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This study examined the phase behaviour and temperature-dependent viscosity of palm stearin and fully hydrogenated soybean oil (FHSBO) mixtures to understand the stability of FHSBO coatings on micronutrient premixes. The Hildebrand equation showed that palm stearin/FHSBO mixtures form liquid solutions, while DSC data indicated partial immiscibility in the solid phase. The melting temperatures and enthalpies of fusion are composition dependent, ranging from 67 °C and 138 J/g for 100 % FHSBO to 13 °C and 71 J/g for 100 % palm stearin. The Arrhenius model provided an excellent fit for the viscosities of the binary mixtures above their melting points, with activation energies of 26-27 kJ/mol and pre-exponential factors of 131-207 MPa.s. At the processing conditions of bouillon cubes, a binary fat coating can form on premix granules and contain approximately 70 % palm stearin at equilibrium. At processing temperatures of 30-60 °C, the premix fat coating contains 68-84 % liquid., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Y.K. Kiki Chan reports financial support was provided by Natural Sciences and Engineering Research Council of Canada. 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 © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Broparestrol has been used as a drug to treat acne in the form of a mixture of its two stereoisomers. Although it has been withdrawn from the market, the binary system is rich in polymorphism and understanding the phase behaviour of the binary system involving the E- and Z-isomers is challenging. Physical mixtures do not immediately give rise to equilibrium phase behaviour, whereas recrystallization often leads to metastable phases and the appearance of stable phases can take years. A new polymorph of E-broparestrol has been found crystallizing in a monoclinic unit cell, space group P2 1 /c, with lattice parameters a = 5.6079(4) Å, b = 16.1206(10) Å, c = 20.250 (1) Å, β = 100.569(4)°, V cell  = 1799.6(2) Å 3 , and Z = 4. This polymorph, I E , is stable at high temperatures, whereas the published form, II E , is stable at room temperature. In the case of Z-broparestrol polymorphism has been observed too; however, it has so far only occurred within the binary phase diagram, and it has not been possible to isolate the new polymorph of Z-broparestrol, II Z . Through the phase behaviour in the binary system, it could be determined that the new Z polymorph, II Z , behaves monotropically in relation to the known triclinic polymorph of the Z-isomer, I Z . Nothing is known about its structure, and it is therefore not clear yet whether II Z may possess a stable domain under pressure. A stable temperature-composition phase diagram of the binary system containing E- and Z-broparestrol is proposed., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: J.-Ll. Tamarit reports financial support was provided by Spanish ministry of science and innovation. J.-Ll. Tamarit reports financial support was provided by Government of Catalonia. 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 © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

Hypothesis: Ellipsoidal particles confined at liquid interfaces exhibit complex self-assembly due to quadrupolar capillary interactions, favouring either tip-to-tip or side-to-side configurations. However, predicting and controlling which structure forms remains challenging. We hypothesize that introducing a polymer-based soft shell around the particles will modulate these capillary interactions, providing a means to tune the preferred self-assembly configuration based on particle geometry and shell properties., Experiments: We fabricate core-shell ellipsoidal particles with defined aspect ratios and shell thickness through thermo-mechanical stretching. Using interfacial self-assembly experiments, we systematically explore how aspect ratio and shell thickness affect the self-assembly configurations. Monte Carlo simulations and theoretical calculations complement the experiments by mapping the phase diagram of thermodynamically preferred structures as a function of core-shell properties., Findings: Pure ellipsoidal particles without a shell consistently form side-to-side "chain-like" assemblies, regardless of aspect ratio. In contrast, core-shell ellipsoidal particles exhibit a transition from tip-to-tip "flower-like" arrangements to side-to-side structures as aspect ratio increases. The critical aspect ratio for this transition shifts with increasing shell thickness. Our results highlight how we can engineer the self-assembly of anisotropic particles at liquid interfaces by tuning their physicochemical properties such as aspect ratio and shell thickness, allowing the deterministic realization of distinct structural configurations., 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.)

The availability of sufficient amounts of form I of benzocaine has led to the investigation of its phase relationships with the other two existing forms, II and III, using adiabatic calorimetry, powder X-ray diffraction, and high-pressure differential thermal analysis. The latter two forms were known to have an enantiotropic phase relationship in which form III is stable at low-temperatures and high-pressures, while form II is stable at room temperature with respect to form III. Using adiabatic calorimetry data, it can be concluded, that form I is the stable low-temperature, high-pressure form, which also happens to be the most stable form at room temperature; however, due to its persistence at room temperature, form II is still the most convenient polymorph to use in formulations. Form III presents a case of overall monotropy and does not possess any stability domain in the pressure-temperature phase diagram. Heat capacity data for benzocaine have been obtained by adiabatic calorimetry from 11 K to 369 K above its melting point, which can be used to compare to results from in silico crystal structure prediction.

