ABSTRACT We report the synthesis and mesomorphic characterisation of two unsymmetric dimeric polycatenar mesogens (A1 and A6) incorporating an odd-membered flexible spacer and a 3,4,5-tris(hexyloxy) polycatenar terminus. The dimers were comprehensively characterised for their mesophase behaviour using differential scanning calorimetry (DSC), polarised optical microscopy (POM), and temperature-dependent small- and wide-angle X-ray diffraction (XRD). Despite combining bent molecular geometry with a multi-chain architecture, both compounds form only enantiotropic smectic phases. Compound A1 displays a single SmA phase (mesophase range 9 K), while A6 shows a SmA phase followed by a second, unidentified lamellar smectic phase of higher positional order (combined smectic range 42 K). X-ray diffraction reveals an intercalated bilayer-like SmA packing for A1 and an essentially monolayer lamellar arrangement for A6. The observation of orthogonal SmA phases in these unsymmetric polycatenar mesogens is discussed in the context of space-filling constraints and cross-sectional mismatch between the rigid core and the terminal chain volume.

Uniform hollow carbon nanoparticles (CNPs) of different shapes were prepared by a reverse microemulsion polymerization method. The main advantage of this method is the ability to control the precise shape of the nanoparticles. The CNPs were prepared by the room temperature polymerization of a butadiyne monomer on self-assembled surfactant templates formed in the ternary system containing sodium bis (2-ethylhexyl)sulfosuccinate (AOT), water, and hexane. The size and shape (spherical, cylindrical and lamellar phase) of the aggregated surfactant template depend on the composition of the ternary system, which varies primarily through the water content parameter. After template removal by simple washing, the CNPs were studied by morphological analysis (transmission electron microscopy) and chemical characterization with a variety of methods, including energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, Auger electron spectroscopy and Raman spectroscopy. Depending on the template shape, CNPs were obtained in the form of hollow spheres, hollow rods or lamellar sheets. Results from various characterization techniques indicate that the obtained nanomaterials are primarily composed of sp2 hybridized carbon.

From micro to macro: modulating the properties of cationic lamellar phases with nanocelluloses.

Exploring the impact of nucleotide length on lipid nanoparticle structure and properties.

Structural analysis of the lyotropic phases in alpha-olefin sulfonate as a function of water content and temperature.

The bacterial actin homolog MreB plays a key role in rod cell shape determination. We recently showed that MreB from the Gram-positive bacterium Geobacillus stearothermophilus (MreBGs) polymerizes into straight pairs of protofilaments in the presence of both ATP and a lipid surface. Membrane interaction is thought to be mediated by electrostatic interactions with anionic lipids, with final anchoring relying on two spatially close hydrophobic motifs that protrude from the MreBGs monomers, forming a putative membrane-insertion domain. Here, we determined the binding properties of ATP and ADP to MreBGs using fluorescence anisotropy and monitored ATP-mediated binding and polymer formation on lipid bilayers using liposome-binding assays and atomic force microscopy, respectively. Finally, we used solid-state NMR to visualize the interaction between the membrane and MreBGs at the atomic level. Our findings reveal that divalent cations are required for nucleotide binding and that, unlike eukaryotic actin, MreBGs has similar affinity for both ATP and ADP. We also show that monomeric MreBGs establishes peripheral contacts with the membrane likely through electrostatic interactions, while Mg⋅ATP-induced MreBGs filaments insert into the lipid bilayer without interfering with the membrane lamellar phase and have a significant local fluidifying effect.

