A supramolecular hydrogel leveraging hierarchical multi-strength hydrogen-bonds hinged strategy achieving a striking adhesive-mechanical balance.

To obtain high-performance tissue-adhesive hydrogel embodying excellent mechanical integrity, a supramolecular hydrogel patch is fabricated through in situ copolymerization of a liquid-liquid phase separation precursor composed of self-complementary 2-2-ureido-4-pyrimidone-based monomer and acrylic acid coupled with subsequent corporation of bioactive epigallocatechin gallate. Remarkably, the prepared supramolecular hydrogel leverages hierarchical multi-strength hydrogen-bonds hinged strategy assisted by alkyl-based hydrophobic pockets, broadening the distribution of binding strength of physical junctions, striking a canonical balance between superb mechanical performance and robust adhesive capacity. Ultimately, the fabricated supramolecular hydrogel patch stands out as a high stretchability (1500 %), an excellent tensile strength (2.6 MPa), a superhigh toughness (12.6 MJ m-3), an instant and robust tissue adhesion strength (263.2 kPa for porcine skin), the considerable endurance under cyclic loading and reversible adhesion, a superior burst pressure tolerance (108 kPa) to those of commercially-available tissue sealants, and outstanding anti-swelling behavior. The resultant supramolecular hydrogel patch demonstrates the rapid hemorrhage control within 60 s in liver injury and efficient wound closure and healing effects with alleviated inflammation and reduced scarring in full-thickness skin incision, confirming its medical translation as a promising self-rescue tissue-adhesive patch for hemorrhage prevention and sutureless wound closure.

Pemetrexed-loaded supramolecular acetal-functionalized pH-responsive nanocarriers selectively induce apoptosis through biotin receptors to enhance antitumor efficacy.

A novel pH-responsive crystalsomes has been developed using acetal-functionalized pillar[5]arenes (AP[5]) and methyl viologen (MV) through host-guest interactions. The successful synthesis of AP[5] was confirmed via 1H-NMR spectroscopy, while the formation of the host-guest complex between AP[5] and MV was also verified using ¹H-NMR. The supramolecular assemblies formed at a 1:1 molar ratio of AP[5] to MV exhibited remarkable colloidal stability, a negative surface charge, and a high association constant.An acetal-functionalized pillara[5]arenes (AP[5]) crystalsomes were fabricated to reduce the toxicity of pemetrexed (PMX) in off-target sites and deliver the therapeutic doses to the active sites. Extensive characterization of the crystalsomes was performed, revealing their morphology and crystalline structure through SEM and TEM imaging. WAXS analysis confirmed the crystalline nature of the assemblies, and SAED patterns indicated that the crystalsome shell consisted of lamellae resembling single crystals with polymer chains oriented parallel to the interface. To enhnace the targeting capabilities, the surface of the crystalsomes was modified with biotin by conjugating viologen with biotin (MV-BT), aiming to target biotin receptors overexpressed on tumor cells. These biotin -modified crystalsomes (PMX-BT@CLs) were designed to be acid-labile facilitating the release of encapsulated drugs upon cellular internalization, as confirmed by confocal laser scanning microscopy (CLSM). In vivo, studies demonstrated that the PMX-loaded crystalsomes remained in circulation for extended period, showing improved pharmacokinetics. The area under the curve (AUC) of PMX-BT@CLs was approxiately 3.9 times higher than that of the free drug. Additionally, the relative tumor volume was found to be about 3.5 times lower in the group treated with biotin-modified crystalsomes compared to those treated with free PMX. The mean survival time was also significantly enhanced in the PMX-BT@CLs group. This study underscores the potential of using host-guest motifs in drug delivery app;ications, demonstrating the PMX can effectively targted to tumor sites with minimal off-target toxicity.

Boosting Chondrocyte Bioactivity with Ultra-Sulfated Glycopeptide Supramolecular Polymers.

