Influence of the flow on the anchoring of nematic liquid crystals on a Langmuir-Blodgett monolayer studied by optical second-harmonic generation

The influence of capillary flow on the alignment of the nematic liquid crystal MBBA on fatty acid Langmuir-Blodgett monolayers was studied by optical second-harmonic generation. The surface dipole sensitivity of the technique allows probing the orientation of the first liquid crystal monolayer in the presence of the liquid crystal bulk. It was found that capillary flow causes the first monolayer of liquid crystal molecules in contact with the fatty acid monolayer to be oriented in the flow direction with a large pretilt (78 degrees), resulting in a quasi-planar alignment with splay-bend deformation of the nematic director in the bulk. itself is affected by the flow. The quasi-planar flow-induced alignment was found to be metastable. Once the flow ceases, circular domains of homeotropic orientation nucleate in the sample and expand until the whole sample becomes homeotropic. This relaxation process from flow-induced quasi-planar to surface-induced homeotropic alignment was also monitored by SHG. It was found that in the homeotropic state the first nematic layer presents a pretilt of 38 degrees almost isotropically distributed in the plane of the cell, with a slight preference for the direction of the previous flow.Comment: LaTeX2e article, 11 figures, 17 EPS files, submitte

Phase-matched second-harmonic generation in a ferroelectric liquid crystal waveguide

True phase-matched second-harmonic generation in a waveguide of crosslinkable ferroelectric liquid crystals is demonstrated. These materials allow the formation of macroscopically polar structures whose order can be frozen by photopolymerization. Homeotropic alignment was chosen which offers decisive advantages compared to other geometries. All parameters contributing to the conversion efficiency are maximized by deliberately controlling the supramolecular arrangement. The system has the potential to achieve practical level of performances as a frequency doubler for low power laser diodes.Comment: 4 pages, LaTeX2e article, 3 figures, 4 EPS files, submitted to Physical Review Letter

A parameter predict ing the foam stability of mixtures of aqueous ionic amphiphile solutions with indifferent electrolyte

Sodium dodecyl sulfate (SDS) is a well-defined model substance for anionic molecular surfactants. Aqueous mixtures of SDS in a surface chemically purified state and high purity NaCl were studied with respect to their equilibrium and dynamic surface tensions at a constant mean ionic activity I-mean of 1 mmol L-1. All studied solutions possessed the same equilibrium surface tension, however they showed striking differences in foam column and foam lamella stability experiments. This observation suggested the interpretation of the results in terms of dynamic interfacial properties. Oscillating bubble experiments were conducted to determine the frequency dependence of the surface dilatational modulus in a range from 5 to 400 Hz. The obtained surface dilatational modulus could be described by the extended Lucassen-van den Tempel (LvdT) model, which allows capturing dissipative processes by the intrinsic surface viscosity. within the interfacial region. A new parameter derived from the fitting parameters of the LvdT model correlates reasonably with direct measurements of the solutions' foam stability. The data suggest the important role of surface rheology for the stability of foams

Measurement of the lifetime of individual foam lamellae

Foams play a crucial role in a number of practical applications. Their analysis in terms of stability is subject to a large number of parameters. An automated, light reflection based device for the measurement of the lifetime of a single foam lamella of aqueous surfactant solutions in contact with the liquid and gas phases is proposed. The capability of the method is shown for the analysis of the cationic and anionic model surfactants hexadecyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) with saturated humidity, respectively. A statistical approach for analysis of the individual foam lamella lifetimes is presented and a comparison to the foam stability parameters obtained from a foam column device is presented. Published by AIP Publishing

The surface rheological signature of the geometric isomers of an azobenzene–surfactant

The equilibrium and dynamic surface properties of a photosensitive azobenzene-surfactant subject to illumination with UV and Vis-light leading to the respective geometric cis- and trans-isomers were studied. The adsorption layers formed by the soluble surfactant were characterized by pendant drop tensiometry and surface rheology using the oscillating bubble technique. Aqueous solutions corresponding to the geometric isomers could clearly be distinguished in terms of both their equilibrium and dynamic surface properties. The frequency dependence of the surface dilatational modulus could be described by the extended Lucassen-van den Tempel (LvdT)-model. These findings can be interpreted in terms of the changes of the dipole moment. Furthermore, they shed some light on the relation between the molecular structure and macroscopic properties of the adsorption layer

The influence of lanthanide-(III)-nitrates on adsorbed monolayers of dodecylphosphorylcholine at the air-water interface