Block copolymers exhibit unique phase separation and structural transitions, making them highly relevant in industrial applications. This review provides a critical analysis of block copolymer systems, focusing on the thermodynamics of micro- and macro-phase separation and their ability to self-assemble into diverse morphologies. Grounded in the Flory-Huggins model, key factors such as segregation strength, solvent selectivity, molecular architecture (e.g. polydispersity and grafting sites), shear forces, and temperature are examined for their impact on phase behaviour in neat systems and in solution. Viscoelastic properties, particularly the storage (G') and loss (G") moduli, are analysed as dynamic indicators of phase transitions, enabling the identification of temperature ranges for phase separation and system dynamics across various morphologies. The influence of external stimuli such as shear and thermal fields is also discussed, with attention to their role in directing morphology across micellar, cubic, hexagonal, and lamellar phases. This review provides an overview of the current knowledge in the field, summarizing key advances and emerging applications. Special attention is given to potential developments in areas such as nanolithography, drug delivery, membrane technology, energy storage, photonics and catalysis. In doing so, the paper highlights emerging research directions and the role of thermodynamic and structural control in designing functional materials. By offering new perspectives on phase behaviour and self-assembly mechanisms, this work aims to guide the development of next-generation polymeric systems for emerging technologies.

Nanostructured self-assembling materials known as lyotropic liquid crystals (LLCs) consist of amphiphilic molecules in a solvent and having a number of mesophases such as cubic, hexagonal, and lamellar phases. Since LLCs are concentration-dependent and not temperature-dependent as it is the case with thermotropic liquid crystals, they are heavily applied in drug delivery, nanotechnology, and the biological sciences. Their ability to entrap hydrophilic and hydrophobic molecules supports controlled and site-specific drug release, promoting therapeutic efficacy and bioavailability. Stimuli-sensitive LLC systems have been found promising as devices for transdermal delivery, ocular delivery of drugs, and cancer therapy due to their sensitivity towards pH changes, temperature changes, or mechanical stress. Characterization techniques such as polarized light microscopy (PLM) and small-angle X-ray scattering (SAXS) are often employed to determine phase structures in order to understand their structural properties and enhance their formulations. Dynamic light scattering (DLS) helps in assessing colloidal stability. The fundamental concepts, types, compositions, and preparation methods—such as top-down and bottom-up strategies—of LLCs are all discussed elaborately in this article. It also addresses new advances in biomedical applications, control release strategies, targeted drug delivery systems, and their application to drug delivery. In addition, several case studies related to LLC formulations laden with anti-tumor drugs and their therapeutic capability are discussed. Formulation developments in LLC form are capable of reshaping present day drug delivery procedures and enhance therapeutic outcomes in biomedical applications.

The limited ductility of conventional titanium alloys significantly limits their application in critical load-bearing components. To overcome this limitation, a Ti-6Al-2Mo-2Nb-2Zr-2Sn titanium alloy (TC21) was subjected to warm rolling at 500 and 600 °C and aging treatment. Subsequently, microstructural characterization was conducted using scanning electron microscopy, electron backscatter diffraction and transmission electron microscopy, while the mechanical properties were tested by uniaxial tensile tests and nanoindentation tests. The sample warm rolled at 600 °C exhibited an optimal combination of strength and ductility, with an ultrahigh yield strength of 1138 MPa and an elongation-to-fracture of 7.3%. Aging treatment further enhanced the yield strength to 1263 MPa, while retaining a good ductility of 9.6%. The improved mechanical properties are mainly associated with the formation of nanoscale secondary α phase (αs) lamellae caused by the aging treatment. Interface strengthening is identified as the primary strengthening mechanism. In particular, the optimal volume fraction and decreasing texture intensity of the soft phase contribute to the enhanced ductility. This work provides a method for viable thermo-mechanical processing for achieving an excellent strength-ductility combination in titanium alloys.

We report on a newly designed bis-ureido-squaramide (USq) (1) monomeric unit, capable to tune its conformation and regulate its self-assembly behavior in solution and in solid state, forming one- (1D) and two-dimensional (2D) assemblies. In chloroform, the bis-USq 1 exists as a folded monomeric form (MonF), stabilized by six intramolecular hydrogen bonds, and polymerizes by increasing concentration and decreasing the temperature. Microscopic observations, supported by theoretical calculations, revealed that 1 does not assemble into the expected main-chain polymers, and instead, a supramolecular 2D polymer (AggA) is formed by the interplay of USq-USq quadruple hydrogen bonds and additional π-π and van der Waals interactions. Remarkably, this 2D assembly was preserved in solid-state as a lamellar phase (1-Lam) after solvent evaporation. However, heating the sample to isotropic and cooling it down revealed a second and more stable polymorph based on a 1D columnar structure (1-Col). Interestingly, both solid-state polymorphs are stabilized by analogous hydrogen bonding patterns but different molecular packing. This work underpins the USq unit as an intriguing hydrogen-bonding moiety suitable for the development of new supramolecular materials but also as a platform to study pathway complexity and polymorphism in solid state and solution.

