Role of Counterions in the Adsorption and Micellization Behavior of 1:1 Ionic Surfactants at Fluid Interfaces─Demonstrated by the Standard Amphiphile System of Alkali Perfluoro-n-octanoates.

In our latest communication, we proved experimentally that the ionic surfactant's surface excess is exclusively determined by the size of the hydrated counterion.[Lunkenheimer , Langmuir, 2017, 33, 10216-1022410.1021/acs.langmuir.7b00786]. However, at this stage of research, we were unable to decide whether this does only hold for the two or three lightest ions of lithium, sodium, and potassium, respectively. Alternatively, we could also consider the surface excess of the heavier hydrated alkali ions of potassium, rubidium, and cesium, having practically identical ion size, as being determined by the cross-sectional area of the related anionic extended chain residue. The latter assumption has represented state of art. Searching for reliable experimental results on the effect of the heavier counterions on the boundary layer, we have extended investigations to the amphiphiles' solutions of concentrations above the critical concentration of micelle formation (cmc).We provided evidence that the super-micellar solutions' equilibrium surface tension will remain constant provided the required conditions are followed. The related σcmc-value represents a parameter characteristic of the ionic surfactant's adsorption and micellization behavior. Evaluating the amphiphile's surface excess obtained from adsorption as a function of the related amphiphile's σcmc-value enables you to calculate the radius of the hydrated counterion valid in sub- and super-micellar solution likewise. The σcmc-value is directly proportional to the counterion's diameter concerned. Taking additionally into account the radii of naked ions known from crystal research, we succeeded in exactly discriminating the hydrated alkali ions' size from each other. There is a distinct sequence of hydration radii in absolute scale following the inequality, Li+ > Na+ > K+ > (NH4)+ > Rb+ > Cs+. Therefore, we have to extend our model of counterion effectiveness put forward in our previous communication. It represents a general principle of the counterion effect.

Orientation phase transitions of undissociated n-decanoic acid at the air/solution interface revealed by surface pressure and electric potential.

The surface pressure (Π) and electric surface potential (ΔV) vs. concentration (c) isotherms of n-decanoic acid (DA) in 1 × 10-3 mol/dm3 HCl were measured at the air/solution interface - the Π with a du Noüy ring, the ΔV with the vibrating plate (named also the dynamic condenser) method. The DA solutions fulfilled criterion of surface-chemical purity. The complementary Π-c and ΔV-c isotherms were jointly evaluated to obtain dependence of quotient of the effective dipole moment to the interface's permittivity, µâŠ¥/εs, as a function of chosen adsorption ordinates such as the bulk concentration, c, partial molar area, A, and surface molar fraction of DA, XDAs. The crucial point for the analysis is knowledge of the surface excess (Γ) dependence on concentration (c). Since, experimental determination of a Γ-c course is problematic, so far, we used Γ-c courses calculated basing on different adsorption models (Gibbsian, the classical Frumkin' model and the Lunkenheimer' and Hirte' two state approach). Despite, the Γ-c courses determined basing on the different adsorption models differ significantly, the µâŠ¥/εs dependences on different adsorption's ordinates (c, A or XDAs) revealed consistently three local µâŠ¥/εs maxima of their height increasing with the adsorption coverage. The µâŠ¥/εs change was recalculated into inclination angle (αincl) of the total dipole moment vector (µâ†’) to the interface, assuming εs = 1. The µâŠ¥/εs which reflects polarization orientation is an order parameter used by us for analysis of 2D phase transitions in the monolayer. The three µâŠ¥/εs local maxima are ascribed by us to three 2D mono-phases, one transferring into the next one of the higher order in the sequence: liquid expanded (L1) → the liquid condensed tilted (L2) → the liquid condensed untilted (L2'). One inflection point appearing in the Π-A isotherm within the region between the µâŠ¥/εs maxima 2 and 3 indicates that transition of the L2 into the L2' 2D phase is of the first order. Decrease of the µâŠ¥/εs above the maximum 3 indicates transition into two phase regime by nucleation of aggregates (possibly in form of lamellas) within the L2' phase.

Role of Counterion in the Adsorption Behavior of 1:1 Ionic Surfactants at Fluid Interfaces-Adsorption Properties of Alkali Perfluoro-n-octanoates at the Air/Water Interface.

