Bifunctional Monomer Research Articles

Self-Adaptive Aromatic Cation-π Driven Dimensional Polymorphism in Supramolecular Polymers for the Photocatalytic Oxidation and Separation of Aromatic/Cyclic Aliphatic Compounds.

The phenomenon of polymorphism is ubiquitous in nature, the controlled manipulation of which not only increases our ontological understanding of nature but also facilitates the conceptualization and realization of novel functional materials. However, achieving targeted polymorphism in supramolecular assemblies (SAs) remains a formidable challenge, largely because of the constraints inherent in controlling the specific binding motifs of noncovalent interactions. Herein, we propose self-adaptive aromatic cation-π binding motifs to construct polymorphic SAs in both the solid and solution states. Using distinct discrete cation-π-cation and long-range cation-π binding motifs enables control of the self-assembly directionality of a C2h-symmetric bifunctional monomer, resulting in the successful formation of both two-dimensional and three-dimensional crystalline SAs (2D-CSA and 3D-CSA). The differences in the molecular packing of 3D-CSA compared with that of 2D-CSA significantly improve the charge separation and carrier mobility, leading to enhanced photocatalytic activity for the aerobic oxidation of thioanisole to methyl phenyl sulfoxide (yield of 99 % vs 57 %). 2D-CSA, which has a vertical extended structure with favorable stronger interaction with toluene though face-to-face cation-π interactions than methylcyclohexane, shows higher toluene/methylcyclohexane separation efficiency than 3D-CSA (96.9 % for 2D-CSA vs 56.3 % for 3D-CSA).

Polysulfide-ene polymerization of bisacrylamides and bismaleimides toward sulphur-rich polymers

Given the ever-increasing importance of developing more sustainable solutions for the fabrication and engineering of polymeric materials, alternative building blocks to the petroleum-derived chemicals are gaining growing interest. In addition to its natural abundance, elemental sulfur is produced industrially in vast quantities which is primarily obtained as a side product from oil refineries and gas purification plants. Thus, elemental sulfur has been prospected as a sustainable resource for the fabrication of structurally diverse polymers. In this study an efficient methodology to obtain sulfur-rich polymers from elemental sulfur-derived polysulfide salts is reported. Polysulfide-ene step growth polymerization of bisacrylamide and bismaleimide-based monomers with bifunctional disodium pentasulfide (Na2S5) generated structurally diverse polyamide and polyimide copolymers incorporating polysulfide chains on the polymer backbones. Copolymers up to 31.8 kDa molecular weight (Mn) and 94% monomerconversions were efficiently obtained under ambient temperature conditions and without the need of any metal or organo-catalyst. By choosing various bifunctional ene monomers, structurally diverse and tailorable linear copolymers were obtained. The methodology was also extended to the fabrication of sulfur-rich crosslinked polymers by employing a multifunctional thiolate-based crosslinker. As a potential application, fabricated crosslinked polymers were employed as adsorbents to remove toxic mercury ions from water. The reported synthetic strategy demonstrated the efficiency of polysulfide-ene reaction to synthesize sulfur-rich polyamide and polyimide polymers and could broaden the available polymerization reaction tools that employelemental sulfur-derived polysulfide salts in functional polymer synthesis.

Dual-source signal amplification electrochemiluminescence sensor combined with molecularly imprinted polymers for the imidacloprid detection

