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ARGET ATRP
MICROPOROUS AND MESOPOROUS MATERIALS · 2017 · IF 3.615

Controllable preparation of polymer brushes from mesoporous silica SBA-15 via surface-initiated ARGET ATRP

Mingsen Chen,Lanmei Qin,Yuanli Liu,Faai Zhang

Surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) was employed for controlled grafting of poly(glycidyl methacrylate) (PGMA) and poly(glycidyl methacrylate)-b-poly(methyl methacrylate) (PGMA-PMMA) brushes from mesoporous silica SBA-15. Initiator 2-bromoisobutyryl bromide (BiBB) was immobilized onto the inner surface of SBA-15 by reaction with free silanol groups. The polymerizations were conducted in the mixed solvents cyclohexanone /N, N-dimethylformamide. The strategy of utilizing mixed solvents gave rise to a suitable polymerization rate and resulted in a good control of the PGMA growth within the SBA-15 framework and could obtain polymer chains with well-preserved chain end functionality. Molecular weight of grafted polymer, structure, morphology, and composition of the functionalized SBA-15 were characterized by using gel permeation chromatography (GPC), X-ray powder diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), N 2 adsorption/desorption measurements, fourier transform infrared spectroscope (FT-IR), and thermogravimetry analysis (TGA), respectively. The thickness, polymer grafting density and molecular weight of the grafted polymer can be controlled by adjusting the polymerization time. The deactivator cannot efficient diffuse to convert the propagating chains to the dormant species when the pores are nearly completely filled with the polymer, therefore, increasing grafting density resulted in higher molecular weight and polydispersity index (PDI) values for the grafted polymer chains. This work provides a facile route for preparation of well-defined mesoporous silica/polymer hybrids.

CAS / MDL: 20769-85-1 3030-47-5
研究领域: 材料科学 · 高分子化学
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2020 ·Vol. 412 ·期 11 ·2413-2421 · IF 3.637

Polysaccharide-enhanced ARGET ATRP signal amplification for ultrasensitive fluorescent detection of lung cancer CYFRA 21-1 DNA

Wang Xia,Zhang Yawen,Zhao Liying,Wang Dazhong,Yang Huaixia,Kong Jinming

An ultrasensitive fluorescence biosensor for detecting cytokeratin fragment antigen 21-1 (CYFRA 21-1) DNA of non-small cell lung carcinoma (NSCLC) is designed using polysaccharide and activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) signal amplification strategy. Thiolated peptide nucleic acid (PNA) is fixed on magnetic nanoparticles (MNPs) by a cross-linking agent and hybridized with CYFRA 21-1 DNA. Hyaluronic acid (HA) is linked to PNA/tDNA heteroduplexes in the form of carboxy-Zr 4+ -phosphate. Subsequently, multiple 2-bromo-2-methylpropionic acid (BMP) molecules are linked with HA to initiate ARGET ATRP reaction. Finally, a large number of fluorescein o-acrylate (FA) monomers are polymerized on the macro-initiators, and the fluorescence signal is significantly amplified. Under optimal conditions, this biosensor shows a significant linear correlation between the fluorescence intensity and logarithm of CYFRA 21-1 DNA concentration (0.1 fM to 0.1 nM), and the limit of detection is as low as 78 aM. Furthermore, the sensor has a good ability to detect CYFRA 21-1 DNA in serum samples and to recognize mismatched bases. It suggests that the strategy has broad application in early diagnosis by virtue of its high sensitivity and selectivity. A novel and highly sensitive fluorescence biosensor for quantitatively detecting CYFRA 21-1 DNA via dual signal amplification of hyaluronic acid and ARGET ATRP reaction was developed. This proposed method has a low detection limit, wide detection range, high selectivity, and strong anti-interference.

CAS / MDL: 109-89-7 2052-01-9
研究领域: 生物技术 · 癌症研究 · 纳米技术 · 分子生物学
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INDUSTRIAL CROPS AND PRODUCTS · 2024 · IF 5.6

A green preparation method: ARGET ATRP method for the preparation of pressed plywood with soy protein adhesive

