Mixed ionic electronic conducting perovskite oxides are promising alternative fuel electrodes for steam and/or carbon dioxide co-electrolysis in solid oxide cells. Among these, molybdenum-doped strontium ferrites (Sr2Fe1.5Mo0.5O6 +/-delta, SFM) are particularly important due to their high redox stability and catalytic properties. Herein, we have functionalized such SFM-based fuel electrodes by promoting exsolution of Fe and FeNi alloy nanoparticles through Ni-doping at their B-site and introduction of A-site deficiency. In situ NEXAFS under reducing conditions indicated that A-site deficiency and Ni doping promote Fe exsolution, leading to the formation of Fe-rich, FeNi bimetallic nanoparticles, with the composition influenced by perovskite stoichiometry. The electrochemical characterizations revealed that both doping and exsolution significantly reduce cell polarization resistance, which enhanced the electrode's electrical efficiency for H2O-CO2 co-electrolysis (25% H2O, 25% CO2) in the absence of hydrogen or carbon monoxide safe gas. Specifically, Ni-doping combined with FeNi or FeNi3 exsolution improved by almost three times the electrocatalytic performance of the bare SFM, with current densities reaching up to 1.3 A cm-2 at 1.6 V and 800 degrees C in a ZrO2-based electrolyte-supported cell. The surface characterization revealed an increase in oxygen exchange rate kinetics and CO2 adsorption capacity in the modified samples which may explain the enhanced performance. Our results provide valuable insight into the required strategy for developing highly efficient fuel electrodes through the combination of rational doping and redox exsolution to advance sustainable electrochemical syngas production from SOECs.

Mixed ionic electronic conducting perovskites decorated with catalytically active FeNi-based nanoparticles are promising alternative fuel electrodes for steam and carbon dioxide co-electrolysis in solid oxide cells.

As the supply of light on Earth is cyclic and asymmetric, living systems that rely on photochemical energy have adapted to accommodate periods of light and darkness. During the day, light energy is available, while throughout the dark phases, thermal relaxation processes can be used to increase functional and structural organization. While light-driven supramolecular assembly has been reported, structural adaptation under alternating light/dark input remains largely unexplored in synthetic supramolecular systems. Here, we show how an oscillating light energy supply can facilitate the structural selection of self-assembling photoswitchable peptides compared to continuous illumination. We demonstrate that polymorphic self-assembled structures are transiently formed and sustained only under light irradiation, while alternating periods of irradiation and darkness favor the formation of a thermodynamically more stable supramolecular architecture. These findings demonstrate the key role that rest (darkness) periods can have in the self-assembly pathway selection of molecular and self-organized supramolecular photosystems.

Glycosylated nanoparticles, inspired by natural systems, hold great promise for biomedical applications such as targeted drug delivery and biosensing. However, achieving precise control over their self-assembly and responsiveness remains a challenge. In this study, we report the design, synthesis, and self-assembly behavior of a novel glycosylated triblock terpolymer with tunable stimulus responsiveness. The terpolymer with stimulus responsiveness was synthesized through reversible addition-fragmentation chain transfer (RAFT) polymerization. The self-assembly of these triblock terpolymers into glycosylated micelles with distinct pH responsiveness was induced by increasing the temperature. Postpolymerization modification of the glycosylated triblock terpolymer enabled the synthesis of glycosylated polyplex micelles via complex condensation. Dynamic light scattering (DLS), transmission electron microscopy (TEM), and cryogenic transmission electron microscopy (cryo-TEM) revealed stimuli-induced structural transitions, including pH-dependent transformations from hierarchical nanoparticles and ‘bead-on-a-string’ assemblies to uniform spherical micelles. Additionally, the glycosylated polyplex micelles exhibited unique ‘breathing’ behavior, characterized by reversible size variations driven by structural adjustments in the stabilizing chains. These stimuli-responsive glycosylated nanoparticles mimic natural systems and present significant potential for biomedical applications such as targeted drug delivery and biosensing. This study lays a solid foundation for the development of advanced glycosylated nanostructures with tailored functionality and responsiveness.

