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RSC Advances · 2017 ·Vol. 7 ·期 74 ·46812-46822 · IF 3.108

Preparation and evaluation of surface-grafted block copolymers and random copolymers via surface-initiated atom transfer radical polymerization for hydrophilic/ion-exchange stationary phases

Chunmiao Bo,Yinmao Wei

Mixed-mode chromatographic (MMC) stationary phases must be functionalized with at least two functional groups to yield multiple interactions. The present study proposed a novel approach of grafting copolymers with monomers with different properties via surface initiated-atom transfer radical polymerization (SI-ATRP) for the development of MMC stationary phases. In the synthesis, block copolymers and random copolymers containing sodium 4-styrenesulfonate (NASS) and dimethylaminoethyl methacrylate (DMAEMA) units were controllably grafted onto a silica surface via SI-ATRP for the preparation of hydrophilic/ion-exchange stationary phases. Upon investigation of their retention behaviors under different chromatographic conditions (i.e. water content, salt concentration and pH in mobile phase, column temperature) compared to a typical diol column, both the block and random copolymer stationary phases presented mixed-mode retention mechanisms involving hydrophilic and ion-exchange interactions. Furthermore, various solutes, such as basic β-agonists, strong polar nucleosides, organic acids, and a real sample of safflower injection, were employed to evaluate the separation selectivities of the stationary phases; similar selectivities and good separation efficiencies were achieved on the two copolymer columns. In conclusion, the method of surface-grafted copolymers via SI-ATRP possesses potential for further applications in the development of various MMC stationary phases.

研究领域: 分析化学 · 材料科学
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Polymer Chemistry · 2020 ·Vol. 11 ·期 35 ·5693-5700 · IF 5.342

Direct fluorination as a one-step ATRP initiator immobilization for convenient surface grafting of phenyl ring-containing substrates

Taijun He,Zhenyu Xing,Yixing Wang,Difeng Wu,Yang Liu,Xiangyang Liu

Generally, surface initiated-atom transfer radical polymerization (SI-ATRP) often suffers from the immobilization of the initiator on the surface-inert substrate. Developing an effective and versatile one-step method to anchor the priming sites while retaining the bulk properties of the substrate still faces challenges. In this work, direct fluorination is proposed to treat the benzene ring-containing substrate and the C–F introduced on the benzene ring can be used as an initiation site to achieve SI-ATRP. Computer and molecular simulation experiments have shown that the C–F added on the phenyl ring is more suitable for initiating ATRP than the C–F on the alkane chain. Thereafter, polyethylene terephthalate (PET) fabric was successfully grafted with fluorinated methacrylate polymer via direct fluorination-initiated ATRP, resulting in durable superhydrophobic properties, which demonstrated the practicability of the method. Furthermore, fluorination-initiated ATRP presents universality with other phenyl ring-containing polymeric substrates, such as aramid fiber, polyimide fiber and poly-p-phenylene benzobisoxazole fiber. Among them, the fluorinated aramid fiber can be grafted with hydroxyethyl methacrylate to obtain increased interfacial shear strength.

研究领域: 材料科学 · 高分子化学
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JOURNAL OF FLUORINE CHEMISTRY · 2013 · IF 1.939

Synthesis, characterization and bulk properties of well-defined poly(hexafluorobutyl methacrylate)-block-poly(glycidyl methacrylate) via consecutive ATRP

Bingyan Jiang,Lei Zhang,Jingzhi Shi,Shoufa Zhou,Bing Liao,Hailu Liu,Jingxin Zhen,Hao Pang

