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Polymer Chemistry · 2023 ·Vol. 14 ·期 47 ·5178-5190 · IF 4.6

Highly differentiated multi-stimuli-responsive fluorescence performance of tetraphenylethylene-containing styrene–maleic acid copolymers induced by macromolecular architecture control

Ranran Gao,Xiaoning Guo,Li Wang,Wantai Yang

Stimuli-responsive aggregation-induced emission (AIE) active polymers with structural diversity and tunability in fluorescence responsive behavior are in high demand in practical applications. Recently, tetraphenylethylene (TPE)-appended maleic anhydride terpolymers were proposed as a multi-stimuli-responsive fluorescence platform by our group. Here, we report TPE-containing styrene–maleic acid copolymers with diverse chain topologies and locations of the TPE moiety by reversible activation-fragmentation transfer polymerization (RAFT) with meticulously designed chain transfer agents and a TPE-containing monomer. The fluorescence responsiveness of the copolymers to the pH value, Ca2+, and bovine serum albumin (BSA) was systematically investigated, which showed an influence substantially on both the “stimuli acceptor” and “signaling” sides of the macromolecular structure. The discovery made in our work accentuates the importance of macromolecular engineering in developing fluorescent probes with highly differentiated performance and provides great flexibility in meeting the wide range of requirements of various applications.

研究领域: 高分子化学 · 材料科学 · 分析化学
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2019 · IF 3.131

Construction of ordered multienzyme systems using multifunctional polymer brush-grafted magnetic nanoparticles as scaffolds

Zhiwu Chen,Xingxing Liang,Rui Yang,Miao Yang,Tianwei Tan,Hui Cao

A block copolymer brush based on functional monomers ( N -succinimidyl acrylate and N -adamantylacrylamide) successfully grew on the surface of Fe 3 O 4 @SiO 2 nanoparticles by surface-initiated reversible addition-fragmentation chain transfer polymerization (SI-RAFT). According to the multiple recognition mechanisms of this material, horseradish peroxidase (HRP) and β-cyclodextrin-modified glucose oxidase (GOx-CD) were constructed into a multienzyme system with an ordered distribution for the cascade reaction , where multifunctional polymer brush-grafted magnetic nanoparticles were used as the scaffolds. The catalytic activity of GOx-CD was enhanced compared with free GOx. In addition to being easily recycled, this multienzyme system exhibited an outstanding conditional stability compared with the free enzyme system. After being reused 8 times, the activity of multienzyme system retained 67.21% of the initial catalytic activity. This strategy provides a novel idea for reusable ordered enzyme immobilization.

研究领域: 生物化学 · 纳米生物学 · 酶工程
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Polymer Chemistry · 2016 · IF 5.687

A multifunctional statistical copolymer vesicle for water remediation

Jiangang Xiao,Jianzhong Du

Multifunctional statistical copolymers can be simply synthesized in one step without tedious and time-consuming procedures. In addition, the fuzzy boundary between different functional groups in the statistical copolymers can facilitate the fabrication of new functional nanomaterials. Herein, we designed a novel multifunctional vesicle based on a statistical copolymer, poly[[2-hydroxy-3-(naphthalen-1-ylamino)propyl methacrylate]-stat-[2-(diethylamino)ethyl methacrylate]] [P(HNA21-stat-DEA35)] which can be synthesized by reversible addition–fragmentation transfer (RAFT) polymerization in one step. The HNA moiety is designed for capturing polycyclic aromatic hydrocarbons (PAHs) by π–π stacking, while the DEA moiety is engineered to immobilize gold nanoparticles for facilitating the reduction of 4-nitrophenol (4-NP) in aqueous solution. This vesicle showed excellent ability in water remediation by absorbing PAHs and accelerating the reduction of 4-nitrophenol (4-NP). Overall, this multifunctional statistical copolymer vesicle provides a new insight for designing multifunctional water remediation materials.

