RESEARCH ON CHEMICAL INTERMEDIATES
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2025
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IF 3.5
Zeng Fang,Zhang Shuyao,Lin Ting,Li Yiqun,Xiao Meng
A novel Cu catalyst immobilized on glycine-functionalized poly(vinyl chloride) (Cu@Gly-PVC) was synthesized conveniently. The as-prepared catalyst was fully characterized by FTIR, SEM, EDS, elemental mapping, XPS, TGA, ICP, and EA analysis. The Cu(II) ions were uniformly distributed on the as-prepared Gly-PVC matrix via coordinated by carboxylic groups in a bidentate bridging pattern. This catalyst can be used at ppm levels in water for alkyne–azide cycloadditions (CuAAC) reactions, producing high yields of 1,2,3-triazoles. The present methodology offers several merits such as low catalyst loading, high catalytic activity, excellent yields, short reaction times, environmentally friendly reactions, simple operations, and compatibility of wide range of substrates. Furthermore, the catalyst can be easily isolated from the reaction mixture through simple filtration and retains remarkable reusability and catalytic activity even after four consecutive reaction cycles. Graphical abstract
研究领域:
有机化学
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材料科学
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绿色化学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
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IF 13.273
Guansong Hu,Junjian Chen,Yan Fan,Haiyan Zhou,Kunzhong Guo,Zhou Fang,Liangxu Xie,Lin Wang,Yingjun Wang
As an effective strategy to develop novel implants with a biomolecule, the efficiency of a copper-catalysed azide-alkyne cycloaddition (CuAAC) urgently requires improvement. Herein, we constructed a facile CuAAC system with catalytic CuSO 4 /sodium borohydride (CuAAC-Bor). As Cu nanoclusters (CuNCs) formed in situ , they showed stronger efficiency in immobilizing 41 types of peptides on Ti implants than traditional CuAAC with CuSO 4 /sodium ascorbate. Then, we mechanically revealed the significance of peptide size on CuAAC efficiency by all-atom molecular dynamics simulation and machine learning, and found that larger peptides preferred to adhere to Ti and CuNCs to increase their reaction opportunity. With CuAAC-Bor, HHC36-engineered implants strongly inhibited 5 types of clinical bacteria in vitro and prevented infection in vivo , and RGD-, DGEA-, QK- or YGFGG-engineered implants had high biocompatibilities with HUVECs / hBMSCs in vitro . Moreover, we demonstrated that QK-engineered implants prepared with CuAAC-Bor promoted the osteogenic differentiation of hBMSCs via the PI3K/Akt signalling pathway and triggered angiogenesis and osteogenesis in vivo . Our study shows that this facile and highly efficient CuAAC-Bor system holds high promise for the preparation of novel biomaterial surfaces.
研究领域:
生物材料
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生物医学工程
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分子生物学
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材料科学
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产品关联
DOI
高影响因子
BIOORGANIC CHEMISTRY
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2024
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IF 4.5
Yuchen Wang,Shi-Chao Lu,Hui Wen,Chunyue Zhao,Yanfei Jiang,Huaqing Cui
The limitations of commonly used sodium ascorbate-based catalyst system for copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction include excess production of reactive oxygen species and rapid catalyst deactivation. In this study instead of using a highly active reducing agent, such as, sodium ascorbate, we chose reducing sugar as a mild reducing agent to build up the catalyst system for CuAAC reaction. Interestingly, the bicinchoninic acid (BCA) assay system containing reducing sugar satisfies the essential elements of the catalyst system for CuAAC reaction. We found that CuSO 4 /BCA/Reducing sugar system can catalyze the CuAAC reaction but with low yield. Rational analyses of various parameters in CuSO 4 /BCA/Glucose catalyst system suggested storage at room temperature might enhance the catalytic activity, which was proven to be the case. Importantly, the system remains stable at room temperature and minimal H 2 O 2 was detected. Notably, our study showed that the coordination between the slow reduction of Cu(I) by reducing sugar and the selective chelation of Cu(I) by BCA is key to developing this system. The CuSO 4 /BCA/Reducing sugar catalyst system was successfully applied to various CuAAC reaction based bioanalyses, and it is suitable for the CuAAC reaction based bioanalyses that are sensitive to ROS or request long reaction time.