A well-defined fluorine-containing copolymer with pendant epoxy groups , poly(2,2,3,4,4,4-hexafluorobutyl methacrylate-block-glycidyl methacrylate) (PHFBMA- b -PGMA), was prepared by sequential atom transfer radical polymerization (ATRP). The amphiphilic copolymer PHFBMA- b -PGMA(OH) with pendant hydroxyl groups was obtained after ring-opening reaction of the epoxy groups from PGMA. The macroinitiator agent PHFBMA-Br and its copolymers were proved to be successfully synthesized by characterization of FTIR, 1 H NMR and gel permeation chromatography (GPC). The chain growth experiment demonstrated that a linear first-order relationship was fitted under the conditions. In addition, the fluorinated copolymers with functional groups in the side chain could keep the contact angle and the advantages of fluoropolymers while improving the hydrophilic property. Meanwhile, TGA testing showed that the copolymers had better thermal stability than its homopolymer. TEM observation indicated that microspheres were embedded in the stable micelles when the final copolymer concentration of aqueous solution was 1   wt%.

研究领域: 高分子化学 · 材料科学 · 纳米医学 · 表面科学 · 生物材料 · 药物递送系统
✓ 已验证 DOI 高影响因子
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RSC Advances · 2015 ·Vol. 5 ·期 81 ·65884-65889 · IF 3.84

Fabrication of amphiphilic fluorescent polylysine nanoparticles by atom transfer radical polymerization (ATRP) and their application in cell imaging

Zengfang Huang,Xiqi Zhang,Xiaoyong Zhang,Shiqi Wang,Bin Yang,Ke Wang,Jinying Yuan,Lei Tao,Yen Wei

Due to the good biocompatibility, ε-polylysine (Ply) has been extensively investigated for various biomedical applications. In this study, a fluorescent monomer (named Flu-MA) was firstly synthesized through acylation reaction of fluorescein by methacryloyl chloride, and the initiator of ε-polylysine bromide (named Ply-Br) was prepared by the introduction of a bromine atom into Ply by the acylation reaction of Ply with α-bromoisobutyryl bromide. Subsequently, a novel amphiphilic fluorescent polymer (Flu-Ply) was successfully fabricated by ATRP via incorporation of Flu-MA monomer into Ply chains for the first time. The structure and properties of the obtained Flu-Ply fluorescent polymer were investigated in detail by 1H NMR, TEM, UV-vis, FL and FTIR, and the results confirmed the successful incorporation of Flu-MA into Ply by ATRP. As a result of Flu-MA and Ply respectively endowing the as-prepared Flu-Ply polymer with fluorescence and water dispersibility, it tended to self-assemble into fluorescent organic nanoparticles (FONs) with excellent biocompatibility. More importantly, the good fluorescence, uniform spherical morphology, excellent biocompatibility and water dispersibility of Flu-Ply FONs exhibited an attractive prospect for bioimaging applications.

✓ 已验证 DOI 高影响因子
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2018 · IF 3.141

Preparation of UV-Blocking Poly(vinylidene fluoride) Films through SI-AGET ATRP Using a Colorless Polydopamine Initiator Layer

Li Dong,Xiangdong Liu,Zhengrong Xiong,Dekun Sheng,Changhong Lin,Yan Zhou,Yuming Yang

Herein, the functional poly(vinylidene fluoride) (PVDF) film that has a superior UV-blocking performance was made through the surface-initiated activators regenerated by electron transfer atom-transfer radical polymerization (SI-AGET ATRP). The colorless polydopamine (PDA) initiator layer was adhered to the alkaline-pretreated PVDF film through the copolymerization of dopamine (DOPA) and initiator-bearing DOPA (DOPA-BIBB). Then the reactive organic UV absorbent [3-(4-benzoyl-3-hydroxyphenoxy)-2-hydroxypropyl] 2-methylprop-2-enoate (BPMA) was incorporated to the initiator layer by the SI-AGET ATRP method, resulting in the formation of a PBPMA-chain-grafted PVDF film (PVDF-g-PBPMA). Furthermore, the effects of the experimental conditions such as the BPMA concentration and reaction time on the performance of as-prepared modified films were investigated. The characterization results indicated the formation of the PBPMA film on the PVDF film surface and the outstanding UV-blocking performance of the modified films. The PVDF-g-PBPMA film fabricated under the optimum conditions could completely block the UV light in the range of 200–370 nm.

