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CARBOHYDRATE POLYMERS · 2024 · IF 10.7

Aldehyde-functionalization of chitin nanocrystals via SI-ARGET ATRP of lignin-derived monomers

Tongjun Yang,Rongli Li,Mingtao Ding,Hong Yu,Lihua Zhang,Haibo Xie

Chitin nanocrystals (ChNCs), prepared from a down-sizing process from chitin, have recently captured great attention to access sustainable nanomaterials. The surface modification of ChNCs is crucial to regulate the surface physicochemical properties and introduce specific functions, thus satisfying their diverse applications. In this study, aldehyde-functionalized ChNCs (ChNCs-PVMA) with enhanced hydrophobicity were developed via surface-initiated activators regenerated by electron transfer for atom transfer radical polymerization (SI-ARGET ATRP) of a lignin-derived polymerizable aldehyde monomer, vanillin methacrylate (VMA). The monomer conversion was determined by 1 H NMR spectroscopy of the reaction mixture based on the change of the relative ratio of VMA and solvent signals. The prepared ChNCs-PVMA were systematically characterized by FTIR, CP/MAS 13 C NMR, XPS, XRD, DSC, TGA, and TEM. The dispersibility of ChNCs and ChNCs-PVMA in water and DMF was evaluated by dynamic light scattering and visual observation, indicating good dispersion of ChNCs-PVMA in organic solvents. Furthermore, based on the available aldehyde groups, the ChNCs-PVMA was reacted with amino acids via Schiff base reaction, demonstrating a rich follow-up chemistry towards diverse functions by the reactive aldehyde groups.

研究领域: 材料科学 · 化学工程 · 生物材料
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ELECTROCHIMICA ACTA · 2026 · IF 5.8

Electrochemical detection of miRNA-21 coupling catalytic hairpin assembly with photo-ATRP amplification

Yunna Li,Zhidan Tian,Liang Zhou,Jinming Kong,Xueji Zhang

Target-triggered CHA generates azide-bearing duplexes on the GCE surface. • CuAAC links CHA-derived DNA assemblies with ATRP initiator sites. • Py-mediated photo-ATRP forms electroactive poly(FMMA) for signal amplification. • The platform shows a 100 aM–100 pM range and a blank-based LOD of 60 aM. • Matrix-matched calibration supports preliminary analysis in 10% diluted NHS. The electrochemical conversion of nucleic acid recognition events into amplified current signals remains important for developing sensitive miRNA biosensors. Herein, we propose a target-programmed and light-triggered interfacial signal-amplification strategy for miRNA-21 detection by coupling catalytic hairpin assembly (CHA), CuAAC click chemistry, and pyrene-mediated photo-induced atom transfer radical polymerization (photo-ATRP). In this design, miRNA-21 first triggers CHA on the H1-modified glassy carbon electrode surface, generating surface-bound H1–H2 duplexes carrying terminal azide groups. These azide-bearing duplexes are subsequently coupled with the alkyne-containing ATRP initiator PBIB through CuAAC, thereby converting the target-triggered DNA assembly product into interfacial polymerization-related sites. Under UV irradiation, pyrene activates the photo-ATRP of ferrocenylmethyl methacrylate (FMMA), leading to the in situ formation of electroactive poly(FMMA) and an enhanced square-wave voltammetry response. The stepwise sensing mechanism was supported by agarose gel electrophoresis, FTIR, component-deletion SWV experiments, EIS/CV characterization, and interfacial morphology analysis. Under optimized conditions, the biosensor showed a linear response toward miRNA-21 from 100 aM to 100 pM, with a blank-based limit of detection of 60 aM. The method also exhibited acceptable selectivity, reproducibility, short-term storage stability, and preliminary recovery performance in 10% diluted normal human serum spiked samples with matrix-matched calibration. This work demonstrates a proof-of-concept electrochemical amplification strategy that links target-catalytic DNA assembly with light-controlled interfacial polymer growth for sensitive miRNA detection. Download: Download high-res image (210KB) Download: Download full-size image