ABSTRACT We report on a newly designed bis‐ureido‐squaramide (USq) ( 1 ) monomeric unit, capable to tune its conformation and regulate its self‐assembly behavior in solution and in solid state, forming one‐ (1D) and two‐dimensional (2D) assemblies. In chloroform, the bis‐USq 1 exists as a folded monomeric form ( Mon F ), stabilized by six intramolecular hydrogen bonds, and polymerizes by increasing concentration and decreasing the temperature. Microscopic observations, supported by theoretical calculations, revealed that 1 does not assemble into the expected main‐chain polymers, and instead, a supramolecular 2D polymer ( AggA ) is formed by the interplay of USq‐USq quadruple hydrogen bonds and additional π–π and van der Waals interactions. Remarkably, this 2D assembly was preserved in solid‐state as a lamellar phase ( 1‐Lam ) after solvent evaporation. However, heating the sample to isotropic and cooling it down revealed a second and more stable polymorph based on a 1D columnar structure ( 1‐Col ). Interestingly, both solid‐state polymorphs are stabilized by analogous hydrogen bonding patterns but different molecular packing. This work underpins the USq unit as an intriguing hydrogen‐bonding moiety suitable for the development of new supramolecular materials but also as a platform to study pathway complexity and polymorphism in solid state and solution.

In recent years, ionic liquid (IL)-based formulations have gained attention for their potential use in drug delivery and antibacterial and antiseptic applications. Molecular dynamics simulations can provide insights into complex interaction mechanisms, serving as valuable tools to guide experimental efforts to design novel formulations. However, to study interactions that involve micellar aggregates and membrane partitioning dynamics, simulations should be able to access time scales of several microseconds, requiring reliably parametrized coarse-grained molecular models. In this study, we investigate the interaction of choline-geranic acid (CAGE)-based ILs with a model phospholipid membrane. In order to develop a coarse-grained CAGE model, we carried out atomistic simulations with the GROMOS54a7, CHARMM36m, OPLS, and OPLS-R force fields. The OPLS-R force field was found to accurately predict experimental structural and dynamic properties of CAGE molecules and was therefore used to parametrize the coarse-grained models within the Martini 2 (M2) and Martini 3 (M3) frameworks. The M3 model was in better agreement with both experimental observations and atomistic simulations and captured the reported micellar phase transition composition with increasing water content. In contrast, the M2 model was found to overestimate the density, with a greater tendency to form a lamellar phase. Using the newly parametrized M3 force field, free energy computations with a dipalmitoylphosphatidylcholine (DPPC) lipid bilayer revealed a favorable free energy of partitioning for geranic acid compared to geranate ions, while choline partitioning was unfavorable. Geranate ion partitioning increased with a higher concentration of geranic acid in the CAGE solution. Micellar aggregates of geranic acid either released molecules in the extracellular space for subsequent membrane uptake or underwent direct fusion with the membrane. Both the area compressibility and order parameters decreased with increasing geranic acid content, which also resulted in an increase in the lipid area. The coarse-grained model developed in this study allows us to study membrane partitioning, micellar breakup, and membrane fusion events which occur on microsecond times scales. These models can potentially be utilized to investigate the influence of CAGE-based chemistry on membrane partitioning, thereby aiding in the development of novel IL-based therapeutic formulations.

