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Abstract: We have designed a peptide with switchable surface activity, where the folded (α-helical) form of the peptide is amphiphilic and the unfolded form is not. To understand the factors influencing the dynamics of the switchability, a model is developed for the transport of the surface active form of the peptide from the solution onto air–water interface. As is the case with the low molecular weight head–tail surfactants, the transport involves the bulk diffusion of the folded form to the surface and the kinetic adsorption onto the interface. Unlike the head–tail surfactants, the diffusion can be augmented by the kinetics of the folding of the peptide from the unfolded form. The model is formulated within the context of the transport of the peptide from a uniform bulk solution onto an initially clean air–water interface in a pendant bubble system, where the transport rate can be measured by recording the reduction in surface tension using the shape analysis of the bubble. Experiments are undertaken and compared to the predictions of the model simulations of the tension reduction for a range of values of the kinetic adsorption constant and the folding kinetic constant. The results indicate that the kinetic adsorption rate of the folded peptide onto air–water interface dominates the dynamic process, which contrasts many head–tail surfactants where diffusion typically dominates over kinetics adsorption. Moreover, our ‘best-fits’ suggest that there is a phase transition at high surface concentrations that slows the long-time adsorption of the peptides to the interface. Finally, the numerical solution is compared with an asymptotic solution, showing agreement with our findings that the fundamental dynamics of the tunable surface-active peptide are indeed controlled by the adsorption step. [Copyright &y& Elsevier]

An aqueous soluble surfactant adsorbing from solution onto an initially clean air/water interface often exhibits an induction period in the surface tension relaxation in which, as the adsorption begins, the tension remains near the clean interface value for an extended period of time before decreasing rapidly to the equilibrium value. In this study, using a model nonionic soluble surfactant, C14E6(CH3(CH2)13–(OCH2CH2)6–OH), we present direct fluorescence evidence that this induction is due to a first-order phase transition from a gaseous (G) to a liquid expanded (LE) phase that the assembling monolayer undergoes at constant surface pressure. An open channel flow cell is initially filled with water, and onto its air/water interface is spread an insoluble amphiphilic dye that fluoresces upon irradiation in the LE phase and whose fluorescence is quenched in the G phase. An aqueous solution of C14E6 is then allowed to flow through the channel. We observe the immediate appearance of bright islands of the LE phase growing in a dark (G) background, confirming the presence of the G/LE phase transition. These islands eventually occupy the entire surface, after which the interface remains uniformly bright. We correlate this phase transition to the induction period by simultaneously measuring the tension of the interface of the open channel, and verifying that as the islands grow the tension remains at the clean value until the bright LE phase occupies the entire surface, whereupon the tension rapidly decreases. We further develop a phase transition surfactant transport model for the induction period in which surfactant diffuses toward and kinetically adsorbs onto the surface, and then rapidly equilibrates between the G and LE phases. For our model surfactant C14E6, we independently measure the surface concentration of the nucleating LE phase, the LE phase surfactant equation of state, the kinetic rate constants for adsorption into the LE phase, and the bulk diffusion coefficient. Using these measurements, we predict induction times for adsorption onto a clean surface without convection. We also measure these induction times in tension relaxation for adsorption onto a pendant bubble using axisymmetric shape analysis, and demonstrate agreement with the simulations with no adjustable constants. [Copyright &y& Elsevier]

Lanthanide Binding Tag (LBT) peptides that coordinate selectively with lanthanide ions can be used to replace the energy intensive processes used for the separation of rare earth elements (REEs). These surface-active biomolecules, once selectively complexed with the trivalent REE cations, can adsorb to air/aqueous interfaces of bubbles for foam-based REEs recovery. Glutaraldehyde, an organic compound that is a homobifunctional crosslinker for proteins and peptides, can be used to enhance the adsorption and interfacial stabilization of lanthanide-bound peptides films. The stability of the interfacial cross-linked films was tested by measuring their dilational and shear surface rheological properties. Surface activity of the adsorbed species was analyzed using pendant drop tensiometry, while surface density and molecular arrangement were determined using x-ray reflectivity and x-ray fluorescence near total reflection. Glutaraldehyde cross-linked REE-peptide complexes enhance the adsorption of lanthanides to air-water interfaces, resulting in thicker interfacial structures. Subsequently, these thicker layers enhance the dilational and shear interfacial rheological properties. The interfacial film stabilization and REEs extraction promoted by the cross-linker presented in this work provides an approach to integrate glutaraldehyde as a substitute of common foam stabilizers such as polymers, surfactants, and particles to optimize the recovery of REEs when using biomolecules as extractants.   • The cross-linking of Lanthanide Binding Tag (LBT):Rare Earth Element (REE) complexes. • The enhancement of adsorbed REEs is due to the formation of thicker surface layers. • The rheological properties of films can be controlled by the degree of cross-linking. • The crosslinked LBT:REE complexes retain the surface selectively between REEs. [ABSTRACT FROM AUTHOR]

