Search

Cell walls of so-called “wood-materials” are constituted by a complex, highly anisotropic and hierarchically organized nanocomposite, characterized by stiff crystalline cellulose nano-fibers, parallel to each other, and embedded in a softer and less anisotropic matrix of hemicelluloses, lignin and water. This matrix is hygroscopic, and therefore swells with increasing humidity. Consequently, wood cells undergo large dimensional changes. A minimal model of wood secondary cell walls to predict water absorption has recently been developed by Bertinetti and co-workers [1] in the form of an Equation of State (EOS) that represents equivalently the water sorption versus relative humidity, as considered in chemical engineering, or the relation between osmotic pressure and volume of solutes, in the physical chemistry equation of state approach initiated by Jean Perrin. We extend hereby this model to the presence of electrolytes adsorbed in the gel part wood cell wall and compare compression wood cell walls to the extreme case of coir. [ABSTRACT FROM AUTHOR]

The formation of U(VI) intrinsic colloids has a non-negligible impact on the dissemination of actinides in the environment. It is therefore essential to better identify their nature, formation conditions, and stability domains. These specific points are especially important since the behavior of these elements in environment is generally estimated by geochemical transport modeling. This modeling relies on the accurate prediction of their speciation in various situations based on thermodynamic databases that have to be continuously updated. In this work, we identified and characterized the U(VI) intrinsic colloids that grow in model solutions having simplified composition that consists of NaCl and NaCl with Na 2 SiO 3 electrolytes at pH comprised between 7 and 10. Using a simple, reliable and systematic method based on geochemical simulations, elemental analyses by ICP-AES and in situ Small and Wide Angle X-ray Scattering characterizations, several characteristics of U(VI) colloids such as their sizes, volumes, concentration and formula were determined and used to calculate the distribution ratio of U(VI) between intrinsic colloids and solution. This distribution ratio is crucial to enhance predictive geochemical calculation, especially to predict the fraction of U(VI) present as colloids that may migrate into natural waters., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: REBISCOUL reports financial support was provided by NEEDS. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Rabies virus (RABV) generates membrane-less liquid organelles (Negri bodies) in the cytoplasm of its host cell, where genome transcription and replication and nucleocapsid assembly take place, but the mechanisms of their assembly and maturation remain to be explained. An essential component of the viral RNA synthesizing machine, the phosphoprotein (P), acts as a scaffold protein for the assembly of these condensates. This intrinsically disordered protein forms star-shaped dimers with N-terminal negatively charged flexible arms and C-terminal globular domains exhibiting a large dipole moment. Our study shows that in vitro self-association of RABV P drives a complex thermoresponsive phase separation with a lower critical solution temperature. Protein dimers assemble already below the saturation concentration, and condensation is driven by attractive conformation-specific interactions leading to reentrant liquid phase separation over a narrow range of salt concentration. We propose a minimal molecular model in which P can adopt three limit conformational states and the disordered N-terminal arms control the interactions between giant dipoles that is consistent with our observations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

In Nature, most known objects can perform their functions only when in supramolecular self-assembled from, e.g. protein complexes and cell membranes. Here, a dendritic polymer is presented that inhibits severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) with an irreversible (virucidal) mechanism only when self-assembled into a Two-dimmensional supramolecular polymer (2D-SupraPol). Monomeric analogs of the dendritic polymer can only inhibit SARS-CoV-2 reversibly, thus allowing for the virus to regain infectivity after dilution. Upon assembly, 2D-SupraPol shows a remarkable half-inhibitory concentration (IC 50 30 nM) in vitro and in vivo in a Syrian Hamster model has a good efficacy. Using cryo-TEM, it is shown that the 2D-SupraPol has a controllable lateral size that can be tuned by adjusting the pH and use small angle X-ray and neutron scattering to unveil the architecture of the supramolecular assembly. This functional 2D-SupraPol, and its supramolecular architecture are proposed, as a prophylaxis nasal spray to inhibit the virus interaction with the respiratory tract., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

We describe the different mixed colloidal solutions that can be obtained when mixing equivalent quantities of a synthetic anionic clay to surfactants forming lamellar phases in the absence of added salt. The important quantity driving toward insertion or depletion is the osmotic pressure, of the lamellar phase and of the clay alone. Competition for water is the main driving force toward dispersion, inclusion or exclusion (phase separation). In the case of a nonionic surfactant ( C 12 E 5 ) mixed with Laponite, undulations quenched by the surfactant-decorated clay lead to swelling; inclusion is not observed due to differences in rigidity. Long-range order is weakened leading eventually to the exclusion of surfactant in excess. In the case of a double anionic system (AOT-Laponite), electrostatic is dominant and the three regimes are encountered. In the catanionic case, admixing the double chain cationic lipid DDAB to the clay (in large charge excess), the platelets are coated by a positively charged bilayer. Long-range order is very efficiently dampened. From a low threshold (2% by weight), there is exclusion of a clay-poor collapsed lamellar phase, detected by the swelling of the main phase. The cationized clay does not interfere with the molecular force balance: the location of the critical point is unchanged. At high Laponite concentration, a very puzzling microstructure is observed. Some phase diagrams as well as representative SANS and SAXS data are extracted from the complete results concerning the lyotropic lamellar phase mixing problem available with all measures and evaluations of osmotic pressures in the PhD of the late Isabelle Grillo., (© 2024. The Author(s), under exclusive licence to EDP Sciences, SIF and Springer-Verlag GmbH Germany, part of Springer Nature.)