研究领域: 材料科学 · 高分子化学 · 光化学
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SCIENCE AND TECHNOLOGY OF ADVANCED MATERIALS · 2026 · IF 6.6

DOX-conjugated unimolecular micelles from benzaldehyde-functionalized star copolymer via metal-free ATRP for pH-responsive drug delivery

Wei Ma,Hongyan Yang,Xinyue Ma,Jiao Huang,Li Chen,Atsushi Takahara

The development of polymer prodrugs with well-defined architectures capable of forming stable nanomicelles is important for achieving precise and efficient drug delivery. Compared with conventional linear systems, star-shaped copolymer prodrugs offer enhanced micellar stability owing to their covalently tethered architecture. However, many existing synthetic approaches rely on transition-metal catalyzed polymerization and customized monomers, which limit their sustainability and practical applicability. Herein, we report a pH-responsive doxorubicin (DOX)-conjugated benzaldehyde-functionalized star-shaped copolymer synthesized via an environmentally benign metal-free atom transfer radical polymerization (ATRP) strategy. A hydroxyl-functionalized star-shaped copolymer scaffold was first prepared from readily available monomers and subsequently modified to introduce pendant benzaldehyde groups, enabling DOX conjugation through acid-labile imine linkages. This approach affords well-controlled polymer architectures while avoiding transition-metal residues and the need for pre-functionalized monomers. The resulting DOX-conjugated star-shaped copolymers form unimolecular micelles with high colloidal stability and exhibit pH-triggered drug release under acidic conditions. In vitro studies further demonstrate effective cellular internalization and a moderated cytotoxic profile toward human large-cell lung carcinoma (H460) cells, supporting the functional viability of this micellar system as a polymer prodrug delivery platform.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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Polymers · 2018 ·Vol. 10 ·期 5 ·557 · IF 2.935

Preparation, Structure, and Properties of Silk Fabric Grafted with 2-Hydroxypropyl Methacrylate Using the HRP Biocatalyzed ATRP Method

Jinqiu Yang,Shenzhou Lu,Tieling Xing,Guoqiang Chen

Atom transfer radical polymerization (ATRP) is a “living”/controlled radical polymerization, which is also used for surface grafting of various materials including textiles. However, the commonly used metal complex catalyst, CuBr, is mildly toxic and results in unwanted color for textiles. In order to replace the transition metal catalyst of surface-initiated ATRP, the possibility of HRP biocatalyst was investigated in this work. 2-hydroxypropyl methacrylate (HPMA) was grafted onto the surface of silk fabric using the horseradish peroxidase (HRP) biocatalyzed ATRP method, which is used to improve the crease resistance of silk fabric. The structure of grafted silk fabric was characterized by Fourier transform infrared spectrum, X-ray photoelectron spectroscopy, thermogravimetic analysis, and scanning electron microscopy. The results showed that HPMA was successfully grafted onto silk fabric. Compared with the control silk sample, the wrinkle recovery property of grafted silk fabric was greatly improved, especially the wet crease recovery property. However, the whiteness, breaking strength, and moisture regain of grafted silk fabric decreased somewhat. The present work provides a novel, biocatalyzed, environmentally friendly ATRP method to obtain functional silk fabric, which is favorable for clothing application and has potential for medical materials.Keywords:horseradish peroxidase;atom transfer radical polymerization;bio-catalysis;silk

CAS / MDL: 9003-99-0
研究领域: 材料科学 · 纺织工程 · 生物化学
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JOURNAL OF MATERIALS SCIENCE · 2015 ·Vol. 51 ·期 3 ·1363-1375 · IF 2.371

Novel multiwalled carbon nanotube grafted with polyethylene glycol-block-polystyrene nanohybrids: ATRP synthesis and detection of benzene vapor