[Display omitted] • Hydrodynamic interactions (HI) affect the aggregation dynamics of colloids straddling a fluid–fluid interface. • For uncharged particles, HI decrease the probability of aggregate formation for all Péclet (Pe) numbers. • For charged particles, HI change the probability of aggregate formation depending on the relative magnitude and influence of electrostatic repulsive interactions. The cluster formation and self-assembly of floating colloids at a fluid/fluid interface is a delicate force balance involving deterministic lateral interaction forces, viscous resistance to relative colloid motion along the surface and thermal (Brownian) fluctuations. As the colloid dimensions get smaller, thermal forces and associated drag forces become important and can affect the self assembly into ordered patterns and crystal structures that are the starting point for various materials applications. Langevin dynamic simulations for particle pairs straddling a liquid–liquid interface with a high viscosity contrast are presented to describe the lateral interfacial assembly of particles in Brownian and non-Brownian dominated regimes. These simulations incorporate capillary attraction, electrostatic repulsion, thermal fluctuations and hydrodynamic interactions (HI) between particles (including the effect of the particle immersion depth). Simulation results are presented for neutrally wetted particles which form a contact angle θ = 90 0 at the interface. The simulation results suggest that clustering, fractal growth and particle ordering become favorable outcomes at critically large values of the Pe numbers, while smaller Pe numbers exhibit higher probabilities of final configurations where particle motion remains uncorrelated in space and particle pairs are found to be more widely separated especially upon the introduction of HI. [ABSTRACT FROM AUTHOR]

[Display omitted] • Hydrodynamic interactions (HI) affect the aggregation dynamics of colloids straddling a fluid–fluid interface. • For uncharged particles, HI decrease the probability of aggregate formation for all Péclet (Pe) numbers. • For charged particles, HI change the probability of aggregate formation depending on the relative magnitude and influence of electrostatic repulsive interactions. The cluster formation and self-assembly of floating colloids at a fluid/fluid interface is a delicate force balance involving deterministic lateral interaction forces, viscous resistance to relative colloid motion along the surface and thermal (Brownian) fluctuations. As the colloid dimensions get smaller, thermal forces and associated drag forces become important and can affect the self assembly into ordered patterns and crystal structures that are the starting point for various materials applications. Langevin dynamic simulations for particle pairs straddling a liquid–liquid interface with a high viscosity contrast are presented to describe the lateral interfacial assembly of particles in Brownian and non-Brownian dominated regimes. These simulations incorporate capillary attraction, electrostatic repulsion, thermal fluctuations and hydrodynamic interactions (HI) between particles (including the effect of the particle immersion depth). Simulation results are presented for neutrally wetted particles which form a contact angle θ = 90 0 at the interface. The simulation results suggest that clustering, fractal growth and particle ordering become favorable outcomes at critically large values of the Pe numbers, while smaller Pe numbers exhibit higher probabilities of final configurations where particle motion remains uncorrelated in space and particle pairs are found to be more widely separated especially upon the introduction of HI. [ABSTRACT FROM AUTHOR]

