Self-organization of surfactant-metal-ion complex nanofibers on graphite surfaces and their application to fibrously concentrated platinum nanoparticle formation

We report the fabrication of self-organized surfactant nanofibers containing platinum ions on a highly oriented pyrolytic graphite (HOPG) surface from mixed solutions of hexadecyltrimethylammonium hydroxide (C16TAOH) and hydrogen hexachloroplatinate (IV) (H2PtCl6). The fibrous surfactant self-assembly was stable in air, even after being soaked in water, in contrast to surfactant hemicylindrical micelles, which are stable only at graphite/solution interfaces. The results show that the graphite surface served as an essential template for the specific formation of fibrous surfactant self-assemblies. In addition, when surfactant nanofibers containing metal ions were treated with hydrazine, platinum nanoparticles concentrated in the nanofibers formed on the HOPG surface. We also prepared surfactant nanofibers containing gold ions on HOPG surfaces and formed gold nanoparticles in the nanofibers.     

Controlled Growth of Gold Nanoparticles in Aerosol-OT/Sorbitan Monooleate/Isooctane Mixed Reverse Micelles

Stable anisotropic gold nanoparticles were prepared by the reduction of tetrachloroauric acid with hydrazine in mixed reverse micelles formed with anionic surfactant Aerosol-OT and nonionic surfactant sorbitan monooleate (Span80) in isooctane. It was found that the Span80 serves not only as a structure modifier but also as a stabilizer for Au particles, to prevent their further growth and precipitation. The control of particle size, shape, and degree of dispersion was achieved by varying the process variables, such as molar ratio of reduction agent to metal salt, size of water droplets (omega(o)), concentration of metal salt, and sequence of addition of metal salt into the mixed reverse micelles. When the HAuCl(4) was injected directly into the mixed reversed micelles containing hydrazine, nonspherical gold nanoparticles, such as rods and cubes, were obtained at the molar ratio of hydrazine to HAuCl(4) of less than 1.0. The nonspherical Au particles were preferably formed at larger omega(o) value and lower gold salt loading. By the analyses of high-resolution electron microscope, electron diffraction pattern, and energy-dispersive X-ray analysis (EDX), the resultant particles have been found to be pure gold of face-centered cubic structure. Copyright 2000 Academic Press.     

Effect of the alkyl chain length on micelle formation for bis(N-alkyl-N,N-dimethylethylammonium)ether dibromides

Dimeric alkylammonium salts – gemini surfactants – due to their unusual very low critical micelle concentration and minimal inhibitory concentration are subject to intensive research as surface active and antimicrobial compounds. Thanks to the presence of two positively charged nitrogen atoms and a large molecular surface, gemini surfactants are also very efficient corrosion inhibitors. To strengthen the electrostatic adsorption of ammonium cations on a metal surface, which is a key parameter in the inhibition of corrosion, heteroatoms (O, S, N, or P) and π-electron systems can be introduced into the gemini surfactant structure to increase chemical adsorption. In this study, we investigated the relationship between the alkyl chain length and critical micelle concentration for gemini surfactants containing an oxygen atom in the spacer, that is, bis(N-alkyl-N,N-dimethylethylammonium)ether dibromides, for potential use as corrosion inhibitors.     

Site‐Selective Oxidation of Monolayered Liquid‐Exfoliated WS2 by Shielding the Basal Plane through Adsorption of a Facial Amphiphile

In recent years, various functionalization strategies for transition‐metal dichalcogenides have been explored to tailor the properties of materials and to provide anchor points for the fabrication of hybrid structures. Herein, new insights into the role of the surfactant in functionalization reactions are described. Using the spontaneous reaction of WS₂ with chloroauric acid as a model reaction, the regioselective formation of gold nanoparticles on WS₂ is shown to be heavily dependent on the surfactant employed. A simple model is developed to explain the role of the chosen surfactant in this heterogeneous functionalization reaction. The surfactant coverage is identified as the crucial element that governs the dominant reaction pathway and therefore can severely alter the reaction outcome. This study shows the general importance of the surfactant choice and how detrimental or beneficial a certain surfactant can be to the desired functionalization.     

