Selective extraction of metal ions from a complex aqueous mixture into an organic phase is used to separate toxic or radioactive metals from polluted environments and nuclear waste, as well as to produce industrially relevant metals, such as rare earth ions. Selectivity arises from the choice of an extractant amphiphile, dissolved in the organic phase, which interacts preferentially with the target metal ion. The extractant-mediated process of ion transport from an aqueous to an organic phase takes place at the aqueous-organic interface; nevertheless, little is known about the molecular mechanism of this process despite its importance. Although state-of-the-art X-ray scattering is uniquely capable of probing molecular ordering at a liquid-liquid interface with subnanometer spatial resolution, utilizing this capability to investigate interfacial dynamical processes of short temporal duration remains a challenge. We show that a temperature-driven adsorption transition can be used to turn the extraction on and off by controlling adsorption and desorption of extractants at the oil-water interface. Lowering the temperature through this transition immobilizes a supramolecular ion-extractant complex at the interface during the extraction of rare earth erbium ions. Under the conditions of these experiments, the ion-extractant complexes condense into a two-dimensional inverted bilayer, which is characterized on the molecular scale with synchrotron X-ray reflectivity and fluorescence measurements. Raising the temperature above the transition leads to Er ion extraction as a result of desorption of ion-extractant complexes from the interface into the bulk organic phase. XAFS measurements of the ion-extractant complexes in the bulk organic phase demonstrate that they are similar to the interfacial complexes.

Thermally-induced gelation in aqueous solutions of methylcellulose (MC) and hydroxypropyl methylcellulose (HPMC) has been studied by rheological, optical microscopy and turbidimetry measurements. The structural and mechanical properties of these hydrogels are dominated by the interplay between phase separation and gelation. In MC solutions, phase separation takes place almost simultaneously with gelation. An increase in the storage modulus is coupled to the appearance of a bicontinuous structure upon heating. However, a thermal gap exists between phase separation and gelation in the case of HPMC solutions. The storage modulus shows a dramatic decrease during phase 2 separation, and then rises in the subsequent gelation. A macroporous structure forms in the gels via "viscoelastic phase separation" linked to "double phase separation".

Eukaryotic cells in living tissues form dynamic patterns with spatially varying orientational order that affects important physiological processes such as apoptosis and cell migration. The challenge is how to impart a predesigned map of orientational order onto a growing tissue. Here, we demonstrate an approach to produce cell monolayers of human dermal fibroblasts with predesigned orientational patterns and topological defects using a photoaligned liquid crystal elastomer (LCE) that swells anisotropically in an aqueous medium. The patterns inscribed into the LCE are replicated by the tissue monolayer and cause a strong spatial variation of cells phenotype, their surface density, and number density fluctuations. Unbinding dynamics of defect pairs intrinsic to active matter is suppressed by anisotropic surface anchoring allowing the estimation of the elastic characteristics of the tissues. The demonstrated patterned LCE approach has potential to control the collective behavior of cells in living tissues, cell differentiation, and tissue morphogenesis.

Ion distributions play a central role in various settings-from biology, where they mediate the electrostatic interactions between charged biomolecules in solution, to energy storage devices, where they influence the charging properties of supercapacitors. These distributions are determined by interactions dictated by the chemical properties of the ions and their environment as well as the long-range nature of the electrostatic force. Recent theoretical and computational studies have explored the role of correlations between ions, which have been suggested to underlie a number of counterintuitive results, such as like-charge attraction. However, the interdependency between ion correlations and other interactions that ions experience in solution complicates the connection between physical models of ion correlations and the experimental investigation of ion distributions. We exploit the properties of the liquid/liquid interface to vary the coupling strength Γ of ion-ion correlations from weak to strong while monitoring their influence on ion distributions at the nanometer scale with X-ray reflectivity and the macroscopic scale with interfacial tension measurements. These data are in agreement with the predictions of a parameterfree density functional theory that includes ion-ion correlations and ion-solvent interactions over the entire range of experimentally tunable correlation coupling strengths (from 0.8 to 3.7). This study provides evidence for a sharply defined electrical double layer for large coupling strengths in contrast to the diffuse distributions predicted by mean field theory, thereby confirming a common prediction of many ion correlation models. The reported findings represent a significant advance in elucidating the nature and role of ion correlations in charged soft matter.liquid surface scattering | ion density profile | surface excess charge | Poisson-Boltzmann | Debye-Hückel hole T he works by Gouy (1) and Chapman (2) introduced the Poisson-Boltzmann (PB) equation to describe the distribution of ions and the accompanying variation of electric potential at the interface between a charged planar electrode and an electrolyte solution (1, 2). This seminal theory considered point-like ions interacting through their mean electric field in a continuum solvent but neglected both chemically specific ion-solvent interactions and correlations between ions. Specific ion interactions are exemplified by the well-known Hofmeister series (3). The study of ion correlations has been motivated by observations of the reentrant condensation of DNA (4) and proteins (5) in solution, in which like-charged biomolecules aggregate in the presence of multivalent ions, and reports of charge reversal in colloidal suspensions, in which the sign of the screened charge on a colloid can be changed by varying the surrounding electrolyte solution (6, 7).Correlations between ions that are caused by their electrostatic interactions are expected to be important when the average electrostatic interaction energy between neighboring ions...

