共查询到20条相似文献,搜索用时 11 毫秒
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Domínguez H 《The journal of physical chemistry. B》2007,111(16):4054-4059
Molecular dynamics simulations of sodium dodecyl sulfate (SDS) molecules on a graphite surface are presented. The simulations were conducted at low and high surface coverage to study aggregation at the water/graphite interface. Results showed that at low surface coverage, the SDS molecules form hemicylindrical aggregates, in agreement with AFM experiments, whereas at high surface coverage, the surfactants form full cylinders. The latter aggregates have not been reported in systems of SDS on hydrophobic substrates, such as graphite. The unexpected results are explained in terms of a water layer adsorbed at the solid surface which was the responsible for the formation of these aggregates. Moreover, the SDS tails in the full cylindrical configuration became straighter than those of the hemicylindrical aggregate. Hydrogen bond formation between water and surfactant head groups was also studied, and it was found that they did not depend on the surfactant concentration. 相似文献
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Rabinovich YI Vakarelski IU Brown SC Singh PK Moudgil BM 《Journal of colloid and interface science》2004,270(1):29-36
Surfactants are widely used to stabilize colloidal systems in a variety of industrial applications through the formation of self-assembled aggregates at the solid-liquid interface. Previous studies have reported that the control of surfactant-mediated slurry stability can be achieved through the manipulation of surfactant chain length and concentration. However, a fundamental understanding of the mechanical and energetic properties of these aggregates, which may aid in the molecular-level design of these systems, is still lacking. In this study, experimentally measured force/distance curves between an atomic force microscope (AFM) tip and self-assembled surfactant aggregates on mica or silica substrates at concentrations higher than the bulk critical micelle concentration (CMC) were used to determine their mechanical and thermodynamic properties. The experimental curves were fitted to a model which describes the interaction between a hard sphere (tip) and a soft substrate (surfactant structures) based on a modified Hertz theory for the case of a thin elastic layer on a rigid substrate. The calculated mechanical properties were found to be in the same order of magnitude as those reported for rubber-like materials (e.g., polydimethylsiloxane (PDMS)). By integrating the force/distance curves, the energy required for breaking the surface aggregates was also calculated. These values are close to those reported for bulk-micelle formation. 相似文献
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Fully atomistic molecular dynamics simulations of amphiphilic graft copolymer molecules have been performed at a range of surface concentrations at a water/air interface. These simulations are compared to experimental results from a corresponding system over a similar range of surface concentrations. Neutron reflectivity data calculated from the simulation trajectories agrees well with experimentally acquired profiles. In particular, excellent agreement in neutron reflectivity is found for lower surface concentration simulations. A simulation of a poly(ethylene oxide) (PEO) chain in aqueous solution has also been performed. This simulation allows the conformational behavior of the free PEO chain and those tethered to the interface in the previous simulations to be compared. 相似文献
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The dynamics of fluids at solid-liquid interfaces is investigated. In particular, we consider a simple Lennard-Jones fluid as well as a melt of hexadecane chains. For the Lennard-Jones fluid, the numerical results are compared with analytical calculations based on the diffusion equation, which shows that the numerical results can very well by described by the solution of the diffusion equation for reflecting surfaces. The diffusion coefficient is practically independent of the position within the film, although the fluid is inhomogeneous perpendicular to the surface. In contrast, the dynamics of the centers of mass of hexadecane molecules perpendicular to repulsive surfaces is severely slowed down due to their extended and anisotropic nature and cannot be described by a single particle diffusion equation. 相似文献
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The dynamics of water near the polar headgroups of surfactants in a monolayer adsorbed at the air/water interface is likely to play a decisive role in determining the physical behavior of such organized assemblies. We have carried out an atomistic molecular dynamics (MD) simulation of a monolayer of the anionic surfactant sodium bis(2-ethyl-1-hexyl) sulfosuccinate (aerosol-OT or AOT) adsorbed at the air/water interface. The simulation is performed at room temperature with a surface coverage of that at the critical micelle concentration (78 Angstrom(2)/molecule). Detailed analyses of the lifetime dynamics of surfactant-water (SW) and water-water (WW) hydrogen bonds at the interface have been carried out. The nonexponential hydrogen bond lifetime