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ACS Applied Materials & Interfaces · 2020 · IF 8.758

An Antifreezing/Antiheating Hydrogel Containing Catechol Derivative Urushiol for Strong Wet Adhesion to Various Substrates

Xianmou Fan,Weikang Zhou,Yiming Chen,Liyu Yan,Yan Fang,Haiqing Liu

Tough adhesive hydrogels that can tightly bond to wet tissue/polymer/ceramic/metal surfaces have great potentials in various fields. However, conventional adhesive hydrogels usually show short-term and nonreversible adhesion ability, as the water component in a hydrogel readily transforms to vapor or ice in response to fluctuation of environment temperature, hindering their applications in extreme conditions such as in freezing Arctic and roasting Africa. For the first time, urushiol (UH), a natural catechol derivative with a long alkyl side chain, is used as a starting material to copolymerize with acrylamide for fabricating adhesive hydrogels, which contain hydrophobic/hydrophilic moieties, antifreezing agent, and adhesive catechol groups. The antifreezer/moisturizer glycerol/water binary solvent dispersed in the hydrogel endows it with antifreezing/antiheating property. The hydrophobic association and π–π interaction from UH moieties of the copolymer greatly improve its mechanical strength (tensile stress: ∼0.12 MPa with strain of ∼1100%, toughness: ∼72 kJ/m3, compression stress: ∼6.72 MPa at strain of 90%). The hydrogel can strongly adhere to various dry/wet biological/polymeric/ceramic/metallic substrates at temperatures ranging from −45 to 50 °C. Under ambient conditions, its adhesion force to porcine skin, glass, and tinplate may reach up to 160, 425, and 275 N/m, respectively. Even stored at −45 or 50 °C for 30 d, the hydrogel still maintains good flexibility and robust adhesion force. It also shows repeatable underwater adhesion to biological tissue, glass, ceramic, plastic, and rubber. This novel antifreezing/antiheating adhesive hydrogel may be applied in extremely cold or hot environments and in underwater conditions.

研究领域: 材料科学 · 生物医学工程
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

Analysis of NADES and its water tailoring effects constructed from inulin and L-proline based on structure, physicochemical and antifreeze properties

Kairong Wu,Hao Zhang,Xinjiang Lou,Xiaodan Wu,Ying Wang,Kuangyu Zhao,Xin Du,Xiufang Xia

The structure, physicochemical and anti-freeze properties of natural deep eutectic solvent (NADES) composed of inulin and L-proline (molar ratio of 1:11) were investigated. Proton nuclear magnetic resonance ( 1 H NMR), Fourier infrared spectroscopy (FTIR), and Raman spectroscopy revealed extensive hydrogen bonding in the pure NADES system, and the addition of water weakens the hydrogen bonding interactions between the components. The smaller transverse relaxation time ( T 2 ) represents the stronger hydrogen bond strength, and NADES+40 % H 2 O exhibited a large T 2 (71.68 ms). When 10 % water was added, the viscosity decreased from 3620 mPa·s to 1777 mPa·s, but the conductivity increased to approximately twice the original value. Furthermore, adding 10 % water lowered the glass transition temperature (T g ) of NADES by 5.6 °C. NADES+10 % H 2 O exhibited favorable thermal stability and freezing resistance, as evidenced by the fact that approximately 82.61 % of the ice crystals area <200 μm 2 after 30 min of crystallization . The changes in the structure, physicochemical, and anti-freezing properties of water-tailored NADES are expected to enable the design of novel antifreeze agents.