Luo Yan-Ling,Bai Rui-Xue,Xu Feng,Chen Ya-Shao,Li Hua,Dai Si-Si,Ma Wen-Bo

Novel multiwalled carbon nanotube graft polyethylene glycol -block -polystyrene copolymer nanohybrids (MWCNTs- g -PEG- b -PS) were prepared via atom transfer radical polymerization using carboxylated MWCNTs (MWCNTs–COOH) as a conductive carrier. The chemical structure and the compositions of graft copolymer nanohybrids were characterized by Fourier transform infrared spectroscopy, Raman spectroscopy, thermogravimetry, and gas chromatography, and the morphologies and dispersion behavior were observed by ultraviolet visible spectrophotometer, scanning electron microscope, and transmission electron microscope etc. The MWCNTs- g -PEG- b -PS-grafted copolymer nanohybrids were fabricated into conductive composite thin film sensors to investigate their responsiveness to benzene vapor. The influence of the molecular weights or compositional ratios of PEG and PS blocks on the conductivity of the conducting polymer nanohybrids and responsibility towards benzene vapor was investigated. The conducting polymer nanohybrid film sensors were demonstrated to possess the characteristics of quick response and good restorability, repeatability, and stability.

CAS / MDL: 3033-62-3 3030-47-5
研究领域: 材料科学 · 化学工程 · 环境监测
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2014 · IF 3.552

Blood compatibility comparison for polysulfone membranes modified by grafting block and random zwitterionic copolymers via surface-initiated ATRP

Tao Xiang,Li-Sha Zhang,Rui Wang,Yi Xia,Bai-Hai Su,Chang-Sheng Zhao

For blood-contacting materials, good blood compatibility, especially good anticoagulant property is of great importance. Zwitterionic polymers have been proved to be resistant to nonspecific protein adsorption and platelet adhesion; however, their anticoagulant property is always inadequate. In this study, two kinds of zwitterionic copolymers (sulfobetaine methacrylate and sodium p-styrene sulfonate random copolymer and block copolymer) with sulfonic groups were covalently grafted from polysulfone (PSf) membranes via surface-initiated atom transfer radical polymerization (SI-ATRP) to improve blood compatibility. Field emission scanning electron microscopy (FE-SEM), attenuated total reflectance–Fourier transform infrared spectra (ATR–FTIR), X-ray photoelectron spectroscopy (XPS), and static water contact angle (WCA) were applied to characterize the morphologies, chemical compositions and hydrophilicity of the modified membranes. All the zwitterionic copolymer modified membranes showed improved blood compatibility, especially the anticoagulant property was obviously enhanced compared to the pristine PSf and simple zwitterionic polymer modified membranes. We also found that the random copolymer modified membranes showed better resistance to platelet adhesion than the block copolymer modified membranes. The zwitterionic copolymer modified membranes with integrated antifouling property and blood compatibility provided wide choice for specific applications such as hemodialysis, hemofiltration, and plasma separation.

研究领域: 生物材料 · 医学工程 · 高分子化学
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JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY · 2014 ·Vol. 52 ·期 20 ·2998-3003 · IF 3.245

One-Pot synthesis of functional poly(methacrylate) by ATRP and 1,8-Diazacyclo-[5,4,0]undec-7-ene catalyzed transesterification

Jinbao Xu,Weizhen Lian,Stergios Pispas,Guangzhao Zhang

A facile one-pot 1,8-diazacyclo-[5,4,0]undec-7-ene (DBU) catalyzed transesterification/atom transfer radical polymerization (ATRP) strategy has been successfully developed through the combination of copper/DBU-catalyzed ATRP and DBU-catalyzed transesterification reactions. Well-defined poly(methacrylate)s with various side ester groups have been synthesized by ATRP and transesterification of acyl donor 2,2,2-trifluoethyl methacrylate with various alcohols, such as benzyl alcohol, n -butanol, iso -propyl alcohol, methanol, triethylene glycol monomethyl ether, propargyl alcohol, and 6-azido-1-hexanol by the one-pot process. Kinetic studies indicate that the ATRP process proceeded in a controllable manner without the interference of the transesterification reactions. Expansion of the binary system to a higher level ternary system has been successfully achieved by the combination of copper(I)-catalyzed azide–alkyne cycloaddition, transesterification, and ATRP reactions. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52 , 2998–3003

