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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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Journal of Environmental Chemical Engineering · 2024 · IF 7.4

Preparation of highly hydrophobic melamine sponge for oil-water separation through copolymerization deposition

Honghui Zeng,Yuchi Zhang,Huazhong Wu,Yuansong Ye,Weiying Zhang,Run Fang

The frequent occurrence of petrochemical spills and the uncontrolled discharge of oily industrial wastewater have caused serious water pollution problems. In this study, a novel modified melamine sponge, namely U-HDA@MS, was prepared by a simple, environmentally friendly, and cost-effective method using urushiol, a natural polymer, as the major modifier. The reaction mechanism of the precipitation copolymerization of urushiol and 1,6-hexamethylenediamine (HDA) and the in-situ deposition of the copolymer were investigated by chemical structure and microscopic morphology analyses. It was found that the self-polymerization of urushiol and the copolymerization of urushiol and HDA produced ethanol-insoluble copolymers. Subsequently, the deposition of the copolymers formed a coating with a micro/nano hierarchical structure and a large number of hydrophobic groups on the sponge skeleton, making U-HDA@MS highly hydrophobic and oleophilic. The water contact angle reached 145° without silanization modification, and the absorption capacity for carbon tetrachloride was up to 122 g/g. The outstanding chemical stability of the deposited coating made U-HDA@MS durable in harsh conditions. It maintained stable hydrophobicity and high absorption capacity over a wide pH range. Absorption-squeezing and continuous absorption experiments verified the outstanding reusability and oil-water selectivity of U-HDA@MS. This demonstrates its promising application in oil-water separation and petrochemical spill cleanup.

研究领域: 环境科学 · 材料科学
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Polymers · 2024 ·Vol. 16 ·期 8 ·1167 · IF 4.7

In Situ Reduction of Silver Nanoparticles/Urushiol-Based Polybenzoxazine Composite Coatings with Enhanced Antimicrobial and Antifouling Performances

Jipeng Chen,Xiaoxiao Zheng,Rongkun Jian,Weibin Bai,Guocai Zheng,Zhipeng Xie,Qi Lin,Fengcai Lin,Yanlian Xu

Marine anti-fouling coatings represent an efficient approach to prevent and control the marine biofouling. However, a significant amount of antifouling agent is added to improve the static antifouling performance of the coatings, which leads to an issue whereby static antifouling performance conflicts with eco-friendly traits. Herein, this work reports an in situ reduction synthesis of silver nanoparticles (AgNPs) within polymers to produce composite coatings, aiming to solve the aforementioned issue. Firstly, urushiol-based benzoxazine monomers were synthesized by the Mannich reaction, using an eco-friendly natural product urushiol andn-octylamine and paraformaldehyde as the reactants. Additionally, AgNPs were obtained through the employment of free radicals formed by phenolic hydroxyl groups in the urushiol-based benzoxazine monomers, achieved by the in situ reduction of silver nitrate in benzoxazine. Then, the urushiol-based benzoxazine/AgNPs composite coatings were prepared by the thermosetting method. AgNPs exhibit broad-spectrum and highly efficient antimicrobial properties, with a low risk to human health and a minimal environmental impact. The composite coating containing a small amount of AgNPs (≤1 wt%) exhibits effective inhibition against various types of bacteria and marine microalgae in static immersion, thereby displaying outstanding antifouling properties. This organic polymer and inorganic nanoparticle composite marine antifouling coating, with its simple preparation method and eco-friendliness, presents an effective solution to the conflict between static antifouling effectiveness and environmental sustainability in marine antifouling coatings.

CAS / MDL: 111-86-4
研究领域: 材料科学 · 海洋生物学 · 环境科学
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ACS Applied Polymer Materials · 2020 · IF 0

Facile Preparation of Hydrophobic Melamine Sponges using Naturally Derived Urushiol for Efficient Oil/Water Separation

Yan Fang,Liyu Yan,Haiqing Liu

In this work, hydrophobic sponges for highly efficient oil/water separation and oil absorption were fabricated by a simple, eco-friendly, economical, and scalable dip-coating of hydrophilic melamine sponges in urushiol (a naturally occurring small compound) solution. Because of the unique catechol group and a long alkyl side chain with unsaturated double bonds, urushiol molecules easily adhered on the sponge wall surface and self-polymerized to form a thin hydrophobic coating layer with the assistance of heat treatment. The urushiol-modified melamine sponge (UMS) displayed a water contact angle of ∼139o and a 3D highly porous structure, so it could effectively separate oil from dynamic oil/water mixtures. The separation flux of n-hexane from an n-hexane/water mixture was as high as 18,356 ± 2200 L·m–2·h–1·bar–1. It could quickly absorb various oils and common organic solvents with an absorption capacity of up to 181 g·g–1 and had excellent recyclability. UMS also displayed robust mechanical stability, flexibility, elasticity, and thermal stability. Therefore, the facile preparation process, low cost, and superior oil separation/absorption would endow UMS with high potential when dealing with oily wastewater.