Understanding how lipid bilayers respond to pressure is essential for interpreting the coupling between membrane proteins and their native environments. Here, we use all-atom molecular dynamics to examine the pressure-temperature behavior of model membranes composed of dimyristoylphosphatidylcholine (DMPC) or its cis-unsaturated analogue Δ9-cis-PC. Within the studied range (288-308 K, 1-2000 bar), DMPC undergoes a liquid-gel transition, while Δ9-cis-PC remains fluid due to unsaturation. The CHARMM36 force field reproduces experimental boundaries with high fidelity: simulated DMPC transitions fall within 5-10 K and 100-300 bar of experimental values, and Δ9-cis-PC exhibits no transition. Hysteresis is modest but most pronounced when starting from low-temperature gels; we propose a split-phase simulation protocol that alleviates the hysteresis problem. We identify the area per lipid, bilayer thickness, and acyl-chain gauche fractions as sensitive phase markers; among these, the gauche fraction provides the most robust signature. Simulations indicate that an interdigitated gel is the equilibrium structure under finite-size conditions, and we propose a novel metric to quantify the extent of this phenomenon. However, at low temperature and high pressure, interdigitation decreases, consistent with the experimental lamellar gel phase. This long-lived interdigitation critically impacts standard order parameters, specifically, area per lipid and membrane thickness. Finally, we discuss in detail how finite-size effects influence phase transition and interdigitation. Overall, these results underscore the accuracy of modern force fields and highlight how simulations are essential to mechanistically complement experimental studies of pressure-sensitive membranes.

Eutectic alloys stand out for their ability to combine high strength and good ductility; a behaviour rooted in their characteristic two-phase microstructure—lamellar or globular—formed at a constant solidification temperature that minimizes segregation and suppresses brittle phases. Their low interfacial energy limits microcrack propagation, while interfacial sliding and dislocation blocking at phase boundaries enhance both strength and toughness. In this work, we investigate how controlled microstructural modifications influence the behaviour of the eutectic high-entropy alloy AlCoCrFeNi2.1, composed of B2 (Ni–Al-rich) and L12 (Co–Fe–Ni-rich) phases. Because these phases exhibit distinct mechanical responses, microconstituent morphology becomes a design parameter. Powder metallurgy is the only processing route capable of providing the level of microstructural control required in this study. It preserves the rapidly solidified eutectic architecture of gas-atomised powders while allowing its intentional transformation during consolidation. Two strategies were implemented: (i) tuning the thermal–electrical input in Spark Plasma Sintering (SPS) and Electrical Resistance Sintering (ERS), and (ii) engineering the particle size distribution, including a bimodal design that enhances surface-energy-driven morphological transitions. SPS enables a gradual lamellar-to-globular evolution, whereas ERS induces ultrafast transformations governed by current intensity. The bimodal PSD significantly accelerates globularisation at lower energy input. EBSD-KAM (Electron Backscatter Diffraction—Kernel Average Misorientation) mapping identifies the lamellar B2 phase as metastable and highly strained, while globular B2 domains show reduced dislocation density. Nanoindentation confirms that intrinsic phase properties remain unchanged, whereas microhardness scales with morphology and lamellar spacing. These results demonstrate that the macroscopic mechanical response is governed by microstructure, establishing powder metallurgy as a uniquely powerful pathway for microstructure-driven design in eutectic HEAs.

Block copolymers (BCPs) are exciting materials owing to their ability to self-organize, resulting in ordered mesophases in bulk. A rich variety of interesting novel ordered phases can be obtained by subjecting the polymer to geometrical confinement. In the present study, we investigate the self-assembly behavior of A2B miktoarm star block copolymer melt under cylindrical and spherical nanopores using self-consistent field theory (SCFT). Compared with the equivalent linear AB diblock copolymer, the A2B miktoarm star block copolymer tends to influence the phase behavior. The structural frustration and chain conformational entropy loss lead to various ordered phases. The role of introducing an additional arm of the A-block to a linear AB diblock copolymer in phase behavior is examined for the wall selective to the majority component. Under cylindrical confinement, when the two A-arms are in the minority and the surface prefers the B-block, the region of helical phases transitions to the perforated lamella (PL1) and concentric lamella (CL1) phases. However, when the A-arms form the majority and prefer the surface, the helical ordering of the minority B-block is favored, and a rich array of ordered phases is obtained, such as single helix (H1), double helices (H2), and toroids (T). Similarly, under spherical confinement, when A-arms constitute the majority, interesting morphologies are obtained, such as double helices (H2), four-hole nanocages (CG4), a pair of toroids (T2), a pair of toroids with one sphere (ST2), and a single toroid flanked by two spheres (ST1S). Overall, the branched chain architecture of A2B alters the phase behavior under confinement vis-à-vis the linear AB diblock copolymer.

