Noncovalent Cross-linking Research Articles

Irreversible and Self-Healing Electrically Conductive Hydrogels Made of Bio-Based Polymers.

Electrically conductive materials that are fabricated based on natural polymers have seen significant interest in numerous applications, especially when advanced properties such as self-healing are introduced. In this article review, the hydrogels that are based on natural polymers containing electrically conductive medium were covered, while both irreversible and reversible cross-links are presented. Among the conductive media, a special focus was put on conductive polymers, such as polyaniline, polypyrrole, polyacetylene, and polythiophenes, which can be potentially synthesized from renewable resources. Preparation methods of the conductive irreversible hydrogels that are based on these conductive polymers were reported observing their electrical conductivity values by Siemens per centimeter (S/cm). Additionally, the self-healing systems that were already applied or applicable in electrically conductive hydrogels that are based on natural polymers were presented and classified based on non-covalent or covalent cross-links. The real-time healing, mechanical stability, and electrically conductive values were highlighted.

Strong and Tough PAm/SA Hydrogel with Highly Strain Sensitivity

The hydrogel is a preferred material for flexible wearable sensors. In practical application, it should have high-efficiency mechanical toughness and self-healing performance. Besides, hydrogel requires good affinity and adhesion because of its contact with the skin. In this experiment, we made an ultra-tough hydrogel with excellent cell affinity and adhesion. We used sodium alginate (SA) and polyacrylamide (PAm) mixture as a flexible base fluid. Polydopamine reduce graphene oxide (prGO) was used as conductive nanofiller, and then PAm-prGO-SA semi-interpenetrating network hydrogel was formed through Am radical polymerization. The presence of prGO endows the hydrogels with excellent electrical conductivity. Simultaneously, some non-reduced GO forms non-covalent cross-links with PAm, SA, and Polydopamine (PDA) in the hydrogel network. The stress of PAm-prGO-SA hydrogel can reach 750 KPa, and the strain is 900%. The hydrogel, combined with its excellent electrical, mechanical properties, and biocompatibility, is expected to be applied in portable, remote, and real-time health monitoring systems.

Tannic acid: a crosslinker leading to versatile functional polymeric networks: a review.

With the thriving of mussel-inspired polyphenol chemistry as well as the demand for low-cost analogues to polydopamine in adhesive design, tannic acid has gradually become a research focus because of its wide availability, health benefits and special chemical properties. As a natural building block, tannic acid could be used as a crosslinker either supramolecularly or chemically, ensuring versatile functional polymeric networks for various applications. Up to now, a systematic summary on tannic-acid-based networks has still been waiting for an update and outlook. In this review, the common features of tannic acid are summarized in detail, followed by the introduction of covalent and non-covalent crosslinking methods leading to various tannic-acid-based materials. Moreover, recent progress in the application of tannic acid composites is also summarized, including bone regeneration, skin adhesives, wound dressings, drug loading and photothermal conversion. Above all, we also provide further prospects concerning tannic-acid-crosslinked materials.

A hierarchical system of covalent and dual non-covalent crosslinks promotes the toughness and self-healing properties of polymer hydrogels.

While it is challenging to simultaneously achieve both high mechanical performance and self-healing ability within one polymer hydrogel network, we, herein, synthesized a novel class of hydrogels based on a combination of chemical and dual non-covalent crosslinks via micellar polymerization of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, end-capped by 2-hydroxyethyl methacrylate (IPDI-HEMA), with acrylamide (AM). The prepared hydrogels were demonstrated to possess a tensile elongation at a break of at least 1900%, a fracture energy of 138.4 kJ m-3, and remarkable self-healing behaviors (e.g., a strong self-healing ability achieved at ambient temperature without the need for any stimulus or healing agent). The multiple crosslinks developed in this study for one polymer hydrogel network are significant steps to construct the desired functional hydrogels with excellent self-healing and mechanical properties.

Hofmeister effects of anions on self-assembled thermogels

Thermogels are temperature-responsive soft biomaterials with numerous biomedical applications. They possess high water content and can spontaneously gelate by forming non-covalent physical crosslinks between their constituent amphiphilic polymers when warmed. However, despite the ubiquity of salts in biological fluids and buffer media, the influence of salts on thermogelling polymers and the overall physical properties of the resulting hydrogels are poorly understood. Herein, we elucidate the effects of common inorganic salts on the gelation and micellization properties of a thermogelling polymer containing poly(ethylene glycol), poly(propylene glycol), and poly(caprolactone) components. The identity of the salts' anions and their concentrations was found to exhibit significant effects on the thermogel properties, in some cases being able to decrease the sol-to-gel phase transition by up to 10 °C. We demonstrate that these notable influences are likely brought about by the changes in solvation of both the polymer's hydrophobic and hydrophilic segments, as well as by direct interactions of poorly hydrated anions with the hydrophobic polymer segments. Our findings show that the effects of salts on amphiphilic thermogelling polymers are non-negligible and hence need to be taken into account for engineering and optimization of thermogel properties for different biomedical applications.