Adsorption layers at the air-water interface formed from the soluble zwitterionic surfactant dodecylphosphorylcholine (DPC) serving as a soluble model substance for phospho-lipids were characterized with respect to their equilibrium and dynamic surface properties. To clarify the effect of ionic interactions with electrolyte present in the bulk phase, surface Theological properties upon addition of Ce(NO3)(3) and Yb (NO3)(3) were determined. In order to account for the surface activity of the nitrate ion, comparative measurements using NaNO3 were carried out additionally. Further experimental information on the bulk hydration characteristics of the aqueous solutions was obtained using dielectric relaxation spectroscopy (DRS). A possible mechanism causing the deviating surface dilatational modulus E in terms of ion specificity is suggested. (C) 2019 Published by Elsevier Inc

The influence of highly charged Ce 4+ -cations on aqueous solutions of SDS

The surface dilatational modulus E is a fundamental system parameter of aqueous surfactant solutions which plays an important role in the physic of foams. In this contribution, we study the influence of highly charged Cerium-ions (Ce4+)-on the surface dilatational modulus E of aqueous sodium dodecyl sulfate (SDS) solutions. The E-modulus has been determined at two concentrations below the critical micellar concentration (cmc) in the frequency range from 3 Hz to 500 Hz using the oscillating bubble technique. The presence of Ce4+-ions increases the surface activity of the surfactant leading to a shift of the equilibrium surface tension isotherm to lower concentrations. The cmc is reduced to 2 x 10(-3) mol L-1. Adsorption layers of aqueous SDS solutions exhibit a surface visco-elastic behavior. The magnitude and the phase of the complex dilatational modulus E increase in a continuous fashion with the frequency indicating a dissipative process within the adsorption layer. The presence of the electrolyte modifies the frequency characteristics of the complex modulus towards the features of a surface elastic system. Furthermore there are pronounced changes in the stability of the corresponding foams. The lifetime of wet foam lamella is significantly reduced by the presence of the Ce4+-ions. The results provide evidence for the decisive impact of surface visco-elastic properties on foam stability of aqueous surfactant solutions. (C) 2016 Elsevier B.V. All rights reserved

The Role of Surface Viscosity in the Escape Mechanism of the Stenus Beetle

Beetles of the species Stenus comma live and hunt close to ponds and rivers, where they occasionally fall on the water surface. To escape this jeopardized state, the beetle developed a strategy relying on the excretion of a secretion containing the substances stenusine and norstenusine. They reduce surface tension and propel the bug to the saving river bank. These substances were synthesized and analyzed with respect to their equilibrium and dynamic adsorption properties at the air-water interface (pH 7, 23 +/- 1 degrees C). The surface dilatational rheological characteristics in a frequency range from 2 to 500 Hz at molar bulk concentrations of 20.6 mmol L-1 were studied using the oscillating bubble technique. Both alkaloids formed surface viscoelastic adsorption layers. The frequency dependence of the surface dilatational modulus E could successfully be described by the extended Lucassen-van den Tempel model accounting for a nonzero intrinsic surface viscosity kappa. The findings confirmed a dual purpose of the spreading alkaloids in the escape mechanism of the Stenus beetle. Next to generating a surface pressure, a transition to surface viscoelastic behavior of the adsorbed layers was observed

Simultaneous measurement of the thickness and the lifetime of a foam lamella

Despite the important role of foams in industrial applications, few methods for determining the stability are present. By extending the existing light reflection-based apparatus, additional information about a single foam lamella can be obtained. Evaluation of these data delivers insight into the thinning process of the lamella. The potential of this technique is shown for the analysis of two surfactants with different head group lengths (Lutensol XP 100 and Lutensol XP 140). Published under license by AIP Publishing

Investigation of the kinetics and mechanism of low endotoxin recovery in a matrix for biopharmaceutical drug products

The inability to detect endotoxin added to undiluted drug samples has been called: Low Endotoxin Recovery (LER). The phenomenon has caused concerns amongst drug manufacturing quality control scientists in that manufactured solutions contaminated with endotoxin could show false-negative results via routine Limulus-based tests. The time-dependent appearance of LER has been analyzed in detail to provide a better understanding of the mechanism. The assumption has been that the root-cause of LER involves the interplay of endotoxin with surfactants and results in aggregate structures that are complexed with surfactants. The endotoxin molecules when complexed with surfactants are not accessible for Limulus-based detection. The results demonstrate a predominant role of complex-forming agents. It was shown that although the presence of surfactants is a strong prerequisite for masking, it does not determine the kinetics of endotoxin masking. Interestingly, the endotoxin concentration itself had no substantial impact on LER kinetics. By adjusting the ratios of complex-forming constituents, including surfactant, chelator and endotoxin, and by testing the order in which the constituents are added, a new model for simulating masking kinetics has been determined. Our work provides for the first time a model to simulate masking kinetics of endotoxin which lends a better understanding of LER