Adsorption stripping voltammetry of phenol at Nafion-modified glassy carbon electrode in the presence of surfactants

In this paper, a new voltammetric method for the determination of phenol is described. In pH 8.00 phosphate buffer and in the presence of long-chain cationic surfactant—cetyltrimethylammonium bromide—phenol has a very sensitive oxidation peak at 0.47 V (vs. SCE) on the Nafion-modified glassy carbon electrode (GCE). The experimental parameters, such as supporting electrolyte and pH values, amounts of Nafion, varieties and concentration of surfactants, accumulation potential and time, as well as scan rate were optimized. The peak current is linear with the concentration of phenol in the range from 8×10⁻⁹ to 1×10⁻⁵ M, and the detection limit is 1×10⁻⁹ M after being accumulated at −0.50 V (vs. SCE) for 3 min. Trace levels of phenol in water samples were determined by using this voltammetric method, the average recovery was calculated to be 99.56%.     

Adsorption behaviour of lipase from Staphylococcus carnosus on a hydrophobic adsorbent.

The adsorption of proteins on a solid surface with a subsequent desorption is a well known final purification step in downstream processing. Here the adsorption behaviour of a microbial lipase on the hydrophobic Fractogel TSK butyl 650 in a crude fermentation supernatant is investigated. The measured equilibrium curves differ from fermentation to fermentation by up to +/- 65%. The adsorption capacity increases with decreasing particle diameter of the adsorbent and is influenced by the method of contacting the supernatant with the adsorbent. The rate of desorption depends largely on the adsorption conditions, which is an indication of different orientations of the adsorbed enzyme.     

Zeta-potentials of self-assembled surface micelles of ionic surfactants adsorbed at hydrophobic graphite surfaces

The zeta-potentials of the self-assembled surface ionic surfactants (sodium dodecyl sulfate—SDS and hexadecyltrimethyl ammonium bromide—CTAB) on graphite surfaces were determined both from streaming potential and electrophoretic mobility measurements. The adsorption of the surfactants at graphite–liquid interfaces has been studied using atomic force microscopy (AFM) soft-contact imaging which shows the formation of linear, parallel hemicylinders with headgroups oriented towards the solution. The magnitude of the zeta-potential increased with an increase in surfactant concentration, reaching a constant value at a concentration corresponding to the point of surface micelle formation as confirmed from AFM imaging. The streaming potential and electrophoretic mobility measurements showed that the zeta-potentials of SDS and CTAB surface micelles adsorbed at the graphite surface were about −75 and +70 mV, respectively, well in agreement with the values reported for bulk phase micelles in the literature.     

Adsorption of codeine on hydrophilic silica and silica surface modified by hydrophobic groups in the presence of electrolytes

The adsorption of codeine from aqueous solution onto colloidal silica and silica surface-modified with chemiadsorbed octadecyl dimethyl silane (ODDMS) or dimethyl silane (DMS) groups was studied in the presence of neutral electrolytes at different pH values. From codeine-hydrochloride solutions codeine cations are strongly bound to negatively charged silica surfaces. Inorganic salts (NaCl, NaNO₃) reduce the adsorption of the organic cation. On silica modified by ODDMS (10% of surface silanol groups are occupied), codeine cations are adsorbed to a higher extent at pH 6, while at pH 8 the adsorbed amounts are lower than on the bare silica surface. Neutral electrolytes reduce codeine adsorption on the ODDMS modified silica. On the hydrophobic silica, completely covered by DMS groups, codeine adsorption is considerably lower than on the bare silica, but neutral salts increase the adsorption. The adsorption of codeine is compared with the adsorption of aggregating surfactant ions. Common and different features of their interactions with silica surfaces are outlined.     

Adsorption of water soluble ionic/hydrophobic diblock copolymer on a hydrophobic surface

Summary We consider the adsorption of aA-B diblock copolymer on a planar hydrophobic surface in aqueous solution. The hydrophobic anchor (A) block is envisioned to avoid water and adsorbs on the solid-liquid interface in a collapsed state. The buoy block (B) is a polyelectrolyte which expands in solution and forms a brush whose structure depends strongly on the ionic strength of the solution. The minimization of the grand canonical free energy of the system gives access to the surface density (), the thickness of the collapsed layer (L _A ) and the thickness of the external polyelectrolyte layer (L _B ). These three parametersL _B ,L _A and are functions of the molecular weight of the anchored block (N _A ), the molecular weight of the buoy block (N _B ), the charge of the polymer (Z) and the ionic strength of the aqueous solution ( _s ).     

