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EUROPEAN POLYMER JOURNAL · 2018 · IF 3.741

Synthesis of sequence-controlled polymers via sequential thiol-ene and amino-yne click reactions in one pot

Lei Yu,Ze Zhang,Ye-Zi You,Chun-Yan Hong

Sequence-controlled polymers are prepared by the combination of thiol-ene click reaction and amino-yne click reaction. Due to the high selectivity of the amine unit and thiol unit toward thiolactone, methacrylate, propiolate, etc., the sequence of the resulting polymers can be easily controlled by monomer-addition sequence. Moreover, thiol-ene click reaction and amino-yne click reaction can be carried out under mild conditions without need of any catalyst. Different kinds of sequence-controlled copolymers have been prepared by the combination of thiol-ene click reaction and amino-yne click reaction in one pot. NMR spectra and GPC traces confirmed the formation of polymers with high molecular weight and controlled sequence structure. Therefore, we provide a new method for the preparation of functional polymers with well-controlled sequences.

研究领域: 高分子化学 · 材料科学
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Polymers · 2017 ·Vol. 9 ·期 10 ·469 · IF 3.364

Fabrication of Hypericin Imprinted Polymer Nanospheres via Thiol-Yne Click Reaction

Yuxin Pei,Fengfeng Fan,Xinxin Wang,Weiwei Feng,Yong Hou,Zhichao Pei

To fabricate molecularly imprinted polymer nanospheres via click reaction, five different clickable compounds were synthesized and two types of click reactions (azide-alkyne and thiol-yne) were explored. It was found that molecularly imprinted polymer nanospheres could be successfully synthesized via thiol-yne click reaction using 3,5-diethynyl-pyridine (1) as the monomer, tris(3-mercaptopropionate) (tri-thiol,5) as the crosslinker, and hypericin as the template (MIP–NSHs). The click polymerization completed in merely 4 h to produce the desired MIP–NSHs, which were characterized by FTIR, SEM, DLS, and BET, respectively. The reaction conditions for adsorption capacity and selectivity towards hypericin were optimized, and the MIP–NSHs synthesized under the optimized conditions showed a high adsorption capacity (Q= 6.03 μmol·g−1) towards hypericin. The imprinting factors of MIP–NSHs towards hypericin, protohypericin, and emodin were 2.44, 2.88, and 2.10, respectively.Keywords:molecular imprinting;hypericin;click reaction;nanospheres

研究领域: 材料科学 · 药物化学
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2017 · IF 2.714

Preparation and enhanced structural integrity of electrospun poly(ε-caprolactone)-based fibers by freezing amorphous chains through thiol-ene click reaction

Jingxin Zhou,Yamei Liu,Tifeng Jiao,Ruirui Xing,Zhiqiang Yang,Jizhou Fan,Jianzhao Liu,Bingbing Li,Qiuming Peng

Facile preparation and UV stabilization of electrospun poly(e-caprolactone) (PCL)/2-methyl-3-(trimethoxysilyl) propylester (M8POSS)/pentaerythritol tetrakis(3-mercaptopropionate) (PETM) composite fibers via thiol-ene click reaction were investigated. The morphological studies clearly showed the M8POSS and PETM macromers were excluded from PCL crystalline phase during electrospinning. The cross-linking reaction occurs in the amorphous phase of PCL fibers and possibly the fiber surface. By locking amorphous PCL chains into the cross-linked M8POSS and PETM through thiol-ene click reaction, we are able to fabricate PCL/POSS composite fibers, which can remain structural stability under UVC for longer period of time. The facile fabrication of the composite fibers via thiol-ene click reaction reported here provided valuable insight into not only the surface coating of medical devices but also new biocompatible composite materials.

CAS / MDL: 67-64-1 67-66-3
研究领域: 材料科学 · 生物医学工程
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Polymer Chemistry · 2020 ·Vol. 11 ·期 17 ·2986-2994 · IF 5.342

Two-stage thiol-based click reactions for the preparation and adhesion of hydrogels