Highly compressible glass-like supramolecular polymer networks.

Supramolecular polymer networks are non-covalently crosslinked soft materials that exhibit unique mechanical features such as self-healing, high toughness and stretchability. Previous studies have focused on optimizing such properties using fast-dissociative crosslinks (that is, for an aqueous system, dissociation rate constant kd > 10 s-1). Herein, we describe non-covalent crosslinkers with slow, tuneable dissociation kinetics (kd < 1 s-1) that enable high compressibility to supramolecular polymer networks. The resultant glass-like supramolecular networks have compressive strengths up to 100 MPa with no fracture, even when compressed at 93% strain over 12 cycles of compression and relaxation. Notably, these networks show a fast, room-temperature self-recovery (< 120 s), which may be useful for the design of high-performance soft materials. Retarding the dissociation kinetics of non-covalent crosslinks through structural control enables access of such glass-like supramolecular materials, holding substantial promise in applications including soft robotics, tissue engineering and wearable bioelectronics.

Super Strong and Tough Polybenzimidazole/Metal Ions Coordination Networks: Reinforcing Mechanism, Recyclability, and Anti-Counterfeiting Applications.

Nature has provided many delicate strategies for optimizing the structural characteristics of biological materials. One such strategy is the strengthening and toughening of matrix materials by aduandant and hierarchically arranged non-covalent crosslinking. However, efficient strengthening and toughening of high-performance aromatic polymers by non-covalent bonds has rarely been reported yet. Herein, we report the preparation and characterizations of a metal coordination bonds crosslinked polybenzimidazole (PBI) network. By optimizing the synthetic parameters, the strength of copper ion (Cu2+ ) crosslinked PBI is improved from 87.8 to 218.4MPa, and the toughness is increased from 19.4 to 111.9 MJ m-3 , corresponding to increments of 148.7 % and 476.8 %, respectively, which surpass all previously reported non-covalent bonds crosslinked high-performance polymers. PBI with varied chain flexibility are then synthesized to deeply understand the stregnening and toughening mechanism. In addition, the glass transition temperature of PBI is dramatically increased by 75 °C after Cu2+ crosslinking. Moreover, the chemical recycling of PBI from crosslinekd network, and the development of a novel high-temperature resistant or high-temperature rewritable anti-counterfeiting films based on Cu2+ crosslinked PBI are also demonstrated. This study is expected to shed light on design principle for future supramolecularly crosslinked and recyclable high-performance polymers.

H-bonds and metal-ligand coordination-enabled manufacture of palm oil-based thermoplastic elastomers by photocuring 3D printing

Thermoplastic elastomers exhibit high softness, stretchability, recoverability, and reprocessibility, but their manufacture requires high cost and long processing time. Photocuring 3D printing is a remedial processing method as it enables rapid fabrication at room temperature. However, it is difficult to print thermoplastic elastomers by photocuring 3D printing because the generated linear polymers easily dissolve in liquid precursors during printing. Herein, stretchable, self-healing, and renewable palm oil (PO)-based elastomers were prepared from UV-responsive vinyl PO monomers via photocuring 3D printing. Fast solid-liquid separation was achieved via hydrogen bonds and Zn 2+ -ligand coordination (non-covalent crosslinking) to slow down the dissolution of crosslinked polymers in the monomer liquid. The non-covalent bonds endowed the elastomers with high tensile strength (~4.2 MPa) and elongation at break (~851%). Additionally, the elastomers are mainly prepared from biobased, renewable, and low-cost PO feedstocks. Most importantly, the dual dynamic crosslinked network resulted in superior stress relaxation, shape programming, and self-healing behavior of the elastomers. The method described may enhance the application scope of thermoplastic elastomers and 3D printing. Highly stretchable, self-healable, and renewable palm oil (PO)-based thermoplastic elastomers were prepared from a UV curable vinyl PO monomer (POFA-EA) via photocuring 3D printing enabled by the construction of hydrogen bonds and Zn 2+ -ligand coordination. • Thermoplastic elastomers were prepared via simple and efficient photocuring 3D printing. • 3D-printing elastomers were preppared via fast solid-liquid separation by H- and metal-ligand coordination bonds. • The palm oil (PO)-based thermoplastic elastomers had excellent tensile stress (~4.2 MPa) and strain (~851%). • The PO-based thermoplastic elastomers had shape programming and self-healing behavior.

