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JOURNAL OF MATERIALS CHEMISTRY · 2011 ·Vol. 21 ·期 34 ·12753-12760 · IF 5.101

“Thiol-ene” photo-cured hybrid materials based on POSS and renewable vegetable oil

Aifang Luo,Xuesong Jiang,Hong Lin,Jie Yin

We demonstrate here a series of hybrid materials based on thiol-contained polyhedral oligomeric silsesquioxane (POSS-OA/SH) and acrylated caster oil (ACO), which can be photo-cured through “thiol-ene” reaction. The fast photo-crosslinking reaction between POSS and ACO was traced by FT-IR, which is insensitive to oxygen gas. Compared with the pure ACO, the hybrid component of POSS-OA/SH and ACO exhibited much faster photo-cured speed upon the exposure of UV-light. The obtained hybrid materials were transparent to visible light and no obvious phase-separation was observed. AFM and SEM demonstrated that POSS nanoparticles were well-dispersed in the ACO matrix without obvious aggregation even if the content of POSS is higher than 60%. The introduction of POSS can decrease the surface energy of the obtained hybrid materials. The thermal stability of the obtained hybrid materials increased with the increase of POSS content. These characteristics gave the obtained hybrid material potential application in coating, and these studies provided a novel alternative approach to prepare the hybrid materials from the renewable source.

研究领域: 材料科学 · 化学工程
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RSC Advances · 2018 ·Vol. 8 ·期 20 ·11036-11042 · IF 2.936

Alginate based antimicrobial hydrogels formed by integrating Diels–Alder “click chemistry” and the thiol–ene reaction

Gang Wang,Jiehua Zhu,Xiaofeng Chen,Hua Dong,Qingtao Li,Lei Zeng,Xiaodong Cao

In recent years medical devices manufacturers have been looking for antimicrobial coatings which are biocompatible and non-toxic for a wide range of medical devices. The demand for these antimicrobial coatings has increased significantly, owing to the increased incidence of hospital-associated infections (HAIs). Hydrogels have been widely used in biomedical applications due to their hydrophilicity, biodegradability, non-toxicity and biocompatibility. In this work, sodium alginate (SA) based antibacterial hydrogels SA/PEG–HHC10 were designed and prepared by combining Diels–Alder (DA) click chemistry and the thiol–ene reaction. The hydrogels were first prepared using DA click chemistry with good mechanical strength, then the cysteine-terminated antimicrobial peptide HHC10–CYS (HHC10) was grafted into the hydrogel by the thiol–ene reaction between the oxy-norbornene group and the thiol group. The results showed that the antimicrobial hydrogels had a strong antibacterial property and good biocompatibility. Therefore, the antimicrobial hydrogels have significant potential application as coatings for implantable medical devices.

CAS / MDL: 9005-38-3
研究领域: 生物医学工程 · 材料科学
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JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS · 2016 · IF 3.652

Mechanism and kinetics of the pyrolysis of β-pinene to myrcene

Huidong Zheng,Jinliang Chen,Chao Li,Jingjing Chen,Yingshu Wang,Suying Zhao,Yanru Zeng

Myrcene, an important intermediate for the production of fine chemicals and pharmaceuticals, is mainly produced by the pyrolysis of β-pinene in the industry. The study of the direct pyrolysis of β-pinene was carried out without a catalyst and carrier gas at 573–873   K and under low pressure. In order to clarify the reaction mechanism, the primary intermediates of β-pinene pyrolysis including myrcene and limonene were also used as raw materials for further pyrolysis. The identification of some small molecules and C 10 H 16 isomers in the products proves that both decomposition reaction and ene reaction take place during the pyrolysis process. Based on the qualitative and quantitative analysis of reaction products, a reaction scheme for the pyrolysis of β-pinene was proposed. With appropriate simplification of the reaction scheme, a phenomenological kinetic model of the competitive parallel and consecutive first-order reaction was built, and exhibited good agreement with the experimental data. The activation energy ( E a ) and pre-exponential factor ( k 0 ) for each pathway were also determined.