Zhanpeng Jiang,Xiaohang Liu,Jingyi He,Huijie Li,Jiuyin Pang,Guiquan Jiang

With the continuous reduction of petroleum resources, synthetic adhesives based on petrochemical products will face the problem of resource shortage. Soy protein is an environmentally friendly biobased material, but it has problems with poor water resistance and poor permeability. Pretreatment of soy protein with green deep eutectic solvent (DES) exposed hydrophobic groups and active sites. Through the measurement of infrared and ultraviolet spectra, the hydrogen bonds of soybean protein pretreated with DES were disrupted, the content of amino acid residues inside the sphere increased, the water contact angle changed from 46.3° to 88.5°, and the hydrophobicity was enhanced. After pretreatment, functional monomers were introduced into modified soy protein and bromine functional groups were introduced to prepare soy protein isolate bromide (SPI-Br) initiator. Through the activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) method, glycidyl methacrylate (GMA) was grafted onto the molecules of soy protein. By controlling the redox reaction of the catalytic system, controllable radical polymerization technology was achieved. This method reduces the influence of oxygen on the reaction and makes the reaction conditions relatively relaxed. Through infrared spectroscopy and nuclear magnetic resonance characterization testing, soy protein isolate-graft-Poly(glycidyl methacrylate) (SPI-g-PGMA) was successfully prepared. By optimizing the hot pressing process through response surface methodology, the bonding strength of plywood can reach 1.090 MPa, which is higher than the set value for Class II plywood using standard testing methods. This method has the advantages of green and environmental protection, making the soy protein copolymer prepared by this method have good industrial application prospects in green and environmental protection.

研究领域: 材料科学 · 环境科学 · 高分子化学
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Journal of Materials Chemistry B · 2024 · IF 6.1

A controllable Y-shaped DNA structure assisted aptasensor for simultaneous detection of AFB1 and OTA based on ARGET ATRP

Mingsan Miao,Liang Guo,Jinyan Xue,Yuzhen Jia,Zhenzhen Cui,Huai-Xia Yang

The development of a simple, rapid, and sensitive technology for the simultaneous detection of mycotoxins is of great significance in ensuring the safety of foods and drugs. Herein, a fluorescence aptasensor with high sensitivity and reproducibility for the simultaneous detection of aflatoxin B1 (AFB1) and ochratoxin A (OTA) was developed. In this sensing system, AFB1 and OTA aptamers were co-immobilized on the surface of magnetic beads (MBs) to form a Y-shaped structure through the principle of complementary base pairing, which were used as recognition probes to specifically capture the target. Activators generated by electron transfer for atom transfer radical polymerization (ARGET ATRP) was used as signal amplification strategy to improve the sensitivity. The initiator modified at the end of the antibody initiates the ARGET ATRP reaction. Different fluorescence signals were designed to achieve simultaneous detection of OTA and AFB1 with the limit of 18.62 and 1.60 fg/mL for AFB1 and OTA, respectively. In addition, experiments were conducted on three types of samples, and the recoveries of the two mycotoxins ranged from 87.30% to 109.50%, with relative standard deviations ranging from 0.50% to 4.92% under reproducible conditions. The results suggest that the developed aptasensor is sufficient to meet the different regulatory requirements of the two mycotoxins in food and drug safety and shows great potential.

研究领域: 分析化学 · 生物技术 · 食品科学 · 毒理学
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WOOD SCIENCE AND TECHNOLOGY · 2021 ·Vol. 56 ·期 1 ·205-218 · IF 2.506

Surface-initiated ARGET ATRP for maintaining the dimension of waterlogged archaeological wood (Pinus massoniana): polymer distribution behaviors and anti-shrinkage mechanism

Zhou Yihang,Wang Kai,Hu Dongbo

Recent studies have discovered that surface-initiated activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) is an effective tool to maintain the dimensions of waterlogged archaeological wood (WAW). However, the polymer distribution behaviors in the WAW and the possible anti-shrinkage mechanism are still unclear and barely discussed. Therefore, experiments with varied conditions were conducted. On the basis of the results, the polymer distribution behaviors in the WAW are deduced to have a close connection to the propagation rate of polymerization. Additionally, the expansion phenomenon when the samples were overtreated and the nearly linear correlation between the weight percentage gains and volume changes suggest expansion stress can be generated during the surface-initiated ARGET ATRP. The residual stress can help counteract the shrinkage stress during the drying process of WAW, which partially accounts for the anti-shrinkage property.