Hypothesis: Specific alkaline cation effects control the area per headgroup of alkylester sulphates, which modifies the spontaneous packing of the surfactants. The resulting effective packing minimizes the total bending energy frustration and results in a Boltzmann distribution of coexisting pseudo-phases. These pseudo-phases constitute of micelles and other structures of complex morphology: cylindrical sections, end-caps, branching points, and bilayers, all in dynamic equilibrium. According to our model, excess of end-caps or excess of branching points lead to low viscosity, whereas comparable amounts of both structures lead to viscosity maxima. Relative occurrence of branching points and end-caps is the molecular mechanism at the origin of the salt-sensitive viscosity peak in the "salt-curve" (viscosity against salt concentration at fixed surfactant concentration). Up to now, and as indicated in former papers, this has been a pure model without microscopic verification., Experiments: In this work, we introduce explicit counting of the number of coexisting pseudo-phases as observed by state-of-the-art cryogenic transmission electron microscopy (cryo-TEM). The model system used, i.e., sodium laurylethersulfate (SLES)/salt/water, is very common as part of cosmetic formulations. As added salts, we used Li + , Na + , K + , and Cs + chlorides. In parallel to imaging, we measured the macroscopic viscosities of the different solutions., Findings: With cryogenic transmission electron microscopy (cryo-TEM), we imaged a variety of morphologies (pseudo-phases) in the different aqueous surfactant/salt solutions: cylindrical micelles with end-caps, discs surrounded by "rims", entangled thread-like micelles with branching points, networks with gliding branching points, and bilayers. The relative chemical potentials of these morphologies could be approximated simply by counting the relative proportion of their occurrence. This simple multi-scale approach avoids any ad-hoc "specificity" assumption of ions, and is based on the bending energy model in an extended version of the Benedek "ladder model". It is capable of explaining and even quantifying the location of all viscosity peaks in the "salt-curves" for the different cations investigated, thus confirming the previously proposed model experimentally, and - thanks to cryo-TEM - for the first time on a microscopic scale. Moreover, this approach can also be applied when the added cations lead to newly observed pseudo-phases, such as discs and vesicles. To the best of our knowledge, this is the first time that cryo-TEM is used, together with a mesoscopic model, to describe a macroscopic property such as viscosity and specific ion effects on it, without any a priori assumption about these effects. So, in total, we could a) confirm the predictions of the previously developed model, b) use cryo-TEM imaging and viscosity measurements to predict and find unusual morphologies when varying the cations of the added salt, and c) count the pseudo-phases in cryo-TEM micrographs to quantitatively explain the different nanostructures., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Motivation: Surfactants like C 8 E 8 CH 2 COOH have such bulky headgroups that they cannot show the common sphere-to-cylinder transition, while surfactants like C 18:1 E 2 CH 2 COOH are mimicking lipids and form only bilayers. Mixing these two types of surfactants allows one to investigate the competition between intramicellar segregation leading to disc-like bicelles and the temperature dependent curvature constraints imposed by the mismatch between heads and tails., Experiments: We establish phase diagrams as a function of temperature, surfactant mole ratio, and active matter content. We locate the isotropic liquid-isotropic liquid phase separation common to all nonionic surfactant systems, as well as nematic and lamellar phases. The stability and rheology of the nematic phase is investigated. Texture determination by polarizing microscopy allows us to distinguish between the different phases. Finally, SANS and SAXS give intermicellar distances as well as micellar sizes and shapes present for different compositions in the phase diagrams., Findings: In a defined mole ratio between the two components, intramicellar segregation wins and a viscoelastic discotic nematic phase is present at low temperature. Partial intramicellar mixing upon heating leads to disc growth and eventually to a pseudo-lamellar phase. Further heating leads to complete random mixing and an isotropic phase, showing the common liquid-liquid miscibility gap. This uncommon phase sequence, bicelles, lamellar phase, micelles, and water-poor packed micelles, is due to temperature induced mixing combined with dehydration of the headgroups. This general molecular mechanism explains also why a metastable water-poor lamellar phase quenched by cooling can be easily and reproducibly transformed into a nematic phase by gentle hand shaking at room temperature, as well as the entrapment of air bubbles of any size without encapsulation by bilayers or polymers., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Inc. All rights reserved.)

We have studied the microemulsion and lamellar phases of two of the most commonly described systems based on nonionic C 12 E 5 and ionic AOT surfactants. We show that C 12 E 5 is best described by the symmetric disordered open connected lamellar model (DOC-lamellar), contrary to the more commonly employed standard flexible model. In the case of AOT, the bicontinuous microemulsion structure is best described by the standard flexible model at high temperatures. Around room temperature, connected cylinders in a molten cubic crystal phase are the only description which corresponds to the data. In the lamellar phase, around one third of the available surface area is lost in fluctuations and defects. Comparing structurally predictive models with results from conductivity measurements show that salt adsorption in the hydrated ethoxy groups is dominant for C 12 E 5 (nonionic). For AOT, our conductivity measurements clarify the role of tortuosity versus cation absorption., (© 2023. The Author(s).)

