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ATRP
POLYMER SCIENCE SERIES B · 2026 ·Vol. 68 ·期 4 ·21 · IF 0.9

Kinetic Study of CuBr2/PPh3 Catalytic ARGET ATRP and Its Application in Acrylate Emulsions Preparation

Xingbing Yang,Tang Cheng,Yan Wenyu,Xie Yi,Xu Xinyue,Li Yanxue,Chen Gang,Zhao Wenting

Activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) represents a significant advancement in reversible deactivation radical polymerization, offering substantially reduced catalyst loadings while maintaining precise control over molecular architecture. This study presents a comprehensive kinetic investigation of CuBr 2 /PPh 3 catalytic ARGET ATRP of ethyl acrylate, methyl methacrylate, and butyl acrylate with particular emphasis on its application in the preparation of acrylate emulsions. The results demonstrate that increasing the ligand concentration effectively enhanced both monomer conversion and the apparent propagation rate constant. The polymerization rate reached a maximum at a catalyst to ligand molar ratio of 1 : 2. At a polymerization temperature of 90°C, both monomer conversion and apparent growth rate attained their peak values, yielding an apparent activation energy of 56.5 kJ/mol. Furthermore, increasing the reducing agent concentration resulted in concomitant increases in both monomer conversion and copolymerization rate. This catalytic system was successfully applied to the emulsion polymerization of three monomers and stability of the isolated emulsions was explored. It is demonstrated that pretty low catalyst loading CuBr 2 /PPh 3 -catalyzed ARGET ATRP could be a plausible practical method for the preparation of acrylate emulsions.

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SENSORS AND ACTUATORS B-CHEMICAL · 2026 · IF 8.3

Molybdenum-catalyzed ATRP polymerization electrochemical biosensor for precise detection of esophageal cancer-associated MiRNA-320b

Shijin Zhou,Nan Ma,Baolin Huang,Qian Yang,Jinming Kong,Xueji Zhang

An ultrasensitive electrochemical biosensor has been developed for the detection of miRNA-320b, an exosomal RNA biomarker associated with lymph node metastasis in esophageal squamous cell carcinoma (ESCC). The platform employs a molybdenum-catalyzed atom transfer radical polymerization (Mo-ATRP) signal amplification strategy, eliminating the need for enzymatic or thermal amplification and enabling cost-effective, early-stage cancer diagnostics. A thiolated peptide nucleic acid (PNA) probe is immobilized on a gold electrode to specifically capture miRNA-320b. Upon hybridization, a sodium molybdate (Na 2 MoO 4 )-catalyzed ATRP reaction, initiated by tetrahydrocurcumin (THC), drives the in situ polymerization of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) monomers, forming redox-active polymer brushes directly on the electrode surface. The electrochemical response is exclusively derived from the surface-confined poly(TEMPO) layer, which forms only upon successful target recognition, ensuring high signal-to-noise performance. The biosensor achieves a detection limit of 0.417 fM with a linear range spanning 1 × 10 −15 to 1 × 10 −10 M ( R 2 = 0.992) and demonstrates excellent selectivity and robustness in complex biological matrices. Its resistance to common interferents and consistent performance under real-sample conditions underscore its suitability for clinical translation. This Mo-ATRP-based highly sensitive approach provides a promising foundation for non-invasive liquid biopsy and early detection of aggressive cancers such as ESCC.

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Nature Protocols · 2025 · IF 16

Biomass-derived carbon dots for the initiation of conventional radical and ATRP-based photopolymerization processes

Luo Xiongfei,Liu Xue,Guo Hongda,Li Ruiping,Wang Min,Li Xiaotong,Li Shujun,Liu Shouxin,Li Jian,Strehmel Veronika,Wang Qunying,Yilmaz Gorkem,Matyjaszewski Krzysztof,Strehmel Bernd,Chen Zhijun

In recent years, there has been increasing interest in using carbon nanodots (CDs) as a component photoinitiator to initiate photopolymerization. These systems support conventional radical photopolymerization and light-mediated atom transfer radical polymerization (photo-ATRP), emphasizing single-component (Type I initiators) and multicomponent systems, which involve at least two reaction partners, specifically, the Type II CD initiator. The latter can function in both photoinduced conventional radical polymerization and photo-ATRP. CDs provide an important advantage by reducing toxicological concerns, as they are nontoxic to cells, and minimizing migration issues typically associated with molecular systems. Here we present two novel photopolymerization methods utilizing biomass-derived CDs as light-sensitive components. The first approach uses biobased furfural to create a Type I CD initiator for photoinduced uncontrolled radical polymerization, which initiates polymerization via homolytic bond cleavage of oxime ester groups attached to the CD surface. The second method employs sodium alginate to generate CDs capable of initiating photoinduced radical polymerization or activating alkyl halides in photo-ATRP processes. Key topics covered in these methods include (1) preparation and characterization of biomass-derived CDs; (2) experimental procedures for CD-assisted photo-induced conventional radical polymerization and photo-ATRP and (3) analysis of the resulting polymers. Preparing and characterizing the CDs takes ~4 d, while photochemical reactions can be conducted within 1 h, depending on requirements. Product separation and analysis take an additional 0.5 h. This protocol is designed for users with experience in polymer chemistry and CD handling.

