Lanthanide binding peptide surfactants at air-aqueous interfaces for interfacial separation of rare earth elements.

Rare earth elements (REEs) are critical materials to modern technologies. They are obtained by selective separation from mining feedstocks consisting of mixtures of their trivalent cation. We are developing an all-aqueous, bioinspired, interfacial separation using peptides as amphiphilic molecular extractants.

X-ray Induced Cycling of Rare-Earth Elements between Bulk and Interfacial Liquid.

Reversible cycling of rare-earth elements between an aqueous electrolyte solution and its free surface is achieved by X-ray exposure. This exposure alters the competitive equilibrium between lanthanide ions bound to a chelating ligand, diethylenetriamine pentaacetic acid (DTPA), in the bulk solution and to insoluble monolayers of extractant di-hexadecyl phosphoric acid (DHDP) at its surface. Evidence for the exposure-induced temporal variations in the lanthanide surface density is provided by X-ray fluorescence near total reflection measurements.

Metastable precipitation and ion-extractant transport in liquid-liquid separations of trivalent elements.

The extractant-assisted transport of metal ions from aqueous to organic environments by liquid-liquid extraction has been widely used to separate and recover critical elements on an industrial scale. While current efforts focus on designing better extractants and optimizing process conditions, the mechanism that underlies ionic transport remains poorly understood. Here, we report a nonequilibrium process in the bulk aqueous phase that influences interfacial ion transport: the formation of metastable ion-extractant precipitates away from the liquid-liquid interface, separated from it by a depletion region without precipitates.

DEHP extractant binding to trivalent lanthanide Er: Fast binding accompanied by concerted angular motions of hydration water.

Solvent extraction of trivalent rare earth metal ions by organophosphorus extractants proceeds via binding of phosphoric acid headgroups to the metal ion. Water molecules in the tightly bound first hydration shell of the metal ions must be displaced by oxygen atoms from phosphoric acid headgroups. Here, we use classical molecular dynamics simulations to explore the event in which a fully hydrated Er binds to its first phosphoric acid headgroup.

Relevance of Surface Adsorption and Aqueous Complexation for the Separation of Co(II), Ni(II), and Fe(III).

During the solvent extraction of metal ions from an aqueous to an organic phase, organic-soluble extractants selectively target aqueous-soluble ions for transport into the organic phase. In the case of extractants that are also soluble in the aqueous phase, our recent studies of lanthanide ion-extractant complexes at the surface of aqueous solutions suggested that ion-extractant complexation in the aqueous phase can hinder the solvent extraction process. Here, we investigate a similar phenomenon relevant to the separation of Co(II), Ni(II), and Fe(III).

Free Thiols Regulate the Interactions and Self-Assembly of Thiol-Passivated Metal Nanoparticles.

Thiol ligands bound to the metallic core of nanoparticles determine their interactions with the environment and self-assembly. Recent studies suggest that equilibrium between bound and free thiols alters the ligand coverage of the core. Here, X-ray scattering and MD simulations investigate water-supported monolayers of gold-core nanoparticles as a function of the core-ligand coverage that is varied in experiments by adjusting the concentration of total thiols (sum of free and bound thiols).

Evolution and Reversible Polarity of Multilayering at the Ionic Liquid/Water Interface.

Highly correlated positioning of ions underlies Coulomb interactions between ions and electrified interfaces within dense ionic fluids such as biological cells and ionic liquids. Recent work has shown that highly correlated ionic systems behave differently than dilute electrolyte solutions, and interest is focused upon characterizing the electrical and structural properties of the dense electrical double layers (EDLs) formed at internal interfaces. It has been a challenge for experiments to characterize the progressive development of the EDL on the nanoscale as the interfacial electric potential is varied over a range of positive and negative values.

Molecular interactions of phospholipid monolayers with a model phospholipase.