A novel lanthanide metal-organic-gel (MOG)-derived material/nitrogen-doped graphdiyne (Tb-Ru-MOG/CeO2/N-GDY) composite with a dual-source signal amplification strategy was prepared and used to construct a molecularly imprinted sensor based on bifunctional monomers for the detection of imidacloprid (IMI) using electrochemiluminescence (ECL). In a green reaction environment, terbium (III) (Tb3+) can undergo multiple coordination reactions with 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine (Hcptpy) and tris(4,4′-dicarboxylicacid-2,2′-bipyridyl) ruthenium (II) dichloride (Ru(dcbpy)32+), and combine with ceria nanoparticles (CeO2 NPs) to form Tb-Ru-MOG/CeO2. Within the Tb-Ru-MOG/CeO2 framework, energy transfer from the double ligands can sensitize the central Tb3+, triggering a distinct antenna effect and energy-transfer, and its polyporous configuration offered a nanoconfined space for Ce3+/Ce4+ to effectively catalyze coreactant radicals (S2O82−), leading to in-situ endogenous activation ECL reactions. The conductive N-GDY accelerated electron movement and increased the loading on the electrode surface, enhancing the exogenous excitation of the ECL signals. Leveraging the synergistic effect of the bifunctional monomer, the synthesized molecularly imprinted polymers (MIPs) ECL sensor demonstrated a wide detection range from 10 nM to 10,000 nM for IMI, with a limit of detection (LOD) of 1.37 nM, showcasing an innovative concept for the dual-source strategy of signal amplification in integrated ECL composites to analyze food and environmental hazards.

Synthesis of magnetic bifunctional monomer molecularly imprinted polymers for highly selective separation of paclitaxel from Taxus cuspidata

Paclitaxel (PTX), an active anticancer compound derived from Taxus cuspidata, possesses considerable economic value. Given the abundance of structural analogs, the selective separation of PTX from T. cuspidata presents a formidable challenge. In this study, the bifunctional monomers magnetic molecular imprinted polymers (MMIPs) with multiple active sites were synthesized using Fe3O4 as the magnetic carrier, PTX as the template, 4-vinylpyridine (4-VP) and methacrylic acid (MAA) as the first-stage and the second-stage pre-assembly functional monomer, respectively. The results indicated that MMIPs exhibited excellent magnetic recovery capability and high adsorption capacity for PTX. Furthermore, the adsorption behaviors were more consistent with Langmuir isotherm model and pseudo-second-order kinetic model. The MMIPs possessed significantly higher selectivity for PTX than five structural analogs (Docetaxel, Baccatin III, 10-Deacetylbaccatin III, and Glucose) and recyclability for up to six cycles. Additionally, the adsorption mechanism analysis indicated that the excellent performance of MMIPs primarily arises from the multiple active binding sites involving hydrogen bonding and π-π stacking. Finally, MMIPs were used for PTX recognition and separation in T. cuspidata extracts. This study provides an efficient method and valuable theoretical basis for the highly selective separation of PTX from T. cuspidata.

An Intrinsic Self-Healable, Anti-Freezable and Ionically Conductive Hydrogel for Soft Ionotronics Induced by Imidazolyl Cross-Linker Molecules Anchored with Dynamic Disulfide Bonds.

Hydrogels are ideal materials for flexible electronic devices based on their smooth ion channels and considerable mechanical flexibility. A substantial volume of aqueous solution is required to enable the smooth flow of ions, resulting in the agony of low-temperature freezing; besides, long-term exposure to bending/tensile tress triggers fatigue issues. Therefore, it is a great challenge to prepare hydrogels with both freeze-resistance and long-term durability. Herein, a polyacrylic acid-based hydrogel with both hydrophobic interaction and dynamic reversible covalent bonding cross-linking networks is preparing (DC-hydrogel) by polymerizing a bi-functional imidazole-type ionic liquid monomer with integrated disulfide and alkene bonds (DS/DB-IL) and an octadecyl methacrylate, achieving self-healing. The DS/DB-IL anchored into the polymer backbone has a high affinity with water, reducing the freezing point of water, while the DS/DB-IL with free ions provides superior ionic conductivity to the DC-hydrogel. The polyacrylic acid with abundant carboxyl gives hydrogel good self-adhesiveness to different substrates. Ionotronics with resistance-type sensors with stable output performance are fabricated and explored its application to joint motion and health information. Moreover, hydrogel-based sensing arrays with high resolution and accuracy are fabricated to identify 2D distribution of stress. The hydrogels have great promise for various ionotronics in many fields.