研究领域: 高分子化学 · 纳米材料 · 光引发 · 绿色化学 · 材料科学
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NEW JOURNAL OF CHEMISTRY · 2019 ·Vol. 43 ·期 7 ·3099-3110 · IF 3.069

Self-healing and tough GO-supported hydrogels prepared via surface-initiated ATRP and photocatalytic modification

Dechao Fan,Wenxiang Wang,Hou Chen,Liangjiu Bai,Huawei Yang,Donglei Wei,Lixia Yang,Zhongxin Xue,Yuzhong Niu

Hydrogels with the properties of self-healing, toughness, stiffness and strength have great potential for use in smart materials. Herein, self-healing and tough hydrogels were successfully prepared after adding modified graphene oxide (GO) composites, which grafted the functional polymers onto the surface of GO. GO@polyacrylonitrile (GO@PAN) was synthesized via surface-initiated atom transfer radical polymerization (SI-ATRP) using GO@BiBB as the ATRP initiator. The nitrile group on GO@PAN was converted to pyridine, for which 2,4,6-triphenylpyrylium tetrafluoroborate (TPPT) was used as the photocatalyst. The prepared GO composite was added into polyacrylic acid (PAA) hydrogels formed by in situ radical polymerization. These tough hydrogels not only have high mechanical strength, but also show excellent self-healing performance. This strategy can provide a novel and universal route for the fabrication of smart hydrogels in biomedical and engineering fields.

CAS / MDL: 20769-85-1 111-40-0
研究领域: 材料科学 · 高分子化学 · 生物医学工程
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JOURNAL OF NANOPARTICLE RESEARCH · 2012 ·Vol. 14 ·期 6 ·1-9 · IF 3.287

Functionalization of graphene and grafting of temperature-responsive surfaces from graphene by ATRP “on water”

Ren Lulu,Huang Shu,Zhang Chao,Wang Ruiyu,Tjiu Weng Weei,Liu Tianxi

Water-dispersible graphene with temperature-responsive surfaces has successfully been synthesized by grafting poly( N -isopropylacrylamide) (PNIPAM) from graphene via surface-initiated atom transfer radical polymerization (ATRP). First, graphene surfaces are functionalized with aminophenol groups by diazonium reaction on water. Subsequently, bromoisobutyrate groups are covalently attached to the phenol-functionalized graphene (G-OH) surface by esterification of 2-bromoisobutyrate with the hydroxyl groups, forming bromoisobutyrate-functionalized graphene (G-Br). Finally, PNIPAM is then grafted from G-Br via ATRP. Data from Raman spectroscopy, 1 H NMR, and transmission electron microscopy (TEM) confirm that PNIPAM chains grow from graphene by ATRP. Thermogravimetric analysis shows that the amount of PNIPAM grown from the graphene increases with the increase of monomer ratios. TEM images also show that functionalized polymer structures (PNIPAM cluster or agglutination) on graphene sheets can be well tuned by controlled polymerization. The obtained graphene-PNIPAM (G-PNIPAM) composite has PNIPAM surface which is highly sensitive to the temperature change. This temperature-responsive and water-dispersible G-PNIPAM composite may find potential applications in environmental devices as well as controlled release drug delivery.

研究领域: 材料科学 · 高分子化学 · 纳米技术
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Polymer Chemistry · 2013 ·Vol. 5 ·期 3 ·882-891 · IF 5.231

Poly(ionic liquid)s-based nanocomposite polyelectrolytes with tunable ionic conductivity prepared via SI-ATRP