Azobenzene liquid crystalline (ALC) ligand contains a cholesteryl group linked to an azobenzene moiety through a carbonyl dioxy spacer (C7) and terminated with an amine group as a polar head. The phase behaviour of the C7 ALC ligand at the air-water (A-W) interface is investigated employing surface manometry. The surface pressure-area per molecule isotherm shows that C7 ALC ligand exhibit two different phases following the phase sequence viz., liquid expanded (LE 1 and LE 2 ) and then collapse to three-dimensional crystallites. Further, our investigations under different pH conditions and in the presence of DNA reveal the following. Compared to the bulk, the acid dissociation constant (pK a ) of an individual amine reduces to 5 at the interfaces. For pH (3.5) < pK a , the protonation of amine groups of C7 ALC ligand facilitates the condensation of the film and enhances the stability. For pH values > pK a , the phase behaviour of the ligand remains the same due to the partial dissociation of the amine groups. The presence of DNA in the sub-phase result in the expansion of isotherm to the higher area per molecule and the compressional modulus extracted reveals the phase sequence; liquid expanded, liquid condensed, followed by a collapse. Further, the kinetics of adsorption of DNA to the amine groups of the ligand is investigated, suggesting the interactions are influenced by surface pressure corresponding to different phases and pH of the sub-phase. Brewster angle microscope studies are carried out at different surface densities of the ligand as well as in the presence of DNA also supports this inference. Atomic force microscope is employed to acquire the surface topography and height profile of C7 ALC ligand (1 layer) after transferring on onto a silicon substrate using Langmuir Blodgett deposition. The difference in the surface topography and thickness of the film indicates the adsorption of DNA onto the amine groups of the ligand. The characteristic UV-visible absorption bands of the ligand films (10 layers) at the air-solid interface are tracked and the hypsochromic shift of these bands is also attributed to these DNA interactions., Competing Interests: Declaration of Competing Interest There are no competing financial interests declared by the authors., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Ionic liquid crystals (ILCs) are soft matter materials with broad liquid crystalline phases and intrinsic electric conductivity. They typically consist of a rod-shaped mesogenic ion and a smaller spherical counter-ion. Their mesomorphic properties can be easily tuned by exchanging the counter ion. ILCs show a strong tendency to form smectic A phases due to the segregation of ionic and the non-ionic molecular segments. Nematic phases are therefore extremely rare in ILCs and the question of why nematic phases are so exceptional in existing ILCs, and how nematic ILCs might be obtained in the future is of vital interest for both the fundamental understanding and the potential applications of ILCs. Here, we present the result of a simulation study, which highlights the crucial role of the location of the ionic charge on the rod-like mesogenic ions in the phase behaviour of ILCs. We find that shifting the charge from the ends towards the centre of the mesogenic ion destabilizes the liquid crystalline state and induces a change from smectic A to nematic phases., (© 2022 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

Machine-learning models were developed to predict the composition profile of a three-compound mixture in liquid-liquid equilibrium (LLE), given the global composition at certain temperature and pressure. A chemoinformatics approach was explored, based on the MOLMAP technology to encode molecules and mixtures. The chemical systems involved an ionic liquid (IL) and two organic molecules. Two complementary models have been optimized for the IL-rich and IL-poor phases. The two global optimized models are highly accurate, and were validated with independent test sets, where combinations of molecule1+molecule2+IL are different from those in the training set. These results highlight the MOLMAP encoding scheme, based on atomic properties to train models that learn relationships between features of complex multi-component chemical systems and their profile of phase compositions., (© 2022 Wiley-VCH GmbH.)

Maintaining water balance is vital for terrestrial organisms. Insects protect themselves against desiccation via cuticular hydrocarbons (CHCs). CHC layers are complex mixtures of solid and liquid hydrocarbons, with a surprisingly diverse composition across species. This variation may translate into differential phase behaviour, and hence varying waterproofing capacity. This is especially relevant when temperatures change, which requires acclimatory CHC changes to maintain waterproofing. Nevertheless, the physical consequences of CHC variation are still little understood. We studied acclimatory responses and their consequences for CHC composition, phase behaviour and drought survival in three congeneric ant species. Colony sub-groups were kept under cool, warm and fluctuating temperature regimes. Lasius niger and Lasius platythorax, both of which are rich in methyl-branched alkanes, showed largely predictable acclimatory changes of the CHC profile. In both species, warm acclimation increased drought resistance. Warm acclimation increased the proportion of solid compounds in L. niger but not in L. platythorax. In both species, the CHC layer formed a liquid matrix of constantly low viscosity, which contained highly viscous and solid parts. This phase heterogeneity may be adaptive, increasing robustness to temperature fluctuations. In Lasius brunneus, which is rich in unsaturated hydrocarbons, acclimatory CHC changes were less predictable, and warm acclimation did not enhance drought survival. The CHC layer was more homogeneous, but matrix viscosity changed with acclimation. We showed that ant species use different physical mechanisms to enhance waterproofing during acclimation. Hence, the ability to acclimate, and thus climatic niche breadth, may strongly depend on species-specific CHC profile., Competing Interests: Competing interests The authors declare no competing or financial interests., (© 2022. Published by The Company of Biologists Ltd.)

