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DYES AND PIGMENTS · 2018 · IF 3.767

Synthesis and biological imaging of fluorescent polymeric nanoparticles with AIE feature via the combination of RAFT polymerization and post-polymerization modification

Yanzhu Liu,Liucheng Mao,Saijiao Yang,Meiying Liu,Hongye Huang,Yuanqing Wen,Fengjie Deng,Yongxiu Li,Xiaoyong Zhang,Yen Wei

In recent years, florescent polymeric nanoparticles (FPNs) containing aggregation-induced emission (AIE) fluorogens have received great intention for their potential applications in biological imaging and theranostic nanomedicine . Herein, we have developed AIE-active FPNs through a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and post-polymerization modification strategies. The salicylaldehyde (SA) containing zwitterionic copolymers are fabricated via RAFT polymerization and further modified by benzophenone hydrazone (BPH) via Schiff base reaction. The obtained AIE-active amphiphilic copolymers BPH-poly(FHMA- co -MPC) can self-assemble in aqueous solution with the hydrophobic fluorogens aggregating together to form the core and the hydrophilic chains to form the protective shell. BPH-poly(FHMA- co -MPC) and the resulting FPNs are characterized by 1 H nuclear magnetic resonance spectroscopy , Fourier transform infrared spectroscopy, transmission electron microscopy and fluorescence spectroscopy . Results demonstrate that BPH-poly(FHMA- co -MPC) are successfully synthesized and as-prepared BPH-poly(FHMA- co -MPC) FPNs exhibit desirable morphology and size, good dispersibility , high brightness, remarkable photostability and large Stokes shifts . More importantly, through cytotoxicity test and cell uptake behavior, these BPH-poly(FHMA- co -MPC) FPNs show low toxicity and excellent cell dyeing behavior. Taken together, we have developed a facile and effective method for the fabrication of AIE-active FPNs, which display great potential for biomedical applications .

CAS / MDL: 78-67-1 30525-89-4
研究领域: 材料科学 · 生物医学工程 · 高分子化学
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Polymer Chemistry · 2018 ·Vol. 9 ·期 30 ·4150-4160 · IF 4.927

Highly efficient luminescent side-chain polymers with short-spacer attached tetraphenylethylene AIEgens via RAFT polymerization capable of naked eye explosive detection

Qian Li,Xiao Li,Zhongying Wu,Yuhao Sun,Jianglin Fang,Dongzhong Chen

Tetraphenylethylene (TPE) is one of the well-known typical aggregation-induced emission (AIE) luminogens (AIEgens) and TPE-containing polymers possess excellent processing properties which facilitates the fabrication of various AIE systems and devices. For AIE active side-chain polymers, increasing the fluorescence quantum yield through suitable molecular design is very appealing. In this work, we present the well-controlled synthesis of a series of TPE polyacrylate side-chain polymers of Pm with short spacers with methylene number m = 0–5 via RAFT polymerization. All the obtained polymers exhibit typical and strong AIE characteristics in THF/H2O solution mixtures and in solid state films. In particular, greatly enhanced fluorescence emission is achieved with reduced spacer lengths, and further significant improvement achieved through annealing, which is ascribed to the restriction of intramolecular motions (RIM) and the blocking of the non-radiative channels due to overcrowding and confinement thanks to the strong positive coupling effect and the jacketing effect of side-chain polymers with very short spacers. The quantum yields of 34.4%, 32.0% and 31.4%, respectively, for the polymer films P0, P1 and P2 are several times higher than those of homologous polymers with longer spacers reported in the literature. Based on these TPE side-chain polymers of very short spacers, a simple, economic and visual method for detection of the explosive 2,4,6-trinitrotoluene (TNT) is demonstrated. Therefore, a facile approach and feasible strategy of simply adopting very short spacers for side-chain AIE active polymer preparation to significantly enhance the luminescence efficiency has been properly established and proposed, which may provide guidance and have a wealth of implications for the rational design and preparation of highly efficient luminescent AIE polymer materials.