CAS / MDL: 100-51-6 71-36-3 67-56-1
研究领域: 高分子化学 · 材料科学
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MATERIALS CHEMISTRY AND PHYSICS · 2017 · IF 2.084

Preparation of polymeric silica composites through polydopamine-mediated surface initiated ATRP for highly efficient removal of environmental pollutants

Qiang Huang,Meiying Liu,Qing Wan,Ruming Jiang,Liucheng Mao,Guangjian Zeng,Hongye Huang,Fengjie Deng,Xiaoyong Zhang,Yen Wei

In this study, we developed a new procedure to prepare monodispersed functionalized SiO 2 (SiO 2 -PDA-PDMC) composites via mussel inspired chemistry and surface initiated atom transfer radical polymerization (SI-ATRP). Samples were characterized by transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and thermal gravimetric analysis (TGA) measurements. TEM results showed that spherical morphology was unchanged after the functionalization. FT-IR results confirmed the successful modification with polydopamine (PDA) and the presence of poly-([2-(Methacryloyloxy) ethyl] trimethylammonium chloride) (PDMC) layer on the surface of SiO 2 spheres. TGA data showed that the PDMC account for about 12.12 wt% in the sample of SiO 2 -PDA-PDMC composites. The XPS analysis further confirmed the existence of PDMC on the surface of SiO 2 -PDA-PDMC composites. The obtained SiO 2 -PDA-PDMC composites were used as adsorbent for the removal of Congo red (CR) from aqueous solution to evaluate the performance in environment application. The effect of contact time, solution pH, initial CR concentration and temperature on the adsorption of CR onto SiO 2 -PDA-PDMC composites was investigated. Adsorption results demonstrated that adsorption of CR onto SiO 2 -PDA-PDMC composites was a fast and efficient process. The adsorption equilibrium reached within 60 min, and the adsorption process followed the pseudo-second-order model. The experimental data of isotherms were better described by the Freundlich model. Thermodynamic study depicted the endothermic nature of adsorption and the process was spontaneous. Results from the effect of solution pH on the CR adsorption showed that the acidic condition favors the adsorption and provided evidence for the contribution of PDMC on the SiO 2 -PDA-PDMC composites in the removal of CR. This study suggests SiO 2 -PDA-PDMC composites can be developed as a new adsorbent for the removal of anionic dyes from aqueous solution.

研究领域: 环境科学 · 材料科学
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CARBOHYDRATE POLYMERS · 2021 · IF 9.381

Surface modification of cellulose nanocrystals via SI-AGET ATRP and application in waterborne coating for removing of formaldehyde

Zhiwei Yu,Qianru Sun,Yu Sheng,Yu Xi,Liangjiu Bai,Wenxiang Wang,Hou Chen,Huawei Yang,Lixia Yang

The hazardous indoor air pollutants of formaldehyde (HCHO) are harmful for human health. Nowadays, it is important to design and fabricate green and efficient HCHO removal materials for HCHO removal from polluted indoor air. In this manuscript, cellulose nanocrystals (CNCs) as green nanomaterials were successfully surface-initiated by 2-(methacryloyloxy)ethyl acetoacetate (MEAA) as functional monomer via surface-initiated Activator Generated by Electron Transfer Atom Transfer Radical Polymerization (SI-AGET ATRP) for the application in removal of HCHO. The employment of CNCs/Poly(2-(methacryloyloxy)ethyl acetoacetate) (CNCs@PMEAA) as nanocomposites were further implanted self-healing waterborne coating for an effective way to remove HCHO. From the result, the HCHO removal efficiency reached 97.5% of CNCs@PMEAA-type coating within 300 min at room temperature , which was much higher than that of the conventional coating (82.8%). This study provides some promising green methods for designing nanocomposite's waterborne coating to remove HCHO at room temperature.

研究领域: 材料科学 · 环境科学 · 绿色化学
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