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MICROCHEMICAL JOURNAL · 2020 · IF 3.594

Ultrasensitive detection of CYFRA 21-1 DNA via SI-RAFT based in-situ metallization signal amplification

Lulu Hao,Liying Zhao,Guangbao Li,Yingying Li,Ligang Ma,Yanju Liu,Wenbin Wang,Jinming Kong

Cytokeratin fragment antigen 21-1 (CYFRA 21-1) DNA is a significant biomarker with relation to non-small cell lung cancer. Here, we described an ultrasensitive electrochemical biosensor for detection of CYFRA 21-1 DNA (target DNA, tDNA) via surface-initiated reversible addition fragmentation chain transfer (SI-RAFT) polymerization-based DNA metallization signal amplification strategy. Specifically, 5′terminal modified thiol peptide nucleic acid (PNA) probes are immobilized on the gold electrode surface (by Au-S selfassembly) for the identification of specific tDNA sequences. After hybridization, the 4-cyano-4-(phenylcarbonothioylthio) pentanoic acid (CPAD) is tethered to the PNA/DNA duplexes by means of the recognized phosphate-Zr 4+ -carboxylate chemistry. Subsequently, in the situation of C 3 H 4 O as the monomer, SI-RAFT polymerization can bring numerous aldehyde groups sites for the subsequent silver mirror reaction. The acrolein-polymers act as reductant to reduce Ag + into Ag 0 , and then the silver particles are deposited on the polymer skeleton, which significantly amplifies the electrochemical signal. Under optimal conditions, the designed sensor for tDNA detection show a wide linear range from 100 aM to 1 nM, and the detection limit is as low as 0.89 aM. Moreover, the proposed biosensor exhibits prominent applicability for analysis of tDNA in serum samples and high selectivity for different mismatched oligonucleotide fragments. Given the proposed biosensor without extra natural enzyme or bio-labels, this method has enormous potential in bioanalysis.

CAS / MDL: 201611-92-9 1633-78-9
研究领域: 生物技术 · 医学诊断 · 分子生物学
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ACS Applied Bio Materials · 2025 · IF 4.7

Synthesis of “Offensive and Defensive Integrated” Cyclodextrin-Grafted N+-borneol Esters Antibacterial Polymer via RAFT

Xiaobing Ma,Xiangbin Sun,Rongmin Wang,Xiaoyu Han,Yuanyuan Xie,Yufeng He,Pengfei Song

Bacterial infection of surface-damaged fruit is one of the troubling issues in daily life. To address this issue, the β-cyclodextrin (CD) grafting N+-borneol ester antibacterial polymer (CD-NBOx), containing borneol with active groups and quaternary ammonium compounds (QACs) positive charges, was successfully synthesized using RAFT and characterized by NMR, Fourier-transform infrared, and gel permeation chromatography. Its antibacterial activity and biofilm inhibition were evaluated against Escherichia coli and Staphylococcus aureus, and the adhesion resistance was measured by crystal violet (CV) staining experiments. It indicated that the antibacterial rate of CD-NBOx reached 99.9 and 87.3% and the biofilm inhibition rates were up to 97.5% against E. coli. Interesting, there was no spoilage of the fruit and only 20% weight loss in the 15-day fruit preservation experiment. CD-NBOx possesses excellent antibacterial and adhesion resistance due to the synergy between cyclodextrin for biocompatibility and N cation for antibacterial and borneol stereochemistry. In summary, CD-NBOx as a constructing “offensive and defensive integrated” is validated as a viable antibacterial material while also expanding potential life applications of N+-borneol ester polymers in fruit preservation in the future.