CAS / MDL: 78-67-1
研究领域: 材料科学 · 高分子化学 · 分析化学 · 纳米技术
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Materials Chemistry Frontiers · 2016 ·Vol. 1 ·期 6 ·1051-1058 · IF 0

A powerful “one-pot” tool for fabrication of AIE-active luminescent organic nanoparticles through the combination of RAFT polymerization and multicomponent reactions

Qing Wan,Ruming Jiang,Liucheng Mao,Dazhuang Xu,Guangjian Zeng,Yingge Shi,Fengjie Deng,Meiying Liu,Xiaoyong Zhang,Yen Wei

Multicomponent reactions (MCRs) have recently received increasing attention for the synthesis of structural complexity in a single step from three or more reactants. They have also been considered as a powerful tool for the construction of sequence-controlled multifunctional polymers owing to their good substrate adaptability, simple operation and high efficiency. In this work, we reported methods that are a combination of the three-component mercaptoacetic acid locking imine (MALI) reaction and reversible addition fragmentation chain transfer (RAFT) polymerization in one pot to form luminescent organic nanoparticles (LONs) with aggregation-induced emission (AIE) features, high-brightness, great water dispersibility, ultra-small nanoscale size and excellent biocompatibility. In the reaction system, the MALI reaction and RAFT polymerization happened simultaneously in a “one-pot” route. On the one hand, the AIE-active organic dye with one amino group ((Z)-3-(4-aminophenyl)-2-(10-hexadecyl-10H-phenothiazin-3-yl)acrylonitrile) (named as Phe-NH2) was conjugated with an aldehyde-containing monomer (10-undecenal) by the MALI reaction, while the aldehyde-containing monomer was copolymerized with the hydrophilic monomer polyethylene glycol methyl methacrylate (PEGMA) through RAFT polymerization at the same time. Compared with other fabrication strategies, “one-pot” strategies possess some advantages such as high efficiency, simplicity, and atom economy. On the other hand, due to the good applicability of RAFT polymerization and the MALI reaction, many other multifunctional AIE-active LONs could also be fabricated via adjusting the function of the substrates. Therefore, this strategy should be a general and important route for fabrication of AIE-active materials for different applications.

研究领域: 材料科学 · 化学 · 生物医学工程
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2019 · IF 4.784

Graft modification of lignin-based cellulose via enzyme-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization and free-radical coupling

Xueming Bao,Xuerong Fan,Yuanyuan Yu,Qiang Wang,Ping Wang,Jiugang Yuan

In this study, a green approach combining enzyme-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization and free-radical coupling was developed for the modification of jute fiber , which is a typical lignin-based cellulose. Jute fiber surface was covered by rich amount of lignin, which offered great opportunities for further functional modification. The controlled polymerization of vinyl monomers , acrylamide (AM) or butyl acrylate (BA), was carried out by horseradish peroxidase (HRP)-initiated RAFT to form well-defined polymers with well-controlled molecular weights and structures. Enzymatic grafting by HRP occurred between the free radicals of well-defined polymers and free radicals of lignin on jute. Gel permeation chromatography (GPC) analysis indicated the alkyl chain length of polymers prepared via HRP-initiated RAFT polymerization was well-controlled. Other results of flourier transformed infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) revealed that well-controlled alkyl chains prepared via enzymatic catalysis were grafted on the exposed lignin of jute. The study explores a new and eco-friendly modification method for lignin-based materials with the controlled graft chain structure via two different catalysis with HRP.

研究领域: 材料科学 · 生物化学
✓ 已验证 DOI 高影响因子
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Polymer Chemistry · 2025 · IF 3.9

Preparation and performance characterization of block cross-linked copolymers PCaPE(Br) and PCaPE(I) via RAFT polymerization and quaternization reaction

Chaoyue Shan,Haohao Zhang,Yan Gao,Hui Wang,Li Han,Yuanyuan Du,Wen He,Mingyuan Pang,Xing Gao,Yen Leng Pak