Use of Micellar-Enhanced Ultrafiltration at Low Surfactant Concentrations and with Anionic-Nonionic Surfactant Mixtures

Micellar-enhanced ultrafiltration is a separation technique which can be used to remove metal ions or dissolved organics from water. Metal ions bind to the surface of negatively charged micelles of an anionic surfactant while organic solutes tend to dissolve or solubilized within the micelles. The mixture is then forced through an ultrafiltration membrane with pore sizes small enough to block passage of the micelles and associated metal ions and/or dissolved organics. Monomeric or unassociated surfactant passes through the membrane and does not contribute to the separation. This paper considers advantages of addition of small concentrations of nonionic surfactant to an anionic surfactant; the resulting anionic-nonionic mixed micelles exhibit negative deviation from ideality of mixing which leads to a smaller fraction of the surfactant being present as monomer and a subsequently larger fraction present in the micellar form. The addition of nonionic surfactant improved the separation of divalent zinc substantially at total concentrations above the critical micelle concentration (cmc) of the anionic surfactant. Both zinc and tert-butylphenol (a nonionic organic solute) show unexpected rejection at surfactant concentrations moderately below the cmc, where micelles are absent. This is considered as due to a higher surfactant concentration in the gel layer adjacent to the membrane where micelles are present. Reduction of this rejection at lower transmembrane pressure drops supports this mechanism. Some rejection of zinc was observed in the absence of surfactant but not of tert-butylphenol, indicating an additional effect of membrane charge for ionic solutes. Copyright 1999 Academic Press.     

Adsorption of insoluble surfactants at the Au(111)/solution interface

The adsorption of surfactants, which form insoluble monolayers on an aqueous substrate, onto a single crystal gold electrode have been described. Adsorption of this class of surfactants have been characterized using a combination of electrochemistry and Langmuir-Blodgett techniques. We have developed a technique to simultaneously measure the film pressure at the gas-solution (GS) interface and the film pressure of the surfactants that spread to the metal-solution (MS) interface. We have shown that surfactants such as octadecanol and stearic acid, which interact weakly with the metal surface, adsorb at an uncharged MS interface (at the potential of zero charge) and progressively desorb when the electrode surface is charged negatively. The electrode potential (charge density at the metal surface) influences the transfer of the surfactant from the GS interface to the MS interface. The transfer ratio is 1:1 at an uncharged MS interface, and is progressively reduced to zero when the MS interface is charged. We have employed 12-(9-anthroloxy) stearic acid, a surfactant dye molecule, to study the mechanism of potential induced desorption and adsorption of the film of insoluble molecules. With the help of electroreflectance spectroscopy and light scattering measurements, we have shown that if desorbed, the surfactant molecules form micelles (flakes or vesicles) that are trapped under the electrode surface. The micelles spontaneously spread back onto the electrode surface when the charge density at the metal approaches zero. The repeatable desorption and readsorption involve micellisation of the film at negative potentials and spontaneous spreading of the micelles to reform the monolayer at potentials close to pzc.     

Second CMC in surfactant micellar systems

Experimental reports of surfactant systems displaying a second critical micelle concentration (second CMC) have been surveyed. It turns out that surfactant micelles usually show a growth behavior with some typical features. (i) Micelles grow weakly at low surfactant concentrations but may switch to a much stronger growth behavior at higher concentrations. The second CMC is defined as the point of transition from weakly to strongly growing micelles. (ii) Micelles are found to be non-spherically shaped below the second CMC. (iii) At the second CMC micelles are found to be much smaller, with aggregation numbers typically 100–200, than expected for flexible micelles. (iv) Micelles of intermediate size are present in a narrow concentration regime close to the second CMC. (v) Micelles grow much stronger above the second CMC than expected from a sphere-to-rod transition. The conventional spherocylindrical micelle model predicts a smooth growth behavior that contradicts the appearance of a second CMC. Modifying the model by means of including swollen end caps neither account for the presence of micelles with intermediate size, nor the strong growth behavior above the second CMC. Taking into account micelle flexibility is not consistent with the rather low micelle aggregation numbers observed at the second CMC. On the other hand, a recently proposed alternative theoretical approach, the general micelle model, have been demonstrated to take into account basically all features that are typical of experimentally observed micellar growth behaviors.     