研究领域: 高分子化学 · 食品科学 · 抗菌材料 · 药物递送 · 表面功能化 · 生物相容性 · 农业化学
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JOURNAL OF POLYMER RESEARCH · 2015 ·Vol. 22 ·期 4 ·1-8 · IF 1.92

Self-healing polymers based on a photo-active reversible addition-fragmentation chain transfer (RAFT) agent

Cheng Chuanjie,Bai Xiongxiong,Zhang Xu,Li Hongxia,Huang Qinghua,Tu Yuanming

A symmetric photo-active trithiocarbonate was designed and synthesized, which can act not only as a functional reversible addition-fragmentation chain transfer (RAFT) agent, but also as a crosslinker in crosslinking poly(methyl methacrylate- co -hydroxy ethyl acrylate) (poly(MMA- co -HEA)) due to interactions of benzophenone moieties of trithiocarbonate and hydroxyl groups of poly(MMA- co -HEA) under UV irradiation. In addition, the crosslinked poly(MMA- co -HEA) demonstrates photo-promoted self-healing properties by reshuffling C-S bonds of trithiocarbonate.

研究领域: 材料科学 · 化学工程
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Nanoscale · 2018 ·Vol. 10 ·期 21 ·10277-10287 · IF 7.233

Construction of dual-functional polymer nanomaterials with near-infrared fluorescence imaging and polymer prodrug by RAFT-mediated aqueous dispersion polymerization

Chun Tian,Jinyun Niu,Xuerui Wei,Yujie Xu,Lifen Zhang,Zhenping Cheng,Xiulin Zhu

The performance of functional polymer nanomaterials is a vigorously discussed topic in polymer science. We devoted ourselves to investigating polymer nanomaterials based on near-infrared (NIR) fluorescence imaging and polymer prodrug in this study. Aza-boron dipyrromethene (BODIPY) is an important organic dye, having characteristics such as environmental resistance, light resistance, high molar extinction coefficient, and fluorescence quantum yield. We incorporated it into our target monomer, which can be polymerized without changing its parent structure in a polar solvent and copolymerized with water-soluble monomer to improve the solubility of the dye in an aqueous solution. At the same time, the hydrophobic drug camptothecin (CPT) was designed as a prodrug monomer, and the polymeric nanoparticles (NPs) with NIR fluorescence imaging and prodrug were synthesized in situ in reversible addition–fragmentation chain transfer (RAFT)-mediated aqueous dispersion polymerization. The dynamic light scattering (DLS) and transmission electron microscopy (TEM) revealed the final uniform size of the dual-functional polymeric NPs morphology. The dual-functional polymeric NPs had a strong absorption and emission signal in the NIR region (>650 nm) based on the fluorescence tests. In consideration of the long-term biological toxicity, confocal laser scanning microscopy (CLSM) results indicated that the dual-functional NPs with controlled drug content exhibited effective capability of killing HeLa cells. In addition, in vivo imaging of the dual-functional NPs was observed in real time, and the fluorescent signals clearly demonstrated the dynamic process of prodrug transfer.

CAS / MDL: 920-46-7
研究领域: 高分子科学 · 生物医学工程 · 材料科学
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Polymer Chemistry · 2025 · IF 3.9

L-Phenylalanine Monomer Coacervation Leads to Well-Controlled Nanocrystal Topochemical Photo-RAFT Polymerization

Yuting Li,Xiyu Wang,Ying Cao,Wenjing Niu,Qing Zheng,Xinhua Lu,Yuanli Cai

We describe self-coacervation and nanocrystal topochemical photo-RAFT polymerization of ionic phenylalanine acrylamide. The charged monomer molecules undergo self-coacervation through nanoclustering, liquid-liquid phase separation, and crystallization in crowded droplets in water at pH 7.0 at 25 °C, leading to ultrathin lamellar nanocrystal-containing droplets capable of well-controlled topochemical photo-RAFT polymerization. Reaction induces pathway-dependent self-assembly involving one-dimensional (non)covalent polymerization of monomer nanoclusters to fibril bundles. Furthermore, monomer molecules within crystal lattice undergo one-dimensional rearrangements guided by growing polymer segments, leading to the nanocrystal transition to perforated lamellar hollow sieves accompanied by decreased crystallinity, and the subsequent interfacial topochemical polymerization of monomer nanoclusters site-specifically along newly activated sites of sieve edges, leading to sieve-centred parallel-growing fibrils. Further reaction leads to densely-charged ultrathin fibril lamellae physically crosslinked by fibril network knots. Consequently, the well-controlled topochemical photo-RAFT polymerization up to >98% conversion was achieved shortly in 1 h, under ecofriendly ambient aqueous conditions. This work provides a robust platform of topochemical photo-RAFT polymerization that proceeds with unprecedentedly high molecular weight controllability.