Hypothesis: The key to prepare a mesostructured porous material by a soft-template route coupled to a colloidal sol-gel process is to control the surfactant-colloid interface. In the case of tetravalent actinide ions, their high reactivity in aqueous media always leads to uncontrolled and irreversible condensation. The addition of a complexing agent to the sol may moderate these reactions and enhances the interaction between the colloids and the surfactant to in fine prepare a mesostructured nanoporous actinide oxide material., Experiments: Several colloidal sols were prepared without and with formic acid as complexing agent by varying the molar ratios between thorium, carboxylic surfactant and pH. Small and Wide Angle X-ray Scattering were used to characterize the nature of the colloids, their interaction with the surfactant and the final ThO 2 materials., Findings: Depending on the colloid nature, hexagonal or worm-like hybrid mesophase is formed. The thermal treatment of the worm-like mesophase with a sufficient amount of Th-formic acid hexameric species coated at the surface of surfactant micelles generates micrometric ThO 2 nanofibers. This material having an accessible porosity opens new perspectives to be impregnated with minor actinide solutions offering a promising safety method for the fabrication of mixed oxide nuclear fuel and the minor actinide transmutation., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Motivation: The monoammonium salt of glycyrrhizic acid (AGA) is known to form fibrillar hydrogels and few studies regarding self-assembly of AGA have been published. Yet, the understanding of the fibrillar microstructures and the gelation remains vague. Thus, we attempt to achieve a deeper understanding of the microstructures and the gelation process of binary solutions of AGA in water. Further, we examine the effect of ethanol on the microstructures to pave the way for potential enhancement of drug loading in AGA hydrogels., Experiments: A partial room temperature phase map of the ternary system AGA/ethanol/water was recorded. Small-angle X-ray and neutron scattering experiments were performed over wide ranges of compositions in both binary AGA/water and ternary AGA/ethanol/water mixtures to get access to the micro-structuring., Findings: Binary aqueous solutions of AGA form birefringent gels consisting of a network of long helical fibrils. 'Infinitely' long negatively charged fibrils are in equilibrium with shorter fibrils (≈25 nm), both of which have a diameter of about 3 nm and are made of around 30 stacks of AGA per helical period (≈9nm), with each stack consisting of two AGA molecules. The interaxial distance (order of magnitude ≈20 nm) varies with an almost two-dimensional swelling law. Addition of ethanol reduces electrostatic repulsion and favors the formation of fibrillar end caps, reducing the average length of shorter fibrils, as well as the formation of small, swollen aggregates. While the gel network built by the long fibrils is resilient to a significant amount of ethanol, all fibrils are finally dissolved into small aggregates above a certain threshold concentration of ethanol (≈30 wt%)., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Water/ethyl acetate/ethanol is widely used as a "green" extractant system. We show that 2 different types of phase separation can be induced upon centrifugation in this ternary system using ethanol as a cosolvent of water and ethyl acetate: centrifuge-induced criticality and centrifuge-induced emulsification. The expected composition profiles of samples after centrifugation can be represented by bent lines in a ternary phase diagram when gravitational energy is added to the free energy of mixing. The experimental equilibrium composition profiles behave qualitatively as expected and can be predicted using a phenomenological theory of mixing. The concentration gradients are small except near the critical point, as expected for small molecules. Nevertheless, they are usable when accompanied by temperature cycles. These findings open new possibilities of centrifugal separation, even if control is delicate during temperature cycles. These schemes are accessible even at relatively low centrifugation speed for molecules that float and sediment with apparent molar masses several hundred times larger than the molecular mass., (Copyright © 2023 Helmut Cölfen et al.)

Swollen cubic lyotropic ternary phases with Pn3m symmetry and reduced hardness were obtained from a specific binary mixture of cubic phase-forming (phytantriol) and lamellar phase-forming (decaglycerol monooleate) compounds. The microstructures were determined by using a small-angle x-ray scattering technique. The softness and temperature-induced phase transitions were investigated by means of rheology. The incorporation of a surface-active fragrance compound (linalool) at concentrations up to 6 wt. % induced a structural transition toward a softer Im3m bulk cubic phase with longer water channels. Higher linalool concentrations allowed for the spontaneous dispersion of the bulk cubic phase into microscopic particles with a cubic structure (cubosomes).

The identification of new colloidal sol-gel routes for the preparation of actinide oxides, which have a homogeneous and accessible porosity that can easily be impregnated by any concentrated actinide solution, opens new perspectives for the preparation of homogeneous nuclear fuel for minor actinide transmutation. This homogeneity allows us to avoid "hot spot" formation due to the local accumulation of more fissile elements. Here, we report the preparation of macro-microporous ThO 2 materials by a colloidal sol-gel route. Using a thorium salt with 6-aminocaproic acid as a complexing agent at a controlled pH, we were able to pilot the condensation of thorium hydroxo species forming colloids of tuned nanometric size and thus the sol stability. After a freeze-drying process to concentrate colloids and a thermal treatment allowing complexing agent removal and macroporosity formation by a brutal gas release during combustion, a loose packing of ThO 2 nanoparticles with an ordered distribution of interparticular porosity and a fraction of nanometric crystallites, whose size depends on the initial colloidal size, were obtained. The sols, pastes, and final materials were characterized by small- and wide-angle X-ray scattering to determine the colloidal size and the final structure of the materials, which was also confirmed by transmission electron microscopy. The most promising material was finally successfully impregnated by a simulating minor actinide solution and thermally treated to prepare a mixed actinide oxide material. This safe technology, relying on the colloidal sol-gel process and the formulation of complex fluids forming tunable precursors, opens new perspectives for the reuse of nuclear waste solutions as new fuel.

The characterization of nanoporous powders of highly absorbing compounds by small-angle X-ray scattering (SAXS) involves overcoming several difficulties before quantitative information related to the porous texture, such as the specific surface and the porous volume, can be derived. In this article, first, the contribution of the grain facet reflectivity and scattering from the bulk of a grain with the density of ThO 2 , a highly absorbing material, were calculated. Microporous ThO 2 powder having micrometric grain size was characterized, in which the scattering signal is predominant. A high-resolution synchrotron instrument was used in order to cover a wider q range and minimize the absorption effect, and the results were compared with those obtained using a laboratory X-ray source. Concerning the absorption problem existing with a laboratory X-ray source, a new and robust experimental method was proposed to correctly determine the scattering intensity of the highly absorbing granular samples on an absolute scale. This method allows one to calculate accurately the porous volume and the specific surface via Porod's law and the invariant using a laboratory SAXS instrument. This last result opens new perspectives for the characterization of the volume and the specific surface of highly absorbing actinide oxide powders., (© Zijie Lu et al. 2022.)