Ping Wang,Yin-Ning Zhou,Jiang-Shui Luo,Zheng-Hong Luo

In this study, a novel kind of organic–inorganic core–shell SiO2-poly(p-vinylbenzyl) trimethylammonium tetrafluoroborate (SiO2–P[VBTMA][BF4]) nanoparticle was well designed and successfully synthesized via surface-initiated atom transfer radical polymerization (SI-ATRP). Fourier transform infrared spectroscopy (FT-IR), 1H nuclear magnetic resonance (1H NMR), X-ray photoelectron spectroscopy (XPS), dynamic light scattering (DLS) and scanning electron microscopy (SEM) were used to confirm the formation of the core–shell nanoparticles and the surface modification. In order to overcome the challenge of the characterization of the number average molecular weight of poly(ionic liquid)s, “sacrificial initiator” method was used here employing a trimethylsilyl (TMS)-labeled initiator as the NMR marker for integration. In addition, good thermal stability of the new hybrid polyelectrolyte was proved by thermogravimetric analysis. The electrochemical impedance measurements revealed that the room temperature conductivity reached 10−4 S cm−1, which is much higher than that of the pure poly(ionic liquid)s and varies with the amount of the grafted polymer and the test temperature. The X-ray diffraction (XRD) tests further investigated the crystal structure of the nanocomposite and pure P[VBTMA][BF4]. The temperature dependence of ionic conductivity conforms to Arrhenius behavior for both of the nanocomposites and the pure polymer. The results indicated that the SI-ATRP approach provided a simple and versatile route to tune the ionic conductivity of the hybrid nanoparticles by changing the chain length of the grafted polymer, which can be potentially used in a variety of electrochemical devices.

CAS / MDL: 13755-29-8 2916-68-9
研究领域: 材料科学 · 电化学
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COLLOID AND POLYMER SCIENCE · 2013 ·Vol. 292 ·期 2 ·333-342 · IF 2.161

Magnetic and hydrophilic imprinted particles via ATRP at room temperature for selective separation of sulfamethazine

Zou Yongli,Zhao Chunyan,Dai Jiangdong,Zhou Zhiping,Pan Jianming,Yu Ping,Yan Yongsheng,Li Chunxiang

In this work, a facile route to prepare hydrophilic molecularly imprinted particles with magnetic susceptibility (MMIPs) was first reported via atom transfer radical precipitation polymerization (ATRPP) in a methanol/water solvent at low temperature (298 K), which can be considered as an environment-friendly system. During the process, 2-hydroxyethyl methacrylate and N , N -methylenebisacrylamide monomers were added to improve the hydrophilicity of the polymers. The obtained materials were characterized in detail by X-ray diffraction, transform infrared spectroscopy, thermogravimetric analysis, vibrating sample magnetometer, scanning electron microscopy and transmission electron microscopy, and then used for the selective separation of sulfamethazine (SMZ) from aqueous medium. The images showed Fe 3 O 4 nanoparticles that were successfully embedded into the polymer particles with the size ranging from 450 to 650 nm, which exhibited great superparamagnetic susceptivity and high thermal stability. Batch adsorption experiments were performed to determine specific adsorption equilibrium, kinetics, and selective recognition and separation. The effect of the ratio of the double monomers used in the adsorption property was also studied. The equilibrium data of MMIPs toward SMZ was well fitted by the Langmuir isotherm model, and the maximum adsorption capacity estimated was 66.67 μmol g −1 . The adsorption kinetics rapidly achieved equilibrium within 1.0 h and was well described by the pseudo-second-order model. The MMIPs synthesized showed outstanding affinity and selectivity toward SMZ over structurally analogous antibiotics and easily achieved magnetic separation under an external magnetic field. In addition, the adsorption performance of the resulting MMIPs was no obviously decreased at least six repeated cycles.

研究领域: 环境科学 · 材料科学 · 分析化学
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APPLIED SURFACE SCIENCE · 2016 · IF 3.15

Surface polyPEGylation of Eu3+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

Guangjian Zeng,Meiying Liu,Chunning Heng,Qiang Huang,Liucheng Mao,Hongye Huang,Junfeng Hui,Fengjie Deng,Xiaoyong Zhang,Yen Wei

The Eu 3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu 3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.

CAS / MDL: 20769-85-1 26915-72-0
研究领域: 材料科学 · 纳米技术 · 生物医学工程
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POLYMER SCIENCE SERIES A · 2021 ·Vol. 63 ·期 6 ·705-711 · IF 1.206

ATRP-tethering Anti-fouling/Anti-fogging Hydrophilic thin Hydrogel Layers on the Surface of Glass Slides

Liu Yena,Seidi Farzad,Song Junlong

Abstract Surface design and engineering is a critical tool to improve the interaction of solid materials with their surroundings. Immobilization of polymeric hydrogels is one of the major strategies to achieve surface modification of solid substrates. Here, we report a simple strategy for tethering hydrophilic layers with anti-fogging and anti-fouling traits on the glass surface by surface-initiated atom transfer radical polymerization. The mixtures of N -acrylamide glycine and N -acrylamide glycinamide with different ratios are utilized for the generation of the hydrogel layer in the absence of any external crosslinking agent. The tethered layers are characterized by XPS, ATR-FTIR, and SEM. By adjusting the acrylamides ratio, layers with high hydrophilicity (contact angle 8°) are achieved. Notably, the modified glasses showed strong anti-fogging and anti-fouling performances. Additionally, the performance of the modified glasses remained almost unchanged after 2 months indicating high stability of the immobilized thin hydrogel layers.