Toward a Theory of Diffusion of a Nonionic Surfactant with Variable Aggregation Number in a Micellar System

Since the aggregation number of micelles always grows with concentration, and, in some cases this dependence is noticeable even for spherical micelles, there is a need to revise the theory of micellization, in which the aggregation number is assumed to be constant. This work reformulates the theory of diffusion of nonionic surfactants in micellar solutions with regard to the variability of the aggregation number. A new formula, which expresses the diffusion coefficient of a surfactant via the diffusion coefficients of monomers and micelles, contains an additional factor capable of increasing the diffusion coefficient with the surfactant concentration. However, this factor is not overly strong, and the “old” part of the formula acts in the opposite direction; as a result, the conventional decrease in the diffusion coefficient of a nonionic surfactant remains prevailing. The analytical consideration has been supplemented with numerical calculations, the results of which are presented in the tables.     

Effects of surfactant micelles on viscosity and conductivity of poly(ethylene glycol) solutions

The neutral polymer-micelle interaction is investigated for various surfactants by viscometry and electrical conductometry. In order to exclude the well-known necklace scenario, we consider aqueous solutions of low molecular weight poly(ethylene glycol) (2-20)x10(3), whose radial size is comparable to or smaller than micelles. The single-tail surfactants consist of anionic, cationic, and nonionic head groups. It is found that the viscosity of the polymer solution may be increased several times by micelles if weak attraction between a polymer segment and a surfactant exists, epsilon相似文献   

Inorganic–organic sol gel hybrid coatings for corrosion protection of metals

Inorganic–organic hybrid coatings by sol–gel process are very suitable for fighting corrosion. Inorganic sols in hybrid coatings not only increase adhesion by forming chemical bonds between metals and hybrid coatings, but also improve comprehensive performances of polymer in the coatings. Different organic polymers or organic functionalities are introduced into gel network to achieve tailored properties, such as hydrophobic properties, increasing cross-linking density, etc. As for corrosion protection of metals organic components of hybrid coatings are selected to repel water and form dense thick films and reduce coating porosity. The factors, such as the ratio of inorganic and organic components, cure temperature, pigments in hybrid coatings, need to be optimized for attaining hybrid films with the maximum corrosion resistance. Electro-deposition technique offers relatively thick homogeneous defect-free hybrid coatings in comparison to dip or spin coating techniques. Green cerium ions and non-ionizable organic inhibitors are more developed in hybrid coatings nowadays than other corrosion inhibitors. Long-term corrosion resistance techniques of inhibitors are discussed. The inhibitors entrapped in the nanocontainers are doped in hybrid films to prolong release of the inhibitors to damaged zones, which is discussed in detail. Among all the nanocontainers of corrosion inhibitors the prospective techniques which show superior corrosion protection are cyclodextrin/organic inhibitor inclusion complexes and layer by layer assembly of organic corrosion inhibitors in nanocontainers. Super-hydrophobic property of hybrid coatings derives from low surface tension and surface roughness of hybrid coatings, which endues the films with excellent corrosion protection for metals, but the durable property of super-hydrophobic coatings needs to be improved for industrial application. An ideal multiple model of hybrid coatings for superior anti-corrosion of metals proposed is a combination of super-hydrophobic hybrid coatings and underlying hybrid coatings doped with sustained release of corrosion inhibitors on metal substrates.     

Experimental and theoretical studies of acridine orange as corrosion inhibitor for copper protection in acidic media