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Journal of Materials Chemistry B · 2013 ·Vol. 1 ·期 16 ·2132-2138 · IF 0

Preparation of a novel immunosensor for tumor biomarker detection based on ATRP technique

Xiaobo Wang,Min Zhou,Yinyan Zhu,Jingjing Miao,Chun Mao,Jian Shen

A novel electrochemical immunosensor for sensitive detection of a tumor marker is reported. This protocol involves the surface-initiated atom transfer radical polymerization (SI-ATRP) of poly(ethylene glycol) monomethacrylate (PEGMA) on an indium tin oxide (ITO) electrode. Using carcinoembryonic antigen (CEA) as a model analyte, capture anti-CEA (Ab1) was conjugated to poly(poly(ethylene glycol) monomethacrylate) (P(PEGMA)) brushes, via activation of hydroxyl groups by succinic anhydride and N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride, and N-hydroxysulfosuccinimide sodium salt (NHS/EDC). After the sandwich immunoreaction, the horseradish peroxidase-labeled signal anti-CEA antibodies were used to conjugate gold nanoparticles (HRP-Ab2–AuNPs bioconjugates). Under optimized conditions, the proposed immunosensor showed a high sensitivity and a linear range from 5 × 10−2 to 20 ng mL−1 with a low detection limit of 1.09 × 10−3 ng mL−1. The assay results of clinical serum samples were in acceptable agreement with the reference values. The designed immunoassay system with ultrahigh sensitivity and being efficient and economical, might have potentially broad applications in protein diagnostics and bioassay.

研究领域: 生物医学工程 · 分析化学 · 肿瘤学
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INDUSTRIAL CROPS AND PRODUCTS · 2022 · IF 6.449

Synthesis of renewable soybean protein and acrylate copolymers via ATRP in ionic liquid

Zeyu Zhang,Guiquan Jiang,Jiuyin Pang,Ling Su

In this paper, acrylate and glycidyl methacrylate (GMA) were grafted onto the main chain of soy protein isolate (SPI) in 1-butyl-2,3-dimethylimidazole chloride ionic liquid ([BDMIM][Cl]), to prepare a renewable soy protein graft copolymer via atom transfer radical polymerization (ATRP). The effect of unfolding degree of soy protein structure on pretreated SPI was studied via Fourier-transform infrared spectroscopy (FT-IR), hydrogen nuclear magnetic resonance spectroscopy (1 H NMR), surface tension (ST) and contact angle (CA) measurements. The results of FT-IR, 1 H NMR and energy dispersive spectrometry (EDS) indicated the successful synthesis of 2-bromoisobutyryl-functionalized SPI.The analysis of FT-IR and 1 H NMR spectra showed that the soybean protein graft copolymer was successfully synthesized. In addition, the grafting of acrylate onto soybean protein enhanced the hydrophobicity of the copolymer, and the static contact angle was above 90°. Differential scanning calorimetry (DSC) analysis revealed that the thermal stability of pretreated SPI was reduced. The new glass transition temperature in the copolymers also proved the successful synthesis of the copolymers. The tensile strength of the carbon fiber multifilament infiltrated with the copolymers was improved, indicating their potential application in the reinforcement of carbon fiber material.

研究领域: 材料科学 · 化学工程 · 生物材料
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GREEN CHEMISTRY · 2013 ·Vol. 16 ·期 4 ·1854-1864 · IF 6.828

Integration of renewable cellulose and rosin towards sustainable copolymers by “grafting from” ATRP

Juan Yu,Yupeng Liu,Xiaohuan Liu,Chunpeng Wang,Jifu Wang,Fuxiang Chu,Chuanbing Tang

