maja S; Rennie, Adrian R; Barker, Robert

    2015-06-15

    The paper describes the adsorption of purified protein from seeds of Moringa oleifera to a sapphire interface and the effects of addition of the anionic surfactant sodium dodecylsulfate (SDS) and the cationic surfactant hexadecyltrimethylammonium bromide (CTAB). Neutron reflection was used to determine the structure and composition of interfacial layers adsorbed at the solid/solution interface. The maximum surface excess of protein was found to be about 5.3 mg m(-2). The protein does not desorb from the solid/liquid interface when rinsed with water. Addition of SDS increases the reflectivity indicating co-adsorption. It was observed that CTAB is able to remove the protein from the interface. The distinct differences to the behavior observed previously for the protein at the silica/water interface are identified. The adsorption of the protein to alumina in addition to other surfaces has shown why it is an effective flocculating agent for the range of impurities found in water supplies. The ability to tailor different surface layers in combination with various surfactants also offers the potential for adsorbed protein to be used in separation technologies.

  10. Influences of Dilute Organic Adsorbates on the Hydration