The corrosion process commonly limits the use of copper in practical applications. The use of corrosion inhibitors is one of the effective methods to reduce the corrosion rate of copper. In this research, the inhibition effect of acridine orange (3,6-bis(dimethylamine)acridine) (AcO) for the protection of copper in 0.5 ?M ?H₂SO₄ solution was studied. For this aim, the change of open circuit potential with exposure time (E_ocp-t), electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR), anodic and cathodic potentiodynamic polarization measurements (PP) and chronoamperometry (CA) techniques were used. Some quantum chemical parameters (E_HOMO, E_LUMO and dipole moment) were calculated and discussed. The AcO film formed over the copper surface was examined by SEM, EDX, AFM and contact angle measurements. The electrochemical data showed that AcO is an effective corrosion inhibitor even at low concentrations (ranging between 99.1% and %99.4 ?at concentrations from 0.01 ?mM to 1 ?mM). The corrosion rate of copper decreases in the presence of the inhibitor by reducing both anodic and cathodic rates, which is depended on its concentration. This compound behaves as mixed-type corrosion inhibitors with predominantly cathodic type. Its adsorption on the copper surface obeys Langmuir adsorption isotherm. The value of adsorption equilibrium constant (K_ads) and the standard free energy of adsorption were ΔG_ads 1.298 x 10³ ?M^?1 and -27.71 ?kJ/mol in the case of 0.5 ?M ?H₂SO₄ solution containing 1.0 ?mM AcO, which shows the adsorption is high and spontaneous. The adsorbed inhibitor film over the metal increase contact angle of the surface, which suggests the more hydrophobic properties of the surface are increasing coming from the orientation of hydrophobic sites to the electrolyte. The zero charge potential (E_pzc) studies showed that the surface charge of the metal is positive in the corrosive media containing the inhibitor. Quantum chemical calculations showed that the binding of inhibitor molecules to the metal surface takes place through N atoms of the inhibitor.     

Metal-driven viscoelastic wormlike micelle in anionic/zwitterionic surfactant systems and template-directed synthesis of dendritic silver nanostructures

In this work, metal ion-induced viscoelastic wormlike micelles in anionic/zwitterionic surfactant solutions (sodium dodecylsulfate/tetradecyldimethylammoniumpropanesulfonate, SDS/TPS) are reported. Steady and dynamic rheology and cryogenic transmission electron microscopy (cryo-TEM) are employed to characterize wormlike micelles in the SDS/TPS/Ca(NO(3))(2) system. Moreover, the surfactant mixing ratio and surfactant tail length are varied to reveal the factors that influence wormlike micelle growth and solution viscoelasticity. A series of metal ions such as Na(+), Mg(2+), Zn(2+), and Al(3+) are proven to promote viscoelastic wormlike micelle formation in the SDS/TPS system. The metal-containing wormlike micelles are expected to be good candidates for directing the synthesis of inorganic nanomaterials. In this article, dendritic silver nanostructures have been prepared in the surfactant wormlike micelle by in situ UV irradiation for the first time.     

Molecular Dynamics and Organization of Micellar Complexes of Poly(acrylic acid) with Poly(ethylene glycol)-Based Surfactants

The structure and molecular dynamics of complexes of poly(acrylic acid) with dodecyl-substituted poly(ethylene glycol)s in aqueous solutions are studied by viscometry and spin probe ESR spectroscopy. It is shown that, at low surfactant concentrations, the complexes have a compact globular conformation. The local mobility of the surfactant molecules in the complexes under consideration is much lower than their mobility in free micelles. As a result of increasing surfactant concentration in solution, the hydrophilic associates of the surfactant micelles with the polyacid having an unfolded coil conformation are formed. In an associate, a significant fraction of poly(ethylene glycol) fragments incorporated into micelles is in the free state, i.e., these fragments are not bound with a polymer chain. The local mobility of the surfactant molecules in the associate is considerably higher than in the complex with a compact conformation, and this mobility grows with the increasing number of micelles involved in the associate.     

Site-Selective Oxidation of Monolayered Liquid-Exfoliated WS2 by Shielding the Basal Plane through Adsorption of a Facial Amphiphile

In recent years, various functionalization strategies for transition-metal dichalcogenides have been explored to tailor the properties of materials and to provide anchor points for the fabrication of hybrid structures. Herein, new insights into the role of the surfactant in functionalization reactions are described. Using the spontaneous reaction of WS₂ with chloroauric acid as a model reaction, the regioselective formation of gold nanoparticles on WS₂ is shown to be heavily dependent on the surfactant employed. A simple model is developed to explain the role of the chosen surfactant in this heterogeneous functionalization reaction. The surfactant coverage is identified as the crucial element that governs the dominant reaction pathway and therefore can severely alter the reaction outcome. This study shows the general importance of the surfactant choice and how detrimental or beneficial a certain surfactant can be to the desired functionalization.     