研究领域: 考古学 · 材料科学 · 高分子化学 · 文物保护科学
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REACTIVE & FUNCTIONAL POLYMERS · 2019 · IF 3.074

Grafting antibacterial polymer brushes from titanium surface via polydopamine chemistry and activators regenerated by electron transfer ATRP

Shuangshuang Wang,Jixuan Song,Yuchao Li,Xingchuan Zhao,Lin Chen,Guang Li,Liping Wang,Zhengfeng Jia,Xiangcai Ge

An environmentally benign and convenient approach to impart titanium (Ti) surfaces with antibacterial functionalities was described in this work. Polydopamine (PDA) was first deposited onto an alkali activated Ti substrates. Then 2-bromoisobutyryl bromide (BIBB) was immobilized on the surface of PDA coated Ti. Finally, the BIBB functionalized Ti initiated the polymerization of N, N -diethylaminoethyl methacrylate (DEAEMA) and N, N -dimethylaminoethyl methacrylate (DMAEMA) to obtain Ti@PDA-g-polymer brushes by activators regenerated by electron transfer atom transfer radical polymerization (ARGET-ATRP). The prepared PDEAEMA and PDMAEMA brushes on Ti surfaces would be subsequently quaternized by using 1-bromooctane, which would impart the obtained products with quaternary ammonium groups. The surface compositions of the functionalized Ti were characterized by X-ray photoelectron spectroscopy (XPS). The hydrophilic/hydrophobic properties of the functionalized Ti surfaces were determined by static water contact angle measurements, and morphologies were characterized by scanning electron microscope (SEM). Antibacterial abilities of quaternized PDEAEMA and PDMAEMA coated Ti were evaluated by the contact killing test, in which live/dead cell staining method was employed. The results showed that the quaternized polymer decorated Ti exhibited good bactericidal effects against Escherichi coli ( E. coli ), and its inhibition rate of E. coli were observed to be nearly 90%.

研究领域: 材料科学 · 生物医学工程
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Journal of Applied Biomaterials & Functional Materials · 2018 · IF 1.397

Surface modification of bacterial cellulose aerogels by ARGET ATRP

Xinhua Liu,Yong Li,Zhaoyang Chu,Yinchun Fang,Hongliang Zheng

Introduction:Bacterial cellulose (BC) aerogels have received more and more attention due to their renewability, biodegradability and other excellent properties in recent years. Modification of BC aerogels using different methods would expand their applications. However, many problems exist for these modifications, such as a low grafting ratio, the larger dosage of metal catalyst required and so on. Activator regeneration by electron transfer (ARGET) for atom transfer radical polymerization (ATRP) is a novel ATRP method which could significantly reduce the amount of metal catalyst required and achieve a high grafting ratio.Methods:Novel nanostructured BC aerogels containing epoxy groups were prepared by the ARGET ATRP method. BC aerogels were functionalized with initiating sites by reaction with 2-bromoisobutyryl bromide (BiBBr), and followed by ARGET ATRP reaction with glycidyl methacrylate (GMA) which was catalyzed by copper(II) bromide (CuBr2) and N,N,N',N,'N"-pentamethyldiethylenetriamine (PMDETA), and then reduced by vitamin C. BC aerogels containing epoxy groups (BC-g-PGMA) were obtained after freeze-drying. The influence factors of the solvent ratio of N,N-dimethyl formamide (DMF)/toluene, monomer concentration, the concentration of CuBr2, the molar ratio of vitamin C (Vc)/CuBr2,reaction temperature and time on the grafting ratio were investigated.Results:The results showed that the optimal DMF and toluene volume ratio was 2:1, the optimal monomer and CuBr2 concentration were 2 mol/l and 1.5 mmol/l. The optimal molar ratio of PMDETA/CuBr2 and Vc/CuBr2 were 4:1 and 1:1. The optimal reaction temperature and time were 60°C and 9 h. Scanning electron microscopy (SEM) images showed that GMA was strongly adhered onto the surface and inside of the BC pellicle.Conclusions:GMA was self-grown on the BC surface and achieved the high grafting ratio of 1052.7% under optimal conditions. The BC-g-PGMA aerogels containing the epoxy groups will provide wider application prospects in drug release, enzyme fixed, functional materials and other fields.

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Polymers · 2019 ·Vol. 11 ·期 7 ·1228 · IF 3.164

Surface-Induced ARGET ATRP for Silicon Nanoparticles with Fluorescent Polymer Brushes

Chun-Na Yan,Lin Xu,Qing-Di Liu,Wei Zhang,Rui Jia,Cheng-Zhi Liu,Shuang-Shuang Wang,Li-Ping Wang,Guang Li