Adsorption and morphology transition of surfactants on hydrophobic surfaces: a lattice Monte Carlo study

In this work, we first show that there are only five independent interchange parameters in the surfactant-solvent-interface system in Larson's model, and then adsorption and morphology transition of surfactants on hydrophobic surfaces are studied by extensive lattice Monte Carlo simulations. In our simulations, we found that there exist six adsorbed morphologies: (1) premature admicelle, (2) hemisphere, (3) hemisphere-hemicylinder mixture, (4) wormlike hemicylinder, (5) perforated monolayer, and (6) monolayer. The surface morphologies and the amount of adsorption on hydrophobic surfaces are found to be affected obviously by two interchange parameters. One is the attractive interaction between tail groups and surface (chiTS), and the other is the solubility of head groups in bulk (chiHW). Phase diagrams in chiHW versus chiTS planes for surfactants with different hydrophobicities (chiTW) and for surfactants with different molecular structures are determined in this work, from which the transitions of surface morphologies and adsorption behaviors are discussed.     

Adsorption states of amphipatic solutes at the surface of naturally hydrophobic minerals: a molecular dynamics simulation study

An initial molecular dynamics simulation study regarding interfacial phenomena at selected naturally hydrophobic surfaces is reported. Simulation results show that, due to the natural hydrophobicity of graphite and talc basal planes, the cationic surfactant dodecyltrimethylammonium bromide preferentially adsorbs at these surfaces through hydrophobic interactions. When a model dextrin molecule is considered, the simulation results suggest that the hydrophobic interaction between the naturally hydrophobic surfaces of graphite, talc basal plane, and sulfur and the hydrophobic moieties (C-H and methylene groups) in the dextrin molecule plays a significant role in dextrin adsorption at these surfaces. The hydroxyl group in the dextrin molecule also contributes to its adsorption at the talc basal plane surface. In contrast, dextrin was not found to adsorb at talc edge surfaces.     

Adsorption properties of highly dispersed silica with a partially hydrophobic surface

Highly dispersed silica samples with different degrees of substitution of silanol groups by trimethylsilyl groups are obtained by the gas-phase modification method. The adsorption of vitamins B1, B6, and E on initial and modified silica samples is studied. It is shown that the modified adsorbents with degrees of substitution of silanol groups up to 40% exhibit higher affinity to vitamin molecules; in this case, adsorption properties of the modified silica samples depend on the nature of the adsorbate and the number of grafted groups.     

Adsorption of non-ionic surfactants on hydrophobic silica particles and the stability of the corresponding aqueous dispersions

The temperature stability of aqueous dispersions of hydrophobic monodisperse silica particles stabilized with nonionic surfactants has been investigated. Adsorption isotherms in conjunction with surface tension measurements showed that the surfactant formed a monolayer on the surface of the particles, where the adsorbed amount depended on the molecular weight of the ethylene oxide headgroup. The temperature stability of these dispersions has been measured by a standard turbidimetric technique and visual observations in terms of their critical flocculation temperature (CFT). Parameters controlling the CFT of the individual dispersions stabilized with a monolayer of surfactant include the thickness of the steric layer, the particle size, and the volume fraction of the particles. Calculations show that the van der Waals attraction between the particles with adsorbed polymer layers increases as the temperature of the dispersion increases, and this largely accounts for the observed CFT behavior.     

Adsorption of hydrophobin proteins at hydrophobic and hydrophilic interfaces

The surface activity of two hydrophobin proteins, HFBII and SC3, at the solid–liquid, liquid–liquid and liquid–vapor interface has been investigated. Hydrophobins are fungal proteins that are known to adsorb and affect the physico-chemical properties of an interface. In this study, the surface activity was determined by measuring the interaction of hydrophobin molecules with various liquids, solid particles and films that are commonly used or produced in industrial processes. We found that a very low concentration of hydrophobin is required to facilitate the wet-in of hydrophobic solid particles, such as Teflon^®, into aqueous solutions. It is also capable of stabilizing aqueous dispersions of Kevlar^® nanopulp, reversing the wettability of hydrophobic films and stabilizing polyunsaturated fatty acid (PUFA) oil-in-water emulsions.     

The stability of hydrophobic sols in the presence of surface active agents

Summary The stability of Thorium dioxide sols at p_H=3.5 was examined as a function of anionic surface active agents spectrophotometrically. At low concentrations of surface active agents, the stability of the sol decreases and attains a minimum value at concentrations 10⁻⁴ to 10⁻³ M. With increasing concentration the stability increases and attains a maximum at concentrations 10⁻³ to 10⁻² M. The effect of the P_H-value, the chain length and the head groups of the surface active agents are also studied. The results were explained on the basis of strong adsorption of these ions at the Stern plane.     