Hypothesis: In a recent paper, we determined the phase behavior of an aqueous solution of octyl ether octaethylene oxide carboxylic acid ([H + ][C8E8c - ], Akypo™ LF2) and with partial replacement of H + by Na + and Ca 2+ . It was found that even the neat surfactants are liquid at room temperature and that they form only direct micelles for any aqueous content and over large temperature ranges. The aim of the present work was to find an explanation for the clouding in these systems as well as for the coacervation observed at very low surfactant content. We expected that very similar phase diagrams would be found for a full replacement of H + by the mentioned ions., Experiments: We established the respective phase diagrams of the above-mentioned salts in water and determined the structures of the occurring phases in detail with small-and wide-angle X-ray scattering, small-angle neutron scattering, dynamic light scattering, heat flux differential scanning calorimetry, as well as surface tension, ESI-MS, and NMR experiments., Findings: To our surprise, we discovered a new type of nematic phase between an isotropic and a hexagonal phase. Based on the complete description of all occurring phases both in the acidic and the charged surfactant systems, we were able to design a coherent and unified picture of all these phases, including the auto-coacervation at low surfactant concentration, the non-conventional clouding at high temperatures, the unusual liquid crystalline phases in a small domain at high surfactant concentrations, and the L β phase at low temperatures and at very low water content. It turned out that all phenomena are a consequence of the subtle interplay between a) the packing constraint due to the very large head-group, b) the relatively small hydrocarbon chain and c) the tunable electrostatic interactions versus entropy., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Surfactants aggregate in water into micelles, and these micelles incorporate organic substances to solubilize them. Hydrotropes are compounds that increase the solubility of hydrophobic substances in water without this form of aggregation. Decreasing the chain length of the classical surfactant Aerosol OT (AOT) from C8 to C5 results in a molecule with intermediate properties. Molecular dynamics simulations and surface tension measurements are performed on this short chain derivative of AOT. This compound shows high solubility and at the same time progressive weak aggregation. The hydration of head groups hinders significant plunging into a hydrophobic core, which leads to well defined liquid chain nanodomains. The transition to bicontinuous aggregates is in the concentration range of 1 mol L -1 . The sulfonate group of the head groups (placed at the water interface of worm-like aggregates) rather than the aggregate-aggregate interaction is responsible for the unusual small angle X-ray scattering pattern.

In this work, we developed a general theoretical description of ternary solutions of small molecules under a centrifugal field, from which we obtained the centrifugation map (CMap) as a general tool to understand observations or to predict composition profiles in centrifugal fields of arbitrary strength. The theoretical formalism is based on the classical density functional theory with established models for liquid mixtures. Thermodynamics also yields a general criterion for apparent aggregation. The strength of the CMap approach is illustrated for a ternary model system where ethanol is a co-solvent.

The phase transfer of ions is driven by gradients of chemical potentials rather than concentrations alone (i.e., by both the molecular forces and entropy). Extraction is a combination of high-energy interactions that correspond to short-range forces in the first solvation shell such as ion pairing or complexation forces, with supramolecular and nanoscale organization. While the latter are similar to the long-range solvent-averaged interactions in the colloidal world, in solvent extraction they are associated with lower characteristic lengths of the nanometric domain. Modeling of such complex systems is especially complicated because the two domains are coupled, whereas the resulting free energy of extraction is around k B T to guarantee the reversibility of the practical process. Nevertheless, quantification is possible by considering a partitioning of space among the polar cores, interfacial film, and solvent. The resulting free energy of transfer can be rationalized by utilizing a combination of terms which represent strong complexation energies, counterbalanced by various entropic effects and the confinement of polar solutes in nanodomains dispersed in the diluent, together with interfacial extractant terms. We describe here this ienaics approach in the context of solvent extraction systems; it can also be applied to further complex ionic systems, such as membranes and biological interfaces.

Microemulsions, as thermodynamically stable mixtures of oil, water, and surfactant, are known and have been studied for more than 70 years. However, even today there are still quite a number of unclear aspects, and more recent research work has modified and extended our picture. This review gives a short overview of how the understanding of microemulsions has developed, the current view on their properties and structural features, and in particular, how they are related to applications. We also discuss more recent developments regarding nonclassical microemulsions such as surfactant-free (ultraflexible) microemulsions or ones containing uncommon solvents or amphiphiles (like antagonistic salts). These new findings challenge to some extent our previous understanding of microemulsions, which therefore has to be extended to look at the different types of microemulsions in a unified way. In particular, the flexibility of the amphiphilic film is the key property to classify different microemulsion types and their properties in this review. Such a classification of microemulsions requires a thorough determination of their structural properties, and therefore, the experimental methods to determine microemulsion structure and dynamics are reviewed briefly, with a particular emphasis on recent developments in the field of direct imaging by means of electron microscopy. Based on this classification of microemulsions, we then discuss their applications, where the application demands have to be met by the properties of the microemulsion, which in turn are controlled by the flexibility of their amphiphilic interface. Another frequently important aspect for applications is the control of the rheological properties. Normally, microemulsions are low viscous and therefore enhancing viscosity has to be achieved by either having high concentrations (often not wished for) or additives, which do not significantly interfere with the microemulsion. Accordingly, this review gives a comprehensive account of the properties of microemulsions, including most recent developments and bringing them together from a united viewpoint, with an emphasis on how this affects the way of formulating microemulsions for a given application with desired properties.

