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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2025 · IF 8.5

Graphene quantum dot-induced photo redox ATRP synthesis of lignin-based copolymers for the fabrication of silver-bearing and camptothecin-loaded micelles

Xiaobing Liang,Jiaxin Li,Zhihui Li,Yibin Lin,Hailiang Li,Duoqu Chen,Yonghui Xiao,Wenjing Lin,Chufen Yang,Guobin Yi

Photo redox atom transfer radical polymerization (ATRP) represents an excellent technique for forming multifunctional polymers. However, there was little report on photo redox ATRP of graphene quantum dots (GQDs). Herein, we reported that introduced GQDs to ATRP in DMF solvent for the first time, significantly reducing the amount of copper catalyst (<500 ppm) required for the synthesis of alkali lignin-poly( N -isopropylacrylamide)-poly( N , N -dimethylaminoethyl methacrylate)-poly(poly(ethylene glycol) methyl ether methacrylate) (AL-(PNIPAM-PDMAEMA-PPEGMA) 2 ). The copolymer had molecular weight of 46,884 and polydispersity index (PDI) of 1.07. The micelles self-assembled from AL-(PNIPAM-PDMAEMA-PPEGMA) 2 in aqueous solution served as an excellent template for the simultaneous in situ preparation of silver nanoparticles (AgNPs) and the encapsulation of the hydrophobic anticancer drug camptothecin (CPT). By adjusting the mole ratio of [DMAEMA]:[AgNO 3 ], a series of AgNPs with controllable sizes (2.5–20.6 nm) could be obtained. AL-(PNIPAM-PDMAEMA-PPEGMA) 2 @Ag@CPT exhibited temperature and pH-sensitive release properties, releasing 80 % of the drug in an acidic and 37 °C tumor environment within 120 h. Furthermore, 150 μg/mL AL-(PNIPAM-PDMAEMA-PPEGMA) 2 @Ag@CPT effectively killed 75 % of cells within 48 h. 800 μg/mL AL-(PNIPAM-PDMAEMA-PPEGMA) 2 @Ag@CPT demonstrated highly efficient antibacterial effects. All these results suggest its potential application value in synergistic antitumor and antibacterial treatment system.

研究领域: 材料科学 · 生物医学工程
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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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GREEN CHEMISTRY · 2014 ·Vol. 16 ·期 9 ·4408-4416 · IF 6.852

Synthesis of a CO2-philic poly(vinyl acetate)-based cationic amphiphilic surfactant by RAFT/ATRP and its application in preparing monolithic materials

Shoucun Zhang,Wei Luo,Wei Yan,Bien Tan

This study provides a new method to prepare CO2-philic amphiphilic surfactants by copolymerizing a less activated monomer (VAc) with an activated monomer (DMAEMA). Initially, the difunctional RAFT agent S-(1-methyl-4-hydroxyethyl acetate) O-ethyl dithiocarbonate, containing the xanthate group and 2-bromopropionyl group in its structure, was synthesized. By successive living radical polymerization, a series of new cationic surfactants poly(vinyl acetate)-block-poly(dimethylaminoethyl methacrylate) (PVAc-b-PDMAEMA) was obtained. PVAc-b-PDMAEMA cationic surfactants can emulsify CO2–H2O systems effectively to obtain high internal phase emulsion that remains stable up to 12 h. Further study indicates that the emulsifying ability of the surfactant is affected by the pH of solution, pressure, etc. After the high internal phase CO2-in-water (40% w/v, acrylamide solution) emulsion was polymerized, polyacrylamide-based highly porous emulsion-templated materials were obtained with tunable size and interconnected pores. These porous materials were then used as scaffolds to guide cellular growth.