研究领域: 材料科学 · 表面工程 · 高分子化学
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CELLULOSE · 2018 ·Vol. 25 ·期 12 ·7261-7275 · IF 3.809

Diallyl dimethyl ammonium chloride-grafted cellulose filter membrane via ATRP for selective removal of anionic dye

Lu Shengchang,Tang Zuwu,Li Wenyan,Ouyang Xinhua,Cao Shilin,Chen Lihui,Huang Liulian,Wu Hui,Ni Yonghao

Abstract In this paper, poly(diallyl dimethyl ammonium chloride) (PDADMAC)-grated cellulose filter membranes (cellulose- g -PDADMAC) were fabricated via atom transfer radical polymerization (ATRP) for selective removal of anionic dye from wastewater. Gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR) showed that PDADMAC was grafted onto the filter membrane surface via a controllable living polymerization. The resultant cellulose- g -PDADMAC membranes exhibit selective removal for anionic methyl orange (MO) through rapid and facile filtration using model MO/rhodamine B (RB) mixture, due to the electrostatic interaction between quaternary ammonium groups of membrane and the sulfonic groups of MO. The decolorization ratio of MO remains higher than 95% when the graft ratio is 13.3% even after 6 cycles. Cellulose- g -PDADMAC also shows effective antimicrobial activities against S. aureus and E. coli . The modified filter membranes are promising for the potential application in wastewater purification. Graphical abstract PDADMAC-grated cellulose filter membranes with good recyclability and high antimicrobial activity were fabricated via atom transfer radical polymerization for selective removal of anionic dye from wastewater.

研究领域: 材料科学 · 环境工程 · 高分子化学 · 水处理
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CHINESE JOURNAL OF POLYMER SCIENCE · 2014 ·Vol. 32 ·期 7 ·880-891 · IF 1.42

Synthesis of membrane adsorbers via surface initiated ATRP of 2-dimethylaminoethyl methacrylate from microporous PVDF membranes

Sun Tian,Zhang Yu-feng,Chen Chun-lin,Gong Xiang-zhuang,Meng Jian-qiang

Surface-initiated atom transfer radical polymerization (SI-ATRP) was used to tether poly(2-dimethylaminoethyl methacrylate) (PDMAEMA) onto microporous PVDF membranes in order to synthesize membrane adsorbers for protein adsorption. The alkaline treatment and bromine addition reaction were used to anchor ATRP initiators on membrane surface. Then PDMAEMA was grafted from the membrane surface via SI-ATRP. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) revealed the chemical composition and surface topography of the PVDF- g -PDMAEMA membrane surfaces. These results showed that PDMAEMA was grafted from the membrane surface successfully and a grafting yield as high as 1500 μg/cm 2 was achieved. The effects of the grafting time and the density of initiators on the static and dynamic binding capacity of bovine serum albumin (BSA) were systematically investigated. Both the static and dynamic binding capacities increase with the bromination and polymerization time. However, the benefits of the initiator density on binding capacities are limited by the graft density of PDMAEMA chains.

研究领域: 材料科学 · 生物医学工程
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RSC Advances · 2012 ·Vol. 2 ·期 13 ·5571-5579 · IF 0

Magnetic ZnO surface-imprinted polymers prepared by ARGET ATRP and the application for antibiotics selective recognition

Longcheng Xu,Jianming Pan,Jiangdong Dai,Zhijing Cao,Hui Hang,Xiuxiu Li,Yongsheng Yan

This paper reports a molecularly imprinted polymers (MIPs) based fluorescence sensor which is synthesized by grafting MIP layers on the surface of ZnO nanorods embedded γ-Fe2O3 nanoparticles via activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP). Methacrylic acid (MAA, functional monomer), 3-(trimethoxysilyl)propyl mathacrylate (MPS) modified γ-Fe2O3 (γ-Fe2O3/MPS, assistant magnetic monomer) and ethylene glycol dimethacrylate (EGDMA, cross-linking monomer) were co-polymerized in anisole at 313 K in the presence of sulfamethazine as a template molecule. Sulfamethazine was then solvent-extracted to obtain ZnO-grafted molecularly imprinted polymers (ZnO-MIPs). ZnO-MIPs were characterized by FE-SEM, TEM, FT-IR, TGA/DSC, VSM, fluorescence spectroscopy and Raman spectroscopy. It was observed that sulfamethazine can quench the luminescence of ZnO-MIPs in a concentration-dependent manner that can be described by a Stern–Volmer-type equation. ZnO-MIPs were used to determine sulfamethazine in a spiked pork sample with good recognition ability. This study therefore demonstrates the potential application in the recognition and separation of antibiotics based on molecularly imprinted polymers.

研究领域: 材料科学 · 分析化学 · 生物医学工程
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