Wen Jing Yang,Wenya Xu,Xi Tao,Wen Wang,Yaqin Hu,Xue Li,En-Tang Kang,Lianhui Wang

The fabrication of adhesive hydrogel systems is quite important for biological applications. Herein, two-stage thiol-based click reactions have been employed for the preparation and adhesion of hydrogels. In the first stage, two self-adhesive hydrogels (HG-1 and HG-2) were constructed via the thiol-based click reactions and thiol–thiol coupling reaction under different stimuli, employing the same functional copolymer poly(propargyl methacrylate-co-N-(3,4-dihydroxyphenethyl) methacrylamide-co-poly(ethylene glycol) methyl ether methacrylate) (poly(PMA-co-DMA-co-PEGMA), polyPDP) and a 4-arm thiol-PEG cross-linker. Subsequently, the two prepared hydrogels achieved responsive self-adhesion properties via the second stage of thiol-based click reactions between the preserved functional groups under different stimuli. Moreover, the self-adhered hydrogels exhibited increased mechanical strength after adhesion. The present strategy thus provides a facile approach for the fabrication of hydrogel systems with on-demand self-adhesive properties.

研究领域: 生物材料 · 化学工程 · 生物医学工程
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POLYMER DEGRADATION AND STABILITY · 2020 · IF 4.032

Tailoring physical machinery and biodegradation properties of unsaturated polyesters through manipulation of synthesis and curing conditions

Chuanhui Gao,Sikai Wang,Jing Zhang,Yuetao Liu,Chuanxing Wang

Unsaturated polyesters, in particular unsaturated polyesters with low volatility or without styrene, are gaining increasing importance in gel coatings, adhesives and molding resins. However, the cured unsaturated polyesters are usually described as non-degradable polyesters, which will lead to environmental and safety problems. In this paper, a kind of unsaturated copolyester with different binary acid composition, named poly (butylene succinate-co-butylene itaconic) (PBISx), was synthesized. Then, a photo-curable polyester(CPBIS) which can degrade under certain conditions was obtained by thiol - ene click reaction without adding styrene curing agent. The physical properties of unsaturated polyester PBISx can be effectively controlled by changing the ratio of raw materials, such as T g from - 23.7 o C to - 45.2 o C, Xc from 38% to 14%, and T m from 109.6 °C to 74.9 °C. It was found that CPBIS completely lost its degradability in lipase when its gel rate exceeded 98%. However, CPBIS could be degraded in GSH regardless of the gel rate, and lipase resumed its degradation in the GSH/lipase mixture, and the degradation rate reached 12% at 70h, attributed to the selective degradation of C-S-C bond by GSH and the secondary degradation of ester bond by lipase.

研究领域: 材料科学 · 环境科学 · 生物学
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JOURNAL OF POLYMER RESEARCH · 2016 ·Vol. 23 ·期 2 ·1-8 · IF 1.969

Regularly grafted polymer brush with degradable PCL backbone by ring-opening polymerization and “click” reaction: synthesis and self-assembly

Chang Ruixue,Qin Jianglei,Wang Haijun

A series of polymer brushes with degradable poly(caprolactone) (PCL) backbones were synthesized via “grafting onto” approach by combination of the ring-opening polymerization (ROP) and “click” reaction. First, P(αClCL) was synthesized by ROP and then the chloride was substituted by azide group to obtain P(N 3 CL) backbone; then polymer brushes were synthesized by “click” reaction of alkynyl-PCL (ay-PCL) and alkynyl-PEO (ay-PEO) onto P(N 3 CL). The products were characterized by gel permeation chromatography (GPC), FT-IR and 1 H NMR. Results indicated that the ay-PCL can be grafted onto P(N 3 CL) backbone quantitatively at 1 : 1 ratio of alkynyl group to azide group and the branch was attached onto each repeating unit because of lower steric resistance and graft density. Also the amphiphilic polymer brushes with various hetero-branches of PEO/PCL ratios were synthesized by one-pot two-step process. The amphiphilic polymer brushes self-assembled into micelles with various PEO/PCL ratios and have potential application in drug loading and delivery.

研究领域: 材料科学 · 高分子化学 · 药物递送
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FOOD CHEMISTRY · 2021 · IF 7.514

Click reaction triggered turn-on fluorescence strategy for highly sensitive and selective determination of steroid hormones in food samples

Qianyu Li,Guoliang Li,Lihua Fan,Yanxin Yu,Jin Liu

The copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) click reaction has becoming noticeable in the field of analytical chemistry. Mild reaction conditions, simple operation, high efficiency, and good regioselectivity make this classical click reaction a perfect strategy for chemical derivatization. Herein, we proposed a promising click fluorescent labeling method with high selectivity for the determination of five steroid hormones in food samples. The labeling strategy depends on the reaction between 3-Azido-7-hydroxycoumarin and the alkynyl group of steroid hormones, which shows a turn-on fluorescence response in the presence of copper (I). The formed fluorescent products were detected by HPLC-FLD. Under the optimized conditions, the proposed method presented excellent performance with good linearity (R 2  ≥ 0.9998) and low detection limit (1.8–7.3 μg L -1 ). Further, satisfactory recoveries were obtained to be 82–107% in spiked meats with relative standard deviations (RSDs) ≤ 5.7%. Finally, the established method was successfully applied for the determination of steroid hormones in meat, indicating the potential prospect of the click reaction in chemical derivatization.