Equilibrium surface tension (σe) versus bulk concentration (c) isotherms of aqueous, surface-chemically pure solutions of various alkali perfluoro-n-octanoates were measured at 295 K. These 1:1 ionic surfactant systems belong to the pseudo nonionic ones. Evaluating the different σe vs log c isotherms by basic adsorption equations reveals that they follow ideal surface behavior. The novelty of this investigation exists in the fact that the surface area demand per molecule adsorbed calculated from the experimental σe vs log c isotherms is identical to that of the hydrated alkali cation. Thus, as long as the counterion's cross-sectional area is greater than that of its amphiphilic anion, the amphiphile's total surface area demand will exclusively be governed by that of its alkali counterion. This, in turn, means that the counterion is nonrandomly bound to the amphiphilic anion in the adsorption layer. Furthermore, the size of the hydrated alkali counterion in the adsorption layer does not differ from that in the bulk phase.

Adsorption properties of surface chemically pure sodium perfluoro-n-alkanoates at the air/water interface: counterion effects within homologous series of 1:1 ionic surfactants.

The unusual behavior of saturation adsorption calculated from experimental equilibrium surface tension (σ(e)) versus logarithm of concentration (c) isotherms within the homologous series of aqueous sodium perfluoro-n-alkanoate solutions represents a particular problem in the adsorption of homologous ionic 1:1 amphiphiles at fluid interfaces. Special precautions were taken to guarantee surface-chemical purity for all solutions, avoiding falsifying effects by surface-active trace impurities. Surprisingly, all homologues' adsorption isotherms reveal ideal surface behavior. The minimal surface area demand per molecule adsorbed for shorter-chain homologues slightly decreases with increasing chain lengths but then goes up steeply after having passed a minimum. A similar feature has been observed with the chemically quite different homologous series of the hydrocarbon surfactants of sodium-n-alkylsulfates. Comparing the corresponding 3D saturation concentrations in the boundary layer and in the bulk, it becomes evident that at high bulk concentrations when boundary layer and bulk concentrations are of the same order of magnitude the adsorption behavior may be treated as that of a pseudononionic surfactant. However, under conditions of the homologues' strongest surface activity, adsorption seems to become increasingly governed by electrostatic repulsion, resulting in increasingly greater cross-sectional areas. Deviation from pseudononionic behavior sets in when the Debye length becomes distinctly greater than the adsorbent's diameter at saturation. Formerly available theories on ionic amphiphiles' adsorption deal either with electrical conditions of surfactant ions and counterions in the adsorption boundary layer or alternatively with pseudononionic behavior neglecting the former theories completely. Warszynski et al.'s novel theoretical model of the "surface quasi-two-dimensional electrolyte" seems to be capable of describing the adsorption of ionic amphiphiles at fluid interfaces in general. We conclude that the conditions of the two alternative approaches may be met within homologous series of ionic amphiphiles as limiting cases only.

In situ removal and purification of biosurfactants by automated surface enrichment.

A new method is described to remove and separate biosurfactants from complex mixtures by compressing and harvesting the liquid surface layer. This method was applied to Bacillus subtilis cultures, in which the lipopeptide antibiotic fengycin as well as the polyketide antibiotic bacillaene were produced. The automated harvesting and collection in a custom-built glass body called 'flounder' was repeated several hundred times. The fengycin concentration in the fractions was found to be four times higher than in the culture centrifugate. Of the overall fengycin, 50% (w/w) were recovered after 300 cycles, 95% (w/w) after 800 harvesting cycles. A separation of fengycin from the less surface-active bacillaene could be achieved due to stronger surface activity of fengycin. The ratio of partition coefficients of fengycin and bacillaene was nine times higher compared to foam fractionation. A stepwise increase of the equilibrium surface tension in the centrifugate from 29 to 33 mN/m indicated a fractionated separation of different surface-active substances. The utilization of cell containing culture broth instead of centrifugate had only slight effects on separation efficiency. These results demonstrate the possibility to separate biosurfactants directly from cultivation without the use of extraction solvents or foam formation.

On the adsorption properties of surface chemically pure CHAPS at the air/water interface.

CHAPS, a surface-active derivative of the steroids' basic structure of the cholic acid [3-[(3-cholamidopropyl)dimethyl-ammonio]-1-propanesulfonate] has become a very important material in biological and pharmaceutical application. Investigations of the adsorption properties of aqueous, surface-chemically pure CHAPS solutions at the air/water interface were performed using surface tension and surface potential measurements. Unlike ordinary extended-chain surfactants, the amphiphilic structure of CHAPS is prone to adopt different concentration-dependent surface states of the adsorption layer. These are well reflected in the adsorption isotherm and in the electric surface properties. They are explained by changes in the adsorbate molecule's orientation and/or conformation as a result of the latter's different surface area demand. The versatile favorable application properties of the CHAPS molecule are obviously due to its complicated molecular structure, which enables it to comply with rather different interfacial and colloidal challenges.

Investigations on foamability of surface-chemically pure aqueous solutions of functionalized alkylaldonamides.

