Search Results (497)

Hybrid supramolecular–nanocomposite hydrogels based on polyethylene glycol (PEG), β-cyclodextrin–adamantane host–guest interactions, and silica nanoparticles represent an important class of hierarchical soft materials with tunable viscoelastic and transport properties. This review critically analyzes recent progress in cyclodextrin–silica hybrid PEG hydrogels, focusing on the mechanistic coupling between stiffness, stress relaxation, and molecular transport arising from the interplay between reversible supramolecular crosslinks and nanoparticle-induced confinement effects. Particular attention is given to how host–guest exchange kinetics regulate dynamic bond rearrangement and affinity-mediated retention of hydrophobic cargo, while silica nanoparticles enhance mechanical reinforcement and modify diffusion pathways through tortuosity and interfacial polymer–particle interactions. The analysis highlights how nanoparticle size, loading level, and surface functionalization influence relaxation spectra and network topology, as well as how environmental stimuli may affect supramolecular bond stability and overall material performance. Comparison with alternative inorganic fillers and mesoporous silica architectures further clarifies the specific advantages of silica in achieving balanced mechanical stability and controlled transport behavior. Overall, current evidence indicates that hybrid CD–silica networks enable partial decoupling of stiffness, relaxation dynamics, and diffusion, although complete independence remains constrained by fundamental polymer physics relationships. These insights support the development of predictive structure–property frameworks for advanced biomedical and controlled release applications. Full article

The molecular electrostatic surface potential (MESP) has become a key theoretical tool for probing reactivity in chemical systems. It reveals electrophilic and nucleophilic regions on molecular surfaces, underpinning the understanding of noncovalent interactions such as hydrogen, triel, tetrel, pnictogen, chalcogen, halogen, matere, and aerogen bonding, among many others. These interactions, driven by Coulombic attraction, govern aggregation in molecular and supramolecular systems across solid, liquid, and gas phases. MESP applications span crystal engineering, polymers, biology, catalysis, photovoltaics, and drug discovery. While limitations exist—such as the arbitrariness in defining isodensity surfaces—its impact on advancing both theoretical and applied chemical research is substantial. This review outlines the conceptual foundations of MESP and highlights its broad relevance across the chemical sciences. Full article

Stimulating electronic transitions and promoting exciton dissociation are key to enhancing the photocatalytic performance of polymer carbon nitride (PCN). Herein, a controllable synthesis strategy based on supramolecular self-assembly and mild salt melting crystallization has been developed, successfully preparing carbon nitride-based photocatalytic materials with tunable crystal phase composition. The mixed crystal phases effectively induced significant n→π* electronic transition, expanding the material’s light response range to the near-infrared region (700 nm). Meanwhile, the homojunction promoted the efficient separation of photogenerated carriers through the built-in electric field. Under visible-light excitation, this material exhibits excellent selective catalytic performance, over 99% for the oxidation and removal of H₂S into elemental sulfur. This synergistic mechanism of crystal phase engineering in regulating electronic structure and interface charge dynamics provides a new material design strategy for efficient non-metallic photocatalysts. Full article

The plugging of fractured gas reservoirs with severe lost circulation during oil and gas drilling and production has long been challenged by technical issues such as low plugging strength and short effective duration. This paper reports the preparation of a high-strength supramolecular gel plugging agent via micellar copolymerization based on the synergistic effects of hydrophobic association and hydrogen bonding. Systematic optimization determined the optimal synthesis formula: acrylamide (AM) 12%, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) 2%, stearyl methacrylate (SMA) 0.4%, sodium dodecyl sulfate (SDS) 1.5%, and potassium persulfate 0.3%, with a reaction temperature of 60 °C. Performance evaluations revealed that the gel possesses a controllable gelation time (120 min) and excellent viscoelastic recovery properties. At a compressive strain of 87%, the compressive stress reached 1.43 MPa while maintaining structural integrity. Swelling behavior analysis indicated that the gel follows a non-Fickian diffusion mechanism, with its swelling process governed by the synergistic interplay of water molecule diffusion and polymer network relaxation. Core plugging experiments demonstrated that the gel achieved plugging efficiencies exceeding 95% for cores with permeabilities ranging from 0.18 to 0.90 μm², with a maximum breakthrough pressure gradient of up to 11.48 MPa/m. These results highlight the gel’s efficient and broad-spectrum plugging capability for fractured lost circulation zones. This preliminary study provides experimental foundations for the material design and performance optimization of supramolecular gel-based long-lasting plugging agents for severe lost circulation gas reservoirs, and further field-scale validation is required for engineering application. Full article