Synthesis,CMC determination and influence of the micelles, β-cyclodextrin,ionic liquids and liposome(dipalmitoylphosphatidylcholine) vesicles on the kinetics of an outer-sphere electron transfer reaction

The surfactant–cobalt(III) complex, cis-[Co(trien)(4AMP)(DA)](ClO₄)₃, trien = triethylenetetramine, 4AMP = 4-aminopyridine, DA = dodecylamine was synthesized and characterized by various spectroscopic and physico-chemical techniques. The critical micelle concentration (CMC) value of this surfactant–cobalt(III) complex in aqueous solution was found out from conductance measurements. The conductivity data (at 303, 308, 313, 318 and 323 K) were used for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (ΔG _m ^° , ΔH_m and ΔS _m ^° ). Also the kinetics of reduction of this surfactant–cobalt(III) complex by hexacyanoferrate(II) ion in micelles, β-cyclodextrin, ionic liquids (ILs) and in liposome vesicles (DPPC) media were studied at different temperature. The rate constant for the electron transfer reaction in micelles was found to increase with increase in the initial concentration of the surfactant–cobalt(III) complex. This peculiar behaviour of dependence of second-order rate constant on the initial concentration of one of the reactants has been attributed to the presence of various concentration of micelles under different initial concentration of the surfactant–cobalt(III) complex in the reaction medium. Inclusion of the long aliphatic chain of the surfactant complex ion into β-cyclodextrin leads to decrease in the rate constant. Below the phase transition temperature of DPPC, the rate decreased with increasing concentration of DPPC, while above the phase transition temperature the rate increased with increasing concentration of DPPC. It is concluded that below the phase transition temperature, there is an accumulation of surfactant–cobalt(III) complex at the interior of the vesicle membrane through hydrophobic effects, and above the phase transition temperature the surfactant–cobalt(III) complex is released from the interior to the exterior surface of the vesicle. In the presence of ionic liquid medium the second order rate constant for this electron transfer reaction for the same complex was found to increase with increasing concentration of ILs has also been studied. An outer-sphere mechanism is proposed for all these reactions and the results have been explained based on the hydrophobicity of the ligand and the reactants with opposite charges.     

The role of the organic layer functionalization in the formation of silicon/organic layer/metal junctions with coinage metals

The design of silicon/alkyl layer/metal junctions for the formation of optimal top metal contacts requires knowledge of the mechanistic and energetic aspects of the interactions of metal atoms with the modified surface. This involves (a) the interaction of the metal with the terminal groups of the organic layer, (b) the diffusion of metal atoms through the organic layer and (c) the reactions of metal atoms with the silicon surface atoms. The diffusion through the monolayer and the metal catalyzed breakage of Si-C bonds must be avoided to obtain high quality junctions. In this work, we performed a comprehensive density functional theory investigation to identify the reaction pathways of all these processes. In the absence of a reactive terminal group, gold atoms may penetrate through a compact alkyl monolayer on Si(111) with no energy barrier. However, the presence of thiol terminal groups introduces a high energy barrier which blocks the diffusion of metals into the monolayer. The diffusion barriers increase in the order Ag < Au < Cu and correlate with the stability of metal-thiolate complexes whereas the barriers for the formation of metal silicides increase in the order Cu < Au < Ag in correlation with the increasing metallic radii. The reactivity of gold clusters with functionalized Si(111) surfaces was also investigated. Metal silicide formation can only be avoided by a compact monolayer terminated by a reactive functional group. The mechanistic and energetic picture obtained in this work contributes to understanding of the factors that influence the quality of top metal contacts during the formation of silicon/organic layer/metal junctions.     

Mesoscopic simulation of self-assembly in surfactant oligomers by dissipative particle dynamics

Self-assembling properties of surfactant oligomers in an aqueous medium is simulated by dissipative particle dynamics (DPD). The critical micellar concentration (CMC) of dimeric (oligomerization = 2) and trimeric (oligomerization = 3) surfactant is much lower than their single-chain counterpart. All surfactants form spherical micelles at the concentration not far above their CMC. The transition from spherical to cylindrical micelles exhibits with increasing surfactant concentration. Lamellar micelles will appear with further increasing the surfactant concentration. For dimeric and trimeric surfactants, cylindrical micelles transform into extremely long “wormlike” or “threadlike” micelles before the transition to lamellar micelles. These results are in qualitative agreement with laboratory experiment. Average aggregation numbers (AN) of micelles increase with a power law of AN  c when the surfactant concentration c CMC. The self-diffusion coefficients will drop with a power law of D  c⁻ when wormlike micelles are formed.     