(a) A surfactant-covered droplet deformed by uniform electric field; (b) Steady deformation as a function of electric capillary number; (c) Unsteady deformation for various dilatational viscosity values. [Display omitted] • Surfactants affect the deformation of a conducting droplet in an electric field. • Steady drop deformation is enhanced by surfactants but reduced by surface elasticity. • Surface dilatational viscosity controls unsteady deformation and delays equilibration. A conducting droplet suspended in an insulating continuous phase, e.g. an aqueous electrolyte in an oil, is deformed by an applied electric field to nonspherical equilibrium shapes, and can even break-up under strong fields. Many technologies use electro-deformation to manipulate fluid dispersions, with surfactants present on the droplet interfaces forming stabilizing monolayers. While surfactants lower the interface tension which facilitates electro-deformation, the monolayer elasticity resists deformation. High molecular weight surfactants, with large dilatational viscosities, can potentially retard the deformation dynamics. A boundary integral method simulates the dynamic interfacial deformation of a perfectly conducting droplet in a dielectric in a uniform field. The interface contains an insoluble monolayer which is a Newtonian fluid with constant dilatational viscosity obeying a Langmuir state equation. A range of initial surfactant surface concentrations are studied, with elasticity proportional to concentration. Equilibrium drop deformations, unaffected by surface viscosity, are strongly resisted by elasticity at high surface concentrations, and field strengths necessary for break-up increase with elasticity. Dilatational viscosity scales with the ratio, κ ∗ , the surface viscosity (divided by the droplet radius) to the bulk viscosity, and can extend the deformation time. Extended times are described by a time rescaling proportional to κ ∗ . [ABSTRACT FROM AUTHOR]

Hypothesis The thermocapillary migration of a spherical drop with a stagnant cap in the presence of a constant applied temperature gradient can be strongly affected by the finite thermal conductivity of the stagnant cap. Numerics The heat conduction of the stagnant cap is analytically modeled. The effects of the additional interfacial stresses generated by the disturbances to the local temperature field due to the presence of the cap at the fluid-fluid interface and the corresponding velocity of migration of the drop are evaluated by solving for the temperature and hydrodynamic field equations in and around the drop. An asymptotic model is derived to predict the terminal velocity in the presence of an infinitely conducting stagnant cap. Findings The effects of the surface conductivity and size of the stagnation region alongside the bulk thermal conductivities and viscosities of the drop and surrounding media are evaluated. The terminal velocity of the drop is shown to have a monotonic dependence on the conductivity of the stagnant cap. The bounds to the terminal velocity increment due to the stagnant cap are derived. These bounds can be of significance to multiphysics problems involving particle laden drops, Pickering emulsions and other multi-phase technologies where the conductivity of the surface adsorbents is non-negligible. • Thermocapillary migration velocity of drop with a conducting stagnant cap under an applied temperature gradient studied. • Asymptotic bounds established for the effect of the stagnant cap conductivity on the migration velocity. • Analyzed the effect of the constitutive properties of the drop and surrounding fluid on the migration velocity. [ABSTRACT FROM AUTHOR]