Microbial polysaccharides are attracting increasing interest as water-processable polymers for extrusion-based additive manufacturing due to their ability to form physically stabilized networks without covalent cross-linking. In this study, a kefiran–propylene glycol (PG) formulation was developed to investigate whether time-dependent supramolecular reorganization can be exploited to control print fidelity. Extrusion performance was assessed through quantitative filament collapse analysis, while rheological behavior was characterized by oscillatory strain, frequency, and time sweep measurements. Filaments printed 5 min after PG addition showed pronounced sagging (δ/(L/2) ≈ 0.35 at the largest spans), whereas after 15 min the normalized deflection decreased below 0.03, indicating a marked improvement in self-supporting capability. Time sweep experiments revealed a continuous increase in storage modulus from ~100 to ~1200 Pa over 1800 s, consistent with progressive viscoelastic stiffening. Freeze-dried constructs exhibited an interconnected porous architecture with a predominant pore population between 6 and 20 µm and an apparent porosity of 60.9 ± 1.2%. Upon rehydration at 37 °C, samples swelled to ~350% within 5 h and showed gradual mass loss over 56 days while remaining intact. ATR–FTIR confirmed the preservation of the polysaccharide backbone without evidence of new covalent functionalities. Extrusion fidelity is therefore governed by progressive supramolecular consolidation within a physically assembled network, rather than by any form of chemical cross-linking. Full article

Lipopolysaccharides (LPSs) are key components of the bacterial outer envelope, determining its structural integrity, barrier properties, and interactions with the surrounding environment. This review analyzes the relationship between the molecular architecture of LPSs and their physicochemical properties. Particular attention is being paid to the organization of LPS-containing supramolecular assemblies, including bacterial outer membranes, bilayers, micelles, and LPS brushes. The review further focuses on theoretical frameworks employed to describe LPS layers and discusses the physical meaning of the parameters involved in these models. The simulations involve a wide range of approaches starting from all-atom molecular treatment and up to polymer and colloidal approaches. When considering these models, we focus on the relationships between parameters that are addressed at each level of modeling. It is shown that biological functions such as membrane stability and bacterial adhesion are largely governed by the molecular organization of LPS. This structure–property relationship provides a basis for predicting the performance of anti-adhesive biomaterials, antimicrobial strategies, and bactericidal agents. Full article

This study investigates the rational design of a dinuclear zinc(II) coordination polymer, (C₃₆H₃₄Br₂N₈O₄S₂Zn₂), to explore how halogen substitution and ligand choice modulate structural architecture, contributing to the development of functional coordination polymers with tailored properties. The complex was synthesized from a bromo-substituted semicarbazone Schiff base ligand (L1) and a rigid bipyridine linker (L2) under solvothermal conditions, and its structure was elucidated using single-crystal X-ray diffraction (SCXRD), complemented by characterization via powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), and infrared (IR) spectroscopy. Crystallographic analysis reveals that the complex crystallizes in the triclinic space group P-1, forming discrete dinuclear units where each Zn(II) center adopts a distorted square–pyramidal geometry; these units are extended into one-dimensional chains by bridging L2 ligands and further assembled into a three-dimensional supramolecular network through hydrogen-bonding interactions. PXRD confirms the high phase purity of the bulk material, TGA indicates notable thermal stability up to 130 °C, and IR spectroscopy validates the coordination modes and hydrogen-bonding network. This work elucidates the critical role of the bromo substituent and rigid ancillary ligands in modulating the solid-state structure of the zinc(II) complex. The revealed structure-directing principles provide a valuable reference for the rational design of functional coordination polymers. Full article