The self-assembly of lipid mixtures in aqueous solution was investigated by dissipative particle dynamics simulation. Two types of lipid molecules were modelled, where three mixed structures, i.e., the membrane, perforated membrane and vesicle, were determined in the self-assembly processes. Phase behaviour was investigated by using the phase diagrams based on the tail chain lengths for the two types of lipids. Several parameters, such as chain number and average radius of gyration, were employed to explore the structural formations of the membrane and perforated membrane in the dynamic processes. Interface tension was used to demonstrate the mechanical properties of the membrane and perforated membrane in the equilibrium state and dynamics processes. Results help us to understand the self-assembly mechanism of the biomolecule mixtures, which has a potential application for designing the lipid molecule-based bio-membranes in solutions.

Hypothesis: Glycolipids in biological membranes are ubiquitous and believed to be involved in the formation of ordered functional domains. However, our current knowledge about such glycolipid-enriched domains is limited because they are inherently difficult to characterize., Experiments: We use grazing-incidence X-ray diffraction, isotherm measurements, and Brewster angle microscopy to investigate the phase behavior and miscibility in Langmuir lipid monolayers containing glycolipids., Findings: Glycolipid-enriched domains give rise to distinct diffraction patterns that allow for a systematic structural investigation and reveal a rich phenomenology, ranging from near-complete demixing to the formation of mixed domains with unique features. The phase behavior is governed by the headgroup chemistry and by the length and saturation of the tails., 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.)

Competing interaction fluids have become ideal model systems to study a large number of phenomena, for example, the formation of intermediate range order structures, condensed phases not seen in fluids driven by purely attractive or repulsive forces, the onset of particle aggregation under in- and out-of-equilibrium conditions, which results in the birth of reversible and irreversible aggregates or clusters whose topology and morphology depend additionally on the thermodynamic constrictions, and a particle dynamics that has a strong influence on the transport behaviour and rheological properties of the fluid. In this contribution, we study a system of particles interacting through a potential composed by a continuous succession of a short-ranged square-well (SW), an intermediate-ranged square-shoulder and a long-ranged SW. This potential model is chosen to systematically analyse the contribution of every component of the interaction potential on the phase behaviour, the microstructure, the morphology of the resulting aggregates and the transport phenomena of fluids described by competing interactions. Our results indicate that the inclusion of a barrier and a second well leads to new and interesting effects, which in addition result in variations of the physical properties associated to the competition among interactions., (© 2022 IOP Publishing Ltd.)

Colloidal dispersions composed of either platelets or rods exhibit liquid crystalline phase behaviour that is strongly influenced by the addition of nonadsorbing polymers. In this work we examined how polymer segment-segment interactions affect this phase behaviour as compared to using either penetrable hard spheres (PHS) or ideal ('ghost') chains as depletants. We find that the simplified polymer description predicts the same phase diagram topologies as the more involved polymer descriptions. Therefore the PHS description is still adequate for qualitative predictions. For sufficiently large polymer sizes we find however that the precise polymer description significantly alters the locations of the phase coexistence regions. Especially the stability region of isotropic-isotropic coexistence is affected by the polymer interactions. To illustrate the quantitative effects some examples are presented., (Creative Commons Attribution license.)

Morniflumate diniflumate, a molecular compound involving niflumic acid and its β-morpholino ethyl ester (morniflumate) in the mole ratio 2:1, is found to crystallize in a triclinic P - 1 space group with a unit-cell volume of 2203.4(5) Å 3 . It is a cocrystal between a morniflumate + niflumate - salt and a neutral niflumic acid molecule. The co-crystalline salt forms endothermically with a positive excess volume and it melts incongruently at 382.3(8) K. Differential scanning calorimetry executed at heating rates above 20 K⋅min -1 , leads to congruent melting at 387.8(9)K with an enthalpy change of Δ fus H = 80(2) J g -1 . The rare occurrence that incongruent and congruent melting can be observed for the same cocrystal may be due to the conformational versatility of the niflumic acid molecule and its slow conversion between the different conformations due to weak intramolecular hydrogen bonding., (Copyright © 2021 Elsevier B.V. All rights reserved.)

A new series of laterally fluorinated mesomorphic compounds, namely 2-fluoro-4-((4-(alkyloxy)phenyl)diazenyl)phenyl 4-substitutedbenzoate ( In x ) were prepared and evaluated for their mesophase behavior. The synthesized series constitutes five members that possess different terminally attached polar groups (X). Their molecular structures were confirmed by elemental analyses and both FT-IR and NMR spectroscopy. Examination of the prepared derivatives was conducted via experimental and theoretical tools. Mesomorphic investigations were carried by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). DSC and POM measurements indicated that except for the un-substituted analogue, all other derivatives were purely nematogenic, possessing their nematic (N) mesophase enantiotropically. This is to say that insertions of terminal polar substituents on their mesogenic structures induced the N phase. In addition, the location of lateral and terminal polar moieties played a considerable role in achieving good thermal N stability. Computational calculations were investigated to determine the deduced optimized molecular structures. Theoretical data indicated that both size and polarity of the terminal substituent (X) have essential impact on the thermal parameters and optical properties of possible geometries.