Hypothesis: The surfactant C 8 EO 8 CH 2 COOH (Akypo LF2) and its salts have a small hydrophobic and a significantly longer hydrophilic part. As a consequence, there must be a significant steric constraint, once these surfactant molecules form micelles. In addition, the partially charged headgroups should bring some additional fine-tuning via electrostatic interactions to this "essentially non-ionic" surfactant., Experiments: Phase diagrams of binary mixtures of water and C 8 EO 8 CH 2 COOH are established over large concentration and temperature ranges, also at different pHs and in the presence of sodium and calcium ions. Surface tensions and osmotic pressures are measured to understand the systems. To evaluate the microstructures, also Dynamic Light Scattering and Small-Angle X-ray Scattering are performed., Findings: Apart from the formation of coacervates at very low surfactant concentrations, spherical micelles persist over the whole concentration and temperature range and do not change in size and shape. At very high surfactant concentrations, above 60% by weight, where the headgroups are no longer fully hydrated, the standard core-shell structure of micelles vanishes and highly stabilized aggregates of 8-26 octyl chains are suspended in interdigitated polyoxyethylene layers and form an "osmotic brush". When the acid is partially transformed to a sodium salt, the repulsion between the micelles increases, whereas bridging between micelles prevails, when the counterions are calcium cations. Remarkably, the negative charges of the headgroups are randomly distributed in the hydrophilic ethylene oxide shell. Altogether, a phase diagram without lyotropic liquid crystalline phases and an extreme shift of the cloud-point in temperature and composition is found, similar to the phase diagram of C 8 EO 8 OH already known in literature. The phase properties can be explained by the curvature and packing constraints together with the Lindemann rule applied to short hydrocarbon chains., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

We use the model system ethanol-dodecane to demonstrate that giant critical fluctuations induced by easily accessible weak centrifugal fields as low as 2000g can be observed above the miscibility gap of a binary liquid mixture. Moreover, several degrees above the phase transition, i.e. in the one-phase region, strong gradients of ethanol concentration occur upon centrifugation. In this case, the standard interpretation of sedimentation equilibrium in the analytical ultracentrifuge (AUC) yields an apparent molar mass of ethanol three orders of magnitude higher than the real value. Notably, these composition gradients have no influence on the distribution gradient of solutes such as dyes like Nile red. The thick opaque interphase formed upon centrifugation does not appear as the commonly observed sharp meniscus, but as a turbidity zone, similar to critical opalescence. This layer is a few millimeters thick and separates two fluids with low compositional gradients. All these effects can be qualitatively understood and explained using the Flory-Huggins solution model coupled to classical density functional theory (DFT). In this domain hetero-phase fluctuations can be triggered by gravity even far from the critical point. Taking into account Jean Perrin's approach to external fields in colloids, a self-consistent definition of the Flory effective volume and an explicit calculation of the total free energy per unit volume is possible.

We propose a general transport theory for pheromone molecules in an atmosphere containing aerosols. Many pheromones are hydrophobic molecules containing polar groups. They are low volatile and have some properties similar to those of hydrotropes. They therefore form a nonsoluble film at the water-air interface of aerosols. The fate of a small pheromone puff in air is computed through reaction-diffusion equations. Partitioning of pheromones between the gas and the aerosol surface over time is studied for various climate conditions (available aerosol surface) and adsorption affinities (energy of adsorption). We show that, for adsorption energy above 30 k B T per molecule, transport of pheromones on aerosols dominates over molecular transport typically 10 s after pheromone emission, even when few adsorbing aerosols are present. This new communication path for airborne chemicals leads to distinctive features including enhanced signal sensibility and increased persistence of pheromone concentration in the air due to slow diffusion of aerosols. Each aerosol droplet has the ability to adsorb thousands of pheromones to the surface, keeping a "history" of the atmospheric content between emission and reception. This new mechanism of pheromone transport leads to dramatic consequences on insect sensing revisiting the way we figure the capture of chemical signals., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

A microfluidic technique is coupled with X-ray fluorescence in order to investigate the origin of the so-called synergy effect observed in liquid-liquid extraction of rare earth elements (REEs) when special combinations of two extractants - one solvating and one ionic - are used. The setup enables kinetic studies by varying the two phases' contact time. The results obtained are compared with those obtained using a standard batch extraction method at identical contact time. We then determine variations of free energies of transfer for five rare earth elements present in a solution together with a non-target ion (Fe3+) at different pH. Analysis of the effect of temperature and of surface charge density of the coexisting cations allows separating electrostatic effects from complexation effects. We finally show that all non-linear (synergic) effects are quadratic in mole fraction. This demonstrates that in-plane mixing entropy of the bent extractant film, in the first nanometer around rare earth ions, is the determining term in the synergy effect. Surprisingly, even when the third phase is present, free energies of transfer could still be measured in the dilute phase, which is reported for the first time, to our knowledge. We hence show that the extractive power of the dense third phase is stronger than that of conventional reverse aggregates in equilibrium with excess water.

In solvent extraction, the self-assembly of amphiphilic molecules into an organized structure is the phenomenon responsible for the transfer of the metal ion from the aqueous phase to the organic solvent. Despite their significance for chemical engineering and separation science, the forces driving the solute transfer are not fully understood. Instead of assuming the simple complexation reaction with predefined stoichiometry, we model synergistic extraction systems by a colloidal approach that explicitly takes into account the self-assembly resulting from the amphiphilic nature of the extractants. Contrary to the current paradigm of simple stoichiometry behind liquid-liquid extraction, there is a severe polydispersity of aggregates completely different in compositions, but similar in the free energy. This variety of structures on the nanoscale is responsible for the synergistic transfer of ions to the organic phase. Synergy can be understood as a reciprocal effect of chelation: it enhances extraction because it increases the configurational entropy of an extracted ion. The global overview of the complex nature of a synergistic mixture shows different regimes in self-assembly, and thus in the extraction efficiency, which can be tuned with respect to the green chemistry aspect.