研究领域: 材料科学 · 环境科学 · 纳米技术
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POLYMER ENGINEERING AND SCIENCE · 2022 ·Vol. 62 ·期 9 ·2769-2778 · IF 2.573

Synthesis and property of EPEG-based polycarboxylate ether superplasticizers via RAFT polymerization

Xiaodong Chen,Xinde Tang,Cuizhen Zhang,Xiao Lu,Haichao Guo,Xuefan Li,Laixue Pang,Yong Yang,Fuying Dong

Polycarboxylate ether superplasticizers (PCEs) with comb-shaped molecular structures have attracted considerable attention in the area of admixtures for construction engineering. However, there are some contradictions in studying the relationship between the molecular structure and property of PCE due to its random structure based on traditional free radical polymerization, which is confused for designing and developing novel PCEs. In this article, a series of reversible addition fragmentation chain transfer (RAFT) polymerization-based polycarboxylate ether superplasticizers (RPCs) were prepared by the copolymerization of acrylic acid (AA) and ethylene-glycol monovinyl polyethylene glycol (EPEG). The chemical structure and composition of RPCs were characterized and their adsorption behavior and dispersion properties were conducted. The results demonstrate that the molecular weights of RPCs do not vary significantly with prolonging reaction time, and the actual monomer ratio in RPCs displays a significant change to the feed one due to the monomer reactivity and conversion at higher reaction temperature, which is different from conventional free radical polymerization. The dispersion and adsorption properties of RPCs to cement were evaluated by slurry fluidity tests and total organic carbon (TOC) experiments. The effect of polymerization temperature and time on the dispersion ability has been systematically studied. The results indicate that the dispersion ability and adsorption capacity of RPCs are closely related to their molecular structures. The dispersion ability of RPCs were enhanced with increasing carboxyl group density in a certain range of monomer molar ratios (≤6:1). This study will provide a new platform for designing and developing high-performance and rational cost-effective superplasticizers with well-defined structure and controlled molecular weight.

CAS / MDL: 78-67-1 1310-73-2
研究领域: 材料科学 · 化学工程 · 建筑材料
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JOURNAL OF THE CHINESE CHEMICAL SOCIETY · 2020 ·Vol. 67 ·期 11 ·2004-2011 · IF 1.554

Noncovalent modification of self-assembled functionalized COF by PNIPAM and its properties of Pickering emulsion

Na Zhang,Fei Wang,Chang-chen Cai,Qian Sun,Kai Zhang,Ai-xiang Li,Jun-ying Weng,Qiu-hong Li

Based on a facile and universal method using noncovalent bonding, here, polymer-modified covalent organic framework materials (COFs) were rapidly prepared. PNIPAM-modified COF (COF-PNIPAM) was synthesized by electrostatic self-assembly between COF prepared by low-cost melamine and terephthalaldehyde and carboxyl-terminated poly( N -isopropylacrylamide) (PNIPAM) prepared via reversible addition-fragmentation chain transfer polymerization. The carboxyl-terminated PNIPAM was characterized by Gel Permeation Chromatography and Ultraviolet and Visible Spectroscopy (UV–vis). COF and COF-PNIPAM were characterized by Fourier Transform Infrared Spectroscopes, Scanning Electron Microscope, Transmission Electron Microscope, X-Ray Diffractomer (XRD), and Brunner-Emmet-Teller (BET) measurements. The results showed that the COF-PNIPAM was successfully prepared. The Pickering emulsion properties of the COF-PNIPAM in a water-to-toluene mixed system were studied, and when the water-to-oil ratio is 2:1, a stable emulsion can be obtained. However, the results show that the PNIPAM chains of COF-PNIPAM nearly lose their temperature responsiveness.

研究领域: 材料科学 · 化学工程 · 胶体与表面化学
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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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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2025 · IF 4.6

Molybdate-driven and cucurbit[7]uril-assembled ultrasensitive miRNA fluorescence sensor

Pengnan Yao,Nan Ma,Jinming Kong,Gengzhi Sun,Xueji Zhang

MicroRNAs (miRNAs) are a class of endogenous, non-coding, single-stranded RNA molecules that are typically 20–25 nucleotides in length. The expression levels of miRNAs in blood, tissue, and other samples are characteristically altered in several disease states. The detection of miRNAs represents a promising avenue for the early diagnosis of various diseases. Consequently, there is a clear need to enhance the sensitivity of miRNA detection to facilitate more accurate disease detection. A fluorescent biosensor was developed that utilizes supramolecular host-guest interactions for assembly and Mo-based materials to initiate a reversible addition-fragmentation chain transfer polymerization (RAFT). The scheme functions by modifying the miRNA on Fe 3 O 4 -magnetic nanoparticles (Fe 3 O 4 -MNPs), followed by linking the initiator of the subsequent RAFT reaction through supramolecular host-guest interaction. Ultimately, polymerization reactions initiated by Mo compounds result in the formation of polymers with fluorescent monomers on Fe 3 O 4 -MNPs. The sensor is extremely sensitive and the detection limit of this sensor is 0.03 fM. Furthermore, the protocol has been demonstrated to be highly effective in the detection of samples in serum, which also serves to illustrate the potential of this fluorescent biosensor for the detection of other kinds of miRNAs.