Colloidal lipidic particles with different space groups and geometries (mesosomes) are employed in the development of new nanosystems for the oral delivery of drugs and nutrients. Understanding of the enzymatic digestion rate of these particles is key to the development of novel formulations. In this work, the molecular structure of the lipids has been systematically tuned to examine the effect on their self-assembly and digestion rate. The kinetic and phase changes during the lipase-catalysed hydrolysis of mesosomes formed by four synthetic cyclopropanated lipids and their cis-unsaturated analogues were monitored by dynamic small angle X-ray scattering and acid/base titration. It was established that both the phase behaviour and kinetics of the hydrolysis are greatly affected by small changes in the molecular structure of the lipid as well as by the internal nanostructure of the colloidal particles., 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 © 2020 Elsevier Inc. All rights reserved.)

Aqueous mixtures of anionic and nonionic/cationic surfactants can form non-trivial self-assemblies in solution and exhibit macroscopic responses. Here, we investigate the micellar phase of pure and mixed aqueous solutions of Sodium Dodecyl Sulfate (SDS) and Dimethyldodecyl Amine Oxide (DDAO) using a combination of Small Angle Neutron Scattering (SANS), Fourier-Transform Infrared Spectroscopy (FTIR) and rheological measurements. We examine the effect of temperature (0-60 °C), on the 20 wt% SDS micellar solutions with varying DDAO (⩽5 wt%), and seek to correlate micellar structure with zero-shear solution viscosity. SANS establishes the formation of prolate ellipsoidal micelles in aqueous solutions of pure SDS, DDAO and SDS/DDAO mixtures, whose axial ratio is found to increase upon cooling. Elongation of the ellipsoidal micelles of pure SDS is also induced by the introduction of the non-anionic DDAO, which effectively reduces the repulsive interactions between the anionic SDS head-groups. In FTIR measurements, the formation of elongated mixed ellipsoidal micelles is confirmed by the increase of ordering in the hydrocarbon chain tails and interaction between surfactant head-groups. We find that the zero-shear viscosity of the mixed surfactant solutions increases exponentially with decreasing temperature and increasing DDAO content. Significantly, a master curve for solution viscosity can be obtained in terms of micellar aspect ratio, subsuming the effects of both temperature and DDAO composition in the experimental range investigated. The intrinsic viscosity of mixed micellar solutions is significantly larger than the analytical and numerical predictions for Brownian suspensions of ellipsoidal colloids, highlighting the need to consider interactions of soft micelles under shear, especially at high concentrations., 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 © 2020 Elsevier Inc. All rights reserved.)

Cocrystallization of ibuprofen and nicotinamide in hot melt extrusion process has been subject of many studies addressing low ibuprofen bioavailability. However, it is observed that the process of cocrystal formation of ibuprofen and nicotinamide might be incomplete. We hypothesized that formation of dimers of ibuprofen-ibuprofen or dimers nicotinamide- nicotinamide might be the cause of such poor cocrystalization process by altering the phase behaviour of the mixture. This paper addresses the molecular thermodynamics of mixtures of ibuprofen and nicotinamide, with special focus on the possibility of formation of these dimers and their corresponding interplay with mixture phase behaviour. For this purpose, density functional theory calculations are used to calculate electron donor-acceptor sizes on each molecule and accordingly possible dimers of each molecule are analysed. The free energies and phase diagram are determined for (1) when a dimer is formed or (2) no dimer is formed, over a wide operating temperature range of 273.15 K-390 K. The binding and solvation energies are calculated to identify/rank dimers. Calculations showed that formation of dimers requires an energy input which can be accessible noting to the external heating in hot melt extrusion process. The calculated solvation energies of the dimers suggest that addition of liquid binder (water) can mitigate the risk of dimer formations. Addition of proper binder/excipient is an easy route to compensate such dimer formation and to engineer ibuprofen and nicotinamide cocrystallization behaviour., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The effects of three polysaccharides on the textural properties and microstructure of myofibrillar protein (MP) gels were studied. The gel strength and rheological properties of composite MP gels were significantly improved with insoluble dietary fibre (DF) and modified starch (MS) addition, while konjac glucomannan (KG) had limited effects at 1% addition. The SEM images indicated that moisture extrusion formed moisture channels and deteriorated the aggregation of MP gel networks during the thermal process. The polysaccharides stabilized moisture and reduced the appearance of moisture channels in the gel network, thereby promoting the formation of compact and integral gel networks. The MP-polysaccharide mixture is a thermally incompatible system and presented two main forms after the thermal process: 1) the "trapped" structure and 2) the "interpenetrated" structure. In the "trapped" structure, the MP was the dominant structure of the composite gel network. In the "interpenetrated" structure, the continuous polysaccharide hydrogel substantially hindered the aggregation of MP gel networks. Principal component analysis showed that the phase behaviour and moisture stability of polysaccharides significantly influenced the textural quality and microstructure of composite MP gelation. The study indicated that polysaccharides that contribute to moisture stability and form a "trapped structure" (phase behaviour) are ideal fat replacements for improving composite gel properties, especially DF., Competing Interests: Declaration of Competing Interest The authors declared that they have no conflicts of interest to this work. We declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted., (Copyright © 2020. Published by Elsevier Ltd.)