Although autologous chondrocyte transplantation can be effective in articular cartilage repair, negative side effects limit the utility of the treatment, such as long recovery times, poor engraftment or chondrogenic dedifferentiation, and cell leakage. Peptide-based supramolecular polymers have emerged as promising bioactive systems to promote tissue regeneration through cell signaling and dynamic behavior. We report here on the development of a series of glycopeptide amphiphile supramolecular nanofibers with chondrogenic bioactivity. These supramolecular polymers were found to have the ability to boost TGFß-1 signaling by displaying galactosamine moieties with differing degrees of sulfation on their surfaces. We were also able to encapsulate chondrocytes with these nanostructures as single cells without affecting viability and proliferation. Among the monomers tested, assemblies of trisulfated glycopeptides led to elevated expression of chondrogenic markers relative to those with lower degrees of sulfation that mimic chondroitin sulfate repeating units. We hypothesize the enhanced bioactivity is rooted in specific interactions of the supramolecular assemblies with TGFß-1 and its consequence on cell signaling, which may involve elevated levels of supramolecular motion as a result of high charge in trisulfated glycopeptide amphiphiles. Our findings suggest that supramolecular polymers formed by the ultra-sulfated glycopeptide amphiphiles could provide better outcomes in chondrocyte transplantation therapies for cartilage regeneration. STATEMENT OF SIGNIFICANCE: : This study prepares glycopeptide amphiphiles conjugated at their termini with chondroitin sulfate mimetic residues with varying degrees of sulfation that self-assemble into supramolecular nanofibers in aqueous solution. These supramolecular polymers encapsulate chondrocytes as single cells through intimate contact with cell surface structures, forming artificial matrix that can localize the growth factor TGFß-1 in the intercellular environment. A high degree of sulfation on the glycopeptide amphiphile is found to be critical in elevating chondrogenic cellular responses that supersede the efficacy of natural chondroitin sulfate. This work demonstrates that supramolecular assembly of a unique molecular structure designed to mimic chondroitin sulfate successfully boosts chondrocyte bioactivity by single cell encapsulation, suggesting a new avenue implementing chondrocyte transplantation with supramolecular nanomaterials for cartilage regeneration.

An injectable self-lubricating supramolecular polymer hydrogel loaded with platelet lysate to boost osteoarthritis treatment.

Globally, osteoarthritis (OA) is the most prevalent joint disease and is characterized by infiltration of M1 macrophages in the synovium, anabolic-catabolic imbalance of the extracellular matrix (ECM), increased articular shear force and overproduction of reactive oxygen species (ROS). Disease-modifying OA drugs are not yet available, and treatments for OA focus solely on reducing pain and inflammation and have limited therapeutic effect. Herein, we developed an injectable self-lubricating poly(N-acryloyl alaninamide) (PNAAA) hydrogel loaded with platelet lysate (PL) (termed "PNAAA@PL") for treating OA. Tribological and drug release tests revealed suitable lubrication properties and sustained release of bioactive factors in PNAAA@PL. In vitro experiments showed that PNAAA@PL alleviated interleukin-1ß (IL-1ß)-induced anabolic-catabolic imbalance of chondrocytes and repolarized pro-inflammatory M1 macrophages to the anti-inflammatory M2 phenotype via intracellular ROS scavenging. Additionally, the PNAAA@PL hydrogel enhanced the migratory capacity and chemotaxis ability of stem cells, which are essential for chondrogenesis. In vivo, the functionalized PNAAA@PL hydrogel acted like synovial fluid following intra-articular injection into a rat OA model with anterior cruciate ligament transection, ultimately attenuating cartilage degeneration and synovitis. According to molecular mechanism studies, PNAAA@PL repairs cartilage in the OA model by inhibiting the NF-ĸB pathway. Overall, this self-lubricating PNAAA@PL hydrogel offers a comprehensive strategy for preventing OA progression by engineering a biophysiochemical microenvironment to generate high-quality hyaline cartilage.

Toughening Healable Supramolecular Double Polymer Networks Based on Hydrogen Bonding and Metal Coordination.

Double polymer networks (DNs) consist of two interpenetrating polymer networks and can offer properties that are not merely a sum of the parts. Here, we report an elastic DN made from two supramolecular polymers (SMPs) that consist of the same poly(n-butyl acrylate) (BA) backbone. The two polymers feature different non-covalent binding motifs, which form dynamic, reversible cross-links. The polymers were prepared by reversible addi-ti-on-frag-mentation chain-transfer polymerization of n-butyl acrylate and either the self-complementary hydrogen-bonding motif 2-ureido-4[1H]pyri-mi-dinone, or the 2,6-bis(1'-methyl-benz--imidazolyl)-pyridine ligand, which forms complexes with metal ions. The supramolecular DN made by these components combines features of the single networks, including high thermal stability and resistance to creep. The DN further exhibits excellent healability and displays a higher extensibility and a higher toughness than its constituents. The mechanical characteristics of the DN can be further enhanced by selectively pre-stretching one of the networks, which is readily possible due to the reversible formation of the supramolecular cross-links and their orthogonal stimuli-responsive-ness.

