Salinity‐gradient energy (SGE), generated from the mixing of waters with different salinities, is a sustainable and widely available source of blue energy. Reverse electrodialysis (RED) is one of the most promising approaches for harvesting SGE, but its performance is largely determined by the ion‐selective membranes employed. Crystalline framework materials, particularly metal–organic frameworks (MOFs) and covalent–organic frameworks (COFs), have recently emerged as attractive membrane platforms because their well‐defined nanochannels and chemically tunable pore environments enable precise control over ion transport, while their high porosity provides abundant parallel pathways for ion conduction. These features offer unique opportunities to improve ion selectivity and permeability simultaneously, thereby alleviating the trade‐off that limits conventional membranes. This review summarizes recent progress in MOF‐ and COF‐based membranes for RED‐driven SGE conversion, with emphasis on membrane fabrication, regulation of ion transport through structural and chemical design, and strategies for improving power output. The key challenges that still hinder practical implementation, including scalable fabrication, defect control, membrane stability, and performance in realistic environments, are also discussed, together with future opportunities for advancing framework‐material‐based membranes toward efficient and durable SGEtechnologies.
Cellulose‐based scaffolds have attracted increasing attention for cultivated meat applications due to their abundance, sustainability, and ability to form porous three‐dimensional structures. In this study, bamboo‐derived cellulose suspensions were processed by high‐pressure homogenization and directional freezing, followed by freeze‐drying, to fabricate porous scaffolds. The suspensions were characterized by using steady‐state and time‐dependent rheological measurements, while the resulting scaffolds were evaluated by optical microscopy, scanning electron microscopy, mechanical testing, and cell‐culture experiments. Although all suspensions exhibited similar shear‐thinning behavior, differences were observed in their time‐dependent viscosity evolution and freezing behavior. These differences were associated with variations in scaffold morphology and mechanical properties. Scaffolds prepared from suspensions homogenized for 13 cycles exhibited a pronounced lamellar architecture and directional mechanical response, whereas scaffolds produced under other homogenization conditions displayed less organized structures and reduced anisotropy. To evaluate their suitability for cultivated meat applications, selected scaffolds were seeded with bovine mesenchymal stem cells. Cell‐culture experiments demonstrated cell attachment, viability, and distribution throughout the scaffold structure, particularly following the incorporation of cellulose nanocrystals to enhance cell–material interactions. The results demonstrate that directional freezing of bamboo‐derived cellulose suspensions can produce porous cellulose scaffolds with structural, mechanical, and biological characteristics relevant to cultivated meat applications.
In the cell wall of Gram-positive bacteria, wall teichoic acid (WTA) is an abundant and conserved virulence factor. WTAs are especially relevant to methicillin-resistant Staphylococcus aureus. Tremendous synthetic efforts have permitted investigations of the terminal end of this glycopolymer. However, the peptidoglycan (PG) linked end which utilizes a phosphodiester linkage, has been understudied due to its demanding synthesis. Two convergent routes, both involving a phospho-donor and an acceptor, were proposed and evaluated. In this work, synthesis of the more efficient route was carried out to obtain the phospho-donor and PG acceptor. Careful phosphoramidite coupling was utilized to establish the phosphodiester linkage between WTA and PG fragments. These WTA-PG conjugates will enable more complex studies between the host innate immune response and invading pathogens.
Weak polyelectrolytes (WPE) are used to prepare responsive materials in a variety ofapplications. When dissolved in highly crowded environments, of biorelevant media or synthetic complex fluids, that contain substantial concentrations of macromolecules, molecular assemblies, or nanoparticles, WPE exhibit deviations from the acid–base equilibrium observed in single‐component solutions. In this mini review, studies of charge regulation (CR) are described in simple yet relevant model systems comprising poly (acrylic acid) (PAA) and high concentrations of non‐charged micelles (Pluronic) or nonadsorbing, short chains of poly (vinyl alcohol) (PVA). Titration experiments reveal in the first mixture significant reduction in the degree of ionization of the PAA. In PAA–PVA mixtures, an unexpected increase in the degree of ionization of PAA is observed. Structural characterization of the solutions, via transmission electron microscopy and small‐angle X‐ray scattering, reveals that the local organization is affected by the interaction between PAA chains and the additives, leading to crowding of the micelles in one case, and crowding of the PAA chains in the other. These systems provide insights into the molecular mechanisms leading to the responsiveness of WPE and the effect of crowding on CR.