研究领域: 分析化学 · 食品安全 · 生物分析
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SENSORS AND ACTUATORS B-CHEMICAL · 2022 · IF 9.221

Water-soluble β-cyclodextrin based turn-on amplifying fluorescent probes for sensitive and selective detection of Hg2+/Hg+ ions

Kaiqi Liu,Luminita Marin,Xinjian Cheng

In this work, fluorescent β- cyclodextrin (β-CD) based probes containing naphthalimide group were synthesized to realize the specific recognition of Hg 2+ /Hg + in aqueous system. Firstly, three small fluorescent molecules (N1, N2 and N3) with -NH 2 groups were synthesized from 4-bromo-1, 8-naphthalene anhydride . Secondly, CH CCH 2 - group was introduced into β-CD by Williamson ether formation reaction. Finally, the target probes (β-CD-PI, β-CD-PY and β-CD-TP) were obtained by Amino-Yne click reaction. These probes can efficiently recognize Hg 2+ /Hg + . β-CD-PI emits bright yellow fluorescence after binding with Hg 2+ /Hg + , which is a turn-on fluorescent probe . When the Hg 2+ /Hg + concentration exceeds 26 μM, the fluorescence intensity amplifies sharply (20 folds). The hydrophobic parts of the probes aggregated together to form a micelle-like structure due to complexation with Hg 2+ /Hg + , resulting in special micelle-sensitizing properties. Meanwhile, the HOMO-LUMO energy levels of the probes were calculated by cyclic voltammetry (CV). The probe is expected to be used for the detection of Hg 2+ /Hg + in aqueous solutions without any organic solvents.

研究领域: 分析化学 · 环境科学 · 材料科学
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Advanced Healthcare Materials · 2023 · IF 10

Intracellular Nitroreductase-Triggered “On” and “Enhanced” Photoacoustic Signals for Sensitive Imaging of Tumor Hypoxia

Xianbao Sun,Lingling Xu,Hai-Dong Xu,Limin Xie,Rui Wang,Zhimou Yang,Wenjun Zhan,Shurong Shen,Gaolin Liang

Current molecular photoacoustic (PA) probes are designed with either stimulus-turned “on” or assembly-enhanced signals to trace biological analytes/events. PA probes based on the nature-derived click reaction between 2-cyano-6-aminobenzothiazole (CBT) and cysteine (Cys) (i.e., CBT-Cys click reaction) possess both “turn-on” and “enhanced” PA signals; and thus, should have higher sensitivity. Nevertheless, such PA probes, particularly those for sensitive imaging of tumor hypoxia, remain scarce. Herein, a PA probe NI-Cys(StBu)-Dap(IR780)-CBT (NI-C-CBT) is rationally designed, which after being internalized by hypoxic tumor cells, is cleaved by nitroreductase under the reduction condition to yield cyclic dimer C-CBT-Dimer to turn the PA signal “ON” and subsequently assembled into nanoparticles C-CBT-NPs with additionally enhanced PA signal (“Enhanced”). NI-C-CBT exhibits 1.7-fold “ON” and 3.2-fold overall “Enhanced” PA signals in vitro. Moreover, it provides 1.9-fold and 2.8-fold overall enhanced PA signals for tumor hypoxia imaging in HeLa cells and HeLa tumor-bearing mice, respectively. This strategy is expected to be widely applied to design more “smart” PA probes for sensitive imaging of important biological events in vivo in near future.