Reversible addition–fragmentation chain transfer (RAFT) polymerization enables precise regulation of polymer chain growth and active center distribution. This study adopted a two-step approach with RAFT polymerization followed by quaternization to synthesize antibacterial materials, specifically tunable porous polymers PCaPE(Br) and PCaPE(I). The work focused on the structure–activity relationship between RAFT-derived block structures and the antibacterial properties of these materials. RAFT-mediated polymerization precisely controlled the block copolymer precursor PE-PDE, which is PEMA-b-P(DMAEA-co-EGDMA), and this control facilitated the subsequent formation of ordered porous structures. When the molar ratio of poly(ethyl methacrylate) (PEMA) to ethylene glycol dimethacrylate (EGDMA) was set to 1 : 6, the final quaternized products PCaPE2(Br) and PCaPE2(I) exhibited porous and fluffy microstructures. These microstructures were characterized by large specific surface area and high porosity. This structure, combined with uniformly distributed quaternary ammonium salt groups from the quaternization of N,N-dimethylaminoethyl acrylate (DMAEA) tertiary amine groups, enhanced the contact between antibacterial active sites and bacteria as well as antibacterial efficacy. PCaPE(Br) and PCaPE(I) showed excellent broad-spectrum antibacterial activity against E. coli and S. aureus. They also maintained good reusability with over 95% activity retention after five cycles. Such advantages support their prospects in biomedicine, agricultural antibacterials and wastewater treatment.

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POLYMER · 2018 · IF 3.483

Synthesis of bioreducible core crosslinked star polymers with N,N′-bis(acryloyl)cystamine crosslinker via aqueous ethanol dispersion RAFT polymerization

Qijing Chen,Fei Han,Chao Lin,Xuejun Wen,Peng Zhao

The aim of this study is to synthesize well-defined bioreducible core crosslinked star (CCS) polymers via heterogeneous reversible addition-fragmentation transfer (RAFT) polymerization in aqueous ethanol solutions. To this end, water-soluble linear arm polymers, poly (poly (ethylene glycol) methyl ether methacrylate) (PPEGMA), poly (2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly ( N , N -dimethylacrylamide) (PDMA), were prepared respectively. Next, heterogenous RAFT polymerization of the polymers with N , N ′-bis(acryloyl)cystamine (BAC) as a crosslinker was systemically investigated in an aqueous ethanol solvent. It was found that these bioreducible CCS polymers with crosslinked BAC core could be prepared successfully depending on polymerization parameters. The formation of PPEGMA-based CCS polymers was affected by water volume fraction ( V w ) of water-ethanol solution, reaction time, arm polymer concentration, and spacing monomer . Besides, at an optimal V w of 80% ( i . e . the molar concentration of water is 44.44 M) and arm polymer concentration of 10% (w/v), PPEGMA-based CCS polymers at >90% yield could be achieved within 1 h. By the same V w and reaction time, PDMAEMA- and PDMA-based CCS polymers could also be prepared with high yield (>75%). The mechanism underlying the formation of the CCS polymers was ascribed to enhanced driving force of polymerization-induced self-assembly at an optimal V w . These CCS polymers were degradable in thiol-containing dithiothreitol, suggesting their potential application for drug release in a reductive intracellular environment.

研究领域: 材料科学 · 生物医学工程
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2018 · IF 2.829

Dispersion copolymerization of acrylamide and sodium 2-acrylamido-2-methylpropanesulfonate in aqueous salt solution stabilized with a macro-RAFT agent

Shaoling Bai,Yaqi Wang,Bin Liu,Yujie Zhu,Ruiwei Guo

Dispersion copolymerization of acrylamide (AM) and sodium 2-acrylamido-2-methylpropanesulfonate (AMPSNa) in aqueous ammonium sulfate (AS) solution was performed without mechanical stirring using a macro-RAFT agent sodium poly(2-acrylamido-2-methylpropanesulfonate) trithiocarbonate (PAMPSNa-TTC) as the stabilizer and 2,2′-azobis(2-methylpropionamide) dihydrochloride as the initiator. The effects of various polymerization parameters were systematically investigated regarding dispersion stability, particle size, molecular weight and apparent viscosity. A new mechanism for particle formation and the particle stability of aqueous dispersion polymerization was proposed.