Substituting the anodic oxygen evolution reaction (OER) with ethanol oxidation offers a promising route to lower the energy consumption of anion-exchange-membrane (AEM) electrolysis, but selective oxidation at industrially relevant current densities is often undermined by the emergence of OER-active states. Here, we identify stabilized Ni3 + oxyhydroxide as the key state that redirects anodic Ni chemistry away from oxygen evolution and toward selective ethanol oxidation under high-current operation. On a metallic Ni/defect-rich NiO heterointerface, anodic polarization triggers surface hydroxylation while retaining strong electronic coupling across the interface. Mechanistic studies combining operando Raman spectroscopy, post-reaction TEM/XPS, and density functional theory reveal that interfacial charge transfer facilitates early Ni2+/Ni3 + conversion, stabilizes Ni3 + oxyhydroxide species, decreases the OH* deprotonation barrier, and inhibits overoxidation toward OER. This mechanism delivers 100 mA cm-2 at only 120 mV and preserves selective, bubble-free ethanol oxidation up to 900 mA cm-2. In an ethanol-hybrid AEM electrolyzer, the corresponding anode lowers the cell voltage by 370 mV at 1.0 A cm-2 compared with conventional water electrolysis and sustains stable electrolysis for 200 h at 0.5 A cm-2. Our results establish Ni3 + oxyhydroxide stabilization as a general design principle for high-rate selective anodic oxidation and energy-efficient hydrogen production.

Stimuli-responsive glycosylated nanoparticles hold great promise for mimicking complex biological glycans, yet current fabrication methods often lack versatility in tuning the morphology and responsiveness. Here, we report a solvent-selective self-assembly approach using multiresponsive glycosylated triblock tercopolymers designed with pH- and temperature-responsive segments. These polymers form well-defined nanoparticles, including spheres, cylinders, and worm-like aggregates, which can be modulated under external stimuli. Furthermore, we fabricated a diverse range of glycosylated nanoparticles by altering the sequence of the blocks within the terpolymers. Their well-defined morphologies were visualized via cryogenic transmission electron microscopy (cryo-TEM), and their size distributions were analyzed via dynamic light scattering (DLS). Our results demonstrate that integrating multiple stimuli-responsive elements in triblock terpolymers enables structural control of glycosylated nanoparticles. The morphological evolution of these nanoparticles corresponds to changes in the macromolecular configuration triggered by variations in the pH, temperature, and block sequence. This approach offers new opportunities for developing biomimetic materials for targeted delivery and glycan-based sensing.

Self-assembly, the spontaneous organization of molecular components into ordered structures without external intervention, offers a powerful route to complex nanomaterials. Yet the molecular pathways that govern hierarchical assembly, particularly under non-equilibrium conditions, often remain poorly understood. Here we establish an integrated experimental platform that couples microfluidic control of the assembly environment with multi-scale optical and structural probes, enabling direct correlation between morphological evolution and excitonic functionality during supramolecular growth. Using this approach, we track in real time the formation of double-walled nanotubes (DWNTs) from the amphiphilic cyanine dye C8S3, a synthetic analogue of the light-harvesting chlorosomes in green sulfur bacteria. The results show that the outer nanotube structures first, while the inner nanotube follows with a delay, ultimately giving rise to electronically coupled coaxial architectures. While the principal excitonic signatures and morphological motifs emerge within minutes of self-assembly, axial elongation and orientational refinement continue over tens of hours through a nucleation-elongation mechanism. Notably, suppressing local concentration gradients through more efficient mixing abolishes DWNT formation, establishing spatial heterogeneity as a key parameter governing hierarchical self-assembly. By linking structural evolution with excitonic functionality in real time, this combined platform provides a framework for dissecting non-equilibrium pathways in supramolecular materials.

A notable characteristic of living organisms is their capacity to adapt to environmental changes and transform external signals into distinct responsiveness, facilitating the execution of diverse functions with motility as a key parameter. To better mimic such lifelike behavior, researchers have developed various supramolecular assembled systems with responsive behavior toward a variety of stimuli. However, exploiting motion along length scales and achieving collective control over the responsiveness to multiple stimuli in supramolecular systems is still challenging. Here we present the development of molecular motor based supramolecular polymers that are responsive toward multi-stimulus and exhibit multi-state assembly and chirality. Taking advantages of aldehyde functionalized motors, we realized photo-responsive supramolecular polymers featuring boosted photo-efficiency, near quantitative photoconversions, programmable behavior and responsiveness to multiple stimuli in a reversible manner in aqueous media. The various stimuli including light and different chemicals could act on the motor building blocks and subsequently trigger the transformation of the supramolecular polymers toward reversible polymerization, direct post-functionalization and chirality modulation. The interplay between the rotary molecular motion and the supramolecular systems assembly process, taking advantage of different external stimuli to govern the assembly state, provides a basis for multi-responsive supramolecular materials