研究领域: 生物医学工程 · 分子影像学 · 肿瘤学
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SENSORS AND ACTUATORS B-CHEMICAL · 2025 · IF 7.7

Target-responsive DNAzyme hydrogel reinforced by click reaction for surface enhanced Raman scattering detection of okadaic acid

Ming Wang,Lizhen Zhao,Yuling Hu,Gongke Li

Shellfish toxins are common marine toxins that have attracted worldwide attention due to their serious threats to food safety and human health. In this work, DNA hydrogel based on rolling circle amplification (RCA) and click reaction was developed for surface enhanced Raman scattering (SERS) detection of okadaic acid (OA) combined with target-responsive DNAzyme signal amplification. The RCA strands containing azido-dCTP were combined with cross-linked strands with ethynyl groups via click reaction to form a DNA hydrogel framework. The click reaction strengthened the DNA hydrogel network, making it more rigid and easier to manipulate during the detection process. The aptamer and DNAzyme were introduced into the DNA hydrogel as functionalized DNA components. Upon the specific recognition of OA by the aptamer, the DNAzyme released via the displacement reaction would continuously cleave the enzyme cutting site within the substrate strand to liberate the SERS signal tag. The functionalized DNA hydrogel concurrently achieved the functions of target recognition, signal conversion and signal amplification. Under optimal conditions, this strategy could detect OA with limits of detection as low as 0.2 nmol/L within 30 min. The SERS signal intensity showed good linear relationship with OA concentration in the range of 1.0–300.0 nmol/L. The practical application was validated for detecting trace amounts of OA in aquatic product samples. The stable DNA hydrogel combined with target-responsive DNAzyme signal amplification offers a universal strategy for rapid detection of trace toxins in complex matrixes.

研究领域: 生物化学 · 分析化学 · 毒理学
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CHINESE JOURNAL OF POLYMER SCIENCE · 2019 ·Vol. 38 ·期 1 ·53-62 · IF 2.804

Bio-based and Biodegradable Electrospun Fibers Composed of Poly(L-lactide) and Polyamide 4

Chen Tao,Zhong Guo-Cheng,Zhang Yuan-Ting,Zhao Li-Ming,Qiu Yong-Jun

Novel bio-based and biodegradable block copolymers were synthesized by “click” reaction between poly(L-lactide) (PLLA) and polyamide 4 (PA4). Upon tuning the molar mass of PLLA block, the properties of copolymers and electrospun ultrafine fibers were investigated and compared with those of PLLA and PA4 blends. PLLA and PA4 were found incompatible and formed individual crystalline regions, along with reciprocal inhibition in crystallization. Electrospun fibers were highly hydrophobic, even if hydrophilic PA4 was the rich component. The crystallinity of either PLLA or PA4 decreased after electrospinning and PLLA-rich as-spun fibers were almost amorphous. Immersion tests proved that fibers of block copolymers were relatively homogeneous with micro-phase separation between PLLA and PA4. The fibrous structures of copolymers were different from those of the fibers electrospun from blends, for which sheath-core structure induced by macro-phase separation between homopolymers of PLLA and PA4 was confirmed by TEM, EDS, and XPS.

研究领域: 材料科学 · 生物学
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JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY · 2010 ·Vol. 48 ·期 13 ·2838-2845 · IF 3.971

A mixed cyclodextrin-biphenyl thermotropic liquid crystal: Synthesis, liquid-crystalline properties, and supramolecular organization

Li Chen,Tian-Hui Hu,He-Lou Xie,Hai-Liang Zhang

A well-defined structure liquid crystal heptakis [6-deoxy-6-(1-H-1,2,3-triazol-4-yl)(methyl)6-(4-methoxybiphenyl-4′-yloxy) hexanoyl]-β-cyclodextrin (H6B-β-CD) was synthesized from propargyl 6-(4-methoxybiphenyl-4′-yloxy) hexanoate (P6B) and heptakis (6-deoxy-6-azido)-β-cyclodextrin ((N 3 ) 7 -β-CD) by click reaction. The chemical structure of H6B-β-CD was confirmed by 1 H NMR, FTIR, and MALDI-TOF MS. The thermal stability of the compound was investigated by thermogravimetric analysis (TGA). The liquid crystalline behavior was studied by differential scanning calorimetry (DSC), polarizing optical microcopy (POM), and wide-angle X-ray diffraction (WAXD) measurement. These investigations have shown that the supramolecular structure of H6B-β-CD are consisted of a large scale ordered lamellar structure and a small scale ordered structure (SmE) at low temperature region. As the temperature increases, the small scale structure becomes disordered relatively in the first instance, from smectic E to smectic A. Then, the lamellar structure collapses and nematic phase and isotropic phase are observed in sequence. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2838–2845, 2010

研究领域: 材料化学 · 超分子化学
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