Recent innovations in metal‐free phosphorothioate synthesis have underscored increased utility as a sustainable alternative to metal‐catalyzed procedures. Green approaches, such as metal‐free coupling reactions and oxidations, radical‐induced methods, electrochemical processes, and multicomponent reactions, were reported from 2020 to 2025 for the successful development of S‐aryl phosphorothioates and S‐heterocyclic phosphorothioates. These methods involve high atom economy, broad functional group tolerance, and mechanistic studies, positioning metal‐free phosphorothiolation as an emergent tool of power and sustainability in modern organic synthesis under a green system.
Metal oxides composed of earth-abundant elements such as Mg and Fe are promising candidates for water electrolysis; however, MgFe2O4 (MFO) suffers from low electrical conductivity and limited active sites. Herein, we report a binder-free synthesis of mesoporous MFO directly on carbon cloth using a molten salt-assisted self-assembly approach. Quenching the calcined material at 500 degrees C in ice water or 0.1 M Ni2+ solution induces surface defects, oxygen vacancies, and Ni incorporation. In addition, phosphate incorporation via phosphoric acid treatment is explored to enhance stability and activity. The optimized sample exhibits an overpotential of 300 mV at 10 mA cm-2 and 350 mV at 100 mA cm-2, along with stable operation for 84 h. The enhanced performance is attributed to modified electronic structure and increased active site density arising from defect formation and surface Ni incorporation. These results demonstrate an effective strategy for improving MFO-based electrocatalysts.
Fungal cell walls are carbohydrate-rich matrices whose structural organization regulates morphogenesis, mechanical integrity, and antifungal susceptibility. Although covalent linkage patterns of alpha- and beta-glucans are well characterized, their conformational structures and higher-order supramolecular architectures and species-dependent variations remain incompletely defined. Here, we integrate high-resolution solid-state nuclear magnetic resonance (NMR) spectroscopy with statistical analysis of 13C chemical shifts to elucidate the structural organization of alpha-1,3- and beta-1,3-glucans in living cells of pathogenic fungi, including species of Aspergillus, Candida, and Cryptococcus. Comparative heatmap analysis reveals that beta-1,3-glucans from diverse species predominantly adopt a conserved triple-helical conformation in most intact cell walls, despite local conformational heterogeneity and branching. In contrast, alpha-1,3-glucans primarily assemble into rigid, hydrogen-bonded bundled-sheet architectures, with minor populations existing as less aggregated forms under specific genetic or pharmacological perturbations. Principal component analysis of ring-carbon 13C chemical shifts further resolves differences in backbone connectivity and branching topology across glucan classes. Together, these findings establish chemical shifts as quantitative reporters of glucan supramolecular architecture and provide a scalable framework for comparative structural analysis of fungal cell walls across species and conditions.
Zirconium-based metal-organic frameworks (Zr-MOFs) are highly attractive for various electrochemical applications owing to their exceptional stability in water, and MOF-808, a Zr-MOF with relatively large pores (around 1.8 nm) and six-connected hexa-zirconium nodes that are capable of further post-synthetic modifications, is especially appealing. Herein, the chemical stability of MOF-808 in nine commonly used unbuffered aqueous electrolytes and nine buffer solutions under 0.1 M was investigated. Crystallinity, morphology, and porosity of MOF-808 samples after the exposure to these solutions were examined, and various characterizing techniques were employed to probe the adsorption of ionic species in MOF-808 after these treatments. Findings here guide the rational selection of aqueous electrolytes and aqueous buffer solutions for the use of MOF-808 and similar Zr-MOFs, not only in various electrochemical processes, but also in other applications requiring buffer solutions.
