External Stimuli-Induced Welding of Dynamic Cross-Linked Polymer Networks.

Thermosets have been crucial in modern engineering for decades, finding applications in various industries. Welding cross-linked components are essential in the processing of thermosets for repairing damaged areas or fabricating complex structures. However, the inherent insolubility and infusibility of thermoset materials, attributed to their three-dimensional network structure, pose challenges to welding development. Incorporating dynamic chemical bonds into highly cross-linked networks bridges the gap between thermosets and thermoplastics presenting a promising avenue for innovative welding techniques. External stimuli, including thermal, light, solvent, pH, electric, and magnetic fields, induce dynamic bonds' breakage and reformation, rendering the cross-linked network malleable. This plasticity facilitates the seamless linkage of two parts to an integral whole, attracting significant attention for potential applications in soft actuators, smart devices, solid batteries, and more. This review provides a comprehensive overview of dynamic bonds employed in welding dynamic cross-linked networks (DCNs). It extensively discusses the classification and fabrication of common epoxy DCNs and acrylate DCNs. Notably, recent advancements in welding processes based on DCNs under external stimuli are detailed, focusing on the welding dynamics among covalent adaptable networks (CANs).

A pH-responsive, injectable and self-healing chitosan-coumarin hydrogel based on Schiff base and hydrogen bonds.

Smart hydrogels have shown great potential applications in disease treatment due to their controlled and local drug-release ability. Herein, a smart hydrogel with pH-responsive, injectable, and self-healing properties for controlled release of taxifolin (TFL) was prepared by freezing-thawing and photo-crosslinking methods. The crosslinking network of hydrogels (CS-CA hydrogels) was constructed by the hydrogen bonds, Schiff base bonds, and cyclobutane rings using chitosan (CS) and coumarin (CA) as raw materials. The CS-CA hydrogel demonstrated a compressive strength of 1.04 MPa, a self-healing efficiency of 99.9 %, and could maintain structural and functional integrity after injection. In addition, the drug release rate and shape of the CS-CA hydrogels were tunable due to its pH sensitivity. The TFL cumulative release reached 60 % within 12 h at pH = 4, and after equilibration, the cumulative release of TFL at pH = 4 (80 %) was significantly higher than at pH = 9.2 (50 %). The CCK8 experiment showed that the resulting hydrogel had no cytotoxicity. Meanwhile, subcutaneous implantation experiments in mice showed that the CS-CA hydrogels had favorable biodegradability and compatibility.

Reversible Complexation Mediated Living Radical Polymerization Using Tetraalkylammonium Chloride Catalysts.

This work reports the first use of organic chloride salts as catalysts for reversible complexation mediated living radical polymerization. Owing to the strong halogen-bond forming ability of Cl- , the studied four tetraalkylammonium chloride catalysts (R4 N+ Cl- ) successfully control the polymerizations of methyl methacrylate, yielding polymers with low dispersities up to high monomer conversion (>90%). Benzyldodecyldimethylammonium chloride is further exploited to other methacrylates and yields low-dispersity block copolymers. The advantages of the chloride salt catalysts are wide monomer scope, good livingness, accessibility to block copolymers, and good solubility in organic media. Because of the good solubility, the use of the chloride salt catalysts can prevent agglomeration of catalysts on reactor walls in organic media, which is an industrially attractive feature. Among halide anions, chloride anion is the most abundant and least expensive halide anion, and therefore, the use of the chloride salt catalysts may lower the cost of the polymerization.

Author Correction: Straightforward preparation of supramolecular Janus nanorods by hydrogen bonding of end-functionalized polymers.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Straightforward preparation of supramolecular Janus nanorods by hydrogen bonding of end-functionalized polymers.

Janus cylinders are one-dimensional colloids that have two faces with different compositions and functionalities, and are useful as building blocks for advanced functional materials. Such anisotropic objects are difficult to prepare with nanometric dimensions. Here we describe a robust and versatile strategy to form micrometer long Janus nanorods with diameters in the 10-nanometer range, by self-assembly in water of end-functionalized polymers. The Janus topology is not a result of the phase segregation of incompatible polymer arms, but is driven by the interactions between unsymmetrical and complementary hydrogen bonded stickers. Therefore, even compatible polymers can be used to form these Janus objects. In fact, any polymers should qualify, as long as they do not prevent co-assembly of the stickers. To illustrate their applicative potential, we show that these Janus nanorods can efficiently stabilize oil-in-water emulsions.

Oligo-Urea with No Alkylene Unit Self-Assembles into Rod-Like Objects in Water.

Long and rigid objects formed by self-assembly in water are useful as templates or for their rheological or biological properties. They are usually obtained by combining hydrogen bonding and strong hydrophobic interactions brought by an alkyl or alkylene chain. A simple access to well-defined rod-like assemblies in water is reported based on a penta-urea sticker directly connected to poly(ethylene oxide) side chains. These assemblies are characterized by an average length of several hundreds of nanometers and a monodisperse radius (4.5 nm) resulting from a reduced lateral aggregation of the stickers.

Janus POSS Based on Mixed [2:6] Octakis-Adduct Regioisomers.

