Flexible strain sensors have received tremendous attention because of their potential applications as wearable sensing devices.However, the integration of key functions into a single sensor, such as high stretchability, low hysteresis, self-adhesion, andexcellent antifreezing performance, remains an unmet challenge. In this respect, zwitterionic hydrogels have emerged asideal material candidates for breaking through the above dilemma. The mechanical properties of most reported zwitterionichydrogels, however, are relatively poor, significantly restricting their use under load-bearing conditions. Traditional improve-ment approaches often involve complex preparation processes, making large-scale production challenging. Additionally,zwitterionic hydrogels prepared with chemical crosslinkers are typically fragile and prone to irreversible deformation underlarge strains, resulting in the slow recovery of structure and function. To fundamentally enhance the mechanical properties ofpure zwitterionic hydrogels, the most effective approach is the regulation of the chemical structure of zwitterionic monomersthrough a targeted design strategy. This study employed a novel zwitterionic monomer carboxybetaine urethane acrylate(CBUTA), which contained one urethane group and one carboxybetaine group on its side chain. Through the direct polym-erization of ultrahigh concentration monomer solutions without adding any chemical crosslinker, we successfully developedpure zwitterionic supramolecular hydrogels with significantly enhanced mechanical properties, self-adhesive behavior, andantifreezing performance. Most importantly, the resultant zwitterionic hydrogels exhibited high tensile strength and tough-ness and displayed ultralow hysteresis under strain conditions up to 1100%. This outstanding performance was attributedto the unique liquid–liquid phase separation phenomenon induced by the ultrahigh concentration of CBUTA monomers inan aqueous solution, as well as the enhanced polymer chain entanglement and the strong hydrogen bon
Siyu BaoHongying WangBaocheng LiuChenhao HuangJingguo DengWenjie RenYongmao LiJianhai Yang
Hydrogen bonds(H-bonds)are the most essential non-covalent interactions in nature,playing a crucial role in stabilizing the secondary structures of proteins.Taking inspiration from nature,researchers have developed several multiple H-bonds crosslinked supramolecular polymer materials through the incorporation of H-bond side-chain units into the polymer chains.N-acryloyl glycinamide(NAGA)is a monomer with dual amides in the side group,which facilitates the formation of multiple dense intermolecular H-bonds within poly(N-acryloyl glycinamide)(PNAGA),thereby exhibiting diverse properties dependent on concentration and meeting various requirements across different applications.Moreover,numerous attempts have been undertaken to synthesize diverse NAGA-derived units through meticulous chemical structure regulation and fabricate corresponding H-bonding crosslinked supramolecular polymer materials.Despite this,the systematic clarification of the impact of chemical structures of side moieties on intermolecular associations and material performances remains lacking.The present review will focus on the design principle for synthesizing NAGA-derived H-bond side-chain units and provide an overview of the recent advancements in multiple H-bonds crosslinked PNAGA-derived supramolecular polymer materials,which can be categorized into three groups based on the chemical structure of H-bonds units:(1)monomers with solely cooperative H-bonds;(2)monomers with synergistic H-bonds and other physical interactions;and(3)diol chain extenders with cooperative H-bonds.The significance of subtle structural variations in these NAGA-derived units,enabling the fabrication of hydrogen-bonded supramolecular polymer materials with significantly diverse performances,will be emphasized.Moreover,the extensive applications of multiple H-bonds crosslinked supramolecular polymer materials will be elucidated.
The photothermal therapy(PTT) has come across as a promising noninvasive therapeutic strategy for tumor treatment. However, low photothermal conversion efficiency(PCE) and hydrophobicity may impede the therapeutic efficacy of organic photothermal agents and an efficient PTT-agent must overcome these two major challenges. In this work, we developed a new strategy to promote higher PCE wherein the intermolecular hydrogen-bonding interaction between the single dye molecule and water facilitated the transformation of the absorbed energy into the heat. A hydrophilic squaraine dye(SCy1) with the second near-infrared region(NIR-II) absorption and extremely low emission were designed to exhibit much higher PCE than that of the analogues of pentamethine-dyes(PCy1, PCy2). The presence of the ‘–O-' at middle of squaric cycle enabled the intermolecular H-bonding formation between the SCy1 and water to promote the energy dissipation channel. Moreover, the introduction of long-chain phenylsulfonate groups helped in to improve the water solubility apart from serving as an additional means of further enhancing PCE through fluorescence quenching. Therefore, SCy1 with a squaraine backbone and long-chain sulfonate moieties revealed outstanding photothermal stability and anti-aggregation activity apart from showing exceptionally high PCE(74%) in water. SCy1 demonstrated excellent therapeutic efficacy when applied in the PTT treatment of tumor-bearing mice under a laser irradiation of 915 nm.