Active matter exhibits remarkable collective behavior in which flows, continuously generated by active particles, are intertwined with the orientational order of these particles. The relationship remains poorly understood as the activity and order are difficult to control independently. Here we demonstrate important facets of this interplay by exploring dynamics of swimming bacteria in a liquid crystalline environment with pre-designed periodic splay and bend in molecular orientation. The bacteria are expelled from the bend regions and condense into polar jets that propagate and transport cargo unidirectionally along the splay regions. The bacterial jets remain stable even when the local concentration exceeds the threshold of bending instability in a non-patterned system. Collective polar propulsion and different role of bend and splay are explained by an advection-diffusion model and by numerical simulations that treat the system as a two-phase active nematic. The ability of prepatterned liquid crystalline medium to streamline the chaotic movements of swimming bacteria into polar jets that can carry cargo along a predesigned trajectory opens the door for potential applications in cell sorting, microscale delivery and soft microrobotics.

Experiments and computer simulations provide a new perspective that strong correlations of counterions with charged nanoparticles can influence the localization of nanoparticles at liquid-liquid interfaces and support the formation of voltage-tunable nanoparticle arrays. We show that ion condensation onto charged nanoparticles facilitates their transport from the aqueous-side of an interface between two immiscible electrolyte solutions to the organic-side, but contiguous to the interface. Counterion condensation onto the highly charged nanoparticles overcomes the electrostatic barrier presented by the low permittivity organic material, thus providing a mechanism to transport charged nanoparticles into organic phases with implications for the distribution of nanoparticles throughout the environment and within living organisms. After transport, the nanoparticles assemble into a two-dimensional (2D) nearly close-packed array on the organic side of the interface. Voltage-tunable counterion-mediated interactions between the nanoparticles are used to control the lattice spacing of the 2D array. Tunable nanoparticle arrays self-assembled at liquid interfaces are applicable to the development of electro-variable optical devices and active elements that control the physical and chemical properties of liquid interfaces on the nanoscale.

We present X-ray reflectivity and interfacial tension measurements of the electrified liquid/liquid interface between two immiscible electrolyte solutions for the purpose of understanding the dependence of interfacial ion distributions on the applied electric potential difference across the interface. The aqueous phase contains alkali-metal chlorides, including LiCl, NaCl, RbCl, or CsCl, and the organic phase is a 1,2-dichloroethane solution of bis(triphenylphosphor anylidene) ammonium tetrakis(pentafluorophenyl)borate (BTPPATPFB). Selected data for a subset of electric potential differences are analyzed to determine the potentials of mean force for Li(+), Rb(+), Cs(+), BTPPA(+), and TPFB(-). These potentials of mean force are then used to analyze both X-ray reflectivity and interfacial tension data measured over a wide range of electric potential differences. Comparison of X-ray reflectivity data for strongly hydrated alkali-metal ions (Li(+) and Na(+)), for which ion pairing to TPFB(-) ions across the interface is not expected, to data for weakly hydrated alkali-metal ions (Rb(+) and Cs(+)) indicates that the Gibbs energy of adsorption due to ion pairing at the interface must be small (<1 k(B)T per ion pair) for both the CsCl and RbCl samples. This paper demonstrates the applicability of the Poisson-Boltzmann potential of mean force approach to the analysis of X-ray reflectivity measurements that probe the nanoscale ion distribution and the consequences of these underlying distributions for thermodynamic studies, such as interfacial tension measurements, that yield quantities related to the integrated ion distribution.

Soft actuators have attracted a lot of attention owing to their biomimetic performance. However, the development of soft actuators that are easily prepared from readily available raw materials, conveniently utilized, and cost-efficient is still a challenge. Here, we present a simple method to fabricate a polyethylene-based soft actuator. It has controllable anisotropic structure and can realize multiple motions, including bidirectional bending and twisting based on dual mechanisms, which is a rare phenomenon. Especially, the soft actuators can response at a very small temperature difference (Δ T ≥ 2.3 °C); therefore, even skin touch can quickly drive the actuator, which greatly broadens its applications in daily life. The soft actuator could demonstrate a curvature up to 7.8 cm accompanied by powerful actuation. We have shown that it can lift an object 27 times its own weight. We also demonstrate the application of this actuator as intelligent mechanical devices.