correlation functions have been analyzed by using the formalism of Luzar and Chandler, which allowed identification of the bound states at the interface and quantification of the dynamic equilibrium between bound and quasi-free water molecules, in terms of time-dependent relaxation rates. It is observed that the water molecules present in the first hydration layer form strong hydrogen bonds with the surfactant headgroups and hence have longer lifetimes. Importantly, it is found that the overall relaxation of the SW hydrogen bonds is faster for those water molecules which form two hydrogen bonds with the surfactant headgroups than those forming one such hydrogen bond. Equally interestingly, it is further noticed that water molecules beyond the first hydration layer form weaker hydrogen bonds than pure bulk water. 相似文献
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Understanding surfactant adsorption on surfaces at the molecular level will provide us with the ability to design specific surfactants for surface modification. We conducted molecular dynamics simulations for sodium dodecyl sulfate (SDS) and hexaethylene glycol monododecyl ether (C(12)E(6)) adsorbed on silica substrates with varying degree of hydroxylation. Our results shed light on the effects of hydroxylation on the surfactant aggregate morphology. The discrete charge distribution on the substrate surface appears to dictate both surfactant adsorption and aggregate morphology. The differences in aggregate morphology observed for anionic SDS and non-ionic C(12)E(6) on silica substrates are discussed quantitatively and compared to available experimental data. 相似文献
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《Supramolecular Science》1994,1(2):85-90
We report on atomic force microscopy (AFM) and scanning tunnelling microscopy (STM) studies of the dynamic structure of adsorbate layers at the interface between highly oriented pyrolytic graphite and solutions of a fluorophore with two alkyl chains in phenyloctane. Layers grown above the saturation concentration showed a stable but highly corrugated surface. Below saturation an adsorbate film with a thickness of several molecular layers formed in equilibrium with the solution. The outer layers exhibit a dynamic supramolecular structure consisting of stripes with a spacing of 7 ± 1 nm. The cross-correlation analysis of several sequences of images revealed a characteristic reorganization time for the pattern of tens of seconds. By scanning at elevated forces (> 5 nN) the outer layers could be removed, thus revealing the structure of the first adsorbate layer, namely a stable stripe pattern. STM images of this first layer confirmed this stripe pattern and revealed details of the molecular arrangement at atomic resolution. 相似文献
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Dedinaite A Lundin M Macakova L Auletta T 《Langmuir : the ACS journal of surfaces and colloids》2005,21(21):9502-9509
The adsorption of a biologically important glycoprotein, mucin, and mucin-chitosan complex layer formation on negatively charged surfaces, silica and mica, have been investigated employing ellipsometry, the interferometric surface apparatus, and atomic force microscopy techniques. Particular attention has been paid to the effect of an anionic surfactant sodium, dodecyl sulfate (SDS), with respect to the stability of the adsorption layers. It has been shown that mucin adsorbs on negatively charged surfaces to form highly hydrated layers. Such mucin layers readily associate with surfactants and are easily removed from the surfaces by rinsing with solutions of SDS at concentrations > or =0.2 cmc (1 cmc SDS in 30 mM NaCl is equal to 3.3 mM). The mucin adsorption layer is negatively charged, and we show how a positively charged polyelectrolyte, chitosan, associates with the preadsorbed mucin to form mucin-chitosan complexes that resist desorption by SDS even at SDS concentrations as high as 1 cmc. Thus, a method of mucin layer protection against removal by surfactants is offered. Further, we show how mucin-chitosan multilayers can be formed. 相似文献
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Thomas JL Roeselová M Dang LX Tobias DJ 《The journal of physical chemistry. A》2007,111(16):3091-3098
Molecular dynamics simulations have been used to investigate the behavior of aqueous sodium nitrate in interfacial environments. Polarizable potentials for the water molecules and the nitrate ion in solution were employed. Calculated surface tension data at several concentrations are in good agreement with measured surface tension data. The surface potential of NaNO3 solutions at two concentrations also compare favorably with experimental measurements. Density profiles suggest that NO3- resides primarily below the surface of the solutions over a wide range of concentrations. When the nitrate anions approach the surface of the solution, they are significantly undercoordinated compared to in the bulk, and this may be important for reactions where solvent cage effects play a role such as photochemical processes. Surface water orientation is perturbed by the presence of nitrate ions, and this has implications for experimental studies that probe interfacial water orientation. Nitrate ions near the surface also have a preferred orientation that places the oxygen atoms in the plane of the interface. 相似文献