研究领域: 化学工程 · 有机化学
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JOURNAL OF APPLIED POLYMER SCIENCE · 2025 · IF 2.8

Preparation of Long-Chain-Alkyl Siloxanes Bridged by Carbon-Sulfur Bond via Thiol–Ene Reaction

Feng-Tao Zheng,Hai-Jun Zhang,Gaoxue Xu

Long-chain-alkyl siloxanes were commonly used as hydrophobic treatment agents in cotton fabrics. In this work, long-chain-alkyl siloxanes (S-Siloxanes) were prepared by thiol–ene reaction between polyvinylmethylsiloxanes (Si  CC) and 1-pentanethiol. Thermal behavior, glass transition temperature (Tg), crystallization property, and hydrophobic treatment performance were investigated and compared with those of commonly used long-chain-alkyl siloxanes (C-Siloxanes) prepared via hydrosilylation reaction with platinum as a catalyst. The results showed that S-Siloxanes were thermally stable up to 350°C and possessed similar Tg and crystallization performance as C-Siloxanes. Water contact angles of glasses and cotton fabrics treated by S-Siloxanes reached 87.67° and 96.33° respectively, which were significantly increased compared to untreated glasses and cotton fabrics of 36.27° and 0°. The results were similar for glasses and cotton fabrics treated by C-Siloxanes. This work provides a milder and greener method to synthesize long-chain-alkyl siloxanes.

研究领域: 材料科学 · 纺织化学
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ELECTROCHEMISTRY COMMUNICATIONS · 2011 · IF 4.287

Thiol-ene click chemistry for the fabrication of Ru(bpy)32+-based solid-state electrochemiluminescence sensor

Kai Zeng,Manli Guo,Yingjun Zhang,Meng Qing,Afang Liu,Zhou Nie,Yan Huang,Yuliang Pan,Shouzhuo Yao

A novel method based on click chemistry for the immobilization of Ru(bpy) 3 2+ derivative on electrode to fabricate a solid state electrochemiluminescence (ECL) sensor was reported. Pentenyl functionalized Ru(bpy′) 3 Cl 2 was synthesized and immobilized on a (3-mercaptopropyl) trimethoxysilane (MPTMS) pretreated indium tin oxide (ITO) substrate via thiol-ene click chemistry reaction between its alkenyl group and the sulfhydryl group of MPTMS. The immobilization method is simple, fast, and efficient. More importantly, the resulting Ru(bpy′) 3 2+ monolayer film exhibited excellent stability in organic solvent, which is superior to many previously reported methods. Using tri- n -propylamine (TPrA) as a model analyte, the ECL sensor gave a wide linear range over 5   ×   10 −   6 to 5   ×   10 −   3   M, with a satisfactory detection limit of 1   ×   10 −   6   M ( S / N   =   3).

研究领域: 分析化学 · 材料科学
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JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY · 2012 ·Vol. 50 ·期 24 ·5170-5176 · IF 3.919

A versatile approach to the synthesis of polyphosphazene derivatives via the thiol–ene reaction

Yue-Cheng Qian,Xiao-Jun Huang,Chen Chen,Ning Ren,Xu Huang,Zhi-Kang Xu

The thiol–ene radical addition reaction has been successfully used to synthesize polyphosphazene derivatives. Poly[bis(allylamino)phosphazene] with pendant allyl groups was reacted with different thiol reagents under UV irradiation. These thiol reagents include 1-pentanethiol, 3-mercaptopropionic acid, 3-mercapto-1,2-propane-diol, and 2,3,4,6-tetra-O-acetyl-1-thio-β- D -glucopyranose. 1 H NMR analyses confirm that the allyl polyphosphazene can be quantitatively modified by the mercaptans. In total, 100% conversion of the allyl groups was reached in <60 min toward the first three mercaptans, whereas about 80% conversion of the allyl groups was reached after 120-min reaction toward the thioglucose. This method is a facile route for the synthesis of functional polyphosphazenes without the needs for protection/deprotection procedures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

