Diffusiophoresis in Polymer and Nanoparticle Gradients.

Diffusiophoresis is the movement of the colloidal particles in response to a concentration gradient and can be observed for both electrolyte (e.g., salt) and nonelectrolyte (e.g., glucose) solutes. Here, we investigated the diffusiophoretic behavior of polystyrene (PS-carboxylate surface) microparticles in nonadsorbing charged and uncharged solute gradients [sodium polystyrenesulfonate (NaPSS), polyethylene glycol (PEG), and nanoscale colloidal silica (SiO2)] using a dead-end channel setup. We compared the diffusiophoretic motion in these gradient types with each other and to the case of using a monovalent salt gradient. In each of the nonadsorbing gradient systems (NaPSS, PEG, and SiO2 nanoparticles), the PS particles migrated toward the lower solute concentration. The exclusion distance values (from the initial position) of particles were recorded within the dead-end channel, and it was found that an increase in solute concentration increases exclusion from the main channel. In the polyelectrolyte case, the motion of PS microparticles was reduced by the addition of a background salt due to reduced electrostatic interaction, whereas it remained constant when using the neutral polymer. Particle diffusiophoresis in gradients of polyelectrolytes (charged macromolecules) is quite similar to the behavior when using a PEG gradient (uncharged macromolecule) in the presence of a background electrolyte. Moreover, we observed PS microparticles under different concentrations and molecular weights of PEG gradients. By combining the simulations, we estimated the exclusion length, which was previously proposed to be the order of the polymer radius. Furthermore, the movement of PS microparticles was analyzed in the gradient of silica nanoparticles. The exclusion distance was higher in silica nanoparticle gradients compared to similar-size PEG gradients because silica nanoparticles are charged. The diffusiophoretic transport of the PS microparticles could be simulated by considering the interaction between the PS microparticles and silica nanoparticles.

Diffusiophoretic Behavior of Polyelectrolyte-Coated Particles.

Diffusiophoresis, the movement of particles under a solute concentration gradient, has practical implications in a number of applications, such as particle sorting, focusing, and sensing. For diffusiophoresis in an electrolyte solution, the particle velocity is described by the electrolyte relative concentration gradient and the diffusiophoretic mobility of the particle. The electrolyte concentration, which typically varies throughout the system in space and time, can also influence the zeta potential of particles in space and time. This variation affects the diffusiophoretic behavior, especially when the zeta potential is highly dependent on the electrolyte concentration. In this work, we show that adsorbing a single bilayer (or 4 bilayers) of a polyelectrolyte pair (PDADMAC/PSS) on the surface of microparticles resulted in effectively constant zeta potential values with respect to salt concentration throughout the experimental range of salt concentrations. This allowed a constant potential model for diffusiophoretic transport to describe the experimental observations, which was not the case for uncoated particles in the same electrolyte system. This work highlights the use of simple polyelectrolyte pairs to tune the zeta potential and maintain constant values for precise control of diffusiophoretic transport.

Diffusiophoresis and Diffusio-osmosis into a Dead-End Channel: Role of the Concentration-Dependence of Zeta Potential.

Chemically induced transport methods open up new opportunities for colloidal transport in dead-end channel geometries. Diffusiophoresis, which describes particle movement under an electrolyte concentration gradient, has previously been demonstrated in dead-end channels. The presence of solute concentration gradients in such channels induces particle motion (phoresis) and fluid flow along solid walls (osmosis). The particle velocity inside a dead-end channel is thus influenced by particle diffusiophoresis and wall diffusio-osmosis. The magnitude of phoresis and osmosis depends on the solute's relative concentration gradient, the electrokinetic parameters of the particle and the wall, and the diffusivity contrast of cations and anions. Although it is known that some of those parameters are affected by electrolyte concentration, e.g., zeta potential, research to date often interprets results using averaged and constant zeta potential values. In this work, we demonstrate that concentration-dependent zeta potentials are essential when the zeta potential strongly depends on electrolyte concentration for correctly describing the particle transport inside dead-end channels. Simulations including concentration-dependent zeta potentials for the particle and wall matched with experimental observations, whereas simulations using constant, averaged zeta potentials failed to capture particle dynamics. These results contribute to the fundamental understanding of diffusiophoresis and the diffusio-osmosis process.

The associations between reading mind in the eyes abilities, alexithymia, empathy, and bullying behavior in Turkish adolescents.