Mixtures of three solvents, with two immiscible liquids and a third one miscible to both - the solvotrope, may exhibit structuration. We explore the phase diagram of n-octanol/ethanol/water, where ethanol is the hydrotrope, varying composition from the water-rich side to the n-octanol-rich side at constant ethanol fraction. We resolve nanometer-sized structures experimentally by mean of four contrasts: three from Small Angle Neutron Scattering (SANS) and one from Small Angle X-ray Scattering (SAXS). On the water-rich side, we confirm the existence of droplets associated to a critical point stabilized by an excess adsorption of the hydrotrope: the ultra-flexible microemulsion (UFME) domain. The n-octanol-rich side is better described as a dynamic random network of chain-like associations of hydroxy groups. The continuous evolution from oil clusters to a dynamic network of hydroxy groups is demonstrated by the features of scattering patterns, successfully compared for all contrasts to Molecular Dynamics (MD) simulations, allowing to illustrate with snapshots the structuration of solvents. The free energy of transfer of the hydrotrope obtained from MD is low (∼1 k B T/molecule). This study suggests that Ouzo spontaneous emulsions may be in dynamic equilibrium with a pre-Ouzo, similarly to nanoemulsions kinetically stabilized by the co-existence of a microemulsion., (Copyright © 2019 The Authors. Published by Elsevier Inc. All rights reserved.)

Hypothesis: The formation of transient networks of giant micelles leads to a viscosity peak when salt is added to aqueous solutions of charged surfactants. It is the consequence of an increase of the packing parameter due to charge screening of the surfactant headgroups, leading to a continuous transformation of the aggregates from spherical to wormlike micelles, and finally to branched networks. It should therefore be possible to predict the macroscopic viscosity of entangled giant micelles by modelling the packing parameter at nanoscale., Experiments: A thermodynamic model is presented with a minimum of adjustable parameters, where branched networks are considered to be built from three coexisting microphases: cylinders, endcaps, and junctions. We use spontaneous packing parameters, in which the whole molecular length instead of the commonly used hydrocarbon chain length is considered. Standard reference chemical potentials and subsequently the occurrence of each microphase can be explicitly derived at specific electrolyte concentrations. Effective micellar length of giant micelles can be obtained from the microphase composition and is subsequently used to calculate the viscosity., Findings: The model successfully predicts position and intensity of the viscosity maximum observed in experimental salt curves of sodium laureth sulfate (SLES). The robustness of the model was further investigated for various types of added salts or fragrance oils that affect differently spontaneous packing parameters or interfacial bending energy. An excellent agreement of the simulated salt curves with experimental data was achieved., (Copyright © 2018 Elsevier Inc. All rights reserved.)

We propose the statistical thermodynamic model for the prediction of the liquid-liquid extraction efficiency in the case of rare-earth metal cations using the common bis(2-ethyl-hexyl)phosphoric acid (HDEHP) extractant. In this soft matter-based approach, the solutes are modeled as colloids. The leading terms in free-energy representation account for: the complexation, the formation of a highly curved extractant film, lateral interactions between the different extractant head groups in the film, configurational entropy of ions and water molecules, the dimerization, and the acidity of the HDEHP extractant. We provided a full framework for the multicomponent study of extraction systems. By taking into account these different contributions, we are able to establish the relation between the extraction and general complexation at any pH in the system. This further allowed us to rationalize the well-defined optimum in the extraction engineering design. Calculations show that there are multiple extraction regimes even in the case of lanthanide/acid system only. Each of these regimes is controlled by the formation of different species in the solvent phase, ranging from multiple metal cation-filled aggregates (at the low acid concentrations in the aqueous phase), to the pure acid-filled aggregates (at the high acid concentrations in the aqueous phase). These results are contrary to a long-standing opinion that liquid-liquid extraction can be modeled with only a few species. Therefore, a traditional multiple equilibria approach is abandoned in favor of polydisperse spherical aggregate formations, which are in dynamic equilibrium.

We develop a minimal model for the prediction of solvent extraction. We consider a rare earth extraction system for which the solvent phase is similar to water-poor microemulsions. All physical molecular quantities used in the calculation can be measured separately. The model takes into account competition complexation, mixing entropy of complexed species, differences of salt concentrations between the two phases, and the surfactant nature of extractant molecules. We consider the practical case where rare earths are extracted from iron nitrates in the presence of acids with a common neutral complexing extractant. The solvent wetting of the reverse aggregates is taken into account via the spontaneous packing. All the water-in-oil reverse aggregates are supposed to be spherical on average. The minimal model captures several features observed in practice: reverse aggregates with different water and extractant content coexist dynamically with monomeric extractant molecules at and above a critical aggregate concentration (CAC). The CAC decreases upon the addition of electrolytes in the aqueous phase. The free energy of transfer of an ion to the organic phase is lower than the driving complexation. The commonly observed log-log relation used to determine the apparent stoichiometry of complexation is valid as a guideline but should be used with care. The results point to the fact that stoichiometry, as well as the probabilities of a particular aggregate, is dependent on the composition of the entire system, namely the extractant and the target solutes' concentrations. Moreover, the experimentally observed dependence of the extraction efficiency on branching of the extractant chains in a given solvent can be quantified. The evolution of the distribution coefficient of particular rare earth, acid, or other different metallic cations can be studied as a function of initial extractant concentration through the whole region that is typically used by chemical engineers. For every chemical species involved in the calculation, the model is able to predict the exact equilibrium concentration in both the aqueous and the solvent phases at a given thermodynamic temperature.

Selectively exchanging metal complexes between emulsified water-poor microemulsions and concentrated solutions of mixed electrolytes is the core technology for strategic metal recycling. Nanostructuration triggered by solutes present in the organic phase is understood, but little is known about fluctuations of the microemulsion-water interface. We use here a modified version of an optoelectric device initially designed for air bubbles, in order to evidence resonant electrically induced surface waves of an oily droplet suspended in an aqueous phase. Resonant waves of nanometer amplitude of a millimeter-sized microemulsion droplet containing a common ion-specific extractant diluted by dodecane and suspended in a solution of rare earth nitrate are evidenced for the first time with low excitation fields (5 V/cm). From variation of the surface wave spectrum with rare earth concentration, we evidence uptake of rare-earth ions at the interface and at higher concentration the formation of a thin "crust" of liquid crystal forming at unusually low concentration, indicative of a surface induced phase transition. The effect of the liquid crystal structure on the resonance spectrum is backed up by a model, which is used to estimate crust thickness.