研究领域: 材料科学 · 化学工程 · 生物医学工程
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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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RSC Advances · 2015 ·Vol. 5 ·期 22 ·17194-17201 · IF 3.84

Synthesis of hybrid silica nanoparticles grafted with thermoresponsive poly(ethylene glycol) methyl ether methacrylate via AGET-ATRP

Zhiping Du,Xiaofeng Sun,Xiumei Tai,Guoyong Wang,Xiaoying Liu

Thermosensitive SiO2 nanoparticles were prepared with graft-on poly(ethylene glycol) methyl ether methacrylate (POEGMA, Mn ∼ 300 or 500 g mol−1) via atom transfer radical polymerization with activators generated through electron transfer (AGET ATRP). CuBr2/PMDETA and ascorbic acid (AA) were employed as the catalyst and reducing agent respectively in the fabrication process. The structure and surface composition of our hybrid materials were analyzed using Fourier Transform Infrared (FTIR) spectroscopy and X-ray Photoelectron Spectroscopy (XPS) in detail. The results of Thermogravimetric Analysis (TGA) show that AGET-ATRP could provide a higher surface grafting density to get more pronounced thermosensitive properties. The morphology of our hybrid SiO2 nanoparticles was characterized by Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM). measurements of turbidity, Dynamic Light Scattering (DLS), and phase transfer were conducted to investigate the thermal responses of the hybrid material. In addition, Pickering emulsions were prepared using such hybrid SiO2-POEGMA as an emulsifier. Moreover, its fast de-emulsification above a lower critical solution temperature (LCST) may be exploited for the efficient separation and recycling of catalysts in future.

研究领域: 材料科学 · 化学工程 · 纳米技术
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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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Polymer Chemistry · 2012 ·Vol. 4 ·期 6 ·1815-1825 · IF 5.321

Synthesis of linear amphiphilic tetrablock quaterpolymers with dual stimulus response through the combination of ATRP and RAFT by a click chemistry site transformation approach

Jiucun Chen,Mingzhu Liu,Honghong Gong,Guangjun Cui,Shaoyu Lü,Chunmei Gao,Feng Huang,Tongtong Chen,Xinyu Zhang,Zhen Liu

Well-defined linear amphiphilic tetrablock quaterpolymers with dual stimulus response, poly(ethylene glycol)-b-poly(styrene)-b-poly(N-isopropylacrylamide)-b-poly(2-(dimethylamino)ethyl methacrylate) (PEG-b-PS-b-PNIPAM-b-PDMAEMA), were successfully synthesized through the combination of ATRP and RAFT by a click chemistry site transformation approach. Bromine-terminated diblock copolymer PEG-b-PS-Br was first prepared by ATRP of styrene initiated with macro-initiator PEG-Br, which was prepared from the esterification of PEG and 2-bromoisobutyryl bromide. PEG-b-PS-Br can then be converted into the azido-terminated diblock copolymer, PEG-b-PS-N3, by nucleophilic substitutions. Site transformation of PEG-b-PS-N3 into a macro-chain transfer agent (CTA) for RAFT polymerization was accomplished using a copper-catalyzed click chemistry approach. Afterwards, the novel linear tetrablock quaterpolymers, PEG-b-PS-b-PNIPAM-b-PDMAEMA, were synthesized by successive RAFT polymerizations of NIPAM and DMAEMA. The polymerization data indicated that both RAFT processes were well controlled. The structures of the linear amphiphilic tetrablock quaterpolymers and the corresponding precursors were characterized by 1H NMR, FTIR and GPC. Containing thermoresponsive PNIPAM and pH-responsive PDMAEMA blocks, the obtained amphiphilic PEG-b-PS-b-PNIPAM-b-PDMAEMA tetrablock quaterpolymers self-assembled into spherical micelles with hydrophobic PS cores and hydrophilic PEG/PNIPAM/PDMAEMA shells at acidic pH and room temperature but self-assembled into PS/PDMAEMA-core micelles at alkaline pH and room temperature, and PS/PNIPAM-core micelles at acidic pH and elevated temperatures.