研究领域:
化学
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生物化学
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分析化学
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催化
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产品关联
DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
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2024
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IF 7.1
Yuan Sang,Xinqi Guan,Hailing Liu,Jiang Yang,Shengke Li,Qiannian Wang,Xiaoxi Huang,Yiming Wang,Qiang Yu,Mengyu Li
The chemical modification of lignin has been hindered by its poor solubility; therefore, expensive polar solvents are required. Herein, this article reports a solvent-free CuAAc reaction on lignin modification through ball-milled mechanochemistry, which avoids solvent use. In this way, not only is the cost reduced but also the reaction goes on the green side. In detail, the hydroxyl groups of lignin are first modified to alkyne end groups. Then, the lignin-alkyne and ethyl azidoacetate are ball-milled with a catalyst of Cu(OAc)2 in a solvent-free condition at 600 rpm. This reaction reached full conversion within 30 min on lignin model compounds of vanillin, 2-methoxy-4-methylphenol, and 2-methoxy-4-propylphenol. For natural lignins, the reaction reached 89% conversion for enzymolysis lignin-alkyne and 93% conversion for dealkali lignin-alkyne within 30 min. Despite intense impact energy in the planetary ball mill, the lignin polymer structure remained intact rather than degraded through the gel permeation chromatography (GPC) study. Then, the ball mill reaction condition was optimized to a 1:1.2 lignin-alkyne to ethyl azidoacetate ratio. The reaction time was minimized to 20 min, and mill balls were optimized to 40 balls of a 3 mm diameter. Lastly, a bunch of azide compounds was reacted with enzymolysis lignin-alkyne, including benzyl azide, 4-azidobenzonic acid, and 1-(azidomethyl)pyrene. 1-(Azidomethyl)pyrene enabled lignin to become a fluorophore. A polymer example, PEG-N3, was grafted onto lignin-alkyne through this solvent-free ball-milled CuAAc. In addition, a bisazide compound, 1,8-diazido-3,6-dioxaoctane, cross-linked lignin into macroscopic flakes. Moreover, the ball mill and solvent syntheses are analyzed metrically to evaluate the green chemistry.
研究领域:
化学工程
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材料科学
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环境科学
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DOI
高影响因子
BIOMACROMOLECULES
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2018
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IF 5.738
Chunyang Bao,Yueheng Yin,Qiang Zhang
Covalent coupling of hydrophobic polymers to the exterior of hydrophilic proteins would mediate unique macroscopic assembly of bioconjugates to generate amphiphilic superstructures as novel nanoreactors or biocompatible drug delivery systems. The main objective of this study was to develop a novel strategy for the synthesis of protein-polymer giant amphiphiles by the combination of copper-mediated living radical polymerization and azide–alkyne cycloaddition reaction (CuAAC). Azide-functionalized succinimidyl ester was first synthesized for the facile introduction of azide groups to proteins such as albumin from bovine serum (BSA) and laccase from Trametes versicolor. Alkyne-terminal polymers with varied hydrophobicity were synthesized by using commercial copper wire as the activators from a trimethylsilyl protected alkyne-functionalized initiator in DMSO under ambient temperature. The conjugation of alkyne-functionalized polymers to the azide-functionalized laccase could be conducted even without additional copper catalyst, which indicated a successful self-catalyzed CuAAC reaction. The synthesized amphiphiles were found to aggregate into spherical nanoparticles in water and showed strong relevance to the hydrophobicity of coupled polymers. The giant amphiphiles showed decreased enzyme activity yet better stability during storage after chemical modification and self-assembly. These findings will deepen our understanding on protein folding, macroscopic self-assembly, and support potential applications in bionanoreactor, enzyme immobilization, and water purification.
研究领域:
生物化学
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纳米生物学
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材料科学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF MATERIALS SCIENCE
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2018
·Vol. 53
·期 14
·10013-10024
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IF 2.993
Ban Qingfu,Zhuang Qiang,Su Kehe,Wu Si,Kong Jie
The existence of toxic Cu ions in the products synthesized by Cu(I)-catalyzed azide–alkyne cycloaddition (CuAAC) click chemistry hinders biomedical applications of these products. Cu ions are difficult to remove because stable Cu(II)–triazole coordination complexes are formed in the CuAAC products. To address this problem, we demonstrate a novel interfacial liquid phase-driven method for the removal of Cu ions. We synthesized small molecules, linear polymers, and hyperbranched polymers by using CuAAC. To remove Cu ions in these products, Cu ions were precipitated using Na 2 S in a solvent mixture that contains water, dimethylformamide, and dichloromethane (DCM). The products and the CuS precipitates were automatically dispersed in the DCM phase and aqueous phase, respectively, resulting in separation of the products and CuS. Compared to the conventional Cu removal methods, our new method is highly efficient, fast, and generally applicable to small molecules and polymers. More than 98% Cu in the CuAAC products can be removed by using our method. Moreover, we tested the biocompatibility of hyperbranched polymers synthesized using CuAAC and purified using our method. These polymers are compatible to cells, indicating our Cu removal method shows promise in purification of biomaterials synthesized using CuAAC.