The intrinsic overexpression of secretory phospholipase A2 (sPLA2) in various pro-inflammatory diseases and cancers has the potential to be exploited as a therapeutic strategy for diagnostics and treatment. To explore this potential and advance our knowledge of the role of sPLA2 in related diseases, it is necessary to systematically investigate the molecular interaction of the enzyme with lipids. By employing a Langmuir trough integrated with X-ray reflectivity and grazing incidence X-ray diffraction techniques, this study examined the molecular packing structure of 1,2-palmitoyl-sn-glycero-3-phosphocholine (DPPC) films before and after enzyme adsorption and enzyme-catalyzed degradation.

Nanoscale view of assisted ion transport across the liquid-liquid interface.

During solvent extraction, amphiphilic extractants assist the transport of metal ions across the liquid-liquid interface between an aqueous ionic solution and an organic solvent. Investigations of the role of the interface in ion transport challenge our ability to probe fast molecular processes at liquid-liquid interfaces on nanometer-length scales. Recent development of a thermal switch for solvent extraction has addressed this challenge, which has led to the characterization by X-ray surface scattering of interfacial intermediate states in the extraction process.

Coupling X-Ray Reflectivity and In Silico Binding to Yield Dynamics of Membrane Recognition by Tim1.

The dynamic nature of lipid membranes presents significant challenges with respect to understanding the molecular basis of protein/membrane interactions. Consequently, there is relatively little known about the structural mechanisms by which membrane-binding proteins might distinguish subtle variations in lipid membrane composition and/or structure. We have previously developed a multidisciplinary approach that combines molecular dynamics simulation with interfacial x-ray scattering experiments to produce an atomistic model for phosphatidylserine recognition by the immune receptor Tim4.

Molecular Structure of Canonical Liquid Crystal Interfaces.

Numerous applications of liquid crystals rely on control of molecular orientation at an interface. However, little is known about the precise molecular structure of such interfaces. In this work, synchrotron X-ray reflectivity measurements, accompanied by large-scale atomistic molecular dynamics simulations, are used for the first time to reconstruct the air-liquid crystal interface of a nematic material, namely, 4-pentyl-4'-cyanobiphenyl (5CB).

Erbium(III) Coordination at the Surface of an Aqueous Electrolyte.

Grazing-incidence (GI) X-ray absorption spectroscopy (XAS) under conditions of total external reflection is used to explore the coordination environment of the trivalent erbium ion, Er(3+), at an electrolyte-vapor interface. A parallel study of the bulk aqueous electrolyte (1 M ErCl3 in HCl at pH = 1.54) shows that the Er(3+) ions have a simple hydration shell with an average Er-OH2 bond distance of 2.

Interfacial localization and voltage-tunable arrays of charged nanoparticles.

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.

Electric Field Effect on Phospholipid Monolayers at an Aqueous-Organic Liquid-Liquid Interface.

The electric potential difference across cell membranes, known as the membrane potential, plays an important role in the activation of many biological processes. To investigate the effect of the membrane potential on the molecular ordering of lipids within a biomimetic membrane, a self-assembled monolayer of 1-stearoyl-2-oleoyl-sn-glycero-3-phosphocholine (SOPC) lipids at an electrified 1,2-dichloroethane/water interface is studied with X-ray reflectivity and interfacial tension. Measurements over a range of electric potential differences, -150 to +130 mV, that encompass the range of typical biomembrane potentials demonstrate a nearly constant and stable structure whose lipid interfacial density is comparable to that found in other biomimetic membrane systems.

X-ray studies of interfacial strontium-extractant complexes in a model solvent extraction system.

The interfacial behavior of a model solvent extraction liquid-liquid system, consisting of solutions of dihexadecyl phosphate (DHDP) in dodecane and SrCl2 in water, was studied to determine the structure of the interfacial ion-extractant complex and its variation with pH. Previous experiments on a similar extraction system with ErCl3 demonstrated that the kinetics of the extraction process could be greatly retarded by cooling through an adsorption transition, thus providing a method to immobilize ion-extractant complexes at the interface and further characterize them with X-ray interface-sensitive techniques. Here, we use this same method to study the SrCl2 system.