研究领域: 高分子化学 · 材料科学 · 胶体科学 · 纳米技术
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Polymers · 2025 ·Vol. 17 ·期 7 ·870 · IF 4.9

Redox-Initiated RAFT Emulsion Polymerization-Induced Self-Assembly of β-Ketoester Functional Monomers

Yanfei Wu,Min Han,Xianrong Shen,Qingping Song,Dongdong Liu,Wei Zhang

Amphiphilic block copolymers are essential for developing advanced polymer nanomaterials with applications in bioimaging, drug delivery, and nanoreactors. In this study, we successfully synthesized functional block copolymer assemblies at high concentrations through redox-initiated reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization of 2-(acetoacetoxy)ethyl methacrylate (AEMA), a β -ketoester functional monomer. Utilizing a redox initiation system at 50 °C, we produced poly(poly(ethylene glycol) methyl ether methacrylate)- b -PAEMA (PPEGMA n -PAEMA m ). Kinetic studies demonstrated rapid monomer conversion exceeding 95% within 30 min, with distinct polymerization phases driven by micelle formation and monomer depletion. Transmission Electron Microscopy (TEM) and Dynamic Light Scattering (DLS) revealed the formation of diverse morphologies, including worm-like, vesicular structures, and spherical micelles, depending on the macro-CTA molecular weight and monomer concentration. Additionally, post-polymerization modification with aggregation-induced emission (AIE) luminogens, such as 1-(4-aminophenyl)-1,2,2-tristyrene (TPE-NH 2 ), resulted in AIE-active polymer assemblies exhibiting strong fluorescence in aqueous dispersions. These AIE-active polymer assemblies also exhibited good biocompatibility. These findings demonstrate the efficacy of redox-initiated RAFT emulsion polymerization in fabricating functional, scalable block copolymer assemblies with potential applications in the field of life sciences.

研究领域: 高分子化学 · 纳米材料科学 · 生物医学工程
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CARBOHYDRATE POLYMERS · 2012 · IF 3.628

Dual stimuli-responsive N-phthaloylchitosan-graft-(poly(N-isopropylacrylamide)-block-poly(acrylic acid)) copolymer prepared via RAFT polymerization

Ke Zhang,Zhengke Wang,Youliang Li,Zhiqiang Jiang,Qiaoling Hu,Minying Liu,Qingxiang Zhao

In order to develop stimuli-responsive hydrogel, chitosan graft copolymer with chitosan back-bone and poly( N -isopropylacrylamide)- block -poly(acrylic acid) (PNIPAAm- b -PAA) branch chains was prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization in DMF. The chain transfer agent was obtained by modification of chitosan with 3-benzylsulfanyl thiocarbonylsulfanyl propionic acid (BPATT) with 68% the degree of substitute. The graft polymerizations possessed controlled/living characteristics. The behavior of the graft copolymer in aqueous solution was investigated by dynamic light scattering, transmission electron microscopy, and UV-visible spectrophotometer. N -Phthaloylchitosan- graft -(poly( N -isopropylacrylamide)- block -poly(acrylic acid)) copolymer ( N -phthaloylchitosan- g -(PNIPAAm- b -PAA)) could assemble to micelles in aqueous solution in range of 200–300   nm with narrow size distribution, and the hydrodynamic diameter could be controlled dependent on length of branch chains and temperature. The LCST values of micelle could be modulated from 34 to 40   °C by controlling the constitution of branch chains, pH, and concentration.