研究领域: 高分子化学 · 纳米材料 · 药物递送 · 智能响应材料 · 生物医用高分子 · 自组装 · 聚合物化学
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JOURNAL OF APPLIED POLYMER SCIENCE · 2017 ·Vol. 135 ·期 7 ·45863 · IF 1.86

Preparation of block copolymers via metal-free visible-light-induced ATRP for the detection of lead ions

Yue Sun,Juan Li,Mengyuan Zhao,Yutong Liu,Jiameng Zhang,Chengwei Lv

Polyacrylamide- b -poly(methacrylic acid) was prepared on the surface of Au electrode (Au/PAM/PMAA) for Pb 2+ ion electrochemical sensing via metal-free visible-light-induced atom transfer radical polymerization, which was very simple, convenient, and environmentally friendly. Au/PAM/PMAA was carefully examined by cyclic voltammetry, electrochemical impedance spectroscopy, and X-ray photoelectron spectroscopy. Further, Au/PAM/PMAA was successfully used for the determination of Pb 2+ ion by differential pulse anodic stripping voltammetry. Under the optimal conditions, a linear response from 1.0 × 10 −11 to 1.0 × 10 −4 mol/L with detection limit of 2.5 × 10 −12 mol/L ( S / N = 3) was achieved from the results of experiments. Comparing with similar Pb 2+ sensors, the broader linear range and lower detection limit suggested the promising prospect of Au/PAM/PMAA. In a word, the work of this article had an important significance for the polymer-modified electrodes and the sensitive detection of Pb 2+ . © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135 , 45863.

CAS / MDL: 625-45-6
研究领域: 材料科学 · 环境科学 · 分析化学
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NEW JOURNAL OF CHEMISTRY · 2024 · IF 2.7

A novel electrochemical biosensor based on WO3@AuNPs and HBP@BIBB macromolecule-triggered ATRP for DR1 detection

Xiaojing Cui,Yaping Zhang,Hanmeng Zhang,Huaixia Yang,Yanju Liu,Fuchun Si

The sensitive detection of down-regulator of transcription 1 (DR1) plays an important role in the early diagnosis and treatment of Hashimoto's thyroiditis (HT). Herein, we report a novel electrochemical sensor based on the nanocomposite of tungsten oxide–gold nanoparticles (WO3@AuNPs) and hyperbranched polymer–2-bromo-isobutyryl bromide (HBP@BIBB) initiated atom transfer radical polymerization (ATRP) for the ultrasensitive assay of DR1. Monolayer WO3 nanosheets, which have high conductivity, were first compounded with AuNPs to obtain the WO3@AuNP nanocomposite. WO3@AuNPs can not only increase the conductivity of the electrode but also provide more active sites for biological molecules, thereby effectively amplifying the output signal. By introducing macroinitiator HBP@BIBB into the ATRP reaction, more electroactive molecules were introduced into the sensor, further amplifying the output signal and making the sensor ultra-sensitive. The optimized sensor demonstrated a wide linear range of 1 × 10−4 –1 × 102 ng mL−1 with a low detection limit of 2.91 fg mL−1. Moreover, the electrochemical biosensor has high selectivity, good stability, and strong anti-interference ability, and is suitable for the determination of DR1 in complex biological matrices. In conclusion, this electrochemical biosensor shows great potential in biomarker detection.

CAS / MDL: 16903-35-8
研究领域: 生物化学 · 分析化学 · 纳米技术 · 医学诊断
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COLLOID AND POLYMER SCIENCE · 2015 ·Vol. 293 ·期 7 ·2035-2044 · IF 1.865

Preparation of pH-sensitive nanoparticles of poly (methacrylic acid) (PMAA)/poly (vinyl pyrrolidone) (PVP) by ATRP-template miniemulsion polymerization in the aqueous solution

Chen Guoxia,Liu Junxiu,Yang Yadong,Zhang Lijuan,Wu Min,Ni Henmei

Employing polymethacrylic acid (PMAA) as the template and N -vinyl pyrrolidone (N-VP) as monomer, the ATRP-template miniemulsion polymerization was carried out in the aqueous medium by using MBP/CuBr/bpy as initiator. The results were characterized by dynamic light scattering (DLS), transmission electron microscope (TEM), and gel permeation chromatography (GPC). It was observed that the stable particles exhibited amphoteric pH sensitivity, namely that in the range of pH 3.0 to 5.0, the particles precipitated, whereas beyond the range the particles were stable and swollen as pH varied. Moreover, the pH range was variable according to the molecular weight of PVP. The results of GPC indicated that the molecular weight of template polymer PMAA was duplicated by the daughter polymer PVP. Being noncross-linked, unlike the common microgels, the hydrodynamic diameter dramatically increased in a very narrow pH range, e.g., pH 5.5 –6 and 2.0–2.5. Finally, the nanoparticles of PMAA/PVP were applied for the controlled release of rifampicin (RFP) and doxorubicin (DOX).