Triple-negative breast cancer (TNBC) exhibits high local-recurrence risk despite modern systemic therapy assisted with surgery or irradiation therapy. Here, we report an injectable nano-in-micro microsphere depot (cPAG) that integrates conductivity enhancement, photothermal conversion, O2 and reactive oxygen species (ROS) generation, and innate immune agonist co-delivery to support staged, local multimodal therapy. Monodispersed Au@GelMA microspheres prepared via microfluidics and photocrosslinking reduced high electrostatic resistance of GelMA hydrogels and provided stable 808 nm laser-responsive heating. The porous surface possessed abundant electrostatic adsorption sites for loading MnOx nanoflowers and anionic stimulator of interferon genes (STING) agonist. MnOx nanoflowers catalyzed H2O2 to generate O2, produced free radical signals and increased pro-inflammatory cytokines secretion in vitro. Co-delivery of agonist and MnOx nanoparticles further increased interferon-β secretion, consistent with induction of type I interferon response. In a 4T1 residual-tumor model established by partial tumor resection, a staged regimen consisting of cPAG-assisted irreversible electroporation followed by cPAG-mediated photothermal therapy showed the strongest suppression of local tumor regrowth among tested groups, with maintained body weight during the study window. Overall, cPAG provides a modular nano-in-micro depot strategy to integrate multiple local treatments for postoperative control of TNBC tumor.

Molecular crowding in the bacterial cytoplasm restricts diffusion of large molecules, impacting cellular processes. To monitor cytoplasmic diffusion and rheology, we used single-particle tracking in Escherichia coli, finding a 3-fold variation in the diffusion of a 40-nm particle across exponential growth conditions. Known determinants of rheology did not account for this variation. Instead, we found a strong anticorrelation between the diffusion coefficient and the abundance of amino acid metabolism proteins (clusters of orthologous groups [COG] category “E”), persisting upon genetic perturbations, and that lower diffusion is associated with increased elasticity. Photoactivated light microscopy revealed that some amino acid metabolism proteins form clusters. Electron microscopy showed that these proteins can form amorphous agglomerates at physiological concentrations in vitro due to their high hydropathy, which also confers low disorder and compactness. These findings show that diffusion is controlled by the formation of protein agglomerates and thus reveal how condition-induced proteome changes affect cytoplasmic rheology.

ABSTRACT The photoluminescence of photoacids in supramolecular assemblies provides crucial insights into proton transfer (PT) processes within biologically relevant confinement. In this work, we present a strategy to activate intermolecular excited‐state PT within the hydrophobic cavities of cyclodextrin‐based nanotubes. Activation is achieved using a specifically designed amphoteric emitter which undergoes a pKa inversion in the photoexcited state. Despite this photophysical behavior, intramolecular PT does not occur due to the spatial separation between the proton donor and acceptor sites in the compound. However, in the presence of γ‐cyclodextrin, the photoacid assembles into guest pairs, enabling pre‐organized PT between neighboring molecules. The effects of confinement on photostability, emission lifetime, and quantum yield indicate a mechanistic shift from excited‐state protolytic dissociation to intermolecular excited‐state PT. Spectroscopic investigation of the assembly mechanism and solvent isotope effect further supports the role of a template effect, reminiscent of enzymatic activation, in facilitating PT in the excited state.

Selective control of excitonic states in supramolecular assemblies remains a fundamental challenge, owing to spectral congestion and the close relation between electronic structure and molecular organization. Here, we demonstrate that controlled optical illumination can be used to selectively reconfigure excitonic functionality in double-walled supramolecular nanotubes. By combining two-dimensional electronic spectroscopy, cryogenic transmission electron microscopy, and polarization-resolved single-nanotube microscopy, we show that light exposure selectively suppresses the outer-wall excitonic response through an oxygen-mediated photooxidative degradation of the chromophores. Structural analysis reveals that the resulting disorder is largely confined to the outer wall, while the cylindrical scaffold and excitonic order of the inner wall are preserved. Measurements on individual nanotubes immobilized in a solid-state matrix further demonstrate that the polarization anisotropy of the inner-wall exciton remains unchanged, indicating that its excitonic symmetry and delocalized character are maintained. Together, these findings establish light as an additive-free and noncontact control parameter for modifying excitonic landscapes in complex supramolecular architectures.

