Structure study of a microemulsion system with an ionic liquid.

We found that an ionic liquid (IL) with a long alkyl chain moiety, 1-tetradecyl-3-methylimidazolium chloride (C14MIM·Cl), forms a single crystal after the addition of octanol in an alkane solvent. But the solution exhibits a structural change after adding a small amount of water. An optically clear solution is found within limits, and it is stable for several months. Since the IL molecule has an amphiphilic property, it behaves as a surfactant in the microemulsion system. But the IL formed a single crystal rather than a lyotropic liquid crystalline structure, unlike a typical surfactant. Therefore, it is important to understand the structure of the microemulsion system. We used the small angle neutron scattering (SANS) technique to investigate the structure. The scattering intensity was analyzed using a spherical core-shell model with the Schultz size distribution, and a contrast matching method was used to study the internal structure. The structure of the solution is confirmed to be a water-in-oil microemulsion system, and the swelling law is obeyed in the microemulsion system.

Dynamic mechanical properties of a polyelectrolyte adsorbed insoluble lipid monolayer at the air-water interface.

Polymers have been used to stabilize interfaces or to tune the mechanical properties of interfaces in various contexts, such as in oil emulsions or biological membranes. Although the structural properties of these systems are relatively well-studied, instrumental limitations continue to make it difficult to understand how the addition of polymer affects the dynamic mechanical properties of thin and soft films. We have solved this challenge by developing a new instrument, an optical-tweezer-based interface shear microrheometer (ISMR). With this technique, we observed that the interface shear modulus, G*, of a dioctadecyldimethylammonium chloride (DODAC) monolayer at the air-water interface significantly increased with adsorption of polystyrenesulfonate (PSS). In addition, the viscous film (DODAC monolayer) became a viscoelastic film with PSS adsorption. At a low salt concentration, 10 mM of NaCl in the subphase, the viscoelasticity of the DODAC/PSS composite was predominantly determined by a particular property of PSS, that is, it behaves as a Gaussian chain in a θ-solvent. At a high salt concentration, 316 mM of NaCl, the thin film behaved as a polymer melt excluding water molecules.

Ion specific effects: decoupling ion-ion and ion-water interactions.

Ion-specific effects in aqueous solution, known as the Hofmeister effect, are prevalent in diverse systems ranging from pure ionic to complex protein solutions. The objective of this paper is to explicitly demonstrate how complex ion-ion and ion-water interactions manifest themselves in the Hofmeister effect based on a series of recent experimental observations. These effects are not considered in the classical descriptions of ion effects, such as the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, and therefore they fail to describe the origin of the phenomenological Hofmeister effect. However, given that models considering the basic forces of electrostatic and van der Waals interactions can offer rationalization for the core experimental observations, a universal interaction model stands a chance of being developed. In this perspective, we separately derive the contribution from ion-ion electrostatic interactions and ion-water interactions from second harmonic generation (SHG) data at the air-ion solution interface, which yields an estimate of the ion-water interactions in solution. The Hofmeister ion effect observed for biological solutes in solution should be similarly influenced by contributions from ion-ion and ion-water interactions, where the same ion-water interaction parameters derived from SHG data at the air-ion solution interface could be applicable. A key experimental data set available from solution systems to probe ion-water interactions is the modulation of water diffusion dynamics near ions in a bulk ion solution, as well as near biological liposome surfaces. This is obtained from Overhauser dynamic nuclear polarization (ODNP), a nuclear magnetic resonance (NMR) relaxometry technique. The surface water diffusivity is influenced by the contribution from ion-water interactions, both from localized surface charges and adsorbed ions, although the relative contribution of the former is larger on liposome surfaces. In this perspective, ion-water interaction energy values derived from experimental data for various ions are compared with theoretical values in the literature. Ultimately, quantifying ion-induced changes in the surface energy for the purpose of developing valid theoretical models for ion-water interactions will be critical to rationalizing the Hofmeister effect.

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

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.

Specific ions modulate diffusion dynamics of hydration water on lipid membrane surfaces.