Ions are ubiquitous in nature. They play a key role for many biological processes on the molecular scale, from molecular interactions, to mechanical properties, to folding, to self-organisation and assembly, to reaction equilibria, to signalling, to energy and material transport, to recognition etc. Going beyond monovalent ions to multivalent ions, the effects of the ions are frequently not only stronger (due to the obviously higher charge), but qualitatively different. A typical example is the process of binding of multivalent ions, such as Ca 2+ , to a macromolecule and the consequences of this ion binding such as compaction, collapse, potential charge inversion and precipitation of the macromolecule. Here we review these effects and phenomena induced by multivalent ions for biological (macro)molecules, from the "atomistic/molecular" local picture of (potentially specific) interactions to the more global picture of phase behaviour including, e. g., crystallisation, phase separation, oligomerisation etc. Rather than attempting an encyclopedic list of systems, we rather aim for an embracing discussion using typical case studies. We try to cover predominantly three main classes: proteins, nucleic acids, and amphiphilic molecules including interface effects. We do not cover in detail, but make some comparisons to, ion channels, colloidal systems, and synthetic polymers. While there are obvious differences in the behaviour of, and the relevance of multivalent ions for, the three main classes of systems, we also point out analogies. Our attempt of a comprehensive discussion is guided by the idea that there are not only important differences and specific phenomena with regard to the effects of multivalent ions on the main systems, but also important similarities. We hope to bridge physico-chemical mechanisms, concepts of soft matter, and biological observations and connect the different communities further., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Hypothesis: Control of the nanostructure of self-assembled systems may be achieved through manipulation of surfactant molecular packing and interfacial curvature. In order to phase engineer the inverse micellar cubosomes in some monoolein-fatty acid systems, lipids with wedge shaped molecular geometry were incorporated to promote the formation of this phase, that is of interest as potential sustained released nanocarriers., Experiments: Liquid crystalline nanoparticle dispersions of monoolein with some cis unsaturated fatty acids were prepared and their partial temperature-composition phase diagrams and structure were established using high throughput Small Angle X-ray Scattering (SAXS) and cryogenic transmission electron microscopy (cryo-TEM). The pH responsiveness of these systems was evaluated in the presence of phosphate buffered saline (PBS)., Findings: The partial temperature-composition phase diagrams of five nanoparticle formulations containing monoolein and unsaturated fatty acids were established and identified the presence of micellar cubosomes in each of these systems. The results indicate that temperature, fatty acid concentration and structure, as well as pH all directly impact the formation and stability of this phase. Low energy inverse micellar cubic to emulsion phase transformations were identified in the monoolein with oleic acid and vaccenic acid systems at physiological temperatures that may be advantageous for staged therapeutic release strategies in nanomedicine., 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 © 2020 Elsevier Inc. All rights reserved.)

Both lamellar and non-lamellar configurations are naturally present in bio-membranes, and the synthetic lipid-based liquid crystalline nano-assemblies, mimicking these unique structures, (including liposomes, cubosomes and hexosomes) are applicable in the controlled delivery of bioactives. However, it remains uncertain whether these nanosystems retain their original phase identity upon contact with blood circulating cells. This study highlights a novel biological cell flow-through approach at the synchrotron-based small angle X-ray scattering facility (bio-SAXS) to unravel their real-time phase evolution when incubated with human monocytic cells (THP-1) in suspension. Phytantriol-based cubosomes were identified to undergo monocytic cell-induced phase transformation from cubic to hexagonal phase periodicity. On the contrary, hexosomes exhibited time-dependent growth of a swollen hexagonal phase (i.e., larger lattice parameters) without displaying alternative phase characteristics. Similarly, liposomes remained undetectable for any newly evolved phase identity. Consequently, this novel in situ bio-SAXS study concept is valuable in delivering new important insights into the bio-fates of various lipid-based nanosystems under simulated human systemic conditions.