Temperature-Dependent Supramolecular Isomeric Co-CPs for Luminescence Recognition and Catalytic Oxidation.

Two Co-based supramolecular isomers were synthesized from a fluorinated carboxylic acid ligand under hydrothermal conditions at varying temperatures. Both exhibited similar one-dimensional chain structures while different bending connections of the aromatic rings led to different supramolecular structures, namely CoCP-1 and CoCP-2, respectively. The structural differences of two isomers resulted in discrepant performance with regards to luminescence sensing and catalysis. CoCP-1 demonstrated more significant luminescence quenching activity toward biomarkers 2,6-dipyridinoic acid (DPA) and high vanilloid acid (HVA), which could be distinguished in the presence of Eu3+. The limit of detection (LOD) was found to be as low as 3.4 and 1.3 µM, respectively. The recovery rate of for HVA and DPA was within the range of 89.6-101.2% and 99.7-117.9% in simulated urine and serum, respectively, indicating potential reliability in monitoring these two analytes in real samples. Notably, CoCP-2 exhibited catalytic activity for the oxidation of thioethers to sulfoxides. Our finding here suggests that the coordination conformation of the ligands within supramolecular isomers plays a pivotal role in determining the structure and luminescence sensing/catalysis performance.

The heterogeneity of aqueous solutions: the current situation in the context of experiment and theory.

The advancement of experimental methods has provided new information about the structure and structural fluctuations of water. Despite the appearance of numerous models, which aim to describe a wide range of thermodynamic and electrical characteristics of water, there is a deficit in systemic understanding of structuring in aqueous solutions. A particular challenge is the fact that even pure water is a heterogeneous, multicomponent system composed of molecular and supramolecular structures. The possibility of the existence of such structures and their nature are of fundamental importance for various fields of science. However, great difficulties arise in modeling relatively large supramolecular structures (e.g. extended hydration shells), where the bonds between molecules are characterized by low energy. Generally, such structures may be non-equilibrium but relatively long-lived. Evidently, the short times of water microstructure exchanges do not mean short lifetimes of macrostructures, just as the instability of individual parts does not mean the instability of the entire structure. To explain this paradox, we review the data from experimental and theoretical research. Today, only some of the experimental results on the lifetime of water structures have been confirmed by modeling, so there is not a complete theoretical picture of the structure of water yet. We propose a new hierarchical water macrostructure model to resolve the issue of the stability of water structures. In this model, the structure of water is presented as consisting of many hierarchically related levels (the stratification model). The stratification mechanism is associated with symmetry breaking at the formation of the next level, even with minimal changes in the properties of the previous level. Such a hierarchical relationship can determine the unique physico-chemical properties of water systems and, in the future, provide a complete description of them.

Supramolecular collagen nanoparticles for anti-wrinkle, skin whitening, and moisturizing effects.

Collagen-based skincare products can replenish collagen in the skin; however, collagen cannot easily penetrate the dermis, limiting its effectiveness. Therefore, nanomaterials that can enable collagen to effectively penetrate the dermis are urgently needed. This study aimed to determine the potential role of the supramolecular collagen nanoparticles, namely, lactoferrin, recombinant human collagen, and palmitoyl tripeptide-5, in improving the effectiveness of skincare products. Lactoferrin and recombinant collagen served as carriers encapsulating palmitoyl tripeptide-5, with an encapsulation rate of 94.18 %. The supramolecular collagen nanoparticles demonstrated good stability after 1 month. Transdermal efficiency was improved by 69.90 %, allowing the nanoparticles to penetrate deeply into the dermis. Within 28 days of use, the moisture content of the stratum corneum increased by 10.51 %, facial elasticity improved by 8.15 %, skin firmness increased by 12.53 %, facial melanin index decreased by 1.84 %, and individual type angle increased by 19.10 %. Within 14 days, there was a 24.69 % reduction in eye bag wrinkles and a 37.61 % reduction in nasolabial wrinkles. Wrinkle lengths decreased by 10.22 % and 21.57 %, and areas decreased by 34.41 % and 27.92 %, respectively. The supramolecular collagen nanoparticles displayed multiple skincare benefits, including moisturizing, whitening, wrinkle reduction, and firming. In conclusion, the supramolecular collagen nanoparticles are promising candidates for cosmetic products.