研究领域: 高分子化学 · 材料科学
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RSC Advances · 2016 ·Vol. 6 ·期 51 ·45193-45201 · IF 3.289

A new approach for the synthesis of sulfur-bridged polysiloxanes via thiol–ene “click” reaction and their post-functionalization to obtain luminescent materials

Yujing Zuo,Zhiming Gou,Jinfeng Cao,Xiaoxiao Li,Shengyu Feng

Polysiloxanes, also known as “silicones”, have received widespread attention as specialty and inorganic backbone polymers since their commercial introduction. However, traditional synthesis routes can only produce polymers with Si–O–Si bonds in the main chains; this limitation influences the rapid development of the silicone industry. As such, new methods for the synthesis of silicones must be developed. This study is the first to introduce the thiol–ene reaction as a modular, efficient, and highly orthogonal method for polymerization. Novel polysiloxanes bearing sulfur atoms in the main chain with adjustable molecular weight were synthesized by the thiol–ene “click” reaction of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. 1,2-Ethanedithiol was subsequently functionalized using the same method. The structure of these polysiloxanes was characterized by 1H NMR, 13C NMR, and GPC analyses. The new structures of polysiloxanes bearing sulfur atoms in the main chain confer novel properties and applications. Furthermore, incorporating sulfur atoms could linearly increase the refractive index of polysiloxane. Finally, hybrid luminescent materials obtained from functionalized polysiloxanes and lanthanide ions exhibited narrow-width green or red emissions.

研究领域: 高分子化学 · 材料科学
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JOURNAL OF POLYMER RESEARCH · 2016 ·Vol. 23 ·期 6 ·1-12 · IF 1.969

Self-healing polymers based on eugenol via combination of thiol-ene and thiol oxidation reactions

Cheng Chuanjie,Zhang Xu,Chen Xinghe,Li Jin,Huang Qinghua,Hu Zhongyu,Tu Yuanming

Eugenol, a relatively cheap and abundant renewable resource, is used to design terminal diene compounds. Thiol-ene click reactions between the terminal diene intermediates and 1,6-hexanedithiol afford the corresponding oligomers with molecular mass of about 1.3 kDa. Finally, the oligomers and tricapto compound trimethylolpropane tris(3-mercaptopropionate) undergo thiol-oxidation reactions to form disulfide-crosslinked polymers. The brown polymers indicate self-healable behavior under UV light irradiation, presumably due to reversible reshuffling of weak disulfide bonds and/or reversible addition-dissociation reaction between benzoxazine and thiol groups.

研究领域: 材料科学 · 有机化学
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APPLIED SURFACE SCIENCE · 2017 · IF 3.387

Vapor-liquid interfacial reaction to fabricate superhydrophilic and underwater superoleophobic thiol-ene/silica hybrid decorated fabric for oil/water separation

Hongqiang Li,Tao Liang,Xuejun Lai,Xiaojing Su,Lin Zhang,Xingrong Zeng

With oil spill accidents and oil industrial wastewater increasing, oil/water separation has attracted much attention in recent years. Herein, we report the fabrication of superhydrophilic and underwater superoleophobic thiol-ene/silica hybrid decorated fabrics for oil/water separation via vapor-liquid interfacial reaction. It is based on sol-gel reaction of tetraethyl orthosilicate (TEOS) to generate silica and thiol-ene reaction between poly(ethylene glycol) dimethacrylate (PEGDMA) and trimethylolpropane tris(3-mercaptopropionate) (TTMP) to form crosslinked hydrophilic polymer on polyester fabric under the catalysis of butylamine/ammonia vapor. The chemical structure of the surfaces on thiol-ene/silica hybrid decorated fabric was confirmed by FTIR and XPS, and obvious micro-nano morphology and roughness were observed with SEM and AFM. The water contact angle of the fabric attained 0° in 0.36   s, and the underwater oil contact angle reached up to 160°. Importantly, the fabric exhibited high separation efficiency at 99.5%, fast water flux above 71600   Lm −2   h −1 and excellent recyclability in oil/water separation. Our findings open a new strategy to fabricate organic-inorganic hybrid superhydrophobic and underwater superoleophobic materials for oil/water separation.