Understanding the evolution of complex traits is among the major challenges in biology. One such trait is the cuticular hydrocarbon (CHC) layer in insects. It protects against desiccation and provides communication signals, especially in social insects. CHC composition is highly diverse within and across species. To understand the adaptive value of this chemical diversity, we must understand how it affects biological functionality. So far, CHCs have received ample research attention, but their physical properties were little studied. We argue that these properties determine their biological functionality, and are vital to understanding how CHC composition affects their adaptive value. We investigated melting behaviour and viscosity of CHCs from 11 ant species using differential scanning calorimetry and a novel microrheological technique. CHCs began melting below -45°C, and often were entirely liquid only above 30°C. Thus, they formed a solid-liquid mixture under ambient conditions, which contrasts to previous assumptions of entirely solid layers in many species. This may be adaptive as only biphasic CHC layers ensure uniform coating of the insect body, which is necessary for waterproofing. CHC viscosity was mostly between 0.1 and 0.2 Pa s -1 , thus similar to motor oils. Surprisingly, chemically different CHC profiles had similar viscosities, suggesting that a certain viscosity level is adaptive and ensures that communication signals can be perceived. With this study, we draw attention to the importance of studying the physics of CHC layers. Only by understanding how chemical and physical mechanisms enable CHC functionality can we understand the causes and consequences of CHC diversification., Competing Interests: Competing interestsThe authors declare no competing or financial interests., (© 2019. Published by The Company of Biologists Ltd.)

The rate of emulsification in surfactant/oil/water systems is influenced by transport of chemicals and mixing of the fluid phases. In porous media applications, complex flow regimes are generated due to three-dimensional connectivity and irregular cross-sections of the pores facilitating the mixing for emulsification. The properties of the resulting emulsified phase depend on the interplay of flow, mixing and emulsification kinetics of the surfactant/oil/water system. Emulsification can be relatively quick. Direct visualization of the process and compositional gradients in three-dimensional pore space during flow requires imaging at few seconds time intervals. In this study, a flow unit was integrated in a synchrotron beamline-based fast X-ray computed micro-tomography set-up. Non-destructive three-dimensional visualization of multi phase flow inside a porous rock at flow conditions became viable. An oil saturated rock sample was first flooded with water, followed by surfactant solution to mobilize the remaining oil by miscible displacement. The sample was continuously imaged during injection; the scans were made at time intervals of 7-60 s. The presence of an emulsified phase in addition to the oil and the aqueous phases required a more advanced image processing workflow compared to the workflows used for the immiscible fluid systems. A newly developed image processing technique was adopted; the grey levels in the images were correlated with the local oil content in the emulsified fluid regions. The visual extractions of the pore space showed that the emulsification occurred within seconds. Compositional gradients were observed in the emulsified phase as the injected surfactant solution reached the remote locations in the pore space. While a significant fraction of the oil was displaced within few seconds, the compositional gradients persisted over several millimeter length for several minutes, illustrating a sequence of mobilization and solubilization of the oil phase. The ability to interpret such compositional gradients in real time in porous space brings capability to study interfacial phenomena in applications where in situ emulsification occurs under flow., (Copyright © 2019 Elsevier Inc. All rights reserved.)

We report the spontaneous formation of multilamellar vesicles (MLVs) from low concentration (<30 wt%) aqueous micellar solutions of sodium linear alkylbenezene sulfonate (NaLAS) upon cooling, employing a combination of optical microscopy (OM), Small Angle Neutron Scattering (SANS), and Cryo-TEM. Upon cooling, MLVs grow from, and coexist with, the surfactant micelles, attaining diameters ranging from hundreds of nanometers to a few micrometers depending on the cooling rate, whilst the d-spacing of internal lamellae remains unchanged, at ≃ 3 nm. While microscale fluid and flow properties of the mixed MLVs and micellar phase depend on rate of cooling, the corresponding nanoscale structure of the surfactant aggregates, resolved by time-resolved SANS, remains unchanged. Our data indicate that the mixed MLV and micellar phases are in thermodynamic equilibrium with a fixed relative volume fraction determined by temperature and total surfactant concentration. Under flow, MLVs aggregate and consequently migrate away from the channel walls, thus reduce the overall hydrodynamic resistance. Our findings demonstrate that the molecular and mesoscopic structure of ubiquitous, low concentration NaLAS solutions, and in turn their flow properties, are dramatically influenced by temperature variation about ambient conditions., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Context: The molecular bases of pore formation in the lipid bilayer remain unclear, as do the exact characteristics of their sizes and distributions. To understand this process, numerous studies have been performed on model lipid membranes including cell-sized giant unilamellar vesicles (GUV). The effect of an electric field on DPPC GUV depends on the lipid membrane state: in the liquid crystalline phase the created pores have a cylinder-like shape, whereas in the gel phase a crack has been observed., Objective: The aim of the study was to investigate the geometry of pores created in a lipid bilayer in gel and liquid crystalline phases in reference to literature experimental data., Methods: A mathematical model of the pore in a DPPC lipid bilayer developed based on the law of conservation of mass and the assumption of constant volume of lipid molecules, independent of their conformation, allows for analysis of pore shape and accompanying molecular rearrangements., Results: The membrane area occupied by the pore of a cylinder-like shape is greater than the membrane area occupied by lipid molecules creating the pore structure (before pore appearance). Creation of such pores requires more space, which can be achieved by conformational changes of lipid chains toward a more compact state. This process is impossible for a membrane in the most compact, gel phase., Discussion and Conclusions: We show that the geometry of the pores formed in the lipid bilayer in the gel phase must be different from the cylinder shape formed in the lipid bilayer in a liquid crystalline state, confirming experimental studies. Furthermore, we characterize the occurrence of the 'buffer' zone surrounding pores in the liquid crystalline phase as a mechanism of separation of neighbouring pores.