Effects of specific ions on the local translational diffusion of water near large hydrophilic lipid vesicle surfaces were measured by Overhauser dynamic nuclear polarization (ODNP). ODNP relies on an unpaired electron spin-containing probe located at molecular or surface sites to report on the dynamics of water protons within ~10 Å from the spin probe, which give rise to spectral densities for electron-proton cross-relaxation processes in the 10 GHz regime. This pushes nuclear magnetic resonance relaxometry to more than an order of magnitude higher frequencies than conventionally feasible, permitting the measurement of water moving with picosecond to subnanosecond correlation times. Diffusion of water within ~10 Å of, i.e., up to ~3 water layers around the spin probes located on hydrophilic lipid vesicle surfaces is ~5 times retarded compared to the bulk water translational diffusion. This directly reflects on the activation barrier for surface water diffusion, i.e., how tightly water is bound to the hydrophilic surface and surrounding waters. We find this value to be modulated by the presence of specific ions in solution, with its order following the known Hofmeister series. While a molecular description of how ions affect the hydration structure at the hydrophilic surface remains to be answered, the finding that Hofmeister ions directly modulate the surface water diffusivity implies that the strength of the hydrogen bond network of surface hydration water is directly modulated on hydrophilic surfaces.

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

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.

Simple super-resolution live-cell imaging based on diffusion-assisted Förster resonance energy transfer.

Despite the recent development of several super-resolution fluorescence microscopic techniques, there are still few techniques that can be readily employed in conventional imaging systems. We present a very simple, rapid, general and cost-efficient super-resolution imaging method, which can be directly employed in a simple fluorescent imaging system with general fluorophores. Based on diffusion-assisted Förster resonance energy transfer (FRET), fluorescent donor molecules that label specific target structures can be stochastically quenched by diffusing acceptor molecules, thereby temporally separating otherwise spatially overlapped fluorescence signals and allowing super-resolution imaging. The proposed method provides two- to three-fold-enhancement in spatial resolution, a significant optical sectioning property, and favorable temporal resolution in live-cell imaging. We demonstrate super-resolution live-cell dynamic imaging using general fluorophores in a standard epi-fluorescence microscope with light-emitting diode (LED) illumination. Due to the simplicity of this approach, we expect that the proposed method will prove an attractive option for super-resolution imaging.

Confinement-induced transition of topological defects in smectic liquid crystals: from a point to a line and pearls.

We report a study on the confinement-induced transition of the topological defects of liquid crystals (LCs) using smectic-A LCs confined in prolate spheroids with homeotropic anchoring. Upon increasing the aspect ratio of a LC droplet, dispersed in a stretched elastomer film, the topological defect undergoes a transition from a point to a line of which the length is a function of the aspect ratio. Additionally, when the size of a droplet is larger than a certain value, the defect has a pearl-necklace-like texture. We propose a simple model to understand the formation of these defects in terms of the misorientation and undulation instability of the smectic layers.

Fourier-transform light scattering of individual colloidal clusters.

We present measurements of the scalar-field light scattering of individual dimer, trimer, and tetrahedron shapes among colloidal clusters. By measuring the electric field with quantitative phase imaging at the sample plane and then numerically propagating to the far-field scattering plane, the two-dimensional light-scattering patterns from individual colloidal clusters are effectively and precisely retrieved. The measured scattering patterns are consistent with simulated patterns calculated from the generalized multiparticle Mie solution.

Polarization holographic microscopy for extracting spatio-temporally resolved Jones matrix.

We present a high-speed holographic microscopic technique for quantitative measurement of polarization light-field, referred to as polarization holographic microscopy (PHM). Employing the principle of common-path interferometry, PHM quantitatively measures the spatially resolved Jones matrix components of anisotropic samples with only two consecutive measurements of spatially modulated holograms. We demonstrate the features of PHM with imaging the dynamics of liquid crystal droplets at a video-rate.

Interface shear microrheometer with an optically driven oscillating probe particle.