Semi-interpenetrating(semi-IPN)hydrogels formed by the continuous interpenetration of cross-linked polymer network and linear non-crosslinked polymer with multifunctionality are widely used in biomedical and other fields.However,the negative impact of linear polymer on the homogeneity of the cross-linked network often leads to a decrease in the mechanical properties of semi-IPN hydrogels and severely limits their applications.Herein,a bioinspired hydrogen-bonding induced phase separation strategy is presented to construct the tough semi-IPN polyvinylpyrrolidone/polyacrylamide hydrogels(named PVP/PAM hydrogels),including the linear polymer polyvinylpyrrolidone(PVP)and cross-linked polyacrylamide(PAM)network.The resultant PVPx/PAM hydrogels exhibit unique phase separation induced by the hydrogenbonding between PVP and PAM and affected by the amount of substance of PVP.Meanwhile,the phase separation of PVPx/PAM hydrogels results in excellent mechanical properties with a strain of 2590%,tensile strength of 0.28 MPa and toughness of 2.17 MJ/m^(3).More importantly,the hydrogenbonding between PVP and PAM firstly disrupts to dissipate energy under external forces,so the PVPx/PAM hydrogels exhibit good self-recovery properties and outperform chemically cross-linked PAM hydrogels in impact resistance and damping applications.It is believed that the PVPx/PAM hydrogels with hydrogen-bonding induced phase separation possess more potential application prospects.
Thermoplastic polyurethane(PU)elastomers have attracted significant attention because of their many important industrial applications.However,the creation of fire-retardant and anti-dripping PU elastomers has remained a grant challenge due to the lack of crosslinking and weak interchain interactions.Herein,we report a mechanically robust,biodegradable,fire-retardant,and anti-dripping biobased PU elastomer with excellent biodegradability using an abietic acid-based compound as hard segments and polycaprolactone diol(PCL)as soft segments,followed by physically crosslinking with cellulose nanocrystals(CNC)through dynamic hydrogen-bonding.The resultant elastomer shows the balanced mechanical and fire-retardant properties,e.g.,a tensile strength and break strain of 9.1 MPa and 560%,a self-extinguishing ability(V-0 rating in UL-94 testing),and an anti-dripping behavior.Moreover,the as-developed PU can be completely degraded in 1.0 wt.%lipase solution at 37℃ in 60 days,arising from the catalytic and wicking effect of CNC on PU chains.This work provides an innovative and versatile strategy for constructing robust,fire-retardant,anti-dripping,and biodegradable PU elastomers,which hold great promise for practical applications in electronic and automobile sectors.
According to the Kamlet-Abraham-Taft(KAT)polarity parameters(α,β,π*),polymers and solvents can be categorized as hydrogen-bond(H-bond)acidic(α>β)or H-bond basic(α<β).Recently,we proposed a quantitative hydrogenbonding(QHB)analysis to predict the solubility of polymers in ionic liquids(ILs)using the product ofΔαΔβ<0 as an indicator,whereΔαis the difference between the H-bond acidic parameters of the polymer and IL,andΔβis the difference in their basicity,while the prerequisite of the“complementary”principle(i.e.,that one component is H-bond acidic and the other is basic)is satisfied.Here,the applicability of QHB analysis was first confirmed by testing the solubilities of carefully chosen polymer/deep eutectic solvent(DES)pairs,as the DESs were eutectic mixtures dominated by hydrogenbonding interactions.Then,our attention focused on the solubility of cellulose in DESs.Our testing results as well as the typical published results were summarized,which indicate that the potential DESs for cellulose dissolution and regeneration must be of the H-bond basic type because the“complementary”principle should be satisfied as a prerequisite.However,the H-bond basic DESs investigated in this study do not show the superior solubility of cellulose that has been commonly observed for H-bond basic ILs,even if the criterion ofΔαΔβ<0 is satisfied for both DESs and ILs.Possible reasons for this discrepancy are given to understand the varying effectiveness in cellulose dissolution for H-bond basic DESs and ILs.
Benzene is a volatile organic compound that can seriously harm human health,while it can serve as a precursor to produce chemicals of more complex structures in chemical industry.Capturing benzene using adsorbents is of great importance for human health,when the separation of hydrocarbons including benzene from crude oil was referred to as one of the“seven chemical separations to change the world”.In this work,we reported the efficient and selective separation of benzene from BTX and cyclohexane by hydrogenbonding self-assembly nonporous adaptive crystals AdaOH for the first time under mild and user-friendly conditions.Separation of benzene and cyclohexane(v/v=1:1)can be achieved by AdaOH with a purity of benzene up to 96.8%.Separation of BTX(v/v;benzene:toluene:o-xylene:m-xylene:pxylene=1:1:1:1:1)can be achieved by AdaOH with a purity of benzene increased from 20%to 82.9%.Our results suggest that separation of benzene using the activated AdaOH as a non-porous adaptive crystal for selectively and efficiently capturing benzene can solve the challenge in separation of benzene from other chemicals such as cyclohexane in chemical industry,and can be helpful for removal of benzene that is released from the vehicles to air.The advantages of commercially availability,easy preparation,high separation efficiency and selectivity for benzene might endow this material with enormous potential for practical uses in areas like petrochemical industry.