Thiazole orange-carboplatin triplex-forming oligonucleotide (TFO) combination probes enhance targeted DNA crosslinking.

We report a new class of carboplatin-TFO hybrid that incorporates a bifunctional alkyne-amine nucleobase monomer called AP-C3-dT that enables dual 'click' platinum(ii) drug conjugation and thiazole orange fluorophore coupling. Thiazole orange enhances the binding of Pt(ii)-TFO hybrids and provides an intrinsic method for monitoring triplex formation. These hybrid constructs possess increased stabilisation and crosslinking properties in comparison to earlier Pt(ii)-TFOs, and demonstrate sequence-specific binding at neutral pH.

Flexible NHC-aryloxido aluminum complex and its zwitterionic imidazolium aluminate precursor in ring-opening polymerization of ε-caprolactone.

Anionic donor-functionalized NHC (N-heterocyclic carbene) complexes of Al are rare. We report one such case here, an NHC-aryloxido AlMe2 complex [Al(L)Me2] (2), following a stepwise synthesis from the proligand [HO-4,6-tBu2-C6H2-2-CH2{CH(NCHCHNAr)}]Br [LH2Br; Ar = 2,6-iPr2-C6H3 (Dipp)] and AlMe3via the zwitterionic intermediate [Al(LH)Me2Br] (1). The ligand's flexibility in 2 is evident from the conformational fluxionality revealed by VT-1H NMR spectroscopic analysis. The ∠O-Al-C (ca. 100.5°) bite angle is also wider than the ∠O-Ti-C (ca. 80.6°) as seen in our recently reported Ti complex [Ti(L)(NMe2)2Br]. DFT analysis showed that the CNHC-Al bond is significantly ionic, as is the CNHC-Ti bond. Both 1 and 2 are active in the ring-opening polymerization (ROP) of ε-caprolactone (CL). 2, similar to [Ti(L)(NMe2)2Br], exhibits bifunctional MLC-type monomer activation, but only at an elevated temperature. However, the 2/BnOH combination is catalytically active at room temperature, likely through a zwitterionic [Al(LH)Me2(OBn)]. The 1/BnOH combination follows a similar mechanism but surprisingly at a faster rate.

Chemically amplified molecular resins for shrinkage-controlled direct nanoimprint lithography of functional oxides: an application towards dark-light dual-mode antibacterial surfaces

The imprinting studies using epoxy/oxetane-based bifunctional monomers of Ti, Zr and Nb showed a reduced feature size shrinkage as low as ∼50%. The TiO2/AgBr nanocomposites displayed high antibacterial efficacy under dark-light dual-mode conditions.

Preparation of rutin imprinted monolith (RIM) by using porogen containing ion liquid [BMIM]PF6 and its molecular recognition

A [BMIM]PF6 ion liquid (IL)-assisted synthesis of a rutin imprinted monolith (RIM) was carried out in an in-situ polymerization method. Bi-functional monomers and a ternary porogen containing IL was used for the RIM preparation and a L9(33) orthogonal factor design performed. Scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR) and N2 adsorption method was for structural characterization of the RIMs. The monolith was directly used as stationary phase in liquid chromatography to test the retention selectivity, adsorption capacity and extraction application. The optimized porogen consists of 900 μL DMF, 144 μL ACN and 216 μL IL. The monolith RIM-13 obtained under the optimized conditions possessed improved adsorption performance, with a dynamic adsorption capacity of 6.695 mg/g, an imprinting efficiency of 4.841 and a selectivity α value of 4.821. Additionally, this monolith had also higher specific surface area, pore volume and permeability than that obtained without IL and the homogeneity of the imprint sites could be improved by using IL. When the RIM-13 was applied to the separation and purification of rutin from tartary buckwheat, a rutin product with a purity higher than 92 % can be obtained by one cycle. This molecular imprint solid-phase extraction (MI-SPE) is of potency to be applied to preparative-scale separation of other natural products.