Synergistic enhancement of strength and ductility in Mg-Gd-Y-Zn-Zr alloys through LPSO phases with multiple morphologies

Effect of solution treatment on the microstructure and mechanical properties of Mg–Zn–Y–Mn-(V) magnesium alloy

Formation of 3D interconnected multiphase heterostructures from CoCrFeMnNi high-entropy alloy via liquid metal dealloying using Cu–Ag melts

Polysaccharides extracted from Japanese pumpkin (Cucurbita maxima Duchesne) possess antioxidant activity and moisturizing effects. To meet the demand for natural skincare, this study aims to develop ultra-micro liquid crystal (ULC) emulsions containing pumpkin seed oil (PO) and Japanese pumpkin polysaccharide (PP). The novelty lies in the synergistic triple-action mechanism of the lipid lamellar structure, emollients and humectants, which together achieve superior moisturization. The formulation is varied by different emulsifiers (Emulgade® PL 68/50 and Olivem® 1000), thickening agents (0.3–0.5% w/w of hydroxyethyl cellulose, xanthan gum, or guar gum), and active concentrations of 2.0–4.0% w/w PO and 0.1% w/w PP. Physicochemical characterization was conducted via polarized light microscopy, particle size analysis, and wide-angle X-ray diffraction (WAXD). Stability was assessed through centrifugation and six heating–cooling cycles, while clinical safety and moisturizing efficacy were evaluated in human volunteers using the Corneometer® and Tewameter®. Polarized light microscopy revealed distinct Maltese cross structures, while WAXD confirmed the presence of α-gel and lamellar (Lα) phases. The ULC emulsion containing PO and PP (F9), comprising 4.5% Emulgade® PL 68/50, 0.3% xanthan gum, 2.0% PO, and 0.1% PP, demonstrated excellent physical stability and a particle size of 4.02 ± 0.02 µm. Clinical results demonstrated that F9 was non-irritating and significantly enhanced skin hydration, while reducing transepidermal water loss compared to the baseline (p < 0.05). Although F9 showed the greatest numerical improvement in barrier function, its efficacy was comparable to placebo cream and ULC emulsion containing PO (F6) (p > 0.05). In conclusion, the successful integration of pumpkin-derived actives into a stable ULC system provides a safe and effective approach for advanced moisturizing skincare applications.

The Gibbs energy due to coherency strain associated with lamellar phase decomposition, including vibrational components, was investigated, using a microscopic perspective combining atomistic calculations based on density functional theory and calorimetric measurements. The model was applied to the lamellar decomposition of alkali feldspar, revealing that the coherency strain energy coefficient does not only depend on temperature and starting composition, as is the case within the macroscopic, i.e., continuum-mechanical approach, but it also depends on the chemical gradient at the lamellar interfaces and on the lamellar thickness. This difference to the macroscopic approach is caused by a realistic relaxation of the structure in the interior of the lamellae. The coherency strain energy coefficient decreases with decreasing chemical gradient. However, the lowering of the chemical gradient causes the unmixing process to be incomplete increasing the Gibbs energy of mixing, which destabilises lamellae with small chemical gradients. This incompleteness of the unmixing process was quantified in a correction procedure, which was then used to calculate the correct Gibbs energy of mixing. A minimisation procedure of the Gibbs energy that contains components from both mixing and coherency strain resulted in the determination of the equilibrium chemical gradient at lamellar interfaces and its dependence on temperature and lamellar thickness. Although the coherency strain energy coefficient depends on lamellar thickness and chemical gradient, the Gibbs energy minimisation results in a single coherent solvus, which is independent of these properties and is found to agree well with experimental data. The new method can be adapted for coherent lamellar decomposition in other binary solid solutions and alloys.