Separation of rare earth compounds from water into an organic phase in practical cases requires the use of specific ion binding ligands in high concentrations. These tend to form complex liquid crystalline phases preferentially at ion-rich locations inside a pertraction membrane. They form a blocking layer above an ion concentration threshold, which is experimentally characterized. It is shown to limit the flux through the membrane, which is studied for the application of rare earth recycling, an example being the phase transfer of Nd from water into organic phase. This feedback leads to a stationary membrane permeation rate that can be modeled without any free parameters in very good agreement with experiment. The ion-specific formation and dissolution of the blocking layer, a feature found also in nature, and its control suggest further studies to enhance permeation as well as its selectivity control.

In this review, we discuss the conditions for forming microemulsions, systems which are thermodynamically stable mixtures of oil and water made stable by the presence of an interfacial film containing surface active molecules. There are several types of microemulsions, depending largely on the stiffness of the amphiphilic monolayer that separates the oily and the aqueous micro-domain. We first discuss and compare the phase behaviour of these different types, starting from the classical microemulsion made from a flexible surfactant film but then also moving on to less classical situations: this occurs when the interfacial film is stiff or when microemulsions are formed in the absence of a classical surfactant. In the second part, we relate these different microemulsion types to the structural features as can be determined via different methodologies by small angle scattering (SAS). Using absolute scaling, general theorems as well as fitting under constraints or to pre-supposed shapes in real space or correlation functions in reciprocal space allows to classify all microemulsions into classical flexible, rigid or ultra-flexible microemulsions with either globular, connected cylinder of locally flat interfaces, with the corresponding conductivity and phase stability properties., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The bending rigidity of small reverse aggregates involved in liquid-liquid extraction processes has been investigated by molecular dynamics simulations. Simulations of a common extractant (DMDOHEMA) with four hydrophobic chains in explicit solvent (n-heptane) and in vacuum have been performed to determine the effect of solvent penetration on film stiffness. Elastic film bending energy that is needed for mesoscopic modelling of transfer of species between complex fluids is harmonic in terms of curvature (Helfrich formalism) and the packing parameter only if the solvent is explicitly taken into account. In terms of the packing parameter of the real molecular film constituting the reverse water in oil aggregates and taking into account molecular volume, area and film thickness (that is in agreement with Tanford's model), the bending rigidity is calculated to be about 16 k B T per extractant molecule (about 40 kJ mol -1 ), which is smaller than the free energy of transfer from an isolated "monomer" molecule to a weak aggregate, but of the order of magnitude of the free energy of transfer used in liquid-liquid extraction processes.

Bligh and Dyer (B & D) or Folch procedures for the extraction and separation of lipids from microorganisms and biological tissues using chloroform/methanol/water have been used tens of thousands of times and are "gold standards" for the analysis of extracted lipids. Based on the Conductor-like Screening MOdel for realistic Solvatation (COSMO-RS), we select ethanol and ethyl acetate as being potentially suitable for the substitution of methanol and chloroform. We confirm this by performing solid-liquid extraction of yeast ( Yarrowia lipolytica IFP29 ) and subsequent liquid-liquid partition-the two steps of routine extraction. For this purpose, we consider similar points in the ternary phase diagrams of water/methanol/chloroform and water/ethanol/ethyl acetate, both in the monophasic mixtures and in the liquid-liquid miscibility gap. Based on high performance thin-layer chromatography (HPTLC) to obtain the distribution of lipids classes, and gas chromatography coupled with a flame ionisation detector (GC/FID) to obtain fatty acid profiles, this greener solvents pair is found to be almost as effective as the classic methanol-chloroform couple in terms of efficiency and selectivity of lipids and non-lipid material. Moreover, using these bio-sourced solvents as an alternative system is shown to be as effective as the classical system in terms of the yield of lipids extracted from microorganism tissues, independently of their apparent hydrophilicity.

The phase diagrams of ternary mixtures of partly miscible solvents containing a hydrotropic co-solvent exhibit a variable miscibility gap and one critical point. This work investigates the entire monophasic region far from and near to the miscibility gap in octan-1-ol/ethanol/water, for which ultra-flexible micro-emulsions (UFMEs) are observed by small-angle scattering techniques. SWAXS (combined small- and wide-angle X-ray scattering) allows the elucidation of these types of structure. Three distinct areas can be identified in the phase diagram, with scattering data resembling those from direct, bicontinuous and reverse local structures. These UFMEs are far more polydisperse than their surfactant-based counterparts. Water-rich and solvent-rich domains are only delimited by a small excess of hydrotrope, instead of a well defined surfactant layer of fixed area per molecule. It is shown that all scattering spectra obtained for the nanostructured compositions can be modelled by a simple unified analytical model composed of two uncorrelated contributions. The main one is the Ornstein-Zernike formula for composition fluctuations which gives information about the pseudo-phase domain size. The second is a Lorentzian that captures the structure of at least one of the coexisting pseudo-phases. No Porod law can be measured in the SAXS domain. The proposed expression gives access to two characteristic sizes as well as one inter-aggregate distance.

Herein, a minimal model for the common case of W/O solubilization of badly soluble compounds present in an excess phase by reverse micellar aggregates in chemical equilibrium with its single compounds is introduced. A simple model of such liquid-liquid extractions is crucial for obtaining predictive parameter for the modelling of nuclear waste management and hydrometallurgic recycling strategies. The standard Gibbs free energy of aggregation and the concentration of the corresponding aggregate is calculated within a multiple-equilibria approach for a set of aggregate compositions of solute and amphiphilic extractant molecules. This minimal model provides potential surfaces estimating the stability of different aggregate compositions with 6.2kJmol(-1) as a generalized bending constant. The complete concentrations of free and aggregated extractant species as well as the favored aggregation numbers, the polydispersity, the activity of the organic solvent, and the critical concentrations are captured by this thermodynamic model. An increase of the apparent critical micelle concentration for an increasing solute content in the aqueous phase is detected by this method., (Copyright © 2016 Elsevier Inc. All rights reserved.)