研究领域: 生物化学 · 分子生物学 · 纳米技术 · 分析化学 · 生物传感器
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Polymer Chemistry · 2017 ·Vol. 8 ·期 38 ·5852-5864 · IF 5.375

Construction of polymer coated core–shell magnetic mesoporous silica nanoparticles with triple responsive drug delivery

Mohammad Hegazy,Pei Zhou,Guangyu Wu,Lei Wang,Nahla Rahoui,Nadia Taloub,Xin Huang,Yudong Huang

Multi-responsive drug delivery systems are playing a very important role in nanomedicine, as they can feature as smart carriers releasing their payload on demand. In this study, magnetic, reductive and thermo triple-responsive nanocarriers based on core–shell magnetic mesoporous silica nanoparticles (MMSNPs) modified with a thermo responsive polymer poly(N-isopropylacrylamide) (PNIPAAm) have been developed. Photoinduced electron/energy transfer-reversible addition fragmentation chain transfer (PET-RAFT) polymerization, mediated by a ruthenium-based photoredox Ru(bpy)3Cl2 catalyst was used to graft PNIPAAm onto MMSNPs. A series of characterization and testing techniques were applied to confirm the structures of the synthesized nanocarriers to assess their efficiency as drug delivery systems. Doxorubicin (DOX) was easily encapsulated into the nanocarriers with a high loading capacity, and quickly released in response to the triple-responsive systems. The MMSNPs remained intact in all synthetic steps, during the loading of the drug and the in vitro release tests. Thus, these multi responsive polymer grafted Fe3O4-capped-MSN models are not only magnetically guided, but also represent a promising candidate in the formulation of targeted delivery of therapeutic agents to temperature and more reductive environment tissues, such as tumors and inflammatory sites.

研究领域: 纳米医学 · 材料科学 · 药学
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CHINESE JOURNAL OF POLYMER SCIENCE · 2020 ·Vol. 38 ·期 8 ·819-829 · IF 3.154

A Self-assembled Nanoparticle Platform Based on Amphiphilic Oleanolic Acid Polyprodrug for Cancer Therapy

Wang Ying-Sa,Li Gui-Liang,Zhu Shang-Bin,Jing Fan-Chen,Liu Run-Dong,Li Sai-Sai,He Jing,Lei Jian-Du

Oleanolic acid (OA) is a pentacyclic triterpenoid compound with extensive biological effects, such as anti-inflammatory and anticancer activities. However, the application of OA in chemotherapy is hampered by its poor solubility and severe adverse effects. To solve the problems, we developed a self-assembled nanoparticle platform based on amphiphilic oleanolic acid polyprodrug, poly[oligo(ethylene glycol) methyl ether methacrylate]- b -poly[oleanolic acid methacrylate] (POEGMA- b -POAMA), encapsulating 10-hydroxycamptothecin (HCPT) to achieve efficient cancer therapy. The polyprodrug was prepared via reversible addition-fragmentation chain transfer polymerization (RAFT), and could self-assemble to prepare POEGMA- b -POAMA/HCPT nanoparticles (NPs). The obtained nanoparticles exhibited appropriate particle size, excellent drug stability, good drug loading capacity, and high drug loading efficiency. In vitro drug release indicated that the drug release was prolonged to 132 h. The POEGMA- b -POAMA/HCPT NPs enhanced cell cytotoxicity in 4T1 cells and MCF-7 cells and could be efficiently uptaken by 4T1 cells. Furthermore, in vivo antitumor efficiency showed that the POEGMA -b -POAMA/HCPT NPs had great antitumor efficiency with considerably low adverse effects in the treatment of the 4T1 mouse breast tumor xenograft tumor. Therefore, POEGMA -b -POAMA/HCPT NPs provide great potential as a platform for drug delivery applications.