Due to its affordability, widespread availability, non-toxicity, biodegradability, and renewability, cellulose is considered a crucial material for addressing the depletion of petroleum resources. In this study, a rotaxane-based supramolecular polymer derived from thermoplastic polyurethane (TPU) was synthesized and combined with cellulose to create a TPU–cellulose composite (TPU-C). This composite was employed as a separator for acrylate-based quasi-solid polymer electrolytes (QPEs). The polymer electrolyte demonstrated a high ionic conductivity of 0.16 mS cm⁻¹ at room temperature, a lithium-ion transference number of 0.63, and an electrochemical stability window extending up to 4.7 V. When paired with a LiFePO₄ (LFP) cathode, the coin cell retained 88.8% of its capacity after 100 cycles at 1 C. A cell assembled with Li and a high-voltage NCM622 cathode maintained a capacity of 65.8% after 100 cycles at 0.3 C. Additionally, the excellent electrochemical performance was analyzed through density functional theory (DFT) calculations to identify the underlying reasons for its outstanding behavior. This study offers new insights into expanding the application potential of cellulose-based composite materials. Full article

Recombinant human bone morphogenic protein-2 (rhBMP-2) use in spinal fusion is limited by dose-dependent complications. Peptide amphiphile (PA) supramolecular polymers presenting a BMP-2–binding epitope have previously been developed to reduce the rhBMP-2 dose required for successful fusion. We evaluated PA implant biodegradation and tissue clearance in a rat posterolateral spinal fusion model as a prerequisite to clinical safety studies. Twenty-three female Sprague–Dawley rats underwent L4–L5 fusion with gadolinium (Gd)-labeled PA implants. Longitudinal magnetic resonance imaging (MRI) was performed up to 13 weeks postoperatively, while the spine and filter organs were harvested for inductively coupled plasma mass spectrometry (ICP-MS) quantification of Gd at multiple time points. Gd concentration at the fusion site decreased from 71% of maximum to 19.5% at 13 weeks, and MRI showed a complete loss of Gd signal enhancement by 8 weeks. In peripheral organs, peak Gd accumulation was 3% in the liver at 4 weeks, declining to 1.4% at 13 weeks, while Gd remained below 0.05% in the spleen, lung, and blood at all time points. These data indicate PA implant localization, with robust degradation and clearance and minimal off-target accumulation, supporting its translational potential for spinal fusion applications. Full article

Metallogels constitute a rapidly expanding class of hybrid soft materials in which metal ions, metal complexes, or metal-containing nanoparticles play a decisive structural and functional role within a three-dimensional gel network. Their unique combination of supramolecular assembly, metal-ligand coordination, and dynamic network behaviour provides tunable mechanical, optical, electrical, redox, and catalytic properties that are not accessible in conventional hydrogels or organogels. This review systematically summarises current knowledge on metallogels, beginning with a classification based on matrix type, dominant metal interaction and functional output, spanning metallohydrogels, metal-organic gels, metal-phenolic gels, nanoparticle-based gels, polymer-based metallogels and low-molecular-weight metallogels. Key synthesis pathways are discussed, including coordination-chemistry-driven formation, metal-ligand self-assembly, in situ reduction, diffusion-mediated strategies, sol-gel-like polymerisation, enzyme-assisted routes, and bio-derived fabrication. Particular emphasis is placed on structure-function relationships that enable the development of catalytic, conductive, luminescent, antimicrobial, and biomedical metallogels. The examples compiled here highlight the versatility and transformative potential of metallogels in next-generation soft technologies, including sensing, energy conversion, wound healing, drug delivery, and emerging applications such as soft electronics and on-skin catalytic or bioactive patches. By mapping current progress and emerging design principles, this review aims to support the rational engineering of metallogels for advanced technological and biomedical applications Full article

The development of sustainable wood-based composites has driven increasing interest in formaldehyde-free, low-odor, and recyclable bonding systems. However, achieving high mechanical performance and dimensional stability in high-density fiberboards (HDFs) without synthetic adhesives remains a challenge. Here, we report a two-step strategy combining oxidative pretreatment of wood fibers with supramolecular assembly of tannic acid (TA) and sodium ions (Na⁺) to fabricate low-odor, recyclable HDF. Oxidation generated abundant carboxyl groups on the fiber surface, enabling strong coordination and hydrogen-bonding interactions between TA and Na⁺, which constructed robust inter-fiber supramolecular networks without formaldehyde-based adhesives. The resulting HDF exhibited excellent mechanical properties, with an internal bond strength of 3.1 MPa, a modulus of rupture of 49 MPa, and 24 h water thickness swelling of only 12%. Odor and VOC analysis revealed only trace benzene, demonstrating markedly low odor. Furthermore, the reversible nature of Na⁺-TA interactions allowed efficient fiber separation and recyclability under mild aqueous conditions. This oxidation-assisted supramolecular approach provides a sustainable route for producing high-performance, low-odor, and recyclable fiberboards, offering a viable alternative to conventional polymer-bonded wood composites. Full article