Well-defined polymer brushes attached to nanoparticles offer an elegant opportunity for surface modification because of their excellent mechanical stability, functional versatility, high graft density as well as controllability of surface properties. This study aimed to prepare hybrid materials with good dispersion in different solvents, and to endow this material with certain fluorescence characteristics. Well-defined diblock copolymers poly (styrene)-b-poly (hydroxyethyl methyl acrylate)–co-poly (hydroxyethyl methyl acrylate- rhodamine B) grafted silica nanoparticles (SNPs-g-PS-b-PHEMA-co-PHEMA-RhB) hybrid materials were synthesized via surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP). The SNPs surfaces were modified by 3-aminopropyltriethoxysilane (KH-550) firstly, then the initiators 2-Bromoisobutyryl bromide (BIBB) was attached to SNPs surfaces through the esterification of acyl bromide groups and amidogen groups. The synthetic initiators (SNPs-Br) were further used for the SI-ARGET ATRP of styrene (St), hydroxyethyl methyl acrylate (HEMA) and hydroxyethyl methyl acrylate-rhodamine B (HEMA-RhB). The results indicated that the SI-ARGET ATRP initiator had been immobilized onto SNPs surfaces, the Br atom have located at the end of the main polymer chains, and the polymerization process possessed the characteristic of controlled/“living” polymerization. The SNPs-g-PS-b-PHEMA-co-PHEMA-RhB hybrid materials show good fluorescence performance and good dispersion in water and EtOH but aggregated in THF. This study demonstrates that the SI-ARGET ATRP provided a unique way to tune the polymer brushes structure on silica nanoparticles surface and further broaden the application of SI-ARGET ATRP.Keywords:dispersibility;rhodamine B;SI-ARGET ATRP;silica nanoparticles

研究领域: 材料科学 · 化学
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NEW JOURNAL OF CHEMISTRY · 2022 ·Vol. 46 ·期 36 ·17479-17486 · IF 3.925

Highly sensitive and specific assessment of ochratoxin A in herbal medicines via activator regeneration by electron transfer ATRP

Zhenzhen Cui,Liang Guo,Zhenyu Jin,Lele Ma,Huaixia Yang,Mingsan Miao

Ochratoxin A (OTA) seriously affects the quality of herbal medicines and threatens the health of patients. Therefore, accurate detection of OTA in herbs is of great significance. Here, we fabricated a signal-off fluorescent biosensor for the highly sensitive detection of OTA by the activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) signal amplification technique. First, the specific aptamer sequence was immobilized on carboxylic MBs by an amide reaction. At the same time, the initiator was attached to the cDNA. Then the aptamer and cDNA formed a double helix structure through complementary base pairing. Afterwards, numerous fluorescent monomers were grafted onto the cDNA by ARGET ATRP, which emitted strong fluorescence. Upon addition of OTA, it could be specifically recognized by the aptamer and displace the cDNA, generating fluorescence quenching. Under optimal conditions, the detection limit of the as-prepared sensor was 7.6 fg mL−1 with a detection range of 2 × 10−3 ng mL−1 to 2 × 103 ng mL−1. Furthermore, this sensor exhibited high selectivity and reproducibility, and was successfully applied to the detection of OTA in samples of forsythia, astragalus, licorice, xanthium and malt. The outstanding performance of this biosensor suggests its possible application in the detection of mycotoxin in herbal medicine samples.

CAS / MDL: 77-98-5
研究领域: 分析化学 · 毒理学 · 药理学
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EUROPEAN POLYMER JOURNAL · 2025 · IF 6.3

Polyolefin based Nano-Objects via ARGET ATRP mediated Polymerization-Induced Self-Assembly process

Xinyue Liang,Jingwei Zhang,Xiaoxiao Wu,Xiaotong Fang,Pengyu Qu,Guowei Wang

Polyolefins (POs) are key materials in industrial applications, and the development of high-performance and high-value-added POs is always a significant and challenging research focus. The major challenge lies in addressing compatibility between non-polar POs and polar functional components. We herein reported a facile strategy to prepare PO-based nano-objects using an activator regenerated by electron transfer atom transfer radical polymerization mediated polymerization-induced self-assembly (ARGET ATRP PISA) process based on hydrogenated polyisoprene- b -poly (glycidyl methacrylate) (HPI- b -PGMA)/poly (glycidyl methacrylate) (PGMA) blends. The dynamic light scattering (DLS) and transmission electron microscopy (TEM) revealed effective control over a wide range of hydrodynamic diameters of stabilized spherical nano-objects. The thermogravimetric analysis (TGA) and microscale combustion calorimetry (MCC) demonstrated the efficient and controllable introduction of phosphoric acid (H 3 PO 4 ) into nano-objects, with POs serving as the shell and flame retardants forming the core. This work was hoped to provide a versatile route to PO-based nano-objects and open a novel avenue for designing PO-based additives.

CAS / MDL: 598-30-1
研究领域: 高分子化学 · 材料科学 · 纳米技术 · 化学工程 · 大分子化学
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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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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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