A class of sustainable and renewable cellulose–rosin copolymers were prepared by immobilizing rosin-derived polymer chains on the backbone of ethyl cellulose (EC) by “grafting from” atom transfer radical polymerization (ATRP). Four different rosin based polymers derived from dehydroabietic acid (DA), one of the major resin acids in natural rosin, were attached to 2-bromoisobutyryl-functionalized EC. Meanwhile, DA-grafted EC was prepared by the simple esterification reaction between DA and EC. Kinetic studies showed that the polymerization of all monomers was controlled. These grafted copolymers adopt a worm-like or rod-like structure in tetrahydrofuran, verified by light scattering experiments. These copolymers have a tunable glass transition temperature and higher thermal stability in contrast to EC. Surface morphology by AFM analysis indicated good film-forming property when rosin polymers were grafted from EC. Additionally, the introduction of DA and rosin polymers remarkably enhanced the hydrophobicity of EC. The static contact angles of all these modified copolymers are above 90°. XPS analysis revealed that the surface of these rosin-modified EC copolymers was dominated by a hydrocarbon-rich rosin moiety. The UV absorption of modified EC composites is indicative of their potential application in UV-absorbent coating materials.

研究领域: 材料科学 · 高分子化学
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NEW JOURNAL OF CHEMISTRY · 2023 ·Vol. 47 ·期 20 ·9905-9912 · IF 3.3

Lysozyme imprinted Fe3O4@SiO2 nanoparticles via SI-ATRP with temperature-controlled reversible adsorption

Jun Tian,Yi Pang,Hongjuan Gu,Dongyan Tang,Zaiqian Yu

Nanoscale molecularly imprinted polymers (MIPs) could offer high binding capacity and fast mass transfer, but their removal after adsorption is costly and time-consuming. In this paper, Fe3O4@SiO2 nanoparticles were synthesized and a lysozyme-imprinted polymer was synthesized via surface initiated atom transfer polymerization on the surface of Fe3O4@SiO2. Temperature-controlled adsorption and desorption of lysozyme were measured, and the adsorption kinetics and isothermal adsorption were determined. The results indicate that the synthesized Fe3O4 has an inverse spinel crystalline structure and Fe3O4@SiO2 is a core–shell structured nanoparticle. The adsorption kinetics followed the Langmuir EXT1 model, and the equilibrium adsorption capacity of the Fe3O4@SiO2@MIP at 40 °C was 117.12 mg g−1 with an imprinting factor of 1.51. SDS-PAGE electrophoresis confirmed the specific adsorption of lysozyme, and 86% of the adsorbed lysozyme could be released by changing the temperature.

研究领域: 生物化学 · 材料科学
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CHINESE JOURNAL OF POLYMER SCIENCE · 2013 ·Vol. 31 ·期 4 ·691-701 · IF 1.27

Synthesis of double-hydrophilic double-grafted copolymers PMA-g-PEG/PDMA and their protein-resistant properties

Tan Lin,Xing Jin-xing,Cao Fu-hu,Chen Li-juan,Zhang Chong,Shi Rong-hua,Wang Yan-mei

A series of double-hydrophilic double-grafted PMA- g -PEG/PDMA copolymers, which contained poly(methacrylate) (PMA) as backbone, poly(ethylene glycol) (PEG) and poly( N,N -dimethylacrylamide) (PDMA) as side chains synthesized successfully by using reversible addition-fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP), were used as physical coatings for the evaluation of protein-resistant properties by capillary electrophoresis (CE). Electroosmotic flow (EOF) measurement results showed that the PMA- g -PEG/PDMA copolymer coated capillaries could suppress electroosmotic mobility in a wide pH range (pH = 2.8–9.8) and EOF mobility decreased with the increase of copolymer molecular mass and PDMA content. At the same time, protein recovery, theoretical plate number of separation and repeatability of migration time demonstrated that antifouling efficiency was improved with the increase of molecular mass and PEG content.