Tunable Anion Exchange Membrane Conductivity and Permselectivity via Non-Covalent, Hydrogen Bond Cross-Linking.

Ion exchange membranes (IEMs) are a key component of electrochemical processes that purify water, generate clean energy, and treat waste. Most conventional polymer IEMs are covalently cross-linked, which results in a challenging tradeoff relationship between two desirable properties─high permselectivity and high conductivity─in which one property cannot be changed without negatively affecting the other. In an attempt to overcome this limitation, in this work we synthesized a series of anion exchange membranes containing non-covalent cross-links formed by a hydrogen bond donor (methacrylic acid) and a hydrogen bond acceptor (dimethylacrylamide). We show that these monomers act synergistically to improve both membrane permselectivity and conductivity relative to a control membrane without non-covalent cross-links. Furthermore, we show that the hydrogen bond donor and acceptor loading can be used to tune permselectivity and conductivity relatively independently of one another, escaping the tradeoff observed in conventional membranes.

Design and Stability Improvement of Pectin-Based Red Blood Cell-Mimicking Microcapsules for Oxygen Therapeutics.

A pectin-oligochitosan microcapsule system has recently been developed for novel oxygen therapeutic design. To improve the stability of the pectin-oligochitosan microcapsules in physiological conditions, both covalent (glutaraldehyde) and noncovalent (Mn2+ and Ca2+) cross-linkers were tested. The chemistry and morphology of the microcapsules were studied using FTIR and SEM, respectively. Results showed that glutaraldehyde is an effective cross-linker, even at low concentrations and short incubation times, and the glutaraldehyde cross-linking does not negatively impact the morphology of the microcapsules. Moreover, it was confirmed that the hemoglobin could be retained within the microcapsules with a minimal release.

Polymeric materials reinforced by noncovalent aggregates of polymer chains

AbstractMechanical performances are among the most fundamental properties that dictate the applicability and durability of polymeric materials. Reinforcement of polymeric materials is eternally pursued to broaden the applications of polymers with light‐weight, low‐cost and easy‐processing advantages. Noncovalent aggregates of biomacromolecules have been found to play a significant role in the mechanical properties of many natural materials, such as the spider silk. Increasing numbers of reports have demonstrated that the in situ formed noncovalent aggregates of polymer chains in polymeric systems are highly effective for enhancing the mechanical properties of artificial polymeric materials, in terms of strength, stiffness, toughness, and/or elasticity. The in situ formed noncovalent aggregates act as additional crosslinking domains and well‐dispersed “hard” nanofillers in the polymer networks, significantly strengthening, stiffening and/or toughening the polymeric materials. Moreover, the noncovalent crosslinking of polymer chains favors the development of healable and recyclable polymeric materials, thanks to the reversible and dynamic properties of noncovalent bonds. This review provides an overview of the recent advances on the enhancement of the mechanical properties of different polymeric materials by the in situ formed noncovalent aggregates of polymer chains. It is expected to arouse inspirations for the development of novel polymeric materials with extraordinary mechanical performances and functionalities.

Independent and Synergistic Modulations of Viscoelasticity and Stiffness of Dynamically Cross-Linked Cell-Encapsulating ClickGels by Covalently Tethered Polymer Brushes

We report independent and synergistic modulations of the stiffness and viscoelasticity of ClickGels, formed by a combination of the bio-orthogonal covalent and dynamic noncovalent cross-linking, by covalently incorporating nonionic, zwitterionic, or anionic polymer brushes. Tethering nonionic and zwitterionic brushes at the cost of noncovalent cross-linking increased stiffness and slowed stress relaxation, respectively, without altering the other properties. Meanwhile, tethering anionic brushes significantly increased ClickGel stiffness, while also slowing its stress relaxation. ClickGels with faster stress relaxation, not reduced stiffness, promoted short-term (24 h) viability and YAP/TAZ nuclear localization of encapsulated bone marrow-derived stromal cells (BMSCs). In contrast, ClickGel stiffness, not viscoelasticity, inversely correlated to the short-term dehydrogenase activity of encapsulated BMSCs. This work highlights the role of the ionic state of polymer brushes in modulating the hydrogel elastic modulus and viscoelasticity and establishes the brush-modified ClickGel as a facile and reproducible tool for manipulating mechanical cues of the synthetic cellular niche.