Observation of a rare earth ion-extractant complex arrested at the oil-water interface during solvent extraction.

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.

Microphase formation at a 2D solid-gas phase transition.

Density modulated micro-separated phases (microphases) occur at 2D liquid interfaces in the form of alternating regions of high and low density domains. Brewster angle microscopy (BAM) images demonstrate the existence of microphases in cluster, stripe, and mosaic morphologies at the buried interface between hexane and water with fluoro-alkanol surfactant dissolved in the bulk hexane. At high temperature, the surfactant assembles at the interface in a 2D gaseous state.

Molecular mechanism for differential recognition of membrane phosphatidylserine by the immune regulatory receptor Tim4.

Recognition of phosphatidylserine (PS) lipids exposed on the extracellular leaflet of plasma membranes is implicated in both apoptotic cell removal and immune regulation. The PS receptor T cell immunoglobulin and mucin-domain-containing molecule 4 (Tim4) regulates T-cell immunity via phagocytosis of both apoptotic (high PS exposure) and nonapoptotic (intermediate PS exposure) activated T cells. The latter population must be removed at lower efficiency to sensitively control immune tolerance and memory cell population size, but the molecular basis for how Tim4 achieves this sensitivity is unknown.

Ion distributions at the water/1,2-dichloroethane interface: potential of mean force approach to analyzing X-ray reflectivity and interfacial tension measurements.

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(-).

Tuning ion correlations at an electrified soft interface.

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.

Communications: Monovalent ion condensation at the electrified liquid/liquid interface.

X-ray reflectivity studies demonstrate the condensation of a monovalent ion at the electrified interface between electrolyte solutions of water and 1,2-dichloroethane. Predictions of the ion distributions by standard Poisson-Boltzmann (Gouy-Chapman) theory are inconsistent with these data at higher applied interfacial electric potentials. Calculations from a Poisson-Boltzmann equation that incorporates a nonmonotonic ion-specific potential of mean force are in good agreement with the data.

Configuration of PKCalpha-C2 domain bound to mixed SOPC/SOPS lipid monolayers.

X-ray reflectivity measurements are used to determine the configuration of the C2 domain of protein kinase Calpha (PKCalpha-C2) bound to a lipid monolayer of a 7:3 mixture of 1-stearoyl-2-oleoyl-sn-glycero-3-phosphocholine and 1-stearoyl-2-oleoyl-sn-glycero-3-phosphoserine supported on a buffered aqueous solution. The reflectivity is analyzed in terms of the known crystallographic structure of PKCalpha-C2 and a slab model representation of the lipid layer. The configuration of lipid-bound PKCalpha-C2 is described by two angles that define its orientation, theta = 35 degrees +/- 10 degrees and phi =210 degrees +/- 30 degrees, and a penetration depth (=7.

Structure and depletion at fluorocarbon and hydrocarbon/water liquid/liquid interfaces.

The results of x-ray reflectivity studies of two oil/water (liquid/liquid) interfaces are inconsistent with recent predictions of the presence of a vaporlike depletion region at hydrophobic/aqueous interfaces. One of the oils, perfluorohexane, is a fluorocarbon whose superhydrophobic interface with water provides a stringent test for the presence of a depletion layer. The other oil, heptane, is a hydrocarbon and, therefore, is more relevant to the study of biomolecular hydrophobicity.

Molecular ordering and phase behavior of surfactants at water-oil interfaces as probed by X-ray surface scattering.

Surfactants have their primary utility, both scientific and industrial, at the liquid-liquid interface. We review recent X-ray surface scattering experiments that probe the molecular ordering and phase behavior of surfactants at the water-oil interface. The presence of the oil modifies the interfacial ordering in a manner that cannot be understood simply from analogies with studies of Langmuir monolayers of surfactants at the water-vapor interface or from the traditional view that the solvent is fully mixed with the interfacial surfactants.