CAS / MDL: 147-85-3
研究领域: 食品科学 · 物理化学
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Self-powered, frost-resistant, and antimicrobial hydrogel with high open-circuit voltage for flexible device energy supply and stimuli feedback

Jing Yang,Yi Yang,Shijie Zeng,Yueyue Jiang,Chunwen Guo,Yasheng Li,Jiabin Li,Xu Xiang

Self-powered hydrogels have gained attention for addressing energy needs of small flexible devices, but creating ones with high voltage and current remains challenging. Here, we report a novel polyacrylamide hydrogel loaded with copper sulfate and ammonium chloride (PAC), which not only exhibits good mechanical properties (maximum strain of 390 %), high conductivity (conductivity of 2.37 S/m), but also possesses excellent antibacterial and antifreeze properties. PAC demonstrates remarkable stimulus responsiveness. When using resistance variation as the output signal, its GF value reaches as high as 5.3 within the strain range of 35 % to 280 %. Additionally, PAC can utilize current variation as an output signal, providing options for various sensor applications. On the other hand, PAC hydrogels can achieve self-powering capabilities through zinc electrodes, with an open-circuit voltage of 0.92 V. By connecting PAC hydrogels in parallel or series, higher output voltage and current can be achieved, providing a strong guarantee for powering small devices. In a stacked series configuration, 8 sets of PACs can generate an output voltage of 7.16 V and an output current of 52.6 mA. In sum, PAC is a high-performance self-powered hydrogel with tremendous potential in the fields of flexible sensing and energy supply.

CAS / MDL: 79-06-1
研究领域: 材料科学 · 生物医学工程
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ACS Applied Polymer Materials · 2025 · IF 4.7

Phytic Acid-Enhanced Superstretched, Self-Adhesive, Antifreeze Conductive Hydrogels for Motion Monitoring and Human–Computer Interaction

Yuerui Li,Min Guo,Yifei Gao,Chunxia Zhao,Jialin Liao,Yuxing Li,Jinbo Cheng,Hui Li,Dong Xiang,Haoran Huang,Yuanpeng Wu

Hydrogels have become an important material in the field of wearable flexible electronics owing to their excellent flexibility and adjustable conductivity. However, due to the large amount of free water contained within the hydrogel, it freezes in low-temperature environments, resulting in poor conductivity and mechanical properties. In this study, an ionically conductive hydrogel was developed by introducing phytic acid (PA), a biomass-based antifreezing material. The addition of PA improved the mechanical, adhesion, and electrical properties, as well as the frost resistance of the hydrogel. The PAM/PVA0.15/Gelatin0.02/PA4 hydrogel prepared in this study exhibited an ultrahigh tensile strain (3083%), excellent adhesion (with adhesion strength to pig skin up to 448.45 kPa), and high conductivity (10.07 S m–1). At the same time, PA endowed the hydrogel with good frost resistance and long-term environmental stability. The hydrogel could remain soft even at −20 °C, as well as retain good electrical properties. In addition, an integrated hydrogel sensor exhibited a wide strain response range (1–1000%), excellent stability, and high sensitivity. Moreover, hydrogel sensors were also successfully used for motion and pipeline flow rate monitoring, as well as simple human–computer interaction applications.

研究领域: 材料科学 · 生物医学工程
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Journal of Materials Chemistry A · 2020 ·Vol. 8 ·期 18 ·9373-9381 · IF 11.301

Fish-inspired anti-icing hydrogel sensors with low-temperature adhesion and toughness

Jiajun Xu,Rining Jing,Xiuyan Ren,Guanghui Gao

Breaking through the conventional way of conferring anti-icing ability on hydrogels with addition of organic solvents or inorganic salts, here a novel anti-icing hydrogel with toughness, adhesiveness and high transparency was successfully fabricated by introducing antifreeze protein (AFPS, inspired by fish) into a chemical crosslinking network copolymerized with acrylamide and 2-acrylamide-2-methylpropanesulfonic acid. The hydrogel exhibited surprising stretchability (up to 2400% tensile strain), high transparency (over 90% transmittance) and outstanding reversible adhesive performance bonding to different materials and even human skin. Meanwhile, the inhibition of ice crystal growth based on AFPS molecules also conferred anti-icing ability on the hydrogels, so that the toughness and adhesiveness of the hydrogels remained stable at −10 °C. Additionally, the existence of sulfonic groups also endowed the hydrogels with deformation sensitivity to act as strain or pressure sensors to accurately monitor human motions and even subtle physiological signals. Therefore, the novel anti-icing strategy would provide new insight for a new generation of hydrogel sensors.