Synthesis of metal-organic framework hybrid nanocomposites based on MOFs@C3N4 with high selective separation ability for luteolin

Complex substrates found in certain extracts-particularly those containing high phenolic compounds with significant medicinal value-pose considerable challenges to developing molecularly imprinted membranes (MIMs) with specific recognition abilities. In this study, UiO-66-NH2, a metal–organic structure (MOF), was chosen as an optimizer to enhance the basic support material C3N4. A composite imprinted membrane based on MOFs was then prepared for the targeted adsorption of luteolin (LTL). This not only increases the surface area and pore capacity of the composite membranes, but also ensures unprecedented control over the membranes structure and good stability. To maximize the proportion of imprinted sites, we utilize an advanced boron affinity sol–gel imprinting technique that capitalizes on the exceptional response of the bifunctional monomer. By finely manipulating the imprinting process, controlled distribution of imprinted sites was achieved. Furthermore, the incorporation of Ag nanoparticles into the composite matrix of MIMs enhances selectivity and efficiency due to their plasmonic properties and high affinity for phenolic compounds, providing increased adsorption surface area and additional binding sites. The results showed satisfactory rebinding ability (56.25 mg g−1) and superselective (βAG/LTL = 4.43 and βCT/LTL = 8.49). It was worth noting that incorporating Ag nanoparticles into composite MIMs for the selective adsorption of LTL demonstrates significant potential. This includes enhanced selectivity, efficiency, and hydrophilicity of the membrane surface. Thus, enhanced hydrophilicity can establish stronger non-covalent interactions, namely hydrogen bonding and van der waals forces, with the target molecules, thereby significantly improving the adsorption capacity of the MIMs. The feasibility of this method was demonstrated via in-situ infrared analysis of the chemical structure changes before and after adsorption.

Enantioselective Amination of 4-Substituted Pyrazolones Catalyzed by Oxindole-Containing Thioureas and by a Recyclable Linear-Polymer-Supported Analogue in a Continuous Flow Process.

A highly efficient organocatalytic amination of 4-substituted pyrazolones with azodicarboxylates mediated by a novel quinine-derived thiourea with a 3,3-diaryl-oxindole scaffold is reported. This synthetic method furnished 4-amino-5-pyrazolones in high yields and with excellent enantioselectivities (up to 97:3 er) at room temperature in short reaction times. Moreover, a linear-polymer-supported bifunctional thiourea, synthesized by reacting a bifunctional aromatic monomer (biphenyl) with isatin in superacidic media and further derivatization, was proven to be also an efficient heterogeneous organocatalyst for this α-amination reaction. The practical value of this process was demonstrated by the use of the immobilized catalyst in recycling experiments, maintaining the activity without additional reactivation, and in flow processes, allowing the synthesis of 4-amino-pyrazolone derivatives in a gram scale with high yield and enantioselectivity.

Fabrication of double imprinted anchor points in cellulose nanocrystals-based hierarchical porous polyHIPEs for selective separation of flavoniods under physiological pH

Previous research had proved that molecular imprinted polymers can be used as separation material for removing Naringin (NRG) from agricultural pomelo wastes effectively. But the adsorption amounts of NRG molecules from traditional MIPs was quite low by using boronic acid as functional monomer because of single affinity interaction. Therefore, we developed the new combination of bifunctional monomers (i.e. low pKa boronate affinity monomer 2,4-difluoro-3-formylphenylboronic acid and dopamine) based on cellulose nanocrystals (CNCs) mixed with polymerized high internal phase emulsion (polyHIPE, PH) through an double layer surface imprinted method. The introduction of polyethylenimine (PEI) can offer abundant anchor units for the growth of more anchor sites to immobilization template molecules. Importantly, largely improved selective adsorption amounts (50.79 μmol g−1), which may be attribute to the fabrication of the uniform growth of double imprinted layers onto the polydopamine (PDA)/boronic acid-based surfaces. In addition, the resulting double recognition molecular imprinted polymers (MIPs) based on hypercrosslinked PH (DR-HCLPH@MIPs) not only exhibited fast adsorption kinetic of NRG molecule, but also possessed excellent selectivity and high adsorption capacities at physiological pH. Meanwhile, the coarse NRG from pomelo waste can be high selectively extracted to 94.74%. Overall, this study provides a versatile approach for fabrication of the sandwich-biscuit-like double imprinting layer porous MIPs for precise identification and ultrafast transport separation of NRG from complex samples.