Ceramide-1-phosphate (C1P) plays an important role in several biological processes, being identified as a key regulator of many protein functions. For instance, it acts as a mediator of inflammatory responses. The mediation of the inflammation process happens due to the interaction of C1P with the C2 domain of cPLA2α, an effector protein that needs the presence of submicromolar concentrations of calcium ions. The aim of this study was to determine the phase behaviour and structural properties of C1P in the presence and absence of millimolar quantities of calcium in a well-defined pH environment. For that purpose, we used monomolecular films of C1P at the soft air/liquid interface with calcium ions in the subphase. The pH was varied to change the protonation degree of the C1P head group. We used surface pressure versus molecular area isotherms coupled with other monolayer techniques as Brewster angle microscopy (BAM), infrared reflection-absorption spectroscopy (IRRAS) and grazing incidence X-ray diffraction (GIXD). The isotherms indicate that C1P monolayers are in a condensed state in the presence of calcium ions, regardless of the pH. At higher pH without calcium ions, the monolayer is in a liquid-expanded state due to repulsion between the negatively charged phosphate groups of the C1P molecules. When divalent calcium ions are added, they are able to bridge the highly charged phosphate groups, enhancing the regular arrangement of the head groups. Similar solidification of the monolayer structure can be seen in the presence of a 150 times larger concentration of monovalent sodium ions. Therefore, calcium ions have clearly a strong affinity for the phosphomonoester of C1P.

Surfactants have been the basis for applications in several industrial sectors for a long time. However, fundamental research was 50 years ago still limited to a small number of academic groups and even basic aspects were controversial. The field has since undergone an enormous expansion and the improved understanding has laid the basis of numerous new products as well as been the basis of important parts of nano-science and -technology.The present author has during 50 years in academia devoted most of his research to amphiphilic compounds, including both surfactants and polymers. Hereby, I had the privilege of following a very exciting development. In 2015, I had the honour to receive the Life-time Achievement Award of IACIS, the International Association of Colloid and Interface Scientists. IACIS organizes since the 1970s a tri-annual symposium, typically the best attended in the field. For the first time since 2000, it was in 2015 organized in Europe, namely Mainz, Germany. This treatise is based on my award lecture in Mainz, which covered developments from my first research as a new Ph D student in Stockholm to current work as an emeritus and visiting professor. Interestingly, discoveries in my very early work contributed to solving problems in now on-going research. Håkan Wennerström kindly wrote a quite comprehensive paper about my achievements a few years ago (Adv Colloid Interf Sci 205:1-8, [1]). In writing the present paper, I have strived at covering mainly topics not treated in detail by Håkan. In fact, I will emphasize very much our early studies as well as our studies of surfactant self-assembly by NMR and in particular look at the developments of our research and connections between different research topics., Competing Interests: The author declares no conflict of interest.

In the current study, the phase behaviour of indomethacin and poly(lactic-co-glycolic acid) (PLGA) formulations was investigated as a function of the molecular weight and the copolymer composition of PLGA. The formulations were prepared by ball milling, and the phase behaviour, comprised of the glass-transition temperature of the formulations and the solubility of indomethacin in PLGA, was measured using modulated differential scanning calorimetry (mDSC). The results determined that the solubility of indomethacin in PLGA at room temperature was very low and increased with a corresponding decrease in the molecular weight of PLGA. The copolymer composition of PLGA had a minor effect on the indomethacin solubility. The effect of PLGA's molecular weight and copolymer composition on the solubility of indomethacin could be modelled using the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) with a high degree of accuracy when compared with the experimental data. The glass-transition temperatures had a negative deviation from the weighted mean of the glass-transition temperatures of the pure substances, which could be described by the Kwei-equation., (Copyright © 2015. Published by Elsevier B.V.)

Asphaltenes are considered to be the heaviest and most polar fractions of crude oils and are frequently implicated in problems encountered during production and refining as a result of phase separation. In recent years, considerable effort has been given to understanding the phase behaviour of these structurally heterogeneous materials from both experimental and computational perspectives. Various experimental studies have confirmed the long-advanced colloidal behaviour of asphaltenes in organic media, and this has inspired a number of modelling strategies. The present review is specifically concerned with advances in modelling asphaltene phase behaviour with emphasis on the use of the statistical associating fluid theory (SAFT), which it attempts to place into the wider context of thermodynamic treatments., (Copyright © 2014 Elsevier B.V. All rights reserved.)