Super-spreading trisiloxane surfactants are a class of amphiphiles which consist of nonpolar trisiloxane headgroups (((CH3)3&z.sbnd;Si&z.sbnd;O)2&z.sbnd;Si(CH3)(CH2)3&z.sbnd;) and polar parts composed of between four and eight ethylene oxides (ethoxylates, &z.sbnd;OCH2CH2&z.sbnd;). Millimeter-sized aqueous drops of trisiloxane solutions at concentrations well above the critical aggregate concentration spread rapidly on very hydrophobic surfaces, completely wetting out at equilibrium. The wetting out can be understood as a consequence of the ability of the trisiloxanes at the advancing perimeter of the drop to adsorb at the air/aqueous and aqueous/hydrophobic solid interfaces and to reduce considerably the tensions of these interfaces, creating a positive spreading coefficient. The rapid spreading can be due to maintaining a positive spreading coefficient at the perimeter as the drop spreads. However, the air/aqueous and solid/aqueous interfaces at the perimeter are depleted of surfactant by interfacial expansion as the drop spreads. The spreading coefficient can remain positive if the rate of surfactant adsorption onto the solid and fluid surfaces from the spreading aqueous film at the perimeter exceeds the diluting effect due to the area expansion. This task is made more difficult by the fact that the reservoir of surfactant in the film is continually depleted by adsorption to the expanding interfaces. If the adsorption cannot keep pace with the area expansion at the perimeter, and the surface concentrations become reduced at the contact line, a negative spreading coefficient which retards the drop movement can develop. In this case, however, a Marangoni mechanism can account for the rapid spreading if the surface concentrations at the drop apex are assumed to remain high compared to the perimeter so that the drop is pulled out by the higher tension at the perimeter than at the apex. To maintain a high apex concentration, surfactant adsorption must exceed the rate of interfacial dilation at the apex due to the outward flow. This is conceivable because, unlike that at the contact line, the surfactant reservoir in the liquid at the drop center is not continually depleted by adsorption onto an expanding solid surface. In an effort to understand the rapid spreading, we measure the kinetic rate constants for adsorption of unaggregated trisiloxane surfactant from the sublayer to the air/aqueous surface. The kinetic rate of adsorption, computed assuming the bulk concentration of monomer to be uniform and undepleted, represents the fastest that surfactant monomer can adsorb onto the air/aqueous surface in the absence of direct adsorption of aggregates. The kinetic constants are obtained by measuring the dynamic tension relaxation as trisiloxanes adsorb onto a clean pendant bubble interface. We find that the rate of kinetic adsorption is only of the same order as the area expansion rates observed in superspreading, and therefore the unaggregated flux cannot maintain very high surface concentrations at the air/aqueous interface, either at the apex or at the perimeter. Hence in order to maintain either a positive spreading coefficient or a Marangoni gradient, the surfactant adsorptive flux needs to be augmented, and the direct adsorption of aggregates (which in the case of the trisiloxanes are bilayers and vesicles) is suggested as one possibility. [Copyright &y& Elsevier]

Abstract: This study demonstrates how luminescent semiconductor nanocrystals (quantum dots or QDs) can be dispersed uniformly in a poly(dimethylsiloxane) (PDMS) matrix by polymerizing a mixture of the prepolymer oligomers and the nanocrystals with a relatively large concentration of crosslinking molecules. A microfluidic device is used to fabricate PDMS microbeads embedded with the QDs by using flow focusing to first form monodisperse droplets of the prepolymer/crosslinker/nanocrystal mixture in a continuous aqueous phase. The droplets are subsequently collected, and heated to polymerize them into solid microbead composites. The degree of aggregation of the nanocrystals in the matrix is studied by measuring the nonradiative resonance energy transfer (RET) between the nanocrystals. For this purpose, two quantum dots are used with maxima in their luminescence emission spectrum at 560nm and 620nm. When the nanocrystals are within the Förster radius (approximately 10nm) of each other, exciton energy cascades from the QDs which emit at the shorter wavelength to the QDs which emit at the longer wavelength. This energy transfer is quantified, for two concentration ratios of the prepolmer to the crosslinker, by measuring the deviation of the microbead luminescence spectrum from a reference spectrum obtained by dispersing the QD mixture in a solvent (toluene) in which the nanocrystals do not aggregate. For a low concentration of crosslinking molecules relative to the prepolymer (5:1 by weight prepolymer to crosslinker), strong RET is observed as the emission of the 620nm QDs is increased and the 560nm QDs is decreased relative to the reference. In the emission spectrum for a higher concentration of crosslinkers (2:1 by weight prepolymer to crosslinker), the resonance energy transfer is less relative to the case of the low concentration of crosslinkers, and the spectrum more closely resembles the reference. This result indicates that the increase in the crosslinker concentration has reduced the nanocrystal aggregation in the cured polymer. The use of crosslinking can serve as a general paradigm for forming, from a prepolymer/nanoparticle mixture, a composite in which the particles are not aggregated. Under the usual conditions the entropic cost to a linearly growing polymer chain of surrounding nanoparticles forces them to aggregate; crosslinking kinetically entraps the particles and circumvents this aggregation driving force. The QD/polymer composite microbeads fabricated in this study find applications in bead-based platforms for high-throughput, multiplexed screening, where the emission spectrum of the QD luminescence can be used as a spectral barcode to label the beads. For microbeads in which the nanocrystals are uniformly dispersed, this barcode is undistorted by energy transfer, and is easily read. [Copyright &y& Elsevier]