Synthesis, Characterization, and Evaluation of Antioxidant and Physical Properties of New Bifunctional Aromatic Monomers Containing Imine and Heterocyclic Rings in The Main Chain.

New various monomers with di amine functional groups have been synthesized, containing di azomethine or di seven-membered heterocyclic rings in the backbone. A condensation reaction of benzidine with 4-amino benzaldehyde with some drops of glacial acetic acid in ethanol absolute prepared bi-functional amino groups monomer with azomethine core P1(4-[(1E)-[4[4-(E)-(4-aminophenyl)methylidene]amino]phenyl}phenylimino methyl aniline). The next step was the Cycloaddition reaction of P1 with succinic, malic, and phthalic anhydrides used to obtain aromatic heterocyclic monomers with oxazepane and oxazepine rings containing lactone and lactam groups. All the synthesized monomers were characterized spectrally with many techniques (FT.IR,1 H1.NMR, C13-NMR) that were used to investigate the functional groups in the structure of monomers. Monitoring the progress and completion of the reaction was performed using thin-layer chromatography (TLC). Physical characterizations, including detecting the melting point, purity, colour, retardation factor, molecular formula, and molecular weight, the polarized optical microscope (POM) used for Image-based microscopic interpretation of prepared compounds. All the prepared monomers are considered effective antioxidant agents as they give free radicals scavenging over 60%, reaching 80 %; this activity makes them useful in large numbers of industries as they can scavenge the free radicals that the industrial product may be exposed, which increases its shelf life and enhance its effectiveness.

An intelligent solvent-responsive surface molecularly imprinted membrane with switchable adsorption/desorption performance for selective separation of psoralen and recognition mechanism

Psoralen (PSO), a natural product in Ficus carica L., exhibits remarkable pharmacological activity and clinical efficacy. However, achieving selective recognition and effective recovery in PSO separation process remains a challenge. In this study, an intelligent solvent-responsive surface molecularly imprinted membranes (SR-SMIMs) with switchable adsorption/desorption behavior was developed and applied to separate PSO. Cellulose membranes were modified with chitosan and polydopamine in sequence, followed by the construction of a surface molecularly imprinting layer using bi-functional monomers (AM and 4-VPBA) and solvent-responsive cross-linking agent (TEGDMA). The TEGDMA drives the swelling or shrinking of polymer chains, resulting in a switch in the adsorption/desorption behavior of SR-SMIMs. Hence, SR-SMIMs exhibited remarkable adsorption capacity of 40.69 mg·g-1 towards PSO in 25% methanol and can be efficiently desorbed with satisfactory efficiency in methanol. The molecular simulation and NMR analysis demonstrated that the recognition mechanism of SR-SMIMs was a synergistic effect of hydrogen bonding, π-π stacking and Van der Waals forces. Furthermore, the SR-SMIMs were effectively employed for the separation of PSO from Ficus carica L. leaves, exhibiting an impressive adsorption capacity of 20.51 mg·g-1 and a high elution recovery rate of 92.54%. This efficient and sustainable SR-SMIMs possessed promising potential for specific separation of target compound from complex natural plants extracts.