研究领域: 材料科学 · 生物医学工程 · 高分子化学
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Gels · 2022 ·Vol. 8 ·期 6 ·374 · IF 4.432

Smart Antifreeze Hydrogels with Abundant Hydrogen Bonding for Conductive Flexible Sensors

Bailin Dai,Ting Cui,Yue Xu,Shaoji Wu,Youwei Li,Wu Wang,Sihua Liu,Jianxin Tang,Li Tang

Recently, flexible sensors based on conductive hydrogels have been widely used in human health monitoring, human movement detection and soft robotics due to their excellent flexibility, high water content, good biocompatibility. However, traditional conductive hydrogels tend to freeze and lose their flexibility at low temperature, which greatly limits their application in a low temperature environment. Herein, according to the mechanism that multi−hydrogen bonds can inhibit ice crystal formation by forming hydrogen bonds with water molecules, we used butanediol (BD) and N−hydroxyethyl acrylamide (HEAA) monomer with a multi−hydrogen bond structure to construct LiCl/p(HEAA−co−BD) conductive hydrogel with antifreeze property. The results indicated that the prepared LiCl/p(HEAA−co−BD) conductive hydrogel showed excellent antifreeze property with a low freeze point of −85.6 °C. Therefore, even at −40 °C, the hydrogel can still stretch up to 400% with a tensile stress of ~450 KPa. Moreover, the hydrogel exhibited repeatable adhesion property (~30 KPa), which was attributed to the existence of multiple hydrogen bonds. Furthermore, a simple flexible sensor was fabricated by using LiCl/p(HEAA−co−BD) conductive hydrogel to detect compression and stretching responses. The sensor had excellent sensitivity and could monitor human body movement.Keywords:intelligent gel;antifreeze conductive hydrogel;flexible sensor

CAS / MDL: 106797-53-9 110-26-9
研究领域: 材料科学 · 生物医学工程 · 软体机器人
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ACS Applied Materials & Interfaces · 2024 · IF 8.3

Antifreezing, Antidrying, and Conductive Hydrogels for Electronic Skin Applications at Ultralow Temperatures

Qiuyan Quan,Tianyu Zhao,Zhuo Luo,Bai-Xue Li,Hao Sun,Hao-Yu Zhao,Zhong-Zhen Yu,Dongzhi Yang

Although conductive hydrogel-based flexible electronic devices have superb flexibility and high conductivities, they tend to malfunction in dry or frigid areas. Herein, an ultralow-temperature tolerant, antidrying, and conductive composite hydrogel is designed for electronic skin applications on the basis of the synergy of double-cross-linked polymer networks, Hofmeister effect, and electrostatic interaction and fabricated by in situ free radical polymerization of 2-acrylamido-2-methyl-1-propanesulfonic acid and acrylic acid in the presence of poly(vinyl alcohol) and conductive MXene sheets, followed by impregnation with LiCl. Thanks to the synergy of LiCl and the charged polar terminal groups of the synthesized polymers, the composite hydrogel can not only bear an ultralow temperature of −80 °C without freezing but also maintain its original mass. Meanwhile, the resultant hydrogel possesses satisfactory self-regeneration ability benefiting from the moisturizing effect of LiCl. The conductive network of MXene sheets greatly improves the ionic conductivity of the hydrogel at low temperatures, exhibiting an ionic conductivity of 1.4 S m–1 at −80 °C. Furthermore, the electronic skin assembled by the multifunctional hydrogel is efficient in monitoring human motions at −80 °C. The antifreezing and antidrying features along with favorable ionic conductivity, high tensile strength, and outstanding flexibility make the composite hydrogel promising for applications in frigid and dry regions.