CAS / MDL: 868-77-9
研究领域: 高分子化学 · 生物医学工程 · 材料科学
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OPTICAL MATERIALS · 2020 · IF 2.779

Synthesis and self-assembly of brush-shaped block copolymer structure via ATRP and ROP

Chen Liang,Jianhua Hou,Yanhui Li,Dajun Liu,Jian Li,Xu Cui,Qian Duan

Well-controlled brush-shaped block copolymers (BBCPs) of high molecular weight with polystyrene (PS) and polylactic (PLA) side chains, (poly (cis-5-norbornene-exo-2,3-dicarboximide-end poly (styrene)))-block-(poly (cis-5-norbornene-exo-2,3-dicarboximide-end poly (lactide))) (PNB- g -PS)- b -(PNB- g -PLA) were synthesized by combining atom transfer radical polymerization (ATRP) and ring opening polymerization (ROP). The synthesis of the (PNB- g -PS)- b -(PNB- g -PLA) was well-controlled with molecular weight and polydispersity index ( M n, GPC  = 1310000 g mol - 1 and M w / M n (GPC) = 1.16). The SEM, XRD and DSC reveal that there are two immiscible cis-5-norbornene-exo-2,3-dicarboximide-end poly(styrene) (NB-PS) and cis-5-norbornene-exo-2,3-dicarboximide-end poly(lactide) (NB-PLA) phases in BBCP after self-assembly, which leads to partial crystallization. Moreover, the effect of the self-assembly temperature on morphology and reflectance of (PNB- g -PS)- b -(PNB- g -PLA) has been investigated. These (PNB-g-PS)-b-(PNB-g-PLA) exhibit obvious pearlescent appearance and wide band reflection after heat-treated at different temperatures (120 °C, 130 °C, 140 °C and 150 °C). Besides, with the increase of the self-assembly temperature, the domain spacing of (PNB- g -PS)- b -(PNB- g -PLA) decreases and the reflectance in visible range of (PNB- g -PS)- b -(PNB- g -PLA) increases. However, the self-assembly temperature does not significantly influence the reflection wavelength range of (PNB- g -PS)- b -(PNB- g -PLA).

研究领域: 材料科学 · 高分子化学
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CELLULOSE · 2017 ·Vol. 24 ·期 10 ·4189-4203 · IF 3.417

Thermoresponsive poly(poly(ethylene glycol) methylacrylate)s grafted cellulose nanocrystals through SI-ATRP polymerization

Zhang Xiuqiang,Zhang Jinlong,Dong Lili,Ren Suxia,Wu Qinglin,Lei Tingzhou

We report a series of thermoresponsive cellulose nanocrystals (CNCs) decorated with poly(poly(ethylene glycol) methylacrylate) copolymers (poly(PEGMA)- g -CNCs) synthesized by surface initiated-atom transfer radical polymerization (SI-ATRP). The chemical structures and surface morphologies were subsequently confirmed by FT-IR, XPS, and AFM measurements. With regard to thermally responsive behavior, poly(PEGMA)- g -CNCs show tunable lower critical solution temperature (LCST) values in the range of 34–66 °C by varying the feeding ratios of comonomers. The reversible morphological transformation from individual nano-rod structures to larger globule aggregates was further verified by AFM during the LCST transition. These functionalized CNCs have potential as smart film filters and biosensors.

研究领域: 材料科学 · 高分子化学
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COLLOIDS AND SURFACES B-BIOINTERFACES · 2013 · IF 3.554

Surface hydrophilic modification of polyethersulfone membranes by surface-initiated ATRP with enhanced blood compatibility