Microwave-assisted supramolecular double crosslinked chitosan-based molecularly imprinted polymer for synergistic recognition and selective recovery of Cd(II) and As(V) from water: Performance and mechanistic insights.

A novel model of the sustainable double crosslinked molecularly imprinted polymer (D-Crosslinked MIP) represented as a supramolecular imprinted polymer was synthesized via the bulk polymerization method. The primary crosslinking was fabricated using biomacromolecule chitosan as a functional monomer and glutaraldehyde as a crosslinker. The primary crosslinked was subjected to dynamic interactions in a secondary crosslinking by binding Al2O3-NPs and TiO2-NPs, forming the supramolecular D-Crosslinked-MIP. The dually crosslinked formed from combining three distinct crosslinkers in one system for the interaction with As(V) and Cd(II). A microwave was employed to evaluate the performance of the designed material in selectivity and extraction of metal ions from water. The FT-IR, XRD, TG/DTA, SEM-EDX, TEM, and XPS were used to verify the characteristics of (D-nano-Al2O3@Crosslinked Chitosan@D-nano-TiO2). The type of solvents, selectivity, interferences, microwave-contact time, pH, temperatures, concentrations, and regeneration were investigated. At 15 s, Cd(II) revealed a recovery capacity of 99.03 %, Qmax 862.07 mg/g, while As(V) demonstrated a recovery capacity of 99.06 %, Qmax 850.75 mg/g. The D-Crosslinked-MIP exhibited BETs of 69.01 m2/g with a pore volume of 0.2340 cm3/g owing to polymeric crosslinking by metal oxide NPs. The kinetics, isotherm models, and mechanisms of dually crosslinking and extraction of toxic metals were discussed.

Ultra-tough Dynamic Supramolecular Ion-conducting Elastomer Induced Uniform Li+ Transport and Stabilizes Interphase Ensures Dendrite-free Lithium Metal Anodes.

Artificial polymer solid electrolyte interphases (SEIs) with microphase-separated structures provide promising solutions to the inhomogeneity and cracking issues of natural SEIs in lithium metal batteries (LMBs). However, achieving homogeneous ionic conductivity, excellent mechanical properties, and superior interfacial stability remains challenging due to interference from hard-phase domains in ion transport and solid-solid interface issues with lithium metal. Herein, we present a dynamic supramolecular ion-conducting poly(urethane-urea) interphase (DSIPI) that achieves these three properties through modulating the hard-phase domains and constructing a composite SEI in situ. The soft-phase polytetrahydrofuran backbone, featuring loose Li+-O coordinating interactions, ensures uniform Li+ transport. Concurrently, sextuple hydrogen bonds in the hard phase dissipate strain energy through sequential bond cleavage, thereby imparting exceptional mechanical properties. Moreover, enriched bis(trifluoromethanesulfonyl)imide anion (TFSI-) in DSIPI promotes the in-situ formation of a stable polymer-inorganic composite SEI during cycling. Consequently, the DSIPI-protected lithium anode (DSIPI@Li) enables symmetric cells with exceptional cyclability exceeding 4,000 hours at an ultra-high current density of 20 mA cm-2, thereby demonstrating excellent cycling stability. Furthermore, DSIPI@Li facilitates stable operation of the pouch cells under the constraints of a high-loading LiNi0.8Co0.1Mn0.1O2 cathode and low negative/positive capacity (N/P) ratio. This work presents a powerful strategy for designing artificial SEIs and high-performance LMBs.

Supramolecular deep eutectic solvents: Current advances and critical evaluation of cyclodextrins from solute to solvent in emerging functional food.