Heparan sulfate (HS) proteoglycans are information-rich macromolecules that can orchestrate extracellular signaling and cargo uptake across diverse cellular contexts. Ligands that can engage cell surface HS possess significant potential as probes to investigate or manipulate cell-matrix interactions. Here, we show that R17, an HS-binding protein from the rodent herpesvirus Peru, actively remodels the glycocalyx of pancreatic cancer cells. Recombinant R17 bound heparin in vitro and associated with the surface of pancreatic cancer cells to promote the dose-dependent clearance of HS via trafficking to lysosomes. R17 also reduced wound closure without detectable cytotoxicity, indicative of the ability of R17 to suppress cellular migration. Notably, HS depletion persisted upon cation-independent mannose-6-phosphate receptor knockdown, suggesting that clearance is independent of this mechanism. These findings identify R17 as an exogenous HS-binding protein that can drive HS clearance via endolysosomal trafficking and suggest an alternative approach to modulate HS-dependent functions.
This research lies at the intersection of two fields, combining their respective unique features: nanosized structures and reverse thermo-responsive (RTR) morphing. Hollow RTR polymeric nanoshells exhibiting a temperature-triggered sharp and notable reversible volumetric change in an aqueous medium, are engineered. These supramolecular structures that shrink above the relevant thermal transition and expand below it, are generated by crosslinking intramicellarly various polyethylene oxide-polypropylene oxide-polyethylaene oxide (PEO-PPO-PEO) amphiphiles, end-capped with C=C double bonds to render them crosslinkable. Systematic variation of the polymeric building blocks enables to engineer various hollow RTR nanoshells with tunable hydrodynamic diameters spanning approximate to 300 to 2500 nm, with broad translational potential in biomedical applications. Collectively, the nanoshells demonstrate extreme volumetric expandability, with volume increases of up to 630x. The objective of this study is to investigate the interplay between the coiling-uncoiling capability of the individual unimeric PEO-PPO-PEO amphiphiles and their collective effect on the resulting temperature-dependent dimensional behavior of the nanoshells. After studying the basic PEO-PPO-PEO dimethacrylate nanoshells, fundamental features of the amphiphiles forming the nanoshells, such as their composition, degree of methacrylation, and molecular weight, are fine-tuned, and their cooperative impact on the morphing of the nanoshells is studied.
The development of efficient and cost-effective electrocatalysts for the hydrogen evolution reaction (HER) is essential for sustainable hydrogen production. Although platinum (Pt) remains the benchmark catalyst due to its near-optimal hydrogen adsorption free energy (Delta G H*), its high cost and scarcity hinder large-scale applications. Ruthenium (Ru), which exhibits Pt-like hydrogen binding characteristics, has emerged as a promising alternative; however, it remains a precious metal, necessitating strategies that minimize its usage while maintaining catalytic efficiency. Here, Ru-modified Cu1.8Se/Cu2Se heterostructured nanosheets are reported that promote HER kinetics through interfacial electronic modulation and increased active site accessibility. The synthesis of Ru-modified copper selenides (Cu1.8Se/Cu2Se@Ru) is reported via solvothermal-annealing method and their HER performance in alkaline media. A mere 2.1 wt% Ru addition achieved a low overpotential of 169 mV at 10 mA cm-2, outperforming pristine (673 mV), 7.4 wt% Ru addition (281 mV), and 11.2 wt% Ru addition (372 mV). Additionally, it exhibits excellent stability for 12 h with negligible degradation. Poststability X-ray photoelectron spectroscopy (XPS) indicates synergistic electronic interactions between Ru and Cu active sites, thus enhancing hydrogen adsorption/desorption. This work highlights Ru-modified copper selenides as a promising pathway for developing efficient and durable HER catalysts as alternatives to Pt-based systems.