Water-Soluble Supramolecular Polymers of Paired and Stacked Heterocycles: Assembly, Structure, Properties, and a Possible Path to Pre-RNA.

The hypothesis that RNA and DNA are products of chemical and biological evolution has motivated our search for alternative nucleic acids that may have come earlier in the emergence of life-polymers that possess a proclivity for covalent and non-covalent self-assembly not exhibited by RNA. Our investigations have revealed a small set of candidate ancestral nucleobases that self-assemble into hexameric rosettes that stack in water to form long, twisted, rigid supramolecular polymers. These structures exhibit properties that provide robust solutions to long-standing problems that have stymied the search for a prebiotic synthesis of nucleic acids. Moreover, their examination by experimental and computational methods provides insight into the chemical and physical principles that govern a particular class of water-soluble one-dimensional supramolecular polymers. In addition to efficient self-assembly, their lengths and polydispersity are modulated by a wide variety of positively charged, planar compounds; their assembly and disassembly are controlled over an exceedingly narrow pH range; they exhibit spontaneous breaking of symmetry; and homochirality emerges through non-covalent cross-linking during hydrogel formation. Some of these candidate ancestral nucleobases spontaneously form glycosidic bonds with ribose and other sugars, and, most significantly, functionalized forms of these heterocycles form supramolecular structures and covalent polymers under plausibly prebiotic conditions. This Perspective recounts a journey of discovery that continues to reveal attractive answers to questions concerning the origins of life and to uncover the principles that control the structure and properties of water-soluble supramolecular polymers.

Supramolecular Click Product Interactions Induce Dynamic Stiffening of Extracellular Matrix-Mimetic Hydrogels.

Progressive stiffening of the extracellular matrix (ECM) is observed in tissue development as well as in pathologies such as cancer, cardiovascular disease, and fibrotic disease. However, methods to recapitulate this phenomenon in vitro face critical limitations. Here, we present a poly(ethylene glycol)-based peptide-functionalized ECM-mimetic hydrogel platform capable of facile, user-controlled dynamic stiffening. This platform leverages supramolecular interactions between inverse-electron demand Diels-Alder tetrazine-norbornene click products (TNCP) to create pendant moieties that undergo non-covalent crosslinking, stiffening a pre-existing network formed via thiol-ene click chemistry over the course of 6 h. Pendant TNCP moieties have a concentration-dependent effect on gel stiffness while still being cytocompatible and permissive of cell-mediated gel degradation. The robustness of this approach as well as its simplicity and ease of translation give it broad potential utility.

High-Strength Hydrogel Adhesive Formed via Multiple Interactions for Persistent Adhesion under Saline.

Hydrogel adhesives have been widely used in wet environments. Nonetheless, strong and stable persistent adhesion remains a challenge. Here, we report a facile yet powerful strategy to construct high-strength hydrogel adhesives for durable adhesion in a saline environment. Such a hydrogel consists of two polymer networks: a hydrophobic-associated polyacrylamide network of covalent and noncovalent cross-links and an alginate network cross-linked by divalent cations in saline. Meanwhile, polydopamine nanoparticles formed through in-situ self-polymerization are distributed evenly throughout the system to provide underwater adhesion. A low and controllable swelling rate and high compressive strength of hydrogels can be achieved via this multiple interaction strategy. Ultimately, this strategy contributes to the persistent underwater adhesion of hydrogels, and the decreasing rate of lap-shear adhesion strength of hydrogels is only 24.79 ± 8.01% after saline immersion for up to 21 days. Moreover, good cytocompatibility of hydrogels is helpful for their application in the biomedical field.

Environmentally Stable Chiral-Nematic Liquid-Crystal Elastomers with Mechano-Optical Properties

Chiral-nematic liquid crystal (N* LC) elastomers exhibit mechano-optical responsive behavior. However, practical sensor applications have been limited by the intrinsic sensitivity of N* LC elastomers to environmental conditions, such as temperature. Although densely cross-linked LC network polymers exhibit high thermal stability, they are not proper for the mechanical sensor due to high glass transition temperatures and low flexibility. To overcome these issues, we focused on enhancing thermal stability by introducing noncovalent cross-linking sites via intermolecular interactions between LC molecules bonded to the polymer network. N* LC elastomers with a cyanobiphenyl derivative as a side-chain mesogen exhibited mechano-optical responsive behavior, with a hypsochromic shift of the reflection peak wavelength under an applied tensile strain and quick shape and color recovery owing to high elasticity. Notably, the N* LC elastomers showed high resistance to harsh environments, including high temperatures and various solvents. Interactions, such as π–π stacking and dipole–dipole interactions, between the cyanobiphenyl units can act as weak cross-links, thus improving the thermal stability of the LC phase without affecting the mechano-optical response. Thus, these N* LC elastomers have great potential for the realization of practical mechano-optical sensors.