The acceptance of nonconventional solvents as viable substitutes for traditional organic solvents has been widely recognized in order to comply with food-safety and sustainability regulations. Cyclodextrins (CDs), derived from starch, are cyclic oligosaccharides with the ability to form inclusion complexes with a variety of functional substances as the result of their distinctive structure, which enables them to effectively encapsulate bioactive compounds, rendering them highly sought after for use in food applications. In the implementing plan to achieve carbon-neutral emissions by 2050, the novel generation of supramolecular deep eutectic solvents (SUPRADES) has garnered increased attention and interest. The approach of utilizing SUPRADES as emerging solvents was just beginning to be applied to food studies. This review summarizes a revision of the current advances and critical evaluation of cyclodextrin-based SUPRADES (CD-based SUPRADES) as promising solvents for the enhancement of the extraction efficiency, solubilization and stability of bioactive compounds, adsorption and separation of food components, packaging materials, and modification of biopolymers. To meet the sustainable processing needs of the food industry, the emerging categories of CD-based SUPRADES need to be further fabricated. Herein, our review will sort out the potential application of CD-based SUPRADES in the food industry, aiming to provide a better understanding of CD-based SUPRADES within the viewpoint of food science. Formulation intricacies and scalability issues in real functional foods using CD-based SUPRADES as media need more efforts.

Thermoresponsive and Supramolecular Polymers: Interesting Biomaterials for Drug Delivery.

How to use and deliver drugs to diseased and damaged areas has been one of the main concerns of pharmacologists and doctors for a long time. With the efforts of researchers, the advancement of technology, and the involvement of engineering in the health field, diverse and promising approaches have been studied and used to achieve this goal. A better understanding of biomaterials and the ability of production equipment led researchers to offer new drug delivery systems to the world. In recent decades, responsive polymers (exclusively to temperature and pH) and supramolecular polymers have received much attention due to their unique capabilities. Although this field of research still needs to be scrutinized and studied more, their recognition, examination, and use as drug delivery systems is a start for a promising future. This review study, focusing on temperature-responsive and supramolecular biomaterials and their application as drug delivery systems, deals with their structure, properties, and role in the noninvasive and effective delivery of medicinal agents.

Crystal structure and supra-molecular features of a host-guest inclusion complex based on A1/A2-hetero-difunctionalized pillar[5]arene.

A host-guest supra-molecular inclusion complex was obtained from the co-crystallization of A1/A2-bromo-but-oxy-hy-droxy difunctionalized pillar[5]arene (PilButBrOH) with adipo-nitrile (ADN), C47H53.18Br0.82O10·C6H8N2. The adipo-nitrile guest is stabilized within the electron-rich cavity of the pillar[5]arene host via multiple C-H⋯O and C-H⋯π inter-actions. Both functional groups on the macrocyclic rim are engaged in supra-molecular inter-actions with an adjacent inclusion complex via hydrogen-bonding (O-H⋯N or C-H⋯Br) inter-actions, resulting in the formation of a supra-molecular dimer in the crystal structure.

Phonon Transport in Supramolecular Polymers Regulated by Hydrogen Bonds.

Supramolecular polymers hold promise in thermal management applications due to their multistability, high responsiveness, and cost-effectiveness. In this work, we successfully regulate phonon transport at the molecular level in supramolecular polymers by adjusting the strength of intermolecular hydrogen bonding. We synthesized three supramolecular polymer fibers with thermal conductivity differences of up to 289% based on melamine (M) and three simple positional isomers of hydroxybenzoic acid. Differential Scanning Calorimetry (DSC) measurement revealed discrepancies in thermal stability of the polymers, where structures with higher stability exhibited enhanced thermal conductivity. Fourier Transform Infrared Spectroscopy (FTIR) measurement and Density Functional Theory (DFT) calculations indicate that these differences arise from variations in hydrogen-bonding strengths at different bonding sites. Higher hydrogen-bonding strength leads to more stable thermal pathways, reduces phonon scattering, and increases thermal conductivity. Our findings provide valuable insights into controlling the thermal conductivity of polymer fibers, paving the way for applications in phonon-based thermal devices.

Responsive Supramolecular Nanomicelles Formed through Self-Assembly of Acyclic Cucurbit[n]uril for Targeted Drug Delivery to Cancer Cells.