研究领域: 材料科学 · 环境科学
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Nanoscale · 2018 ·Vol. 10 ·期 48 ·22818-22829 · IF 7.233

Urushiol-functionalized mesoporous silica nanoparticles and their self-assembly into a Janus membrane as a highly efficient hemostatic material

Jiawen Chen,Wei Cheng,Shuning Chen,Wenqin Xu,Jinhuo Lin,Haiqing Liu,Qinhui Chen

Quick hemostasis plays a very important role in preventing hemorrhagic shock and death by controlling blood loss from trauma in civil and military accidents. An ideal quick hemostat should have tissue-adhesive functional groups, clotting factor activating components, and a plasma non-permeable hydrophobic layer. Inspired by the adhesive behavior of mussels, a novel efficient hemostat of urushiol-functionalized mesoporous silica nanoparticles (MSN@U) with a core–shell structure was synthesized and their hemostatic performance was evaluated for the first time. MSN@U could form an amphipathic Janus membrane (a hydrophobic layer and a hydrophilic layer in one membrane) by interfacial self-assembly. The morphology and structure of MSN@U were characterized. The results showed that MSN@U possessed a large specific surface area of 448.91 m2 g−1 and a rich porous structure with an average pore diameter of 3.94 nm. The hydrophilic catechol groups and the long hydrophobic alkyl groups of urushiol allowed MSN@U to self-assemble at the blood/air interface. The former made MSN@U tightly adhere onto blood vessel tissue through covalent bonds, while the latter formed a hydrophobic barrier layer which hindered blood from oozing. Meanwhile, MSN@U would accelerate clotting cascade reactions. These three effects made MSN@U a very quick hemostat with a hemostatic time of 22 ± 2 s on a rat liver laceration. Both in vitro and in vivo tests showed that they had a better hemostatic effect and blood compatibility than MSN. Cell viability evaluations indicated that MSN@U had no cytotoxicity. MSN@U will be a safe and promising hemostatic agent for clinical applications.

研究领域: 生物医学工程 · 材料科学 · 医学
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INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES · 2018 ·Vol. 19 ·期 10 ·3184 · IF 3.687

Novel C15 Triene Triazole, D-A Derivatives Anti-HepG2, and as HDAC2 Inhibitors: A Synergy Study

Zhiwen Qi,Chengzhang Wang,Jianxin Jiang,Caie Wu

A series of novel C15 urushiol derivatives were designed by introducing a pechmann structure and F-, Cl-, and Br-nitro substituents with different electronic properties into its alkyl side chain, as well as a triazolyl functional group in its aromatic oxide. Their chemical structures were determined based on the analysis of the NMR (nuclear magnetic resonance) spectroscopic and mass spectrometric data. The results showed that compound4exhibited a strong inhibition of the HepG2 cell proliferation (half maximal inhibitory concentration (IC50): 2.833 μM to human hepatocellular carcinoma (HepG2), and 80.905 μM to human normal hepatocytes (LO2)). Furthermore, it had an excellent synergistic effect with levopimaric acid. The nitrogen atom of the triazole ring formed a hydrogen-bonding interaction with Gly103, Gly154, and Tyr308, which made compound4bind to histone deacetylase (HDAC)2 more tightly. One triazole ring and His33 formed a π–π stacking effect; the other, whose branches were deep into the pocket, further enhanced the interaction with HDAC2. Meanwhile, compound4involved a hydrophobic interaction with the residues Phe210 and Leu276. The hydrophobic interaction and π–π stacking provided powerful van der Waals forces for the compounds.Keywords:urushiol;triazole;diels-alder;pechmann;anti-tumor;HDAC2

研究领域: 药理学 · 肿瘤学 · 分子生物学
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2025 · IF 21.1

Surface and spatial engineering of ZnAl hollow multi-shelled structures for photothermal synergistic catalysis of glycerol carbonate synthesis

Hongpeng Zhang,Jie Wang,Jielin Huang,Haonan Duan,Li Dong,Suojiang Zhang

The synthesis of glycerol carbonate (GC) under mild conditions, a process constrained by thermodynamics, requires the simultaneous and efficient activation of both urea and glycerol. In this study, we developed a hydroxyl-rich Zn-Al-based hollow multi-shelled structure (ZnAl HoMS) catalyst that significantly enhances the urea alcoholysis reaction. Through optimization of its surface properties and spatial structure, this catalyst achieved a remarkable GC yield of 94.4 % under photo-thermal synergistic catalysis. Notably, even at a lowered temperature of 130 °C, it maintained excellent photo-thermal performance, delivering a GC yield of 78.2 % (selectivity>98 %), significantly higher than the 37.3 % yield obtained by pure thermal catalysis, representing a substantial increase of 40.9 %. Combined characterization and theoretical simulations revealed that the exceptional catalytic activity originates from the synergistic effect between its surface chemical properties and unique HoMS architecture. The surface Lewis acid-base sites effectively activate the carbonyl group of urea and the hydroxyl groups of glycerol, while the surface hydroxyl groups drastically reduce the energy barrier for the intramolecular cyclization step from 0.62 eV to 0.1 eV. Furthermore, the HoMS structure enhances light harvesting and promotes charge separation efficiency, facilitating the generation of photo-induced active species. These species work in concert with the acid-base sites to promote C-N bond cleavage and O-H bond dissociation. The rational design of surface properties and spatial structure of the catalyst in this work enables effective coupling of thermal and photocatalytic pathways, leading to a dramatic enhancement in reaction efficiency. This study provides new insights into the design of multifunctional catalysts and opens novel avenues for developing sustainable organic synthesis routes.

研究领域: 催化化学 · 材料科学 · 化学工程 · 光催化 · 绿色化学 · 纳米材料
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