Adsorption of sugar surfactants at the air/water interface

The adsorption isotherms of n-decyl-β-D-glucoside (β-C(10)G(1)) as well as various n-alkyl-β-D-maltosides (β-C(n)G(2)) with n=8, 10, 12 and 14 were determined from surface tension measurements. Based on the analysis of the adsorption isotherms, the total free energy change of adsorption was determined and a novel method was proposed to determine the maximum adsorbed amount of surfactant. It can be concluded that the driving force for adsorption first increases with increasing adsorbed amount of the sugar surfactants and then levels off in a plateau. This peculiar behaviour is interpreted as formation of a thin liquid-like alkane film of overlapping alkyl chains at the air/water interface once a certain adsorbed amount is exceeded. The driving force of adsorption depends on the alkyl chain length only and is not affected by the type of the head group. The hydrophobic contribution to the standard free energy change of adsorption was compared with the values of sodium alkylsulfate and alkyltrimethylammonium bromide surfactants. This comparison reveals that the hydrophobic driving force of adsorption is the largest for the sodium alkylsulfates, whereas it is the same for the sugar surfactants and the alkyltrimethylammonium bromides.     

Adsorption of ionic surfactants at an expanding air-water interface

A quantitative model for the kinetics of adsorption of ionic surfactants to an expanding liquid surface is presented for surfactant concentrations below and above the critical micelle concentration (cmc). For surfactant concentrations below the cmc, the electrostatic double layer is accounted for explicitly in the adsorption isotherm. An overflowing cylinder (OFC) was used to create nonequilibrium liquid surfaces under steady-state conditions. Experimental measurements of the surface excess for solutions of cationic surfactants CH3(CH2)n-1N+(CH3)3 Br- (CnTAB, n = 12, 14, 16) and the anionic fluorocarbon surfactant sodium bis(1H,1H-nonafluoropentyl)-2-sulfosuccinate (di-CF4) in the OFC are in excellent agreement with the theoretical predictions for diffusion-controlled adsorption for all concentrations studied below the cmc. For surfactant concentrations above cmc, the diffusion ofmicelles and monomers are handled separately under the assumption of fast micellar breakdown. This simplified model gives excellent agreement for the system C14TAB + 0.1 M NaBr above the cmc. Agreement between theory and experiment for C16TAB + 0.1 M NaBr is less good. A plausible explanation for the discrepancy is that micellar breakdown is no longer fast on the time scale of the OFC (ca. 0.1 s).     

Interaction of a new surface sensitive probe compound with anionic surfactants of varying hydrophobic chain length

The amide derivative of a bis-phenylethynyl compound meta linked to 2,6-pyridine (BPEAP) poses inherent equilibrium between its neutral and zwitterionic forms in the excited state. BPEAP has been found to bind to the surface of anionic micelles instead of penetrating inside. This phenomenon has been exploited to attempt controlling the process of equilibrium using sodium dodecyl sulfate (SDS) at its pre-micellar and near-micellar aggregation concentrations. The anionic surfactant has been found to alter the equilibrium between the said forms of BPEAP depending on its concentration in solution. The process has been further verified by using sodium decyl sulfate (SDeS), which has smaller hydrophobic chain length than SDS as also varies in the critical micellar concentration (CMC) and aggregation number. The binding constant of the probe to the surfactant aggregates varies depending on the extent of surface available to the fluorophore for attachment.     

Experimental observations on the scaling of adsorption isotherms for nonionic surfactants at a hydrophobic solid-water interface

The self-assembly of nonionic surfactants in bulk solution and on hydrophobic surfaces is driven by the same intermolecular interactions, yet their relationship is not clear. While there are abundant experimental and theoretical studies for self-assembly in bulk solution and at the air-water interface, there are only few systematic studies for hydrophobic solid-water interfaces. In this work, we have used optical reflectometry to measure adsorption isotherms of seven different nonionic alkyl polyethoxylate surfactants (CH3(CH2)I-1(OCH2CH2)JOH, referred to as CIEJ surfactants, with I = 10-14 and J = 3-8), on hydrophobic, chemically homogeneous self-assembled monolayers of octadecyltrichlorosilane. Systematic changes in the adsorption isotherms are observed for variations in the surfactant molecular structure. The maximum surface excess concentration decreases (and minimum area/molecule increases) with the square root of the number of ethoxylate units in the surfactant (J). The adsorption isotherms of all surfactants collapse onto the same curve when the bulk and surface excess concentrations are rescaled by the bulk critical aggregation concentration (CAC) and the maximum surface excess concentration. In an accompanying paper we compare these experimental results with the predictions of a unified model developed for self-assembly of nonionic surfactants in bulk solution and on interfaces.