We show that three different morphologies exist near the two-phase boundary of ternary systems containing a hydrotropic cosolvent. Based on synchrotron small- and wide-angle X-ray scattering combined with molecular dynamics, we rationalize the specific scattering signature of direct, bicontinuous, and reverse mesoscale solubilization. Surprisingly, these mesostructures are resilient toward strong acids, which are required in industrial applications. However, on a macroscopic scale, the phase boundary shifts in salting-in and salting-out in the direct and respectively reverse regime, leading to a crossing of the binodals.

The coalescence behavior of two sessile drops that contain different chemical reactants (cerium nitrate and oxalic acid) and its impact on the formation of the solid precipitate (cerium oxalate) are investigated. With different liquids, the surface tension difference in the moment of drop-drop contact can induce a Marangoni flow. This flow can strongly influence the drop-drop coalescence behavior and thus, with reacting liquids, also the reaction and its products (through the liquid mixing). In our study we find three distinctly different coalescence behaviors ("barrier", "intermediate", "noncoalescence"), in contrast to only two behaviors that were observed in the case of nonreacting liquids. The amount of liquid mixing and thus the precipitation rate are very different for the three cases. The "intermediate" case, which exhibits the strongest mixing, has been studied in more detail. For high oxalic acid concentrations, mainly needle-like aggregates, and for low concentrations, mainly flower-like precipitate morphologies are obtained. In a transition range of the oxalic acid concentration, both morphologies can be produced. With the applied coalescence conditions, the different aggregate particles are arranged and fixed in a precipitate raft in a regular, periodic line pattern. This confirms the drop-drop coalescence configuration as a convection-reaction-diffusion system, which can have stationary as well as oscillatory behavior depending on the system parameters.

Quantitative experiments on the evaporation from sessile droplets of aqueous saline (NaCl) solutions show a strong dependence on salt concentration and droplet shape. The experiments were performed with seven decades of initial NaCl concentrations, with various droplet sizes and with different contact angles. The evaporation rate is significantly lower for high salt concentrations and small contact angles than what is expected from the well-accepted diffusion-controlled evaporation scenario for sessile droplets, even if the change of the vapor pressure due to the salt is taken into account. Particle tracking velocimetry reveals that this modification of the evaporation behavior is caused by marangoni flows that are induced by surface tension gradients originating from the local evaporative peripheral salt enrichment. In addition it is found that already very low salt concentrations lead to a pinning of the three phase contact line. Whereas droplets with concentration ≥10(-6) M NaCl are pinned as soon as evaporation starts, droplets with lower salt concentration do evaporate in a constant contact angle mode. Aside from new, fundamental insights the findings are also relevant for a better understanding of the widespread phenomenon of corrosion initiated by sessile droplets.

A very small concentration of NaBr is added to ternary, transparent, and thermodynamically stable mixtures of water, ethanol, and octanol. Measuring the electrical conductivity along lines with constant water to ethanol ratios reveals remarkable composition dependencies similar to those found in classical surfactant-based microemulsions. Indeed, light-scattering experiments along the same composition lines and additional surface tension measurements confirm the onset of aggregation and possibly direct, bicontinuous, and reversed structures in these surfactant-free systems such as in classical microemulsions.

Iron-uranium selectivity in liquid-liquid extraction depends not only on the mole fraction of extractants, but also on the nature of the diluent used, even if the diluent has no complexation interaction with the extracted ions. Modeling strong nonlinearity is difficult to parametrize without a large number of parameters, interpreted as "apparent constants". We determine in this paper the synergy curve versus mole fraction of HDEHP-TOPO (di(2-ethylexyl) phosphoric acid/tri-n-octyl phosphine oxide) and compare the free energy of aggregation to the free energy of extraction in various diluents. There is always a concomitant maximum of the two quantities, but with a gradual influence on intensity. The diluent is wetting the chains of the reverse aggregates responsible of the extraction. We show here that the intensity of the unexplained synergy peak is strongly dependent on the "penetrating" or "nonpenetrating" nature of the diluent. This experimental determination allows us to attribute the synergy to a combination of entropic effects favoring extraction, opposed to perturbation of the first coordination sphere by penetration as well as surfactant film bending energy.

Salt-free catanionic systems based on fatty acids exhibit a broad polymorphism by simply tuning the molar ratio between the two components. For fatty acid combined with organic amino counter-ions, very few data are available on the phase behavior obtained as a function of the molar ratio between the counter-ion and the fatty acid. We investigated the choline hydroxide/myristic acid system by varying the molar ratio, R=n(choline hydroxide)/n(myristic acid), and the temperature. Myristic acid ionization state was determined by coupling pH, conductivity and infra-red spectroscopy measurements. Self-assemblies were characterized by small angle neutron scattering and microscopy experiments. Self-assembly thermal behavior was investigated by differential scanning calorimetry, wide angle X-ray scattering and nuclear magnetic resonance. For R<1, ionized and protonated myristic acid molecules coexisted leading to the formation of facetted self-assemblies and lamellar phases. The melting process between the gel and the fluid state of these bilayers induced a structural change from facetted or lamellar objects to spherical vesicles. For R>1, myristic acid molecules were ionized and formed spherical micelles. Our study highlights that both R and temperature are two key parameters to finely control the self-assembly structure formed by myristic acid in the presence of choline hydroxide., (Copyright © 2015 Elsevier Inc. All rights reserved.)