Fluorescence Recovery after Merging a Droplet to Measure the Two-dimensional Diffusion of a Phospholipid Monolayer

We introduce a new method to measure the lateral diffusivity of a surfactant monolayer at the fluid-fluid interface, called fluorescence recovery after ...

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Synthesis of multifunctional micrometer-sized particles with magnetic, amphiphilic, and anisotropic properties.

Dynamics within surfactant monolayers.

At low mole fractions, cholesterol segregates into 10- to 100-nm-diameter nanodomains dispersed throughout primarily dipalmitoylphosphatidylcholine (DPPC) domains in mixed DPPC:cholesterol monolayers. The nanodomains consist of 6:1 DPPC:cholesterol "complexes" that decorate and lengthen DPPC domain boundaries, consistent with a reduced line tension, λ. The surface viscosity of the monolayer, ηs, decreases exponentially with the area fraction of the nanodomains at fixed surface pressure over the 0.1- to 10-Hz range of frequencies common to respiration. At fixed cholesterol fraction, the surface viscosity increases exponentially with surface pressure in similar ways for all cholesterol fractions. This increase can be explained with a free-area model that relates ηs to the pure DPPC monolayer compressibility and collapse pressure. The elastic modulus, G', initially decreases with cholesterol fraction, consistent with the decrease in λ expected from the line-active nanodomains, in analogy to 3D emulsions. However, increasing cholesterol further causes a sharp increase in G' between 4 and 5 mol% cholesterol owing to an evolution in the domain morphology, so that the monolayer is elastic rather than viscous over 0.1-10 Hz. Understanding the effects of small mole fractions of cholesterol should help resolve the controversial role cholesterol plays in human lung surfactants and may give clues as to how cholesterol influences raft formation in cell membranes.

Effect of cholesterol nanodomains on monolayer morphology and dynamics.

Understanding the distinctive phase behaviors in random packing due to particle shapes is an important issue in condensed matter physics. In this paper, we investigate the random packing structure of two-dimensional (2D) snowmen via wax-snowman packing experiments and Brownian dynamics simulations. Both experiments and simulations reveal that neighboring snowmen have a strong short-range orientational correlation and consequently locally form particular conformations. A chiral conformation is dominant for high area fractions near the jamming condition (φ>0.8), and the proportion of the chiral conformation increases with γ. We also found that the attractive interaction does not have a significant impact on the results. The geometry of chirally ordered snowmen causes a mismatch with 2D crystalline symmetries and thus inhibits the development of long-range spatial order, despite the strong orientational correlation between neighbors.

Shape-induced chiral ordering in two-dimensional packing of snowmanlike dimeric particles.

We demonstrate large-area, closely-packed optical vortex arrays using self-assembled defects in smectic liquid crystals. Self-assembled smectic liquid crystals in a three-dimensional torus structure are called focal conic domains. Each FCD, having a micro-scale feature size, produces an optical vortex with consistent topological charge of 2. The spiral profile in the interferometry confirms the formation of an optical vortex, which is predicted by Jones matrix calculations.

Optical vortex arrays from smectic liquid crystals.

Adding small fractions of cholesterol decreases the interfacial viscosity of dipalmitoylphosphatidylcholine (DPPC) monolayers by an order of magnitude per wt %. Grazing incidence X-ray diffraction shows that cholesterol at these small fractions does not mix ideally with DPPC but rather induces nanophase separated structures of an ordered, primarily DPPC phase bordered by a line-active, disordered, mixed DPPC-cholesterol phase. We propose that the free area in the classic Cohen and Turnbull model of viscosity is inversely proportional to the number of molecules in the coherence area, or product of the two coherence lengths. Cholesterol significantly reduces the coherence area of the crystals as well as the interfacial viscosity. Using this free area collapses the surface viscosity data for all surface pressures and cholesterol fractions to a universal logarithmic relation. The extent of molecular coherence appears to be a fundamental factor in determining surface viscosity in ordered monolayers.

Influence of molecular coherence on surface viscosity.

Optical trapping of nanometer-sized lipid vesicles has been challenging due to the low refractive index contrast of the thin lipid bilayer to the aqueous medium. Using an "optical bottle", a recently developed technique to measure interactions of nanoparticles trapped by an infrared laser, we report, for the first time, quantitative measurements of the trapping energy of charged lipid vesicles. We found that the trapping energy increases with the relative amount of anionic lipids (DOPG) to neutral lipids (DOPC) in vesicles. Moreover, as monovalent salt is added into the exterior solution of vesicles, the trapping energy rapidly approaches zero, and this decrease in trapping energy strongly depends on the amount of anionic lipids in vesicles. A simple model with our experimental observations explains that the trapping energy of charged lipid vesicles is highly correlated with the surface charge density and electric double layer. In addition, we demonstrated selective trapping of a binary mixture of vesicles in different mole fractions of charged lipids, a strategy that has potential implications on charge selective vesicle sorting for engineering applications.

Surface charge effects on optical trapping of nanometer-sized lipid vesicles.

We study electrostatic interactions of polystyrene particles at an oil/water interface controlled by a chemical reaction of carboxylate surface functional groups. By replacing the carboxyl functional groups with hydrocarbon chains using the well-known EDC (1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide) coupling reaction, the surface charge density decreases while the hydrophobicity of the colloid surface increases. Direct visualization of the particle-laden interface reveals that, depending on the extent of hydrocarbon coupling, the strength of the electrostatic repulsion can be regulated: the repulsive interaction increases with the reaction, removing aggregates, but rapidly decreases if the reaction proceeds too much, forming a large aggregation. This simple reaction, thus, dramatically changes the structures of the colloidal monolayers at the oil/water interface. We conclude that such structural change is the result of change of the repulsive interactions from the oil phase, although interactions in the water phase are also changed slightly.

Surface charge regulation of carboxyl terminated polystyrene latex particles and their interactions at the oil/water interface.

We present a novel technique to measure diffusion coefficients of insoluble surfactant monolayers. We merge a surfactant-coated droplet with a fluorescently labeled planar monolayer. During the merging process, a monolayer on a droplet displaces the existing planar monolayer, leaving a dark area when viewed under a fluorescence microscope. We measure fractional intensities as the dyes recover, which allows diffusion coefficients to be computed. We validate this technique with the two most common phospholipid monolayers (DPPC and DOPC) and study the diffusion of their mixtures. The proposed technique has several advantages over the FRAP technique and is potentially capable of measuring the diffusion of any soluble/insoluble surfactant monolayers.

Fluorescence recovery after merging a surfactant-covered droplet: a novel technique to measure the diffusion of phospholipid monolayers at fluid/fluid interfaces.

Siyoung Q. Choi

Information and Electrical Research Institute

KAIST

Fluorescence Recovery after Merging a Droplet to Measure the Two-dimensional Diffusion of a Phospholipid Monolayer

Siyoung Q. Choi

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Information and Electrical Research Institute

KAIST

Fluorescence Recovery after Merging a Droplet to Measure the Two-dimensional Diffusion of a Phospholipid Monolayer

Information and Electrical Research Institute