研究领域: 材料科学 · 药学
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CELLULOSE · 2021 ·Vol. 28 ·期 4 ·2433-2443 · IF 5.044

An aqueous approach to functionalize waterlogged archaeological wood followed by improved surface-initiated ARGET ATRP for maintaining dimensional stability

Zhou Yihang,Wang Kai,Hu Dongbo

A previous study on consolidation of waterlogged archaeological wood (WAW) via surface initiated ARGET ATRP of the cell walls has shown its potential of maintaining the dimensional stability. But the defects lie in the unsuitable initiator immobilization methods and polymerization conditions, which impedes its application. Therefore, we are proposing a novel functionalization method for initiator immobilization in water or water/ethanol solution and an improved thermo-initiated ARGET ATRP system. First, mercaptoethylamine (MEA) was used to functionalize WAW with amino groups in water under circumneutral conditions. Then, quinone-based initiators reacted with those amino groups realizing its immobilization. Finally, by using less active reductants such as ascorbic acid 2-glucoside and glucose, monomer, catalyst, and reductant were able to permeate into the WAW samples at room temperature and polymerization was initiated by heating to 60 °C (for ascorbic acid 2-glucoside) or 80 °C (for glucose). Both satisfying uniformity and dimensional stability (77.0–85.1% ASE) can be achieved through the described approach. Moreover, the described functionalization methods may also provide reference for WAW consolidation material designs and applications in other lignocellulosic materials in the future.

CAS / MDL: 20769-85-1 97-88-1
研究领域: 考古学 · 高分子科学 · 文物保护科学
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APPLIED SURFACE SCIENCE · 2017 · IF 3.387

Preparation and controlled drug delivery applications of mesoporous silica polymer nanocomposites through the visible light induced surface-initiated ATRP

Long Huang,Meiying Liu,Liucheng Mao,Dazhuang Xu,Qing Wan,Guangjian Zeng,Yingge Shi,Yuanqing Wen,Xiaoyong Zhang,Yen Wei

The mesoporous materials with large pore size, high specific surface area and high thermal stability have been widely utilized in a variety of fields ranging from environmental remediation to separation and biomedicine. However, surface modification of these silica nanomaterials is required to endow novel properties and achieve better performance for most of these applications. In this work, a new method has been established for surface modification of mesoporous silica nanoparticles (MSNs) that relied on the visible light induced atom transfer radical polymerization (ATRP). In the procedure, the copolymers composited with itaconic acid (IA) and poly(ethylene glycol)methyl acrylate (PEGMA) were grafted from MSNs using IA and PEGMA as the monomers and 10-Phenylphenothiazine(PTH) as the organic catalyst. The successful preparation of final polymer nanocomposites (named as MSNs-NH 2 -poly(IA- co -PEGMA)) were evidenced by a series of characterization techniques. More importantly, the anticancer agent cisplatin can be effectively loaded on MSNs-NH 2 -poly(IA- co -PEGMA) and controlled release it from the drug-loading composites with pH responsive behavior. As compared with conventional ATRP, the light induced surface-initiated ATRP could also be utilized for preparation of various silica polymer nanocomposites under rather benign conditions (e.g. absent of transition metal ions, low polymerization temperature and short polymerization time). Taken together, we have developed a rather promising strategy method for fabrication of multifunctional MSNs-NH 2 -poly(IA- co- PEGMA) with great potential for biomedical applications.

研究领域: 材料科学 · 纳米技术 · 生物医学工程 · 化学
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