Palladium-catalyzed ring olefin bond difunctionalization through arylfluorination of selected five-, six-, and seven-membered functionalized cycloalkenes has been studied. The arylfluorinative ring olefin bond difunctionalization was performed with phenylboronic acid, in the presence of Selectfluor and a palladium catalyst using azacyclic ligands in solvents. The arylfluorinations were found to be highly substrate and functional group dependent. Unfortunately, despite our efforts, reactions proceeded with modest yields. Surprisingly, however, they gave relatively unpredictable products. Possible mechanistic routes regarding the outcome of these interesting types of olefin bond difunctionalizations are also described.
With the rapid development of reticular chemistry, metal-organic frameworks (MOFs) have evolved from esthetically appealing porous crystals into function-tailorable materials that can be precisely designed at the molecular level, enabling broad opportunities in gas storage and separation, catalysis, sensing, and biomedical-related technologies. Nevertheless, most MOFs are obtained as fragile crystalline powders, and their limited processability remains a major barrier to implementation in pressure/temperature/vacuum swing adsorption, membrane-based separations, and other continuous industrial processes. Therefore, a central challenge lies in achieving macroscopic shaping and interfacial stabilization while preserving framework integrity and pore accessibility. Guided by the principles of reticular chemistry, this review systematically summarizes recent advances in transforming MOFs from porous crystals into processable and integrable materials. Three representative engineering routes-particle engineering, membrane fabrication, and surface coating-are highlighted, with emphasis on their distinct mechanisms for maintaining structural connectivity, regulating interfaces, and enhancing multiscale stability. By comparing these strategies with respect to porosity retention, mechanical robustness, and process compatibility, this review establishes a structure-interface-performance framework that provides conceptual guidance for translating MOFs from laboratory materials into practical engineering systems.
This study reports an efficient Appel-type protocol for the synthesis of acyl fluorides using tribromoisocyanuric acid (TBCA) and triphenylphosphine in the presence of Olah's reagent (Py.(HF)x). The reaction conditions were optimized using 4-nitrobenzoic acid as a model substrate, achieving good yields with minimal reagent quantities. The methodology tolerates a variety of carboxylic acids, including aromatic substrates with electron-donating or electron-withdrawing groups and aliphatic acids. The formation of acyl fluorides was confirmed by 19F NMR spectroscopy, which revealed substituent-dependent chemical shift variations. Computational studies using DFT and Born-Oppenheimer Molecular Dynamics elucidated a mechanistic pathway involving acylium ion formation and fluorination via a Grotthuss-like proton hopping mechanism in the HF.pyridine medium. This protocol provides a practical and environmentally conscious approach to acyl fluoride synthesis.
2,2-Difluoro-1,3-dimethylimidazolidine (DFI) is useful in deoxyfluorination reactions-converting alcohols, aldehydes, and carboxylic acids to the corresponding organofluorine products. This manuscript surveys the chemistry of this compound.
WS2 nanotubes (NTs) are layered transition-metal dichalcogenides whose diameter strongly influences strain and optical properties. Alloying sulfur with selenium in W(SxSe1-x)(2) NTs provides compositional tunability, yet the link between precursor composition, alloy formation, and optical response remains unclear. In this work, W(SxSe1-x)(2) (WSSe) NTs with controlled S/Se ratios were synthesized and characterized using Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, STEM-EDS, and X-ray diffraction. The synthesis produced high yields of small-diameter NTs (<30 nm). Compositional analysis revealed sulfur enrichment relative to the nominal precursor ratio, while the interlayer spacing increased from 0.62 to 0.66 nm with increasing selenium content. To examine incorporation of heavier chalcogens, tellurium (Te) was introduced during synthesis. Owing to its larger atomic radius and lower chemical reactivity compared with sulfur and selenium, Te incorporation presents a significant kinetic limitation during NT growth. Elemental analysis shows that Te is incorporated only at trace dopant levels (<1 at%) rather than forming a quaternary alloy phase. Despite this low incorporation, Te doping induces a measurable red shift of the A-exciton transition, indicating a slight reduction in bandgap energy. Core-shell WS2@WSSe NTs were also synthesized, exhibiting nonlinear optical effects. These findings may enable alloyed TMD NTs for nanoscale optoelectronic and photodetection devices.