The supramolecular drug delivery systems (SDDSs) based on host-guest recognition through noncovalent interactions, capable of responsive behavior and dynamic switching to external stimuli, have attracted considerable attention in cancer therapy. In this study, a targeted dual-functional drug delivery system was designed and synthesized. A hydrophilic macrocyclic host molecule (acyclic cucurbit[n]uril ACB) was modified with folic acid (FA) as a targeting ligand. The guest molecule consists of a disulfide bond attached to adamantane (DA) and cannabidiol (CBD) at both ends of the response element of glutathione. Recognition and self-assembly of host and guest molecules successfully functionalize supramolecular nanomicelles (SNMs), targeting cancer cells and releasing drugs in a high glutathione environment. The interactions between host and guest molecules were investigated by using nuclear magnetic resonance (NMR), fluorescence titration, Fourier-transform infrared spectroscopy (FT-IR), and thermal analysis (TGA). Transmission electron microscopy (TEM) and dynamic light scattering (DLS) confirmed the nanostructure of the SNMs. Experimentation with 5,5'-dithiobis (2-nitrobenzoic acid) (DTNB) demonstrated the responsiveness of SNMs to glutathione (GSH). In vitro cytotoxicity assays demonstrated that SNMs had a greater targeting efficacy for four types of cancer cells (HeLa, HCT-116, A549, and HepG2) compared to normal 293T cells. Cellular uptake studies revealed that HeLa cells more readily absorbed SNMs, leading to their accumulation in the tumor cell cytoplasm. Fluorescence colocalization assays verified that SNMs efficiently accumulated in organelles related to energy metabolism and signaling, including mitochondria and the endoplasmic reticulum, affecting cellular metabolic death. Both flow cytometry and confocal nuclear staining assays confirmed that SNMs effectively induced apoptosis over time, ultimately resulting in the death of cancer cells. These findings demonstrate that SNMs exhibit excellent targeting ability, responsiveness, high bioavailability, and stability, suggesting significant potential in drug delivery applications.

Spontaneous formation of polymeric nanoribbons in water driven by π-π interactions.

A simple method was developed to produce polymeric nanoribbons and other nanostructures in water. This approach incorporates a perylene diimide (PDI) functionalized by hydrophilic triethylene glycol (TEG) as a hydrophobic supramolecular structure directing unit (SSDU) into the core of hydrophilic poly(N,N-dimethylacrylamide) (PDMAc) chains using RAFT polymerization. All PDI-functional polymers dissolved spontaneously in water, forming different nanostructures depending on the degree of polymerization (DPn): nanoribbons and nanocylinders for DPn = 14 and 22, and spheres for DPn > 50 as determined by cryo-TEM and SAXS analyses. UV-VIS absorption spectroscopy was used to monitor the evolution of the PDI absorption signal upon dissolution. In solid form, all polymers show a H-aggregate absorption signature, but upon dissolution in water, the shortest DPn forming nanoribbons evolved to show HJ-aggregate absorption signals. Over time, the J-aggregate band increased in intensity, while cryo-TEM monitoring evidenced an increase in the nanoribbon's width. Heating the nanoribbons above 60 °C, triggered a morphological transition from nanoribbons to nanocylinders, due to the disappearance of J-aggregates, while H-aggregates were maintained. The study shows that the TEG-PDI is a powerful SSDU to promote 2D or 1D self-assembly of polymers depending on DPn through simple dissolution in water.

Supramolecular Reconstruction of Self-Assembling Photosensitizers for Enhanced Photocatalytic Hydrogen Evolution.

Natural photosynthetic systems require spatiotemporal organization to optimize photosensitized reactions and maintain overall efficiency, involving the hierarchical self-assembly of photosynthetic components and their stabilization through synergistic interactions. However, replicating this level of organization is challenging due to the difficulty in efficiently communicating supramolecular nano-assemblies with nanoparticles or biological architectures, owing to their dynamic instability. Herein, we demonstrate that the supramolecular reconstruction of self-assembled amphiphilic rhodamine B nanospheres (RN) through treatment with metal-phenolic coordination complexes results in the formation of a stable hybrid structure. This reconstructed structure enhances electron transfer efficiency, leading to improved photocatalytic performance. Due to the photoluminescence quenching property of RN and its electronic synergy with tannic acid (T) and zirconium (Z), the supramolecular complexes of hybrid nanospheres (RNTxZy) with Pt nanoparticles or a biological workhorse, Shewanella oneidensis MR-1, showed marked improvement in photocatalytic hydrogen production. The supramolecular hybrid particles with a metal-phenolic coordination layer showed 5.6- and 4.0-fold increases, respectively, in the productivities of hydrogen evolution catalyzed by Pt (Pt/RNTxZy) and MR-1 (M/RNTxZy), respectively. These results highlight the potential for further advancements in the structural and photochemical control of supramolecular nanomaterials for energy harvesting and bio-hybrid systems.