Tao Xiang,Wen-Wen Yue,Rui Wang,Su Liang,Shu-Dong Sun,Chang-Sheng Zhao

Surface-initiated atom transfer radical polymerization (SI-ATRP) was used to tailor the functionality of polyethersulfone (PES) membranes. A two-step method including nitration reaction and amination reaction was used to synthesize aminated polyethersulfone (PES-NH 2 ) for the preparation of PES/PES-NH 2 membranes. Covalently tethered hydrophilic polymer brushes of poly( N -vinylpyrrolidone) (PVP) were prepared via SI-ATRP at low temperature in an aqueous solvent. Attenuated total reflection–Fourier transform infrared (ATR–FTIR), scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS), and water contact angle were used to characterize the modified membranes surfaces. The PVP-grafted PES membranes showed lower protein adsorption and suppressed platelet adhesion compared with the pristine PES membrane. Moreover, the activated partial thromboplastin time (APTT) for the PVP-grafted PES membranes was increased. These results indicated that the surface hydrophilic modification by grafting PVP brushes provided practical application for the PES membranes with good blood compatibility.

研究领域: 材料科学 · 生物医学工程
✓ 已验证 DOI PubMed 高影响因子
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Nanoscale Research Letters · 2012 ·Vol. 7 ·期 1 ·1-7 · IF 2.726

Silica nanoparticles functionalized via click chemistry and ATRP for enrichment of Pb(II) ion

Li Wei,Xu Yaohui,Zhou Yang,Ma Wenhui,Wang Shixing,Dai Yongnian

Silica nanoparticles have been functionalized by click chemistry and atom transfer radical polymerization (ATRP) simultaneously. First, the silanized silica nanoparticles were modified with bromine end group, and then the azide group was grafted onto the surface via covalent coupling. 3-Bromopropyl propiolate was synthesized, and then the synthesized materials were used to react with azide-modified silica nanoparticles via copper-mediated click chemistry and bromine surface-initiated ATRP. Transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis were performed to characterize the functionalized silica nanoparticles. We investigated the enrichment efficiency of bare silica and poly(ethylene glycol) methacrylate (PEGMA)-functionalized silica nanoparticles in Pb(II) aqueous solution. The results demonstrated that PEGMA-functionalized silica nanoparticles can enrich Pb(II) more quickly than pristine silica nanoparticles within 1 h.

研究领域: 材料科学 · 环境化学 · 纳米技术 · 分析化学 · 污染治理
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POLYMER SCIENCE SERIES B · 2025 · IF 1

Emulsion and Dynamics of Acrylate Prepared by ARGET-ATRP under a Compound Initiation System

Xingbing Yang,Li Wei,Wu Qian,Zhang Qin,Li Jingyi,Jiang Tingting,Xiao Qin

Acrylate emulsions were prepared through atom transfer radical polymerization (ARGET-ATRP) with methyl methacrylate (MMA), ethyl acrylate (EA) and butyl acrylate (BA) as monomers using electron transfer-activated regenerative catalysts, with benzyl bromide (BBB) and ethyl 2-bromoisobutyrate (EBIB) as a complex initiation system and copper bromide and bipyridine as a catalytic system. The effects of the temperature, the compound initiator ratio, the compound emulsifier ratio, the ligand type and the content on the polymerization dynamics were examined, and the polymer was characterized by infrared spectroscopy and 1H NMR. This study revealed that the monomer conversion rate and the apparent polymerization rate are positively correlated with the reaction temperature, and the apparent activation energy of the reaction was E a  = 57.63 KJ/mol. When benzyl bromide was used as the initiator alone, the initiation efficiency of the system was low. After EBIB was added, the initiation effect was greater for benzyl bromide : EBIB = 7 : 3, and the conversion rate and polymerization rate were positively correlated with the amount of reducing agent. The monomer conversion rate and apparent growth rate constant were the greatest when the mass ratio of the emulsifier sodium dodecyl sulfate and sodium dodecyl benzene sulfonate was 7 : 3. Different ligands affected the monomer conversion rate and apparent growth rate constant, and with increasing ligand content, the monomer conversion rate and apparent polymerization rate constant increased. According to the results of infrared spectroscopy and nuclear magnetic hydrogen spectroscopy, the compound initiator successfully triggered the polymerized monomer to generate the ternary copolymer.

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