We report the first experimental demonstration of an active interfacial shear microrheometer (ISMR) that uses a particle trapped by oscillating optical tweezers (OT) to probe the shear modulus G(s)(*)(ω) of a gas/liquid interface. The most significant advantages of the oscillating OT in a rheology study are: (1) very high sensitivity compared to other active microrheology methods and (2) the ability to measure both the real and imaginary components of the complex shear modulus without relying on the use of Kramers-Kronig relation, which can be problematic at low frequencies for most of the passive methods. We demonstrate the utilities of our ISMR in two case studies: (1) a 1,2-dipalmitoyl-sn-glycero-3-phosphocholine monolayer and (2) a composite of poly(styrene sulfonate) and dioctadecyldimethylammonium at the air/water interface in regimes where no other active instruments can explore.

Nanoscale assembly in biological systems: from neuronal cytoskeletal proteins to curvature stabilizing lipids.

The review will describe experiments inspired by the rich variety of bundles and networks of interacting microtubules (MT), neurofilaments, and filamentous-actin in neurons where the nature of the interactions, structures, and structure-function correlations remain poorly understood. We describe how three-dimensional (3D) MT bundles and 2D MT bundles may assemble, in cell free systems in the presence of counter-ions, revealing structures not predicted by polyelectrolyte theories. Interestingly, experiments reveal that the neuronal protein tau, an abundant MT-associated-protein in axons, modulates the MT diameter providing insight for the control of geometric parameters in bio- nanotechnology. In another set of experiments we describe lipid-protein-nanotubes, and lipid nano-tubes and rods, resulting from membrane shape evolution processes involving protein templates and curvature stabilizing lipids. Similar membrane shape changes, occurring in cells for the purpose of specific functions, are induced by interactions between membranes and proteins. The biological materials systems described have applications in bio-nanotechnology.

Excess charge density and its relationship with surface tension increment at the air-electrolyte solution interface.

The adsorption isotherms of probe cationic molecules were measured at various electrolyte solution interfaces by resonant second harmonic generation. The excess charge density was obtained by analyzing the isotherms; it increases with square root of the bulk electrolyte concentration. Its value is ion-specific and the amount of probe molecular adsorption follows the Hofmeister series. By calculating the pressure anisotropy at the interface, it is found that the ratio of surface tension increment to the bulk electrolyte concentration decreases with the square of the excess charge density. This is in good agreement with the experimental observations.

Second harmonic generation study of malachite green adsorption at the interface between air and an electrolyte solution: observing the effect of excess electrical charge density at the interface.

Understanding the differential adsorption of ions at the interface of an electrolyte solution is very important because it is closely related, not only to the fundamental aspects of biological systems, but also to many industrial applications. We have measured the excess interfacial negative charge density at air-electrolyte solution interfaces by using resonant second harmonic generation of oppositely charged probe molecules. The excess charge density increased with the square root of the bulk electrolyte concentration. A new adsorption model that includes the electrostatic interaction between adsorbed molecules is proposed to explain the measured adsorption isotherm, and it is in good agreement with the experimental results.

Liquid-crystal periodic zigzags from geometrical and surface-anchoring-induced confinement: origin and internal structure from mesoscopic scale to molecular level.

We figured out periodic undulations of lamellae "zigzags" in liquid crystals under confinement by glass and patterned silicon hybrid cell, but in the absence of applied fields. The optical and internal structures of zigzags have been investigated from mesoscopic scale to molecular level by convoluting real and reciprocal space probes, such as polarized light microscopy, scanning electron microscopy, and microbeam x-ray diffraction. The homeotropic anchoring happens at air/liquid crystal, while planar one appears at glass or patterned silicon surfaces. The wetting and displacement of lamellae near the glass surface give rise to tilting and bending in the stacking of lamellae. This can provide a solution for the origin of periodic zigzags: asymmetric strain exerted to lamellae at two-dimensional glass surface and one-dimensional-like pattern. This can give a hint for potential photonic applications such as optical gratings and modulators due to its high periodicity.

Confined self-assembly of toric focal conic domains (the effects of confined geometry on the feature size of toric focal conic domains).

A smectic liquid crystal (LC) containing a rigid biphenyl group and semifluorinated chains exhibits a high density of toric focal conic domains (TFCDs) arranged in an ordered array when confined within a microchannel. The formation of the TFCDs is strongly influenced by the width (W) and depth (h) of the confined microchannels, most importantly, by the channel depth. We studied a broad variety of microchannels, with varying width in the range of 3-200 mum and depth in the range of 2-10 mum. The radius of the TFCDs increases with increases in the width until the saturated radius is achieved, which is determined by the depth of the channel. We used the elastic-anchoring model of TFCD formation to explain the experimental observations. The model allows one to trace the dependence of the TFCD radius on the channel depth h, to explain why the TFCDs do not form in channels that are too shallow or too narrow.