CAS / MDL: 7440-38-2
研究领域: 高分子化学 · 材料科学
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MACROMOLECULES · 2010 · IF 4.539

Synthesis of CO2-philic Xanthate−Oligo(vinyl acetate)-Based Hydrocarbon Surfactants by RAFT Polymerization and Their Applications on Preparation of Emulsion-Templated Materials

Keping Chen,Neil Grant,Liyun Liang,Haifei Zhang,Bien Tan

Amphiphilic block copolymers poly(ethylene glycol)-block-oligo(vinyl acetate) (PEG-b-OVAc) and OVAc-b-PEG-b-OVAc have been demonstrated to be effective surfactants for CO2-in-water (C/W) emulsions. However, the high cost and difficulty of synthesis process can render the economics of CO2 process unfavorable. In this work, by reversible addition−fragmentation chain transfer (RAFT) polymerization, a series of well-defined CO2-philic triblock copolymers X−OVAc-b-PEG-b-OVAc−X (where X stands for xanthate group) were synthesized. The structures and molecular weights of these copolymers were characterized by 1H NMR and GPC. The results of GPC analysis exhibited relatively narrow polydispersity (PDI < 1.35). The process of preparation of X−OVAc-based surfactants was much more simple, inexpensive and also easy to control, which could promote industrial-scale applications. The X−OVAc-based surfactants were found effectively to produce highly concentrated stable C/W emulsions. Porous emulsion-templated materials were prepared by the polymerization of the continuous phase of C/W emulsions. The open-cell morphology of the emulsion-templated materials was evidenced by scanning electron microscope. To tune the morphology of the porous structures, the influence of the surfactant concentration and molecular weight of OVAc block were also investigated. It was shown that X−OVAc-based surfactants can outperform perfluorinated surfactants and approach OVAc-based surfactants for such applications.

研究领域: 高分子化学 · 材料科学 · 表面活性剂化学
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MACROMOLECULAR BIOSCIENCE · 2017 ·Vol. 17 ·期 7 ·1600444 · IF 3.238

Novel Anti-Biofouling Soft Contact Lens: l-Cysteine Conjugated Amphiphilic Conetworks via RAFT and Thiol–Ene Click Chemistry

Chengfeng Zhang,Ziyuan Liu,Haiye Wang,Xiaofeng Feng,Chunju He

A unique l -cysteine conjugated antifouling amphiphilic conetwork (APCN) is synthesized through end-crosslinking of well-defined triblock copolymers poly(allyl methacrylate)- b -poly(ethylene glycol)- b -poly(allyl methacrylate) via a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and thiol–ene “click” chemistry. The synthesized poly(ethylene glycol) macro-RAFT agent initiates the polymerization of allyl methacrylate in a controlled manner. The vinyl pendant groups of the precursor partially conjugate with l -cysteine and the rest fully crosslink with mercaptopropyl-containing siloxane via thiol–ene click chemistry under UV irradiation into APCNs, which show distinguished properties, that is, excellent biocompatibility, more than 39.6% water content, 101 barrers oxygen permeability, optimized mechanical properties, and more than 93% visible light transmittance. What's more, the resultant APCNs exhibit eminent resistance to protein adsorption, where the bovine serum albumin and lysozyme adsorption are decreased to 12 and 21 µg cm −2 , respectively. The outstanding properties of APCNs depend on the RAFT controlled method, which precisely designs the hydrophilic/hydrophobic segments and eventually greatly improves the crosslinking efficiency and homogeneity. Meantime, the l -cysteine monolayer can effectively reduce the surface hydrophobicity and prevent protein adsorption, which exhibits the viability for antifouling surface over and under ophthalmic devices, suggesting a promising soft contact lens.

研究领域: 材料科学 · 聚合物化学 · 生物医学工程
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RSC Advances · 2014 ·Vol. 5 ·期 14 ·10611-10618 · IF 3.708

One-pot synthesis of magnetic molecularly imprinted microspheres by RAFT precipitation polymerization for the fast and selective removal of 17β-estradiol

Jinhua Li,Ruichen Dong,Xiaoyan Wang,Hua Xiong,Shoufang Xu,Dazhong Shen,Xingliang Song,Lingxin Chen