研究领域: 材料科学 · 环境科学
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JOURNAL OF ORGANOMETALLIC CHEMISTRY · 2015 · IF 2.173

A facile route to multifunctional cage silsesquioxanes via the photochemical thiol–ene reaction

Lei Xue,Liguo Li,Shengyu Feng,Hongzhi Liu

Starting from octavinylsilsesquioxane (OVS), several multifunctional cage silsesquioxanes were successfully prepared by the photo–induced thiol–ene reaction with the corresponding commercially available thiols. These cage compounds were fully characterized by FTIR , NMR, ESI–MS and element analysis .

研究领域: 材料科学 · 化学工程
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PROGRESS IN ORGANIC COATINGS · 2023 · IF 6.6

UV-curable silicone pressure-sensitive adhesive based on thiol-ene reaction

Yu Zhou,Zuyi Zhao,Zhaoxia Liu,Hongxiang Chen,Hongye Yan,Junjie Tan,Fan Li

In order to improve the curing efficiency and reduce energy consumption of silicone pressure-sensitive adhesive (SiPSA), a kind of UV-curable SiPSA based on thiol-ene reaction was prepared with methyl vinyl MQ resin as hard segment, methyl vinyl silicone rubber (110-2S) as soft segment and mercaptyl silicone oil as cross-linker. The UV-cured SiPSA exhibited excellent thermal stability and water resistance. Its physical features such as chemical composition, cross-linking extent and dispersion of MQ resin in silicone rubber were directly related to the vinyl content in MQ resin, the thiol/ene ratio and the resin/rubber ratio, which further affected mechanical properties and adhesive properties of SiPSA. With the vinyl content in MQ resin of 56 mmol/100 g, the thiol/ene molar ratio of 0.8 and the resin/rubber mass ratio of 1.4, the UV-cured SiPSA-B1.4–0.8 had better mechanical properties, moreover it had higher tensile shear strength of >2.0 MPa and showed interface failure on the surface of substrates, indicating that it had great potential applications as PSA.

CAS / MDL: 24650-42-8 107-06-2
研究领域: 材料科学 · 化学工程
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Small · 2021 ·Vol. 17 ·期 34 ·2101048 · IF 13.281

Facile Surface Functionalization Strategy for Two-Photon Lithography Microstructures

Junning Zhang,Haibo Ding,Xiaojiang Liu,Hongcheng Gu,Mengxiao Wei,Xiaoran Li,Shengnan Liu,Sen Li,Xin Du,Zhongze Gu

Two-photon lithography (TPL) is a powerful tool to construct small-scale objects with complex and precise 3D architectures. While the limited selection of chemical functionalities on the printed structures has restricted the application of this method in fabricating functional objects and devices, this study presents a facile, efficient, and extensively applicable method to functionalize the surfaces of the objects printed by TPL. TPL-printed objects, regardless of their compositions, can be efficiently functionalized by combining trichlorovinylsilane treatment and thiol–ene chemistry. Various functionalities can be introduced on the printed objects, without affecting their micro-nano topographies. Hence, microstructures with diverse functions can be generated using non-functional photoresists. Compared to existed strategies, this method is fast, highly efficient, and non photoresist-dependent. In addition, this method can be applied to various materials, such as metals, metal oxides, and plastics that can be potentially utilized in TPL or other 3D printing technologies. The applications of this method on the biofunctionalization of microrobots and cell scaffolds are also demonstrated.

研究领域: 材料科学 · 生物医学工程
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