The incorporation of carbon nanostructures into polymer composites is of significant importance for the development of novel sensor materials, due to the excellent mechanical strength and variable electrical conductivity that these structures provide. It is evident that the significance of polylactide (PLA) and carbon nanotube (CNT) systems is attributable to two key factors. Firstly, these systems are notable for their environmental sustainability. Secondly, they exhibit enhanced functional properties. Despite the fact that a considerable number of studies have been conducted on conductive PLA/CNT composites, there has been limited research focusing on the supramolecular ordering of the polymer matrix and its impact on electromechanical properties. This factor, however, has been demonstrated in this study to significantly influence their response to applied stress and, consequently, their potential application as stress sensors. The present study has demonstrated that the precipitation method is an effective means of producing conductive PLA/MWNTs nanocomposites. This method is effective in ensuring the uniform dispersion of the filler in the polymer matrix, which creates an interesting prospect for mechanical sensors. It is evident that the durability of the nanocomposites is a key factor in ensuring the ordering of the supramolecular structure of the PLA matrix into the α form. The materials obtained were found to have a low percolation threshold of 0.2 wt.%. Furthermore, the practical application of these sensors, in the form of resistive strain sensors, was demonstrated for materials containing 5 wt.% of carbon nanotubes. The results presented here demonstrate that this methodology provides a novel perspective on the production of sensor materials, with the supramolecular ordering of the PLA matrix being a key factor. Full article

Gel-based depots are increasingly recognized as platforms to extend the intratissue residence of local anesthetics (LAs) while reducing systemic exposure. Hydrogels, organogels, and emerging bigels represent three distinct architectures defined by their continuous phases and drug–matrix interactions. Hydrogels provide hydrated polymer networks with predictable injectability, tunable degradation, and diffusion- or stimulus-responsive release, enabling sustained analgesia in perineural, peri-incisional, intra-articular, and implant-adjacent settings. Organogels, formed by supramolecular assembly of low-molecular-weight gelators in lipids or semi-polar solvents, strongly solubilize lipophilic LA bases and enhance barrier partitioning, making them suitable for dermal, transdermal, and mucosal applications in outpatient or chronic pain care. Bigels integrate aqueous and lipid domains within biphasic matrices, improving rheology, spreadability, and dual-solubilization capacity, although their use in LA delivery remains at the formulation stage, with no validated in vivo pharmacology. This narrative review synthesizes the design principles, release mechanisms, and translational evidence across these platforms, highlighting domain-specific advantages and barriers related to mechanical robustness, sterilization, reproducibility, and regulatory feasibility. We propose a platform-level framework in which depot selection is aligned with LA chemistry, anatomical context, and clinical objectives to guide the development of workflow-compatible next-generation LA depots. Full article

Reversible adhesives enable temporary yet robust bonding between surfaces, allowing controlled detachment without structural or interfacial damage. This capability is gaining increasing recognition as a crucial requirement for sustainable technologies, where repairability, reusability, and minimal waste are key objectives. Among the diverse strategies explored for reversible adhesion (including supramolecular assemblies, bioinspired dry adhesives, and stimuli-responsive polymers), hydrogel-based systems have emerged as particularly versatile candidates due to their tunable mechanics, elasticity, and intrinsic biocompatibility. Recent studies highlight the use of renewable or biodegradable polymers to develop sustainable, water-rich hydrogel networks with controllable adhesive properties, minimizing environmental impact while maintaining performance. Despite these advances, significant challenges still hinder full implementation: biopolymer-based systems such as chitosan or starch often exhibit strong but poorly controllable adhesion, compromising reversibility and reusability. This review provides a comprehensive overview of strategies for developing hydrogel-based reversible adhesives, focusing on sustainable material selection, molecular design principles, and the underlying mechanisms of bonding and debonding. Furthermore, characterization methodologies, from conventional mechanical testing to surface-sensitive and dynamic techniques, are discussed in detail to establish structure–property–function relationships. Finally, emerging directions and application opportunities are outlined, offering a framework for the rational design of next-generation, sustainable adhesive systems. Full article