The foamability of the aqueous solutions of functionalized, surface-chemically pure surfactants of the nonionic saccharide-type: N,N-di-n-alkylaldonamides, N-alkyl-N-(2-hydroxyethyl)aldonamides, and N-cycloalkylaldonamides, derivatives of D-glucono-1,5-lactone and/or D-glucoheptono-1,4-lactone, were investigated. The approach of Lunkenheimer and Malysa for the characterization of the foamability and foam stability of these surfactant solutions was applied for these investigations. Using standard parameters related to the different physical stages of the foaming process, foam stability can be described in a simple and easy manner. In general, the investigated alkylaldonamides form foams of medium stability. However, for some homologues a transition from unstable to stable foam systems is observed with increasing concentration. Modifications of the molecular structure of the alkylaldonamides are distinctly reflected in their foam properties. This fact concerns not only changes of the hydrophobic moiety and its functionalization but also slight variations of the saccharide residue. Each homologous series reveals an exceptional foam behavior. In the case of the N,N-di-n-alkylaldonamides the increase of the n-alkyl chain length is accompanied by an increase of the foam stability. The aqueous solutions of the N-alkyl-N-(2-hydroxyethyl)aldonamides reveal most favorable foaming properties for homologues with average alkyl chain lengths. Moreover, it was found that the occurrence of a phase transition in the adsorption layers of the N-cyclooctylgluconamides previously observed by surface tension and surface potential measurements is also remarkably reflected in their foam stability.

Adsorption behavior of surface chemically pure N-cycloalkylaldonamides at the air/water interface.

Equilibrium surface tension (sigma(e)) and electric surface potential (DeltaV(e)) versus concentration isotherms of the homologous series of N-cycloalkylaldonamides synthesized from cycloalkylamines (from cyclopentyl- to cyclododecylamine) and D-glucono-1,5-lactone (c-C(n)GA) or D-glucoheptono-1,4-lactone (c-C(n)GHA) (c-n(C) = 5-12) were investigated at the air/water interface. The measurements were performed with aqueous, surface chemically pure surfactant solutions. Equilibrium surface tension vs concentration isotherms were evaluated to get the adsorption parameters, i.e., standard free energy of adsorption, DeltaG degrees (ads), saturation surface concentration, Gamma(infinity), minimum surface area demand per molecule adsorbed, A(min), and interaction parameter, H(s). Increasing the size of the cycloalkyl moiety leads to a significant increase of the minimum surface area demand per molecule adsorbed. This fact, together with a decrease of the intermolecular interaction parameter suggests that the introduction of a more bulky cycloalkyl ring (c-n(C) = 7 and 8) causes an attenuation of the hydrogen-bond network. This goes in line with the exceptional finding that the higher homologues revealed improved solubility in water. In addition, surface tension investigations suggest occurrence of a phase transition for the N-cyclooctylaldonamides at relatively small surface coverage. This observation is well supported by the surface potential measurements, for which the effect of possible changes in the molecules' surface orientation is even more pronounced. Moreover, the concentration intervals of N-cyclooctylaldonamide in which the change in orientation is observed for either the surface tension or the surface potential isotherms are in very good agreement.

Synthesis of novel N,N-di-n-alkylaldonamides and properties of their surface chemically pure adsorption layers at the air/water interface.

A homologous series of new surface-active N,N-di-n-alkyl-substituted amides derived from delta-D-gluconolactone and alpha-D-glucoheptonic-gamma-lactone were synthesized. The adsorption isotherms of their surface-chemically pure solutions were measured and evaluated to obtain the adsorption parameters of standard free energy of adsorption (DeltaG(0)(ad)), surface excess (Gamma( infinity )), cross-sectional area of the adsorbed surfactant molecule (A(min)), and surface interaction parameter (H(s)). The surfactants possess comparatively low solubilities and do not form micelles at room temperature. This behavior is opposite to that of the other types of sugar surfactants showing excellent solubility and a strong tendency to association/micellization. The derivatives of gluconamide reveal surface activity slightly higher than that of the derivatives of glucoheptonamide, especially for long alkyl chains (n(C)>4). An increase in A(min) of about 6 A(2)/molecule for the gluconic series is observed.

On the adsorption kinetics of surface-chemically pure n-dodecanoic acid at the air/water interface.

The dynamic surface tension data for n-dodecanoic acid in 0.005 M hydrochloric acid, for as-received as well as for surface-chemically pure solutions, show the presence of a prolonged induction period, clearly indicating that the adsorption of this nonionic surfactant is not simply diffusion-controlled. A kinetic model for the reversible formation of monolayer islands, long known in the field of electrochemistry, is shown to also apply to the adsorption of n-dodecanoic acid at the air/water interface. The rate constant increases linearly with increasing bulk concentration, while the induction time decreases exponentially. The phenomenon of nucleation at the air/water interface is consistent with the direct experimental observation of the formation of solid-like patches as the interfacial region is drastically compressed.