Exploring SEI Characteristics in Propylene Carbonate-Based Electrolyte with 2-Isocyanatoethyl Methacrylate at Graphite Electrode

Propylene carbonate (PC) has the advantage of a much lower melting point than ethylene carbonate (EC), but it cannot suppress the exfoliation of graphite layers because of its cointercalation with Li+ before forming a stable solid electrolyte interface (SEI). This paper introduces 2−isocyanatoethyl methacrylate (ICEMA) as an additive in PC−based electrolytes. ICEMA is a bifunctional monomer in which the isocyanate group is linked by the ethyl group to the acrylate group, which reacts through thermal polymerization. The isocyanate moiety is initiated as a radical during the initial charging process to induce electropolymerization and reaction with the PC radical. Radicals propagate through the entire reaction at the electrode to form a stable SEI. The modified interface suppresses the cointercalation of Li+−PC to graphite electrode. In situ Fourier transform infrared effectively showed the polymerization of the isocyanate and active reaction with the PC radical. Consequently, the reaction mechanisms to form the stable SEI in PC−based electrolytes were determined.

Enhanced Photothermal Property of NDI-Based Conjugated Polymers by Copolymerization with a Thiadiazolobenzotriazole Unit.

Solar steam generation (SSG) is a promising photothermal technology to solve the global water storage issue. The potential of π-conjugated polymers as photothermal materials is significant, because their absorption range can be customized through molecular design. In this study, naphthalenediimide (NDI) and thiadiazolobenzotriazole (TBZ) were employed as bifunctional monomers to produce conjugated polymers. There are two types of polymers, P1 and P2. P1 is based on NDI, while P2 is a copolymer of NDI and TBZ in a ratio of 9:1. Both polymers had high molecular weights and sufficient thermal stability. UV-vis-near-infrared (NIR) absorption spectra revealed that both polymers have large extinction coefficients ascribed to the NDI and TBZ chromophores. Notably, the absorption spectrum of P2 exhibited a significant red shift compared to P1, resulting in a narrow optical bandgap and absorption in the NIR range. This result suggested that P2 has a higher light absorption than P1. Photoluminescence (PL) spectra were measured to elucidate the conversion of the absorbed light into thermal energy. It was found that P2 has a reduced fluorescence quantum yield as a result of the TBZ unit, signifying a proficient conversion of the photothermal energy. Based on the results, it appears that the P2 film has a greater photothermal property compared to that of the P1 film. The surface temperature of the P2 film reached approximately 50 °C under the investigated conditions. In addition, copolymer P2 exhibited an impressive SSG efficiency of 72.4% under 1 sun (1000 W/m2) irradiation. All the results suggested that narrow bandgap conjugated polymers containing the TBZ unit are highly effective materials for achieving optimal performance in SSGs.

Development of hydroxypropyl cellulose and graphene oxide modified molecularly imprinted polymers for separation and enrichment of podophyllotoxin

A novel hydroxylpropyl cellulose (HPC) modified graphene oxide (GO)-based molecularly imprinted polymers (HPC-GO-MIP) have been developed as a solid phase extraction (SPE) material for the selective separation and extraction of podophyllotoxin. In this strategy, the cellulose with rich hydroxyl groups was introduced to form bi-functional monomers with methacrylic acid to provide more recognition sites for the improving of extraction efficiency, then GO was added as a two-dimensional substrate for MIP to improve the material morphology and surface area. The extraction performances of obtained HPC-GO-MIP material were tested, and the results prove its high efficiency and selectivity for podophyllotoxin extraction. The saturated adsorption capacity reached 23.1 μg/mg, and high enrichment efiiciency of 463.8 folds was realized under the premise of ensuring the recovery rate. The selective imprinting factor was much higher than those of kaempferol and quercetin, which were the main compounds in podophyllum fruit. Under the optimized SPE conditions, the HPC-GO-MIP based SPE-HPLC method showed the detection limit of 14.2 ng/mL for podophyllotoxin assay. When applied to podophyllum fruit samples, the material showed excellent ability of selective separation and enrichment of podophyllotoxin, and the relative standard deviations (RSD) of intra and inter batches were less than 8.1 % and 5.7 % in real samples detection. The HPC-GO-MIP SPE method broadened the application for high multiple extraction in trace analyte samples and provided a valuable solution to improve the selective separation and detection.