A facile strategy was developed to prepare magnetic molecularly imprinted microspheres (MMIMs) for the selective recognition and effective removal of 17-beta-estradiol (17β-E2) by reversible addition-fragmentation chain transfer precipitation polymerization. One-pot synthesis was employed, which could simplify the imprinting process and shorten the experimental period. The resultant MMIMs displayed fast kinetics and high binding capacity, and the adsorption processes followed Langmuir–Freundlich isotherm and pseudo-second-order kinetic models. Excellent recognition selectivity toward 17β-E2 was attained over other phenolic estrogens such as 17-alpha-E2, estriol and estrone. The magnetic property of MMIMs provided fast and simple separation, and the recycling process for magnetic solid phase extraction (MSPE) was sustainable at least five times without obvious efficiency decrease. Furthermore, the MMIMs-MSPE presented satisfactory recoveries within 71.7–108.3% with the precisions of 1.1–6.0% for spiked 17β-E2 in water, soil and food samples. The developed MMIMs-based method proved to be a convenient and practical way in sample pretreatment and targeted pollutants removal.

CAS / MDL: 80-05-7 100-58-3
研究领域: 环境科学 · 分析化学
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RSC Advances · 2013 ·Vol. 3 ·期 44 ·21817-21823 · IF 2.562

Mussel inspired modification of carbon nanotubes using RAFT derived stimuli-responsive polymers

Xiaoyong Zhang,Jinzhao Ji,Xiqi Zhang,Bin Yang,Meiying Liu,Wanyun Liu,Lei Tao,Yiwang Chen,Yen Wei

A novel strategy for surface modification of multi-walled carbon nanotubes (MWCNTs) using reversible addition fragmentation transfer (RAFT) derived pH- and thermo-responsive polymers was developed via a combination of mussel inspired chemistry and a Michael addition reaction. In this procedure, pristine MWCNTs were first coated with polydopamine through self polymerization of dopamine under alkine solution, and then RAFT derived stimuli-responsive polymers were further grafted onto PDA modified MWCNTs via a Michael addition reaction. The successful modification of MWCNTs was confirmed by a series of characterization techniques including transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, thermal gravimetric analysis and X-ray photoelectron spectrometry. These polymer modified CNTs showed enhanced dispersibility in various solutions and pH-/temperature-responsive properties. Due to the strong adhesion of polydopamine to various materials surface, the method described in this work could also be extended to the surface modification of other nanomaterials.

CAS / MDL: 2210-25-5 79-41-4
研究领域: 材料科学 · 聚合物化学 · 纳米技术
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Polymers · 2017 ·Vol. 9 ·期 3 ·89 · IF 3.364

RAFT Polymerization of Styrene and Maleimide in the Presence of Fluoroalcohol: Hydrogen Bonding Effects with Classical Alternating Copolymerization as Reference

Fangjun Yao,Qingqing Liu,Zhengbiao Zhang,Xiulin Zhu

The impacts of hydrogen bonding on polymerization behavior has been of interest for a long time; however, universality and in-depth understanding are still lacking. For the first time, the effect of hydrogen bonding on the classical alternating-type copolymerization of styrene and maleimide was explored.N-phenylmaleimide (N-PMI)/styrene was chosen as a model monomer pair in the presence of hydrogen bonding donor solvent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), which interacted with N-PMI via hydrogen bonding. Reversible addition-fragmentation chain transfer polymerization (RAFT) technique was used to guarantee the “living” polymerization and thus the homogeneity of chain compositions. In comparison with the polymerization in non-hydrogen bonding donor solvent (toluene), the copolymerization in HFIP exhibited a high rate and a slight deviation from alternating copolymerization tendency. The reactivity ratios of N-PMI and St were revealed to be 0.078 and 0.068, respectively, while the reactivity ratios in toluene were 0.026 and 0.050. These interesting results were reasonably explained by using computer simulations, wherein the steric repulsion and electron induction by the hydrogen bonding between HFIP and N-PMI were revealed. This work first elucidated the hydrogen bonding interaction in the classical alternating-type copolymerization, which will enrich the research on hydrogen bonding-induced polymerizations.Keywords:alternating copolymerization;hydrogen bonding;N-phenylmaleimide;fluoroalcohol;reversible addition-fragmentation chain transfer (RAFT) copolymerization

CAS / MDL: 75-89-8
研究领域: 高分子化学 · 物理化学
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