Minimal cells offer a platform to uncover the fundamental physicochemical principles of cellular life. While genomes, proteomes, and metabolic networks of cells have been elucidated, the lipidome, which determines the physicochemical identity of the membrane, remains only partially characterized. Yet, the membrane is a central determinant of cellular viability, regulating solute permeability, mechanical stability, and environmental cues. Here, we investigate membranes that recapitulate the lipid composition of the minimal cell JCVI-syn3A, which is distinguished by an unusually high cholesterol content and simple composition. Combining cryo-electron microscopy, Langmuir monolayer experiments, permeability assays, and coarse-grained molecular dynamics simulations, we demonstrate that cholesterol and sphingomyelin act as dominant condensing agents that stabilize the membrane while preserving an ordered yet fluid state. These lipids enhance lipid packing and acyl-chain order, whereas cardiolipin, POPC, and DOPG counterbalance condensation by promoting fluidity and compressibility. Cholesterol–sphingomyelin interactions emerge as a key thermodynamic driver that fine-tunes membrane order, fluidity, and permeability. Remarkably, membranes containing up to 60 mol% of cholesterol remain permeable to water and physiologically relevant osmolytes at rates compatible with growth of JCVI-syn3A. Together, our results define the physicochemical principles underlying minimal cell membranes and reveal how lipid composition enables passive permeation while maintaining membrane integrity. JCVI-syn3A, a model of minimal cellular life, relies on a cholesterol-rich membrane whose properties remain poorly understood. Here, authors show how cholesterol and sphingomyelin balance membrane order, fluidity, permeability, and mechanical stability to support minimal cell function.

Achieving efficient and stable hydrogen evolution reaction (HER) with earth-abundant electrocatalysts is pivotal for boosting the efficiency of alkaline water electrolysis. Here, we report an oxygen vacancy (O-v)-rich Cu2O/NiO heterostructure, which triggers a peculiar interfacial charge transfer from NiO to Cu2O, creating catalytically active Ni & sup3; (+)-Cu0/+ dual sites to synergistically promote water dissociation and hydrogen adsorption. The Cu2O/NiO heterostructure exhibits a low overpotential of 19.7 mV at 10 mA cm(-)& sup2; with Tafel slope of 36 mV dec(-)& sup1; , outperforming most of the reported catalysts. The anion exchange membrane (AEM) electrolyzer equipped Cu2O/NiO electrode enables 1.78 V to reach 1.0 A cm(-)& sup2; for >200 h of continuous operation. Thorough characterizations including HRTEM/XPS/EPR/XANES and DFT calculations exemplify the interfacial charge transfer dynamics in the Cu2O/NiO heterostructure during HER, offering a new paradigm for rational design of noble metal-free HER electrocatalysts for AEM water electrolysis.

The elimination of synthetic dyes from industrial effluents represents a persistent environmental challenge. Developing sustainable and effective adsorbents is essential to preserve global water resources. In this study, we introduce an efficient and facile strategy for methylene blue removal from aqueous systems using halloysite nanotubes functionalized with polydopamine. The polydopamine coating generated a dense array of active adsorption sites, as confirmed by X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy, thermogravimetric analysis, and zeta potential measurements. Porosity characterization and X-ray diffraction provided complementary insight into the structure and morphology of the hybrid nanotubes. We systematically investigated the influence of contact duration and solution pH on dye uptake by pristine and functionalized nanotubes. Kinetic evaluation revealed excellent agreement with the pseudo-second-order model (R2 > 0.999), yielding rate constants of 0.002 and 0.003 g·mg-1·min-1 for samples treated with polydopamine for 6 and 24 h, respectively. The equilibrium adsorption data were analyzed using Langmuir and Freundlich isotherms, showing that functionalized nanotubes achieved a maximum adsorption capacity of 86 mg·g-1 at 25 °C and pH 10 - almost double that of pristine HNTs (47 mg·g-1). The high adsorption efficiency, comparable to conventional adsorbents such as zeolites, together with the simplicity and environmental compatibility of the functionalization procedure, underscores their suitability for real-world wastewater applications. Additionally, the demonstrated applicability of this modification method to other dye-adsorbent systems highlights its adaptability and broad potential.