Multilayer, Broadband Infrared Reflectors Based on the Photoinduced Preparation of Cholesteric Liquid Crystal Polymers.

This paper focuses on preparing broadband reflective liquid crystal films through the diffusion of monofunctional and bifunctional monomers in a photoinduced trilayer system. By combining the hydrophilic and hydrophobic liquid crystal glass surface treatment technologies, the polymer network of polymer-stabilized cholesteric liquid crystal (PSCLC) itself serves as a diffusion channel to form a trilayer cholesteric liquid crystal composite system containing bifunctional monomers, a nematic liquid crystal composite system, and a cholesteric liquid crystal composite system containing monofunctional monomers. Utilizing the difference in the polymerization rates of monofunctional and difunctional polymerizable monomers, the monomers and chiral compounds diffuse relative to each other, so that the liquid crystal pitch exhibits a gradient distribution, and the broadened reflective width can reach up to 1570 nm. There is no doubt that new and improved processes and technologies offer important possibilities for preparing and applying PSCLC films.

High-Performance Supramolecular Organogel Adhesives for Antimicrobial Applications in Diverse Conditions.

Supramolecular organogel coatings that can disinfect the deposited microbial pathogens are emerging as an effective vehicle to prevent pathogen transmission. However, the development of anti-pathogen supramolecular adhesives with mechanical robustness and controlled oil inclusion is technically challenging. Here, we report supramolecular adhesives with mechanical integrity and robust interfacial adhesion over a wide range of biogenic antimicrobial oil. Bifunctional monomers are synthesized and assembled into linear polymers with semicrystalline stackings through hierarchical hydrogen bonds, where incorporated bioactive oil could regulate the semicrystalline stackings into nanosized crystalline domains through intermolecular hydrogen bonds. The abundant bonding motifs provided by the supramolecular cross-linked networks could accommodate oil molecules with high inclusion capability and provide more interfacial binding sites with high adhesion strength, and the nanosized crystalline domains could stabilize the organogel network and compensate for the interactions with oil molecules to enhance structural and mechanical stability. In addition, rapid healing, robust adhesion, and antimicrobial and antiviral properties of the resultant organogel coatings are demonstrated. This study paves the way for the development of high-performance antimicrobial supramolecular adhesives with controlled oil inclusion, showing potential applications in soft robotics, tissue engineering, and biomedical devices.

Controlled, supramolecular polymer formulation to engineer hydrogels with tunable mechanical and dynamic properties

AbstractNature uses combined covalent (chemical bonds) and non‐covalent (physical bonds) synthesis in a highly, controlled multi‐step fashion to create functional materials with different mechanical and dynamic properties out of similar building blocks. Surprisingly, this control in fully synthetic systems remains elusive, even though the effects of formulation pathways on the assembly processes have been emphasized—highlighting the importance of and relationship between energy landscapes and function in synthetic systems. Here, we control multiple, coherent supramolecular assembly processes (fiber formation and crosslinking) to formulate hydrogels with tunable mechanical and dynamic properties. Hydrogels are prepared via two different formulation methods using similar building blocks (monofunctional and bifunctional supramolecular monomers), including (1) the mixing of the supramolecular monomers under basic conditions (Fbasic) and (2) the mixing of the supramolecular monomers under neutral conditions (Fneutral). In Fbasic, network formation is induced via simultaneous fiber formation and crosslinking, yielding homogeneously mixed networks which are dense, stiff (~10 kPa) and robust. In Fneutral, network formation is induced through sequential fiber formation and crosslinking, yielding heterogenous, soft (~2 kPa) and dynamic networks. With these results, we advance towards the controlled, multistep, non‐covalent synthesis to create larger hierarchical, functional structures, similar to nature.