In-situ observation of the inside-to-outside molecular transport of a liposome.

The first in-situ and real-time observation of the molecular transport from inside to outside of a liposome was shown by using the second harmonic generation (SHG) technique. The transport of an organic cationic molecule across the liposome bilayer could be switched on and off using the structural change of the lipid bilayer caused by temperature change. This approach can be helpful for the understanding and control of the molecular transport in the liposome vehicle.

Internal structure visualization and lithographic use of periodic toroidal holes in liquid crystals.

The formation of a large-area ordered structure by organic molecular soft building blocks is one of the most exciting interdisciplinary research areas in current materials science and nanotechnology. So far, several distinct organic building blocks--including colloids, block copolymers and surfactants--have been examined as potential materials for the creation of lithographic templates. Here, we report that perfect ordered arrays of toric focal conic domains (TFCDs) covering large areas can be formed by semi-fluorinated smectic liquid crystals. Combined with controlled geometry, that is, a microchannel, our smectic liquid-crystal system exhibits a high density of TFCDs that are arranged with remarkably high regularity. Direct visualization of the internal structure of the TFCDs clearly verified that the smectic layers were aligned normal to the side walls and parallel to the top surface, and merge with the circular profile on the bottom wall surface. Moreover, we demonstrate a new concept: smectic liquid-crystal lithography. Grown in microchannels from a mixture of liquid-crystal molecules and fluorescent particles, TFCDs of the smectic liquid crystals acted as a template, trapping particles in an ordered array. Our findings pose new theoretical challenges and potentially enable lithographic applications based on smectic liquid-crystalline materials.

Topographic control of lipid-raft reconstitution in model membranes.

Liquid-ordered (L(O)) domains reconstituted in model membranes have provided a useful platform for in vitro studies of the lipid-raft model, in which signalling membrane molecules are thought to be compartmentalized in sphingolipid- and cholesterol-rich domains. These in vitro studies, however, have relied on an uncontrolled phase-separation process that gives a random distribution of L(O) domains. Obviously, a precise control of the size and spatial distribution of the L(O) domains would enable a more systematic large-scale in vitro study of the lipid-raft model. The prerequisite for such capability would be the generation of a well-defined energy landscape for reconstituting the L(O) domain without disrupting the two-dimensional (2D) fluidity of the model membrane. Here we report controlling the reconstitution of the L(O) domains in a spatially selective manner by predefining a landscape of energy barriers using topographic surface modifications. We show that the selective reconstitution spontaneously arises from the 2D brownian motion of nanoscale L(O) domains and signalling molecules captured in these nanodomains, which in turn produce a prescribed, concentrated downstream biochemical process. Our approach opens up the possibility of engineering model biological membranes by taking advantage of the intrinsic 2D fluidity. Moreover, our results indicate that the topographic configuration of cellular membranes could be an important machinery for controlling the lipid raft in vivo.

Ordered patterns of liquid crystal toroidal defects by microchannel confinement.

In this article we present experimental results demonstrating an approach to controlling the size and spatial patterning of defect domains in a smectic liquid crystal (LC) by geometric confinement in surface-modified microchannels. By confining the LC 4'-octyl-4-cyanobiphenyl in mum-sized rectangular channels with controlled surface polarity, we were able to generate defect domains that are not only nearly uniform in size but also arranged in quasi-2D ordered patterns. Atomic force microscopy measurements revealed that the defects have a toroidal topology, which we argue is dictated by the boundary conditions imposed by the walls of the microchannel. We show that the defects can be considered to be colloidal objects, which interact with each other to form ordered patterns. This method opens the possibility for exploiting the unique optical and rheological properties associated with LC defects to making new materials. For example, the control of the shape, size, and spatial arrangement of the defects at the mesoscale suggests applications in patterning, templating, and when extended to lyotropic LCs, a process leading to uniform-sized spherical particles for chemical encapsulation and delivery.