CAS / MDL: 920-46-7
研究领域: 药学 · 纳米技术 · 癌症研究 · 材料科学
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JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY · 2013 ·Vol. 52 ·期 1 ·87-95 · IF 3.543

Design and synthesis of fluorescent core–shell nanoparticles with tunable lower critical solution temperature behavior and metal-enhanced fluorescence

Aihua Li,Jingquan Liu,Guozhen Liu,Jizhen Zhang,Shengyu Feng

In this article, the preparation of fluorescent nanohybrids with core–shell structure and metal-enhanced fluorescence (MEF) effect was presented. The fluorescent core–shell nanohybrids were prepared using silver nanoparticles (AgNPs) as cores and fluorophore tethered thermoresponsive copolymers with tunable lower critical solution temperature (LCST) from 15 to 90 °C as shells. These thermoresponsive copolymers were synthesized by the random copolymerization of oligo(ethylene oxide) acrylate and di(ethylene oxide) ethyl ether acrylate using reversible addition–fragmentation chain transfer polymerization and grafted on to AgNPs surface via Ag–S coordination interaction. By thermal manipulation of polymer spacer between AgNPs and fluorophores, the tunable MEF was achieved. It was also revealed that the fluorescent nanohybrids would exhibit maximal MEF when the polymerization degree was tuned to 350. The manipulation of the solution temperatures below and above LCST resulted in switchable MEF behavior. In addition, the phase transition process of the thermoresponsive copolymer was also studied by MEF effect using this fluorescent core–shell nanohybrid design. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52 , 87–95

研究领域: 材料科学 · 纳米技术 · 高分子化学 · 物理化学 · 光学 · 表面科学
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ENERGY & FUELS · 2024 · IF 5.2

Synthesis via Reversible Addition–Fragmentation Chain Transfer Polymerization and Deep Control Property of Amphiphilic Self-assembled Poly(ethylene oxide)-block-polystyrene

Yuchen Li,Dayu Liu,Xin Peng,Mengjiao Cao,Chenwei Zou,Bin Yuan,Yining Wu

Deep profile control is crucial for enhancing oil recovery due to the depletion of oil and gas resources in the near-well zone. However, using waterflooding to displace the oil in far-well zones with low permeability faces challenges related to limited swept volume and low recovery efficiency. In response, we synthesized PEO-b-PS amphiphilic self-assembled polymer nanoparticles using the reversible addition–fragmentation chain transfer polymerization (RAFT) method. The PEO-b-PS polymers with PS as the core-forming block and PEO as the outer stabilizer self-assemble into uniform spherical particles in water with a size of 100 nm, as demonstrated through DLS/AFM/TEM experiments. These PEO-b-PS nanoparticles do double duty as plugging agents in water breakthrough channels and oil displacement agents once encountering oil. The NMR online displacement experiment shows that the PEO-b-PS nanoparticles can migrate into in-depth formations and plug preferential water pathways. In addition, following the plugging of preferential water pathways, the PEO-b-PS amphiphilic self-assembled polymer emulsifies crude oil and enhances the oil displacement efficiency. Overall, this PEO-b-PS amphiphilic self-assembled polymer offers a pragmatic solution for enhanced oil recovery.

研究领域: 化学工程 · 高分子科学 · 石油工程 · 材料科学
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POLYMER · 2012 · IF 3.438

Dual stimuli-responsive polymers derived from α-amino acids: Effects of molecular structure, molecular weight and end-group

Chunhui Luo,Bin Zhao,Zhibo Li

Four kinds of well defined poly( N -methacryloyl-L-amino acid)s were prepared via reversible addition fragmentation chain transfer polymerization . The effects of molecular structure, molecular weight , and end-group on their responsive properties in water were investigated. We found that the monomer structure is critical for the polymer to exhibit stimuli-responsive properties in water; only polymers derived from aspartic acid showed defined dual thermo- and pH-responsive properties. To study the effects of molecular weight and end group on the lower critical solution temperature behavior of poly( N -methacryloyl- L -β-isopropyl aspartic acid) (PMAIPAC), a series of PMAIPAC homopolymers with controlled molecular weights and narrow polydispersities were prepared and treated with excess radical initiators to give defined end groups. The cloud point of PMAIPAC was found to increase with the increase of solution pH, due to the ionization of carboxylic acid groups, and decrease with the increase of molecular weight. The structure of end groups also affects the cloud point of PMAIPAC particularly for low molecular weight samples at low pH.

研究领域: 高分子化学 · 材料科学 · 胶体与表面化学
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