研究领域: 材料科学 · 生物医学工程
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

Environmentally stable, Adhesive, Self-healing, Stretchable and Transparent Gelatin based Eutectogels for Self-Powered Humidity Sensors

Lina Xu,Xiaomeng Li,Jianliang Gao,Manqing Yan,Qiyang Wang

Intrinsic environmental and stability limitations of hydrogels have inhibited their practical applications as a flexible wearable device due to water evaporation or freezing in complex environments such as low temperatures and arid environments. In this work, a multifunctional gelatin based ionic conductive eutectogel with double network structure is designed via ternary deep eutectic solvent (DES) (acrylic acid (AA), choline chloride (ChCl) and ethylene glycol (EG)). In this system, the introduction of ethylene glycol (EG) can be used to dissolve gelatin. The resulting DESG eutectogel exhibited excellent adhesion, mechanical robustness, anti-freeze, anti-drying, and self-healing. Interestingly, the DESG gels showed high humidity sensitivity in a wide humidity detection range (11 %–83 %), which can be assembled as a self-powdered humidity sensor to monitor human mouth and nose breathing. This work is expected to bring new prospect to construct high performance humidity sensors using gelatin based humidity-responsive materials for a wide range of potential applications in respiratory diagnostics, sleep monitoring, electronic skin and wearable electronics.

研究领域: 材料科学 · 生物医学工程 · 传感技术
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Journal of Materials Chemistry C · 2019 ·Vol. 8 ·期 7 ·2326-2335 · IF 6.641

Thermo-responsive shape memory sensors based on tough, remolding and anti-freezing hydrogels

Tianyu Yang,Mian Wang,Fei Jia,Xiuyan Ren,Guanghui Gao

Recently, hydrogel-based sensors have been rapidly developed due to their excellent flexibility, stretchability and toughness. However, it is still necessary to develop a hydrogel sensor with shape memory and remolding performance for multi-field applications. Here, a dual physically cross-linked shape memory hydrogel sensor was fabricated via blending poly vinyl alcohol (PVA), cationic chitosan and graphene oxide in water and glycerol. The introduction of cationic chitosan endows the hydrogels with excellent electrical conductivity. Therefore, the hydrogel can be integrated as a strain sensor to repeatedly monitor human motions. Meanwhile, the hydrogel can be used as a thermo-responsive shape memory sensor by virtue of orientation of PVA molecular chains under force and disorientation after heating. Besides, the hydrogel possesses anti-freezing properties with mechanical flexibility at −20 °C. Due to the dual physical cross-linking, the hydrogels can effectively dissipate energy and reconstruct the network; thus, the hydrogels gain excellent strength and remolding properties. In a word, this strategy provides a feasible method to prepare multifunctional shape memory hydrogels applied as wearable strain sensors and shape memory sensors.

研究领域: 材料科学 · 生物医学工程
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2025 · IF 8.5

Mechanically robust, flexible, conductive, and anti-freezing hydrogels reinforced by cellulose of wood skeleton

Luzhen Wang,Muqiu You,Jinhao Xu,Jing Zhou,Yongcan Jin,Dagang Li,Zhaoyang Xu,Junshuai Li,Chuchu Chen

Hydrogels are soft and wet materials, but their applications are always limited by insufficient mechanical strength and toughness, and they are prone to freezing at low temperatures. In this study, we introduced an eco-friendly approach to developing wood-based hydrogels reinforced by the naturally aligned wood skeleton (WS) through the Hofmeister effect. The resulting wood-based composite hydrogels exhibited a high tensile strength of 20 MPa and a strain of 35 % in the longitudinal direction. This impressive mechanical performance was primarily due to densely packed hydrogen bonding, physical entanglements, and van der Waals forces between the cellulose of WS, polyacrylamide (PAM), and poly(vinyl alcohol) (PVA) chains during polymerization. Notably, the polymerization was induced using wood carbon dots as initiators, imparting additional fluorescence features to the hydrogels. Afterward, by incorporating a metal salt (sodium chloride), the developed wood-based hydrogels maintained high conductivity (3.0 S/m) and mechanical properties even under low-temperature conditions (−20 °C). Moreover, the conductive hydrogels exhibited multifunctional sensing capabilities, including strain, temperature, and ultraviolet (UV) irradiation detection, making them highly suitable for applications in human motion monitoring and healthcare, particularly under harsh environmental conditions.