研究领域:
材料科学
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生物医学工程
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高分子化学
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DOI
高影响因子
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
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2015
·Vol. 53
·期 20
·2374-2380
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IF 3.113
Heng Chen,Jiqiong Jia,Xiao Duan,Zhen Yang,Jie Kong
In this contribution, we present new reduction-cleavable hyperbranched disulfide bonds-containing poly(ester triazole)s with limited intramolecular cyclization, which can be synthesized by the Cu(I)-catalyzed azide–alkyne cycloaddition (CuAAC) of A 2 monomer of dipropargyl 3,3′-dithiobispropionate and B 3 monomer of tris(hydroxymethyl)ethane tri(4-azidobutanoate). The hyperbranched poly(ester triazole)s possess numerous terminal groups and weight-average molecular weight up to 20,400 g mol −1 with a polydispersity index in the range 1.57–2.17. The CuAAC introduces rigid triazole units into the backbones of hyperbranched poly(ester triazole)s and reduces intramolecular cyclization, which is proved by topological analysis and 1 H NMR spectroscopy. The disulfide bonds on backbones endow the reduction-cleavable feature to the hyperbranched poly(ester triazole)s at the presence of dithiothreitol. It gives a novel and convenient methodology for the synthesis of reduction-responsive functional polymer with controlled topologies, and the reduction-cleavable hyperbranched poly(ester triazole)s with limited intramolecular cyclization are expected to possess potential in the application of stimuli-responsive anticancer drug nanocarriers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53 , 2374–2380
研究领域:
高分子化学
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材料科学
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药物递送系统
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DOI
高影响因子
POLYMER COMPOSITES
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2025
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IF 4.7
Miao Zhang,Peng Zhu,Jian Shi,Chunhong Zhu,Mengya Wang,Huapeng Zhang,Fang-Chang Tsai,Yanjun Tang
Enhancing the interface performance of carbon fibers (CF) reinforced composite materials has always been a hot topic. Here, polyethylene imine (PEI) and cellulose nanocrystals (CNC) were used in synergy to construct a “flexible-rigid” interfacial layer on CF via copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) click chemistry to enhance their interfacial performance in epoxy resin. Firstly, the aldimine condensation was proposed to anchor propargylamine (PPA) to the reducing end of CNC. Secondly, PEI was covalently bonded with acyl chloride functionalized CF. The retained amine groups of PEI were subsequently modified by diazotization. Finally, the above two were site-specifically grafted together via CuAAC click chemistry. The results show that the surface free energy of CF-PEI (43.2 mJ/m 2 ) increased by 142.70% compared to untreated-CF (17.8 mJ/m 2 ), while that of CF-PEI-Click-CNC (70.5 mJ/m 2 ) increased by 296.07%. Especially, the interfacial shear strength (IFSS) of CF-PEI was 54.94 MPa, an increase of 68.84% compared to untreated-CF (32.54 MPa), while that of CF-PEI-Click-CNC was 77.65 MPa, an increase of 138.63%. This modification strategy would yield CF samples with an enhanced mechanical meshing effect and chemical reactivity. Additionally, the “flexible-rigid” interfacial layer, alleviating the modulus difference between CF and epoxy resin, would thereby reduce the stress concentration at the interphase.
研究领域:
材料科学
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聚合物复合材料
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表面化学
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纳米材料
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复合材料界面
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产品关联
DOI
高影响因子
Nano Today
·
2024
·
IF 13.2
Hui Huang,Wendi Xuan,Jiakang Hai,Xue Wang,Meng Chen,Guobing Hong,Xinyue Dai,Lili Xia,Wei Feng,Yu Chen
Bioorthogonal reaction refers to chemical reactions that occur within a biological system without interfering the normal biochemical process, offering the unprecedented versatility in engineering chemical reactions within cells. However, the precise regulation of bioorthogonal reaction in living systems is mired by the complexity of the physiological environment and the toxicity of catalysts. Herein, considering the deeper tissue penetration and reduced phototoxicity compared to visible light and ultraviolet, a second near infrared (NIR-II) light-activated Cu-based bioorthogonal reaction is developed to achieve precise spatiotemporal control and effective switching for Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) mediated chemical transformations in tumor, reducing the off-target effects. The catalytic activity of Cu catalyst through valence state interconversion between Cu(II) and Cu(I) can be precisely regulated in a reversible manner under NIR-II light irradiation-induced photoelectron transfer, which controls the extent of desired drug synthesis in bioorthogonal reaction. Meanwhile, the adverse effects of Cu(I) can be substantially mitigated within normal tissues due to their oxygen-rich condition. By utilizing NIR-II light and oxygen level, the Cu bioorthogonal catalyst achieves a balance between catalytic activity and biocompatibility. The ability to achieve precise spatiotemporal control and reversible catalysis makes this NIR-II light-mediated CuAAC platform an efficient and adaptable tool for bioorthogonal chemistry in living systems.