PROBLEM: The development of any program to reduce bullying is possible with a better understanding of the associated underlying factors with its emergence. This study, therefore, aimed to investigate three different social cognitive abilities: abilities to read minds in the eyes, alexithymic personality traits, and empathy, in association with bullying behaviors in adolescents. Although these factors have been studied separately, our data highlighted their effect, relationship, and interconnectivity. METHODS: The participants consisted of 351 adolescents (57.8% girls) aged 13-16 years (mean: 14.32 ± 0.73 for girls, 14.38 ± 0.86 for boys). The data used in this cross-sectional study were collected using self-reported questionnaires. Pearson's moment product correlation analysis and hierarchical linear regression analysis were performed to evaluate the associations between variables. FINDINGS: Bullying behavior levels were higher in male adolescents compared with females. The results indicated that bullying behavior was associated with low levels of reading minds in the eyes abilities, alexithymic personality traits, and low affective empathy levels. CONCLUSION: These findings highlight the critical impact of the poor comprehension of mental states and emotional statuses of other people and low emphatic thinking capacity in the emergence of bullying behaviors among adolescents. Therapeutic interventions focusing on improving these factors may therefore be useful in prevention and management programs for bullying behavior.

Identification and sorting of particle chirality using liquid crystallinity.

Particles dispersed in liquid crystals (LCs) have been shown to assemble due to the elastic interactions arising from the molecular anisotropy. Studies have shown that the alignment of the particles within LCs were strongly dependent on the surface director of LCs on particles. Different from the past studies involving particles with degenerate planar anchoring of LCs, this study shows that the azimuthal surface director can be used to control and finely tune the positioning of the particles in LCs. Specifically, polymeric particles with two flat surfaces that mediate parallel or non-parallel (chiral) anchoring were synthesized and dispersed in nematic 5CB with spatial variations in the director profile. Besides demonstration of their positioning, it was observed that the particles with same chiral handedness with the LC twist were distributed within the LC film, whereas particles with opposite handedness were repelled from the LC medium due to the elastic energy contributions. In addition, a pronounced effect of the surface anchoring of the particles were present on their orientation during non-equilibrium events such as sedimentation. Overall, the studies presented here will find potential use in sensors, separations, optics or soft robotic applications that will take advantages of chirality or chiral interactions.

Design Parameters and Principles of Liquid-Crystal-Templated Synthesis of Polymeric Materials via Photolithography.

The design parameters and principles for the synthesis of polymeric microscopic objects using a method that combines photolithography and liquid crystal (LC) molecular templates have been demonstrated. Specifically, mixtures of a reactive mesogen (RM257) and nonreactive LC (E7) were polymerized using UV light and a photomask. We used photomasks with circular, triangular, rectangular, square, star-shaped, and heart-shaped features to provide initial shapes to the objects. Then, the unreacted parts were extracted and the polymeric objects were allowed to shrink anisotropically as defined by the ordering symmetry of the LC mixture. The initial configuration of the LC mixtures played a critical role in determining the final shapes of the polymeric objects formed after shrinking, which resulted in chiral twisting and bending, leading to more than 20 different shapes. We found that the pitch size of the bulk chiral twisted objects depends linearly on the angle of chiral twist of the LCs, whereas it was independent of their thickness and length ranging from 1.5 to 160 µm and 100 µm to 2.45 cm, respectively. The shapes of the polymeric objects synthesized from LC films with bent LC ordering, however, were critically dependent on the thickness of the objects due to the interplay between the elastic energy and surface anchoring of the LCs. The critical role of LC elasticity was observed for thicknesses below 20 µm, above which surface anchoring was dominant in determining the shapes. Overall, the proposed method was shown to provide a precise control over the three-dimensional architectures of the objects with size range that covers the micro and macro scales, which would find use in fields ranging from emulsion stabilization and catalysis to micromachines and artificial muscles.

Liquid Crystal Templates Combined with Photolithography Enable Synthesis of Chiral Twisted Polymeric Microparticles.

Liquid crystals (LC), when combined with photolithography, enable synthesis of microparticles with 2D and 3D shapes and internal complexities. Films of nematic LCs are prepared using mixtures of reactive (RM257) and non-reactive mesogens with controlled alignment of LCs at the confining surfaces, photo-polymerized the RM257 using a photomask, and then extracted the unreacted mesogens to yield the polymeric microparticles. The extraction results in a controlled anisotropic shrinkage amount dependent on the RM257 content and the direction dependent on LC alignment. Control over the aspect ratio, size, and thickness of the microparticles are obtained with a coefficient of variance less than 2%. In addition, non-parallel LC anchoring at the two surfaces results in a controllable right- or left-handed twisting of microparticles. These methods may find substantial use in applications including drug delivery, emulsions, separations, and sensors, besides their potential in revealing new fundamental concepts in self-assembly and colloidal interactions.