Oligoheterocycles are widely used in drug discovery and materials science, where they serve as attractive alternatives to peptide fragments. There is strong interest in understanding the structural correspondence between heterocycles and amino acid motifs to recapitulate key binding elements while improving metabolic stability. A frame-shifted synthetic strategy was recently introduced in which iterative heterocycle formation replaced the assembly of prefabricated units, enabling concise access to oligoheterocycles from simple feedstock-derived building blocks. Here, this approach is extended to novel vinamidinium salts for chemodivergent assembly of versatile peptide-heterocycle hybrids. This work includes the design and analysis of new vinamidinium reagents and demonstrates their utility in the efficient incorporation of beta-amino acid-mimicking heterocyclic inserts into peptide frameworks.
Carbohydrates are integral to drug discovery, serving as versatile templates for the development of small-molecule therapeutics. However, their success in antiviral, anticancer, and antidiabetic therapy is not immediatly apparent, as they have long been considered challenging building blocks. On the one hand, their high density of stereocenters and evolutionarily shaped conformations make them ideal targets for drug development. On the other hand, this promiose is counterbalanced by challenges in synthesis stability, and pharmacokinetics. In this review, we examine how advances in synthetic strategies have accelerated carbohydrate drug development. We discuss successful drug candidates that exemplify strategic design principles, such as the prodrug concept, late-stage functionalization, and the formation of more stable metabolites (for example, C-glycosides). We highlight how these approaches were optimized for effective medicines, considering both industrial-scale manufacturing routes and academic innovations. Finally, we link synthetic methods to clinical translation by summarizing therapeutic potential and relevant clinical trials.
Activated carbon derived from jellyfish (JF) biomass offers a sustainable solution for water remediation, transforming invasive marine waste into high-performance adsorbents. Here, said biomass is chemically activated with KOH after pyrolysis, yielding a material with a hierarchical porous structure (Brunauer-Emmett-Teller (BET) surface area of above 1000 m2 g-1), surpassing commercial benchmarks, as confirmed by analyses. Adsorption experiments demonstrate rapid, high-capacity removal of organic (methylene blue (MB), approximate to 30 wt%) and metallic (Pb + 2, approximate to 7 wt%) contaminants, outperforming commercial counterpart, with pseudosecond-order kinetics indicating chemisorption dominance. Competitive adsorption experiments reveal Pb selectivity, suppressing MB uptake while boosting Pb capacity (approximate to 1.7-fold) which is attributed to lead-MB (Pb-MB) complexation. This first demonstration of chemically activated JF-derived activated carbon establishes it as a superior, multifunctional adsorbent, addressing applications and enabling scalable waste valorization for pollutant removal.
Solid-state lithium metal batteries represent a pivotal advancement in energy storage technology, prized for their superior safety and high-energy density. The combination of high ionic conductivity, high-voltage stability, and lithium dendrite suppression has prompted the investigation of new solid-state electrolyte (SSE) systems. In this work, a SSE is reported based on a 4,4 '-diamino-2,2 '-stilbenedisulfonic acid constructed hydrogen-bonded organic framework (DS-HOF). The DS-HOF single crystal, leveraging its abundant hydrogen-bonding sites and polar groups, demonstrates an ionic conductivity of 1.65 mS cm-1, a lithium transference number of 0.42, and a wide electrochemical stability window of 5.5 V. The assembled lithium symmetric battery achieved stable cycling for over 1,300 h and uniform deposition, mainly due to the uniform transport of Li+ through aligned Li+ transport channels in DS-HOF and the buffering of structural changes during lithium deposition by flexible hydrogen-bonding networks. Furthermore, full cells assembled with LiFePO4 cathodes retain 88% of their capacity after 200 cycles at 0.5 C, coupled with a high Coulombic efficiency of 99.92%. The electrolyte also demonstrates compatibility with a high-voltage NCM811 cathode, supporting stable cycling for 50 cycles without short-circuiting. These findings collectively underscore the significant potential of HOF-based materials as an emerging platform for next-generation SSEs.