Adsorption behavior of surface-chemically pure N-alkyl-N-(2-hydroxyethyl)aldonamides at the air/water interface.

N-alkyl-N-(2-hydroxyethyl)aldonamides (alkyl: n-C6H13, n-C8H17, n-C10H21, n-C12H25, and n-C14H29) were obtained in the reaction of long-chain N-alkyl-N-(2-hydroxyethyl)amines with D-glucono-1,5-lactone and D-glucoheptono-1,4-lactone. The adsorption isotherms were obtained from surface tension measurements of aqueous solutions of surface-chemically pure surfactants. The experimental equilibrium surface tension versus concentration isotherms were evaluated by the Frumkin adsorption equation to get the adsorption parameters, namely, standard free energy of adsorption, deltaG(o)ad, saturation adsorption, gammainfinity minimum surface area demand per molecule adsorbed, Amin, and interaction parameter, Hs. The investigated functionalized alkylaldonamides show improved solubility in comparison with the corresponding sugar derivatives of the primary amines. The introduction of the -CHOH moiety into the saccharide headgroup causes a noticeable increase of the hydrophobic character of surfactant. The minimum surface area demand, Amin, is slightly greater for glucoheptonamides than for the corresponding gluconamides. The practically constant Amin value within the homologue series of the aldonamides indicates that the obtuse hydroxyethyl residue is the determining factor for the arrangement of the adsorbed surfactants in the interfacial layer.

Quantitative Brewster angle microscopy of the surface film of human broncho-alveolar lavage fluid.

The morphology, thickness and surface pressure of the surfactant film of broncho-alveoalar lavage (BAL) fluid from patients with sarcoidosis were investigated during spontaneous adsorption of the BAL's surface active material at the air/aqueous buffer interface at 37 degrees C. The biochemical parameters of the BAL fluid determined were protein (Lowry), total phospholipids (from phosphate after ashing) and the individual phospholipids (HPLC). During the spontaneous adsorption of the pulmonary surfactant the surface pressure increased from initially 26 mN/m to 44 mN/m in the equilibrium state. Simultaneously to the increase of the surface pressure, a continuous increase of the reflectivity signal was observed by quantitative Brewster angle microscopy (BAM). The film thickness is calculated from the reflectivity values using an optical model. The effect of the uncertainty of the refractive index, which has to be estimated, is discussed. The BAM images show the inhomogeneous nature of the surfactant film with three distinct phases of different reflectivity, even at relatively low surface pressures. For the brightest phase, the thickness amounts to approximately 12 nm in the equilibrium state of adsorption. This suggests a multilamellar structure. Additionally, we found visual evidence for an adsorption mechanism involving the spreading of vesicles at the interface, in agreement with published results. Differences in the morphology and thickness of the pulmonary surfactant film reported in the literature are obviously due to the varying experimental conditions and materials. We think that the experimental conditions chosen in our study provide a more realistic view of the structure in the lungs in vivo.

Interfacial Behavior of n-decyl-beta-D-maltopyranoside on hydrophobic interfaces and the effect of small amounts of surface-active impurities.

The effect of small amounts of surface-active impurities on the interfacial properties of n-decyl-beta-D-maltopyranoside was investigated using various methods. The n-Decyl-beta-D-maltopyranoside was used both as received from Sigma (<98% by GC) and after being purified with the surfactant-purifying apparatus developed by Lunkenheimer, which removes impurities that are more surface active than the major component. Surface tension measurements demonstrate that the surface elasticity of the surfactant-loaded liquid-vapor interface increased after purification. Measurements of interactions across single foam films revealed that the purified solution formed considerably less charged and less stable films compared with the as-received sample. These results are consistent with the lower foam stability for the purified sample as determined by simple shaking experiments. The lower film stability for the purified solution was attributed to the lower double-layer force. The forces acting between spherical silanated glass surfaces across surfactant solutions were determined with the MASIF (measurement and analysis of surface interaction forces) technique. On approach, the same interactions were experienced in solutions of the as-received and purified surfactant. On the other hand, the adhesion force was lower after purification. Both for the as-received and the purified sample it was observed that the adhesion increased with increasing contact time up to a certain limit. This was explained in terms of partial pressure-induced desorption of surfactants from the disordered silane layers. Wetting experiments also indicated that the surfactants were difficult to remove completely from this surface.