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Luo M Mazyar OA Zhu Q Vaughn MW Hase WL Dai LL 《Langmuir : the ACS journal of surfaces and colloids》2006,22(14):6385-6390
We have used molecular dynamics simulations to investigate the in situ self-assembly of modified hydrocarbon nanoparticles (mean diameter of 1.2 nm) at a water-trichloroethylene (TCE) interface. The nanoparticles were first distributed randomly in the water phase. The MD simulation shows the in situ formation of nanoparticle clusters and the migration of both single particles and clusters from the water phase to the trichloroethylene phase, possibly due to the hydrophobic nature of the nanoparticles. Eventually, the single nanoparticles or clusters equilibrate at the water-TCE interface, and the surrounding liquid molecules pack randomly when in contact with the nanoparticle surfaces. In addition, the simulations show that the water-TCE interfacial thickness analyzed from density profiles is influenced by the presence of nanoparticles either near or in contact with the interface but is independent of the number of nanoparticles present. The nanoparticles, water molecules, and TCE molecules all exhibit diffusion anisotropy. 相似文献
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Molecular dynamics simulations are utilized to simulate a model liquid-vapor-amphiphile system. Amphiphilic surfactant molecules are modeled as dimers composed of a hydrophilic head and a hydrophobic tail. Three dimer models with three different head sizes and two different head-to-tail size ratios are studied. The surfactant molecules distribute preferentially at the interfaces at low concentrations and form micelles in the bulk liquid phase as the concentration increases. We find that the surface tension decreases as molecular concentration increases, with a reduction in the rate of decrease after micellization occurs. The extent to which a surfactant can reduce the surface tension at a given concentration is found to depend on the head size. Furthermore, the head size and concentration dependence of the surfactant tilt-angle distribution is studied and compared to experimental data. 相似文献
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Brian J. Teppen Ching-Hsing Yu David M. Miller Lothar Schfer 《Journal of computational chemistry》1998,19(2):144-153
The adsorption of trichloroethene, C2HCl3, on clay mineral surfaces in the presence of water has been modeled as an example describing a general program that uses molecular dynamics simulations to study the sorption of organic materials at the clay mineral/aqueous solution interface. Surfaces of the clay minerals kaolinite and pyrophyllite were hydrated at different water levels corresponding to partial and complete monolayers of water. In agreement with experimental trends, water was found to outcompete C2HCl3 for clay surface sites. The simulations suggest that at least three distinct mechanisms coexist for C2HCl3 on clay minerals in the environment. The most stable interaction of C2HCl3 with clay surfaces is by full molecular contact, coplanar with the basal surface. This kind of interaction is suppressed by increasing water loads. A second less stable and more reversible interaction involves adsorption through single-atom contact between one Cl atom and the surface. In a third mechanism, adsorbed C2HCl3 never contacts the clay directly but sorbs onto the first water layer. To test the efficacy of existing force field parameters of organic compounds in solid state simulations, molecular dynamics simulations of several representative organic crystals were also performed and compared with the experimental crystal structures. These investigations show that, in general, in condensed-phase studies, parameter evaluations are realistic only when thermal motion effects are included in the simulations. For chlorohydrocarbons in particular, further explorations are needed of atomic point charge assignments. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 144–153, 1998 相似文献
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Direct observation of single-molecule generation from a chemical reaction was achieved at a solid-liquid interface. The reaction between fluorescamine and immobilized N'-(3-trimethoxysilylpropyl)diethylenetriamine (DETA) was studied at the single-molecule level. Time-lapse fluorescence images of single-molecule products, excited by the evanescent field generated at a quartz-liquid interface, were recorded to follow the chemical reaction to its completion. The reactions were restricted to the approximately 1 nm thick layer nearest to the interface. Analysis of the photoelectron intensity of the fluorescent product of the reaction and its distribution shows that the reaction kinetics goes through a transition from zeroth-order to first-order as the reaction proceeds. This approach offered a novel means to study single-molecule reactions at the solid-liquid interface. It also enabled the investigation of reaction kinetics and chemical mapping of surface heterogeneity at the single-molecule level. 相似文献