A series of regioisomeric Janus-type polyhedral oligomeric silsesquioxanes (POSS) with multiple, mixed surface functional groups has been successfully synthesized based on the cubic T8 -POSS framework in two consecutive thiol-ene reactions. The first thiol-ene addition of ß-mercaptoethanol leads to a statistical mixture of multi-adducts where the regioisomers of bis-adducts (ortho, meta, and para isomers) can be isolated at synthetically useful quantities by flash column chromatography. Then, the second thiol-ene reaction readily installs a variety of functional groups onto the remaining vinyl groups of each regioisomer, providing an easy access to precisely defined, hetero-bifunctional Janus POSS nano-building blocks. The configurations and structures of the products have been unambiguously proven by using (1) H, (13) C, and (29) Si NMR spectroscopy as well as MALDI-TOF mass spectrometry.

Stochastic/Controlled Symmetry Breaking of the T8 -POSS Cages toward Multifunctional Regioisomeric Nanobuilding Blocks.

Precise synthesis of nanobuilding blocks with accurately positioned functional groups presents a daunting challenge. Herein, a practical synthesis and thorough characterization of a series of T8 -polyhedral oligomeric silsesquioxane (POSS) di- and triadducts is reported. Upon addition of triflic acid across the double bonds in octavinylPOSS (V8 T8 ) followed by hydrolysis, the cubic symmetry of the T8 -POSS cage (Oh ) is broken into C2v (ortho-), C2v (meta-), and D3d (para-) for diadducts and further to Cs (oom-), Cs (omp-), and C3v (mmm-) for triadducts in a stochastic fashion. Their structures and regioconfigurations have been unambiguously demonstrated by (1) H, (13) C, and (29) Si NMR spectroscopy, as well as MALDI-TOF mass spectrometry. The assignment of the diadducts was further corroborated by converting each individual diadduct into triadduct(s), the structure of which is controlled by the symmetry of the precursor. Except for the C3v triadduct, they can all be prepared in synthetically useful quantities. The presence of two types of highly reactive and mutually orthogonal functional groups facilitates further modification into complex nanostructures and composite materials. These unique regioisomers provide a versatile platform for constructing giant molecules and Janus silsesquioxanes.

Hydrogen bond and proton transport in acid-base complexes and amphoteric molecules by density functional theory calculations and 1H and 31P nuclear magnetic resonance spectroscopy.

Intermolecular and intramolecular hydrogen bond (H-bond) and proton transport in acid-base complexes and amphoteric molecules consisting of phosphonic acid groups and nitrogenous heterocyclic rings are investigated by density functional theory calculations and (1)H NMR and (31)P NMR spectroscopy. It is concluded that a phosphonic acid group can act both as H-bond donor and H-bond acceptor, while an imine nitrogen atom can only act as H-bond acceptor and an amine group as H-bond donor. And the intramolecular H-bond is weaker than the intermolecular H-bond attributing to configurational restriction. In addition, the strongest H-bond interaction is observed between a phosphonic acid and a 1H-indazole because of the formation of double H-bonds. The (1)H NMR and (31)P NMR chemical shifts for the acid-base complexes are consistent with the density functional theory calculations. From the (1)H NMR chemical shifts, fast proton exchange is observed between a phosphonic acid and 1H-benzimidazole or 1H-indazole. Finally, it is proposed that polymeric material tethered with 1H-benzimidazole or 1H-indazole rings is a favorable component for high-temperature proton exchange membranes based on acid-base complexes or acid-base amphoteric molecules.

Proton transport pathways in an acid-base complex consisting of a phosphonic acid group and a 1,2,3-triazolyl group.

The proton transport pathways in an acid-base complex consisting of a phosphonic acid group and a 1,2,3-triazolyl group were studied using density functional theory (DFT) calculations in terms of stable configurations and transition states of the molecular or ionic dimers and trimers and verified by proof-of-concept experiments including experimental measurements of overall conductivity and (1)H NMR and FTIR spectroscopy of the methylphosphonic acid (MPA) and 1,2,3-triazole (Tri) complex as well as overall proton conductivity of polymeric blend of poly(vinylphosphonic acid) (PVPA) and poly(4-vinyl-1H-1,2,3-triazole) (PVTri). From the DFT calculations of dimers and trimers composed of ethylphosphonic acid (EPA), Tri, and their deprotonated counterparts, it was concluded that the intermolecular hydrogen bonds of the transition states corresponding to proton transport are much shorter than those of stable configurations, but the O-H and N-H bonds are much longer than those of stable configurations. The tautomerization activation energy decreases from 0.927-1.176 eV in Tri-Tri dimers to 0.336-0.444 eV in the EPA-Tri dimers. From the proof-of-concept experiments, about a 50 fold increase in overall conductivity was observed in the MPA-Tri complex consisting of 10% (molar ratio) MPA compared to pure Tri, and the calculated activation energy is consistent with the experimental activation energy evaluated from temperature dependence of proton conductivity of pure Tri and the MPA-Tri complex. In addition, the fast proton exchange between MPA and Tri, consistent with the DFT calculations, was verified by (1)H NMR and FTIR spectroscopy. Finally, a polymeric blend of PVPA and PVTri was prepared, and its proton conductivity at about 2.1 mS·cm(-1) in anhydrous state at 100 °C was observed to be significantly higher than that of PVPA or of poly(VPA-co-1-vinyl-1,2,4-triazole). The proton conductivity of the polymeric PVPA and PVTri blend in humidity state is in the same range as that of NAFION 117.