研究领域:
生物医学工程
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癌症治疗
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纳米技术
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光化学
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药学
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产品关联
DOI
高影响因子
ANALYTICA CHIMICA ACTA
·
2021
·
IF 6.558
Shuting Chen,Weijia Wang,Shaohua Xu,Caili Fu,Shuyi Ji,Fang Luo,Cuiying Lin,Bin Qiu,Zhenyu Lin
In this work, an auto-identify sensor was constructed for rapid and high-precision detection of L-histidine. The proposed strategy is based on the auto-identify algorithm and the aggregation of alkynyl and azide functionalized gold nanoparticles induced by the Cu + catalyzed azides and alkynes cycloaddition (CuAAC) reaction. Specially, the color of scattering light spots for the aggregated gold nanoparticle (AuNPs) caused by CuAAC reaction was quite different from that of the monomers . However, L-histidine can bind to Cu 2+ and inhibits the production of Cu + , hence preventing the aggregation of AuNPs. Therefore, there is a distinct change of color as the addition of L-histidine under dark-field microscopy. Then, L-histidine can be quantitatively detected by combining the color change with the Meanshift algorithm accurately and automatically. Such proposed method has been successfully applied for the detection of L-histidine in serum sample with satisfying result.
研究领域:
分析化学
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纳米技术
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生物化学
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产品关联
DOI
PubMed
高影响因子
ANALYST
·
2019
·Vol. 145
·期 1
·172-176
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IF 4.019
Qian-Yu Zhou,Xin-Ying Zhong,Ling-Li Zhao,Li-Juan Wang,Ying-Lin Zhou,Xin-Xiang Zhang
Single nucleotide polymorphisms (SNPs) have been proven to be important biomarkers for disease diagnosis, prognosis and disease pathogenesis. Here, taking the advantages of a self-assembled oligonucleotide sandwich structure and robust chemical reactions, we have developed a simple, high-throughput and effective colorimetric analytical technique termed CuAAC-based ligation-assisted assays (CuAAC-LA) for SNP detection using a DNA-BIND 96-well plate. With the 5′-azide and 3′-alkyne groups labelled on two oligonucleotide probes, the target DNA can direct a Cu(I)-catalyzed alkyne–azide cycloaddition (CuAAC) click reaction. Since the small difference in duplex stability caused by a single-nucleotide mismatch was amplified by the steric effects of these reactive groups for the ligation reaction of an unstable duplex, CuAAC-LA exhibited an ultra-sensitive discrimination ability for a mutant type target in the presence of large amounts of wild type targets. As low as 0.05% SNP could be clearly detected, which was better than most previously reported methods by various DNA ligases, indicating that a simple and rapid synthetic method i.e., the DNA template-directed click reaction held the potential to replace the ligase for SNP detection.
研究领域:
分子生物学
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基因组学
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生物技术
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分析化学
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产品关联
DOI
PubMed
高影响因子
SENSORS AND ACTUATORS B-CHEMICAL
·
2022
·
IF 9.221
Fengjing Cao,Fu Jiao,Shixiang Ma,Daming Dong
New strategies for super-sensitive detection of toxic heavy-metal-ion pollutants are urgently needed. Here, we outline a simple and highly sensitive assay for copper(II) ions. The method is based on click chemistry and uses laser-induced breakdown spectroscopy (LIBS) as the readout method. Copper(I) ions formed in situ by the reduction of copper(II) ions in the presence of sodium ascorbate (AA) can catalyze the cycloaddition reaction between an alkyne and an azide (CuAAC). In the presence of copper(II) ions and AA , the AgNPs-BSA-Azide can be clicked with the BSA-Alkyne via a cycloaddition reaction to form a BSA-triazole-BSA-AgNPs sandwich conjugate based on this CuAAC&LIBS system. The intensity of the LIBS signal from the residual AgNPs-BSA-Azide in the supernatant is inversely proportional to the concentration of copper(II) ions. The sensor shows a good detection limit of 0.045 nM and a linear relationship between copper ions concentration and the LIBS signal. This click-based method will broaden the potential applications of LIBS for metal detection in drinking water and environment.
研究领域:
分析化学
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环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）