研究领域: 高分子化学 · 生物材料 · 药物递送系统 · 纳米医学 · 智能水凝胶
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Polymer Chemistry · 2024 ·Vol. 15 ·期 29 ·2992-3002 · IF 4.1

Precision synthesis of a biobased myrcene thermoplastic elastomer by using an amphiphilic macro-RAFT agent via emulsion polymerization in aqueous medium

Wen Li,Guoyu Chen,Youfang Zhang,Jianyun Ding,Jie Liu,Runguo Wang,Dean Shi,Weiwei Lei,Liqun Zhang

In recent years, myrcene has emerged as a biobased alternative to isoprene for the manufacture of thermoplastic elastomers due to its similarity to isoprene, a building block for natural rubber. Through the use of highly reactive tert-butyl acrylate as a hard segment monomer, a structurally well-defined poly(tert-butyl acrylate)-b-poly(β-myrcene)-b-poly(tert-butyl acrylate) (BMB) thermoplastic triblock copolymer elastomer was synthesized by a mild reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization method utilizing a precisely devised amphiphilic macro-RAFT agent. The block copolymer BMB was confirmed by NMR, FTIR, and GPC analyses. BMB thus exhibits typical thermoplastic elastomeric properties, as indicated by its mechanical properties with an ultimate tensile strength of 3.0 MPa and an elongation at break of 195% with tert-butyl acrylate added at 50% mass ratio. The properties of BMB can be easily tuned by adjusting the hydrolysis degree, facilitating cooperative interactions in the hard phase and enhancing tensile properties. This carboxyl interaction is an effective strategy for controlling medium strength thermoplastic elastomers.

研究领域: 材料科学 · 高分子化学
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RSC Advances · 2015 ·Vol. 5 ·期 17 ·12517-12529 · IF 3.84

Synthesis of novel ion-imprinted polymers by two different RAFT polymerization strategies for the removal of Cs(I) from aqueous solutions

Xiangguo Meng,Yan Liu,Minjia Meng,Zheyu Gu,Liang Ni,Guoxing Zhong,Fangfang Liu,Zhaoyong Hu,Rui Chen,Yongsheng Yan

In this work, two novel Cs(I) ion-imprinted polymers (Cs(I)-IIP1 and Cs(I)-IIP2) have been prepared by surface imprinting technique based on support matrix of SBA-15. The strategy was carried out by introducing two different reversible addition–fragmentation chain transfer (RAFT) polymerization including using the free RAFT agent in solution and surface-anchored RAFT agent with appropriate initiation method, which is expected to generate a well-defined surface ion-imprinted polymer with excellent adsorption capacity. The materials were verified by FT-IR, SEM, TEM, nitrogen adsorption–desorption and TGA. Owing to the intrinsic advantages of surface-anchored RAFT polymerization, the resultant surface ion-imprinted polymer (Cs(I)-IIP2) exhibited more homogeneous and thinner polymer layer (15 nm) with excellent macrostructure in comparison to Cs(I)-IIP1 (75 nm) prepared by using the free RAFT agent in solution. Furthermore, the adsorption capacity of both polymers are compared, indicating that Cs(I)-IIP2 displays higher adsorption property and excellent selectivity for Cs(I).

研究领域: 材料科学 · 环境科学
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Macromolecular Reaction Engineering · 2014 ·Vol. 9 ·期 2 ·90-99 · IF 1.543

Branching in RAFT Miniemulsion Copolymerization of Styrene/Triethylene Glycol Dimethacrylate and Control of Branching Density Distribution

Xiaohui Li,Wen-Jun Wang,Bo-Geng Li,Shiping Zhu

This work reported branching studies in reversible addition-fragmentation chain transfer (RAFT) miniemulsion copolymerization of styrene and triethylene glycol dimethacrylate (TEGDMA), and control of branching density distribution using a model-based computer-programed monomer feeding strategy. Highly branched polystyrenes (PS) were produced with small amount of TEGDMA. The branching density experienced drifting in a batch operation. A semi-batch kinetic model by combining the kinetic model for RAFT miniemulsion copolymerization with a semi-batch reactor model was used to design the monomer feeding rate profiles for targeted branching density distributions. A series of hyperbranched PSs with the designed branching density distributions were synthesized.