Enhanced physical and antimicrobial properties of alginate/chitosan composite aerogels based on electrostatic interactions and noncovalent crosslinking

In this study, the alginate/chitosan composite aerogels based on electrostatic interactions and noncovalent crosslinking were fabricated using sol-gel method followed by freeze-drying process. The solution property results showed that with the addition of chitosan in alginate solution, a tighter network was induced by the more entangled molecular chains. The aerogel morphology observations showed that the pore diameter decreased with the increasing weight ratio of chitosan in the aerogels, but was even much lower after the crosslinking of excess alginate with calcium ions. After crosslinking, the aerogels presented the improved thermal stability and higher mechanical properties, as well as stronger antibacterial activities against Staphylococcus aureus and Escherichia coli. Therefore, the enhanced physical and antimicrobial properties of the alginate/chitosan aerogels may be achieved by modulation of electrostatic interactions and noncovalent crosslinking, suggesting the promising applications of these composite aerogels as active food packaging materials for antimicrobial purpose.

Protein-Based 3D Biofabrication of Biomaterials.

Protein/peptide-based hydrogel biomaterial inks with the ability to incorporate various cells and mimic the extracellular matrix’s function are promising candidates for 3D printing and biomaterials engineering. This is because proteins contain multiple functional groups as reactive sites for enzymatic, chemical modification or physical gelation or cross-linking, which is essential for the filament formation and printing processes in general. The primary mechanism in the protein gelation process is the unfolding of its native structure and its aggregation into a gel network. This network is then stabilized through both noncovalent and covalent cross-link. Diverse proteins and polypeptides can be obtained from humans, animals, or plants or can be synthetically engineered. In this review, we describe the major proteins that have been used for 3D printing, highlight their physicochemical properties in relation to 3D printing and their various tissue engineering application are discussed.

Molecular Recognition: Perspective and a New Approach.

This perspective presents an overview of approaches to the preparation of molecular recognition agents for chemical sensing. These approaches include chemical synthesis, using catalysts from biological systems, partitioning, aptamers, antibodies and molecularly imprinted polymers. The latter three approaches are general in that they can be applied with a large number of analytes, both proteins and smaller molecules like drugs and hormones. Aptamers and antibodies bind analytes rapidly while molecularly imprinted polymers bind much more slowly. Most molecularly imprinted polymers, formed by polymerizing in the presence of a template, contain a high level of covalent crosslinker that causes the polymer to form a separate phase. This results in a material that is rigid with low affinity for analyte and slow binding kinetics. Our approach to templating is to use predominantly or exclusively noncovalent crosslinks. This results in soluble templated polymers that bind analyte rapidly with high affinity. The biggest challenge of this approach is that the chains are tangled when the templated polymer is dissolved in water, blocking access to binding sites.

Systematic Modification of the Glass Transition Temperature of Ion-Pair Comonomer Based Polyelectrolytes and Ionomers by Copolymerization with a Chemically Similar Cationic Monomer.

Ion-pair comonomers (IPCs) where both the anion and cation contain polymerizable functional groups offer a route to prepare polyampholyte, ion-containing polymers. Polymerizing vinyl functional groups by free-radical polymerization produces bridging ion-pairs that act as non-covalent crosslinks between backbone segments. In particular the homopolymerization of the IPC vinyl benzyl tri-n-octylphosphonium styrene sulfonate produces a stiff, glassy polymer with a glass transition temperature (Tg) of 191 °C, while copolymerization with a non-ionic acrylate produces microphase separates ionomers with ion-rich and ion-poor domains. This work investigates the tuning of the Tg of the polyelectrolyte or ion-rich domains of the ionomers by copolymerizing with vinyl benzyl tri-n-octylphosphonium p-toluene sulfonic acid. This chemically similar repeat unit with pendant rather than bridging ion-pairs lowers the Tg compared to the polyelectrolyte or ionomer containing only the IPC segments. Rheological measurements were used to characterize the thermomechanical behavior and Tg of different copolymers. The Tg variation in the polyelectrolyte vs. weight fraction IPC could be fit with either the Gordon–Taylor or Couchman–Karasz equation. Copolymerization of IPC with a chemically similar cationic monomer offers a viable route to systematically vary the Tg of the resulting polymers useful for tailoring the material properties in applications such as elastomers or shape memory polymers.