This work examines the influence of essential oil composition on emulsification with rhamnolipids and their use as therapeutic antimicrobial agents against two opportunistic pathogens, methicillin-resistant Staphylococcus aureus (MRSA) and Candida albicans. Rhamnolipids, produced by Pseudomonas aeruginosa, with waste frying oil as the carbon source, were composed of eight rhamnolipid homologues. The rhamnolipid mixture was used to produce emulsions containing essential oils (EOs) of Melaleuca alternifolia, Cinnamomum verum, Origanum compactum and Lavandula angustifolia using the titration method. Ternary phase diagrams were designed to evaluate emulsion stability, which differed depending on the essential oil. The in vitro antimicrobial activity of the EOs alone and the emulsions was evaluated. The antimicrobial activity presented by the essential oils alone increased with emulsification. The surface properties of rhamnolipids contribute to the positive dispersion of EOs and thus increase their availability and antimicrobial activity against C. albicans and S. aureus. Therefore, rhamnolipid-based emulsions represent a promising approach to the development of EO delivery systems., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Tuneable and stable surface-chemical gradients in supported lipid bilayers (SLBs) hold great promise for a range of applications in biological sensing and screening. Yet, until now, no method has been reported that provides temporal control of SLB gradients. Herein we report on the development of locked-in SLB gradients that can be tuned in space, time and density by applying a process to control lipid phase behaviour, electric field and temperature. Stable gradients of charged Texas-Red-, serine- or biotin-terminated lipids have been prepared. For example, the Texas-Red surface density was varied from 0 to 2 mol %, while the length was varied between several tens to several hundreds of microns. At room temperature the gradients are shown to be stable up to 24 h, while at 60 °C the gradients could be erased in 30 min. Covalent and non-covalent chemical modification of the gradients is demonstrated, for example, by FITC, hexahistidine-tagged proteins, and SAv/biotin. The amenability to various (bio)chemistries paves the way for novel SLB-based gradients, useful in sensing, high-throughput screening and for understanding dynamic biological processes., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Hypothesis: Initial studies (Hopkins Hatzopoulos et al. (2013)) have shown that ionic hydrotropic additives can drive a sphere-to-cylinder (ellipsoid) transition in water-in-oil (w/o) microemulsions stabilized by the anionic surfactant Aerosol-OT; however the origins of this behaviour remained unclear. Here systematic effects of chemical structure are explored with a new set of hydrotropes, in terms of an aromatic versus a saturated cyclic hydrophobic group, and linear chain length of alkyl carboxylates. It is proposed that hydrotrope-induced microemulsion sphere-to-cylinder (ellipsoid) transitions are linked to additive hydrophobicity, and so a correlation between the bulk aqueous phase critical aggregation concentration (cac) and perturbation of microemulsion structure is expected., Experiments: Water-in-oil microemulsions were formulated as a function of water content w (= [water]/[AOT]) and concentration of different hydrotropes, being either cyclic (sodium benzoate or sodium cyclohexanoate), or linear chain systems (sodium hexanoate, sodium heptanoate and sodium octanoate). Phase behaviour studies were performed as a function of w, additive type and temperature at total surfactant concentration [ST]=0.10M and constant mole fraction x=0.10 (x=[hydrotrope]/[ST]). Microemulsion domain structures were investigated by small-angle neutron scattering (SANS), and these data were fitted by structural models to yield information on the shapes (spheres, ellipsoids or cylinders) and sizes of the nanodroplets., Findings: Under the conditions of study hydrotrope chemical structure has a significant effect on microemulsion structure: sodium cyclohexanoate does not induce the formation of cylindrical/ellipsoidal nanodroplets, whereas the aromatic analogue sodium benzoate does. Furthermore, the short chain sodium hexanoate does not cause anisotropic microemulsions, but the more hydrophobic longer chain heptanoate and octanoate analogues do induce sphere-to-ellipsoid transitions. This study shows that underlying microemulsion structures can be tuned by hydrotropes, and that the strength of the effect can be identified with hydrotrope hydrophobicity in terms of the bulk aqueous phase cac., (Copyright © 2014 Elsevier Inc. All rights reserved.)

This work evaluated the occlusive versus non-occlusive application of microemulsion (ME) for the transdermal delivery of progesterone. The mechanisms of enhanced skin penetration were investigated. ME comprised of oleic acid, Tween 80, propylene glycol, and water, was used neat or with ethanol as a volatile cosurfactant. The ME formulations enhanced progesterone transdermal flux compared to the saturated drug solution in 14% aqueous propylene glycol (control). Ethanol-containing ME (EME) was better than the ethanol-free system (EFME). Open application of EFME produced a marginal reduction in flux compared to occlusive application. For EME, open application reduced the flux by 26-28% with the flux remaining significantly higher than that obtained with EFME. The mechanistic studies revealed synergism between ethanol and EFME with EME, producing greater flux than the sum of fluxes obtained from 40% ethanol in water and EFME. Penetration enhancement and supersaturation played a role in enhanced transdermal delivery, but other mechanisms were also possible. This study thus introduced EME as a transdermal delivery system for progesterone with good potential for open application as a spray.