研究领域: 材料科学 · 生物工程
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ACS Nano · 2024 · IF 15.8

Nanolignin-Facilitated Robust Hydrogels

Xiaofeng Pan,Xiang Li,Zhongkai Wang,Yonghao Ni,Qinhua Wang

Recently, certain challenges and accompanying drawbacks have emerged in the preparation of high-strength and tough polymer hydrogels. Insights from wood science highlight the role of the intertwined molecular structure of lignin and crystalline cellulose in contributing to wood’s strength. Herein, we immersed prestretched poly(vinyl alcohol) (PVA) polymer hydrogels into a solution of nanosized lignosulfonate sodium (LS), a water-soluble anionic polyelectrolyte, to creatively reconstruct this similar structure at the molecular scale in hydrogels. The nanosized LS effectively fixed and bundled the prestretched PVA polymers while inducing the formation of dense crystalline domains within the polymer matrix. Consequently, the interwoven structure of crystalline PVA and LS conferred good strength to the composite hydrogels, exhibiting a tensile strength of up to ∼23 MPa, a fracture strain of ∼350%, Young’s modulus of ∼17 MPa, toughness of ∼47 MJ/m3, and fracture energy of ∼42 kJ/m2. This hydrogel far outperformed previous hydrogels composed directly of lignin and PVA (tensile strength <1.5 MPa). Additionally, the composite hydrogels demonstrated excellent antifreezing properties (<−80 °C). Notably, the LS-assisted reconstruction technology offers opportunities for the secondary fixation of PVA hydrogel shapes and high-strength welding of hydrogel components. This work introduces an approach for the high-value utilization of LS, a green byproduct of pulp production. LS’s profound biomimetic strategy will be applied in multifunctional hydrogel fields.

CAS / MDL: 9002-89-5
研究领域: 材料科学 · 木材科学 · 高分子化学
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EUROPEAN POLYMER JOURNAL · 2025 · IF 6.3

Ultra-anti-freezing robust hydrogel snesor

Jingwen Lan,Zihan Wei,Rukuan Liu,Airong Xu

Although hydrogel sensors have broad application prospects in wearable devices, biomedical electronic skin, human–computer interaction and other fields, the hydrogel sensor with the synergy of robust mechanical behaviors, super freeze-resistant ability and signal output stability still remain challenged. To overcome the challenge, here, a novel hydrogel sensor AICG were developed using polyvinyl alcohol (PVA), glycidyl trimethyl ammonium chloride (EPTAC), polyethyleneimine (PEI) and ethylene glycol (EG). The effects of PVA, PEI, EPTAC and EG contents in AICG hydrogel on mechanical properties were systematically investigated. The notably boosted mechanical properties (antibreakage performance, fatigue-resistant ability) and super freeze-resistant performance are primarily ascribed to the superhydrogen-bond networks of PVA with PEI, EPTAC and EG. The hydrogel is so strong that it can load a 60 Kg boy and endure super low temperature (−120 ℃). Besides rendering AICG hydrogel good conductivity (5.56 mS·cm −1 ), EPTAC was used to graft it on the PVA/PEI macromolecular chains of AICG hydrogel via ring-opening reaction of EPTAC, thus impeding the leakage of EPTAC from the hydrogel as much as possible and improving conductive stability. On being used a sensor, it can accurately detect human joint movements and simulate electronic skin due to high sensitivity and stable signal output ability. It is expected that this study can provide valuable information for the design and fabrication of the hydrogel sensor with desired high performances.

研究领域: 材料科学 · 生物医学工程
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