Effect of Increasing Concentration of Each of Three Polar Solvents (1,4-Dioxane, Dimethyl Sulfoxide, N,N-Dimethylformamide) on Changes in the Shape of Polysorbate 20 Micelles

The effect of increasing concentration of each of three polar solvents [0–40 % (v/v) 1,4-dioxane, 0–40 % (v/v) dimethyl sulfoxide (DMSO), and 0–60 % (v/v) N,N-dimethylformamide (DMF)] on changes in the shape of the surfactant polysorbate 20 (Tween 20) micelles in the aqueous, polar solvent, sodium phosphate buffer solutions (pH = 7.2, ionic strength 2.44 mmol·L^?1) were investigated by using small-angle X-ray scattering. The effect of increasing concentration of 1,4-dioxane is that the micelle shape changed from core–shell cylindrical micelles to core–shell disc micelles between concentrations of 10 and 20 % (v/v) 1,4-dioxane, and then from core–shell disc micelles to core–shell elliptic disc micelles between concentrations of 30 and 40 % (v/v) 1,4-dioxane. The effect of increasing concentration of DMSO is that the micelles changed from core–shell cylindrical micelles to core–shell disc micelles between concentrations of 0 and 10 % (v/v) DMSO. The effect of increasing concentration of DMF is that it changed the core–shell cylindrical micelles to core–shell disc micelles between concentrations of 30 and 40 % (v/v) DMF. The common effect is that the solvents shortened the height of the micelle, that is, they squashed the micelle. Moreover, the specific effect of 1,4-dioxane is that this solvent squashed and squeezed the micelle.     

Superactivity of peroxidase solubilized in reversed micellar systems

Vaccinium mirtyllus peroxidase solubilized in reversed micelles was used for the oxidation of guaiacol. Some relevant parameters for the enzymatic activity, such as pH,w _o (molar ratio water/surfactant), surfactant type and concentration, and cosurfactant concentration, were investigated. The peroxidase showed higher activities in reversed micelles than in aqueous solution. The stability of the peroxidase in reversed micelles was also studied, namely, the effect ofw _o and temperature on enzyme deactivation. The peroxidase displayed higher stabilities in CTAB/hexanol in isooctane reversed micelles, with halflife times higher than 500 h.     

Kinetics of the autoxidation of adrenaline and [copper(II)(adrenaline)]2+ in alkaline aqueous and micellar media

The kinetics of autoxidation of adrenaline and [Cu(adrenaline)]²⁺ complex by dissolved oxygen in alkaline aqueous and micellar media has been studied. The reaction is initiated by the removal of amino-H⁺ protons of adrenaline by hydroxide ion, followed by cyclization. The values of (1/k _obs) for the autoxidation of both species were found to be linearly dependent upon 1/[OH^?]. The reaction follows a consecutive pathway in which the intermediate adrenochrome remains stable for few minutes, and then undergoes further reactions to yield adrenolutin and other products. The [Cu(adrenochrome)]⁺ complex is stable for a few hours. Studies on the effects of cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) on the reactivity of both species revealed different behaviors. The micelles of CTAB catalyzed the rates of autoxidation for both species, whereas SDS micelles inhibited the autoxidation of adrenaline but catalyzed the rate of autoxidation of [Cu(adrenaline)]²⁺. Addition of the reactive counterion surfactant, cetyltrimethylammonium hydroxide (CTAOH) initially increased the rate constant with the increasing [CTAOH], until it reached a plateau for k _ψ ?[CTAOH]. Salts such as NaCl, NaBr, tetramethyl ammonium bromide, and tetraethyl ammonium bromide increased the rate when added at lower concentrations, but had negligible effect at higher concentrations. The results obtained in micellar media were treated according to Berezin’s Pseudophase Model. The various kinetic parameters for the reactions occurring in aqueous and in micellar media are reported.