Liquid-liquid phase separation (LLPS) is a crucial process in natural and artificial systems, capable of maintaining cellular behavior and realizing material functions. While supramolecular assemblies provide a versatile platform for understanding natural phenomena and developing adaptive materials, their LLPS remains largely unexplored, particularly with respect to reversible control. Here, we report a molecular motor-driven LLPS system, where nanoscale rotary motion modulates LLPS of supramolecular assemblies. Systematic molecular modification and photothermal isomerization studies comprehensively reveal that subtle changes in molecular structure affect the hydrophobicity of molecules, which in turn decrease the critical phase separation temperature and promotes the phase separation. During the rotary of molecular motor, these assemblies undergo in situ formation and dissolution of droplets across multiple non-equilibrium states. Our findings establish an orthogonal strategy to tune phase separation by light and temperature, providing an avenue for designing out-of-equilibrium biomedical materials and adaptive soft matter systems.

A preformulative study was conducted to produce and characterize ethosomes for the transdermal delivery of gossypin. This plant-derived compound possesses many pharmacological properties, including antitumoral potential. Ethosome dispersions were designed as transdermal delivery systems for gossypin, employing two different production procedures. The evaluation of vesicle size distribution by photon correlation spectroscopy, morphology by cryogenic transmission electron microscopy, and gossypin entrapment capacity, as well as in vitro release and permeation by vertical diffusion cells, enabled us to select a production strategy based on the injection of a phosphatidylcholine ethanolic solution in water. Indeed, vesicles prepared by this method were almost unilamellar and measured roughly 150 nm mean diameter while displaying an entrapment capacity higher than 94%. Moreover, vesicles prepared by the ethanol injection method enabled us to control gossypin release and to improve its permeation with respect to the solution of the drug. To obtain semi-solid forms suitable for cutaneous gossypin administration, ethosome dispersions were thickened with 0.5% w/w xanthan gum, selected by a spreadability test. These ethosome gels were then further characterized by small- and wide-angle X-ray scattering, while their antioxidant activity was demonstrated in vitro by a radical scavenging assay. Finally, in vitro biological studies were conducted on A375 melanoma cell lines. Namely, wound healing and cell migration assays confirmed the potential antitumoral effect of gossypin, especially when loaded in the selected ethosomal gel. The promising results suggest further investigation of the potential of gossypin-loaded ethosomal gel in the treatment of melanoma.

While light-driven molecular motors (MMs) hold immense potential to control cell function, low biocompatibility and solubility have hampered their implementation. We developed a novel polypeptide-conjugated MM by linking a propargyl-derivatized light-driven MM to a poly-l-glutamic acid-based carrier (P) with inherent mitochondria tropism through click chemistry, denoted P-MM. P-MM effectively maintained the parental stability and unidirectional rotational capabilities of MM upon irradiation at 405 nm. Light-induced supramolecular conformational changes significantly increased cell uptake compared to non-irradiated controls while retaining the subcellular targeting capacity of P. P-MM exhibited minimal cytotoxicity and reactive oxygen species production, suggesting a non-disruptive interaction with cell membranes. Overall, we establish a connection between irradiation and enhanced biological responses, demonstrating the potential of integrating MMs with targeted polymeric nanocarriers for controlled, light-responsive behavior in biological systems and innovative applications in advanced therapeutic/diagnostic strategies.

Due to their high energy density (2600 Wh/kg), low cost, and low environmental impact, lithium-sulfur batteries are considered a promising alternative to lithium-ion batteries. However, their commercial viability remains a formidable scientific challenge mainly because of the sluggish reaction kinetics at the cathode and the so-called "shuttling effect" of soluble polysulfides, which results in capacity decay and a shortened lifespan. Herein, molecular imprinting with Li$_2$S$_8$ as a target molecule in combination with a two-dimensional material, MXene, is proposed to overcome these issues. Molecularly imprinted polymer-coated nitrogen-doped Ti-based MXene was successfully synthesized and demonstrated to exhibit an appealing electrochemical performance, namely a high specific capacity of 1095 mAh/g at 0.1 C and an extended cycling stability (300 mAh/g at 1.0 C after 300 cycles). X-ray photoelectron spectroscopy was applied to elucidate the underlying mechanisms and proved that Li$_2$S$_8$-imprinted polymer polyacrylamide serves as a polysulfide trap through strong chemical affinity towards the long-chain lithium polysulfides, while N-doped Ti-based MXene promotes the redox kinetics by accelerating the conversion of lithium polysulfides. This distinct interfacial strategy is expected to result in more effective and stable Li-S batteries.