Highly Conductive Supramolecular Salt Gel Electrolyte for Flexible Supercapacitors.

Conductive gels have greatly facilitated the development of flexible energy storage devices, including supercapacitors, batteries, and triboelectric nanogenerators. However, it is challenging for gel electrolytes to tackle the trade-off issues between mechanical properties and conductivity. Herein, a strategy of all inorganic salt-driven supramolecular networks is presented to construct gel electrolytes with high conductivity and reliable mechanical performance for flexible supercapacitors. The salt gel is successfully fabricated by combining a salt supramolecular network constructed by NH4Mo7O24·4H2O and FeCl3·6H2O and a polymer network of poly(vinyl alcohol). The inorganic salt supramolecular network serves as a rigid self-supporting framework in the hydrogel system for improving the mechanical properties and providing abundant active sites for accelerating ion transport. Furthermore, the salt gel-enabled supercapacitors are equipped and exhibit a high specific capacitance (199.4 mF cm-2) and excellent energy density (27.69 µWh cm-2). Moreover, the flexible supercapacitors not only present remarkable cyclic stability after 3000 charging/discharging cycles but also exhibit good electrochemical stability even under severe deformation conditions. The strategy of salt-gel-driven flexible supercapacitors would provide fresh thinking for the development of advanced flexible energy storage fields.

Engineering crystal network of supramolecular Oleogel via kinetical regulation for improved lutein bioaccessibility.

This study presented an approach for controlling supramolecular oleogel crystal network by regulating kinetical factors - specifically, a combination of cooling temperature and aging period. Results indicated that only under long aging period, supramolecular oleogels prepared at different cooling temperature exhibited distinct crystal morphology compared to those under short aging period. The physicochemical properties of oleogels were affected by different crystal networks. Therefore, further research on oleogels under longed aging was explored. For lutein encapsulation, it was observed that supramolecular oleogels with denser crystal network exhibited higher lutein bioaccessibility. This was probably because the denser crystal network providing a solid physical barrier that effectively protected lutein unaffected by gastric acid degradation. Additionally, the micellar capacity was also enhanced to accommodate lutein due to release of long chain fatty acid from the gelator glycerol monostearate (GMS). Collectively, kinetical factors regulation facilitated rational design of oleogels for delivery of lipid-soluble bioactive compounds.

Supramolecular polymer cross-linking gel electrolyte for highly stable quasi-solid-state lithium metal batteries.

Lithium (Li) metal batteries have the advantage of high energy density, but the Li dendrites risk piercing the separator and causing a short circuit in the battery. Replacing the liquid electrolytes with gel electrolytes is considered an effective strategy to solve the issues. Herein, a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)-based gel electrolyte, improved with multifunctional supramolecular polymer (MSP), was prepared to enhance the cycling stability and energy density of quasi-solid-state Li metal batteries. The MSP addictive constructs a cross-linked network structure with PVDF-HFP matrix and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) through hydrogen bonding, improving the mechanical strength of the composite gel electrolyte (PH-10%MSP-GE) to against the growth of Li dendrites. Moreover, the pre-lithiated sulfonic acid groups, conductive polyether groups of MSP, and the attraction of TFSI- anions, promote the Li-ion transportation of the composite gel electrolyte. Finally, the Li||Li symmetric cell cycle stably for over 450 h. The Li||LiFePO4 full cell demonstrates a high energy density and excellent cycling stability for over 600 cycles, with a capacity retention rate of up to 98.7%. This work provides valuable insights into the preparation of multifunctional composite gel polymer electrolytes and competitive quasi-solid-state Li metal batteries.