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Sarangi SS Raju SG Balasubramanian S 《Physical chemistry chemical physics : PCCP》2011,13(7):2714-2722
The influence of alkyl chain symmetry of the imidazolium cation on the structure and properties of the ionic liquid-vapour interface has been addressed through molecular dynamics simulations. The anion chosen is bis(trifluoromethylsulfonyl)imide (NTf(2)). Profiles of number densities, orientation of cations, charge density, electrostatic potential, and surface tension have been obtained. At the interface, both cations and anions were present, and the alkyl chains of the former preferred to orient out into the vapour phase. A large fraction of cations preferred to be oriented with their ring-normal parallel to the surface and alkyl chains perpendicular to it. These orientational preferences are reduced in ionic liquids with symmetric cations. Although the charge densities at the interface were largely negative, an additional small positive charge density has been observed for systems with longer alkyl chains. The electrostatic potential difference developed between the liquid and the vapour phases were positive and decreased with increasing length of the alkyl group. The calculated surface tension of the liquids also decreased with increasing alkyl chain length, in agreement with experiment. The surface tension of an ionic liquid with symmetric cation was marginally higher than that of one with an asymmetric, isomeric cation. 相似文献
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The adsorption of trans 1,4 polyisoprene was studied on alumina and silica gel at four temperatures. The solvents were cyclohexane, toluene, and 1:1 mixture of the two. The adsorption was found to decrease from cyclohexane >toluene >mixed solvent. The amount of adsorption was an inverse function of temperature. For almost all the systems, the adsorption isotherms were of Langmuir type, though solvent characteristic seems to be a more dominating factor than adsorbent in determining the shape of the isotherm. 相似文献
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Summary Adsorption studies of polyvinylpyrrolidone (PVP) on the surface of colloidal silicas, Aerosil 300 and Aerosil R-972 are reported. The adsorption isotherms of PVP at the hydrophilic silica/aqueous solution interface were greater than that at the hydrophobic silica R-972. The PVP adsorption shows that the amount adsorbed decreases with the concentration.The isotherms contain a minimum when water is used as the solvent. The minimum disappears when Na2SO4 0.55 M is used as the solvent. The PVP adsorption behavior could be due to a different adsorption rate of the various molecular species of the fractions. The orientation of macromolecules adsorbed on the surface would depend on the polymer-solvent interaction in solution. The adsorption would be governed by the surface structural characteristics and would be a function of the molecular weight of the polymer depending on the macromoleculer orientation within the interface.
With 4 figures and 1 table 相似文献
Zusammenfassung Es wird über Adsorption von Polyvinylpyrrolidone (PVP) an der Oberfläche der Kieselgele Aerosil 300 and Aerosil R-972 berichtet. Die Adsorptionsisothermen von PVP auf der hydrophilen Kieselgel/Wasserlösungs-Grenzphase erwiesen sich als größer als die auf dem hydrophoben Kieselgel R-972. Die adsorbierte Menge nimmt mit der Konzentration ab. Die Isothermen zeigen ein Minimum, wenn Wasser als Lösungsmittel benutzt wird. Das Minimum verschwindet, wenn eine 0.55M wäßrige Natriumsulphat-Lösung verwendet wird. Das Adsorptionsverhalten des PVP könnte auf einer verschiedenen Adsorptionsgeschwindigkeit für die verschiedenen molekularen Spezies in den Fraktionen beruhen. Die Orientierung von den an der Oberfläche adsorbierten Makromolekülen würde von der Wechselwirkung zwischen Polymer und Lösungsmittel in der Lösung abhängen. Die Adsorption wurde von den strukturellen Eigenschaften der Oberfläche beherrscht werden und eine Funktion des Molekulargewichtes des Polymers sein, abhängig von der Orientierung der Makromoleküle in der Grenzphase.
With 4 figures and 1 table 相似文献
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Adsorption of nanoparticles at the solid-liquid interface 总被引:1,自引:0,他引:1
Brenner T Paulus M Schroer MA Tiemeyer S Sternemann C Möller J Tolan M Degen P Rehage H 《Journal of colloid and interface science》2012,374(1):287-290
The adsorption of differently charged nanoparticles at liquid-solid interfaces was investigated by in situ X-ray reflectivity measurements. The layer formation of positively charged maghemite (γ-Fe(2)O(3)) nanoparticles at the aqueous solution-SiO(2) interface was observed while negatively charged gold nanoparticles show no adsorption at this interface. Thus, the electrostatic interaction between the particles and the charged surface was determined as the driving force for the adsorption process. The data analysis shows that a logarithmic particle size distribution describes the density profile of the thin adsorbed maghemite layer. The size distribution in the nanoparticle solution determined by small angle X-ray scattering shows an average particle size which is similar to that found for the adsorbed film. The formed magehemite film exhibits a rather high stability. 相似文献