CAS / MDL: 544-76-3 109-16-0
研究领域: 高分子化学 · 材料科学
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Polymer Chemistry · 2012 ·Vol. 3 ·期 9 ·2656-2664 · IF 5.321

One-pot RAFT synthesis of core cross-linked star polymers of polyPEGMA in water by sequential homogeneous and heterogeneous polymerizations

Chunlei Zhang,Miao Miao,Xueteng Cao,Zesheng An

The arm-first approach is well accepted for the synthesis of core cross-linked star (CCS) polymers, which typically involves two separate steps, i.e., the initial synthesis and purification of the arm polymers followed by a second step synthesis of CCS. We report here a one-pot approach for the RAFT synthesis of a well-defined CCS in water without the separation and purification of the arm polymers. This novel approach consists of a homogeneous polymerization step to prepare the arm polymer, polyPEGMA, and a heterogeneous polymerization step to assemble the arm polymers into CCS polymers. Various parameters affecting the formation of the CCS were studied, including the type of cross-linker, spacing monomer, arm polymer concentration and arm polymer molecular weight. Cross-linkers of longer length provided the flexibility required to form high-quality CCS polymers. The use of spacing monomers in conjugation with cross-linkers reduced the stress during cross-linking and also provided enhanced driving force to produce well-defined CCS polymers. High-quality CCS polymers were prepared at relatively high polymer concentration (≥10%). The higher molecular weight arm polymer exhibited increased steric hindrance for CCS formation. Overall, this one-pot approach is highly efficient, environmentally benign and amenable to a variety of reaction conditions.

CAS / MDL: 6606-59-3 13048-33-4
研究领域: 高分子化学 · 材料科学
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CHEMICAL ENGINEERING JOURNAL · 2017 · IF 6.216

Facile preparation of fluorescent nanodiamond-based polymer composites through a metal-free photo-initiated RAFT process and their cellular imaging

Junyu Chen,Meiying Liu,Qiang Huang,Long Huang,Hongye Huang,Fengjie Deng,Yuanqing Wen,Jianwen Tian,Xiaoyong Zhang,Yen Wei

Nanodiamond (ND)-based fluorescent probes have been extensively researched in cell imaging applications. Several outstanding properties of fluorescent NDs (FNDs), such as their excellent biocompatibility, intensive fluorescence and chemical stability in organisms, have made them the most promising carbon materials in biomedicine. However, the production of FNDs with nitrogen-vacancy defect centers was rather complicated and costly, which limited their wide application in the biomedical field. Moreover, the particle size of these types of FNDs was much larger than that of NDs produced by the detonation method; thus, it is difficult for them to penetrate the cell membrane. In this present work, a facile and ultrafast photo-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization was introduced for the fabrication of FND-based polymer composites. The photo-initiated RAFT polymerization is time saving, environmentally friendly and highly efficient. To prepare these FNDs, fluorescein was converted into diacryloyl fluorescein (AcFl), which was used not only as the photocatalyst but also a fluorescent comonomer. The functional monomer 2-methacryloyloxyethyl phosphorylcholine (MPC) was introduced to improve the water dispersibility of the FNDs. The successful fabrication of FNDs-polyMPC composites was proven by a series of characterization methods. These FNDs-polyMPC composites show high water dispersibility, strong fluorescence and low toxicity. The cell uptake behavior suggested that FNDs-polyMPC composites can be facilely internalized by cells. Taken together, FNDs-polyMPC composites can be fabricated by a photo-initiated RAFT polymerization. These FNDs-polyMPC composites possess excellent physicochemical and biological properties and are promising candidates for cell imaging applications.

研究领域: 材料科学 · 生物医学工程 · 细胞生物学
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