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JOURNAL OF NANOBIOTECHNOLOGY · 2017 ·Vol. 15 ·期 1 ·1-18 · IF 4.946

Dual stimuli-responsive Fe3O4 graft poly(acrylic acid)-block-poly(2-methacryloyloxyethyl ferrocenecarboxylate) copolymer micromicelles: surface RAFT synthesis, self-assembly and drug release applications

Wang Yuan,Zhang Xue-Yin,Luo Yan-Ling,Xu Feng,Chen Ya-Shao,Su Yu-Yu

Background Stimuli-responsive polymer materials are a new kind of intelligent materials based on the concept of bionics, which exhibits more significant changes in physicochemical properties upon triggered by tiny environment stimuli, hence providing a good carrier platform for antitumor drug delivery. Results Dual stimuli-responsive Fe 3 O 4 graft poly(acrylic acid)- block -poly(2-methacryloyloxyethyl ferrocenecarboxylate) block copolymers (Fe 3 O 4 - g -PAA- b -PMAEFC) were engineered and synthesized through a two-step sequential reversible addition-fragmentation chain transfer polymerization route. The characterization was performed by FTIR, 1 H NMR, SEC , XRD and TGA techniques. The self-assembly behavior in aqueous solution upon triggered by pH, magnetic and redox stimuli was investigated via zeta potentials, vibration sample magnetometer, cyclic voltammetry, fluorescent spectrometry, dynamic light scattering, XPS, TEM and SEM measurements. The experimental results indicated that the Fe 3 O 4 - g -PAA- b -PMAEFC copolymer materials could spontaneously assemble into hybrid magnetic copolymer micromicelles with core–shell structure, and exhibited superparamagnetism, redox and pH stimuli-responsive features. The hybrid copolymer micromicelles were stable and nontoxic, and could entrap hydrophobic anticancer drug, which was in turn swiftly and effectively delivered from the drug-loaded micromicelles at special microenvironments such as acidic pH and high reactive oxygen species. Conclusion This class of stimuli-responsive copolymer materials is expected to find wide applications in medical science and biology, etc., especially in drug delivery system.

研究领域: 材料科学 · 生物医学工程 · 纳米医学
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Journal of Materials Chemistry A · 2018 ·Vol. 7 ·期 5 ·2055-2065 · IF 9.931

Fabrication of poly(β-cyclodextrin)-conjugated magnetic graphene oxide by surface-initiated RAFT polymerization for synergetic adsorption of heavy metal ions and organic pollutants

Jingjing Wang,Wenhui Zhang,Jun Wei

In order to realize synergetic adsorption of heavy metal ions and organic pollutants, poly(β-cyclodextrin)-conjugated magnetic graphene oxide (MGO@poly(β-CD)) was designed and fabricated. The MGO@poly(β-CD) was characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray diffraction and vibrating sample magnetometry, respectively. Results indicated that the MGO@poly(β-CD) was successfully prepared and the adsorbent could be separated easily once an external magnetic field was applied. The adsorption behaviors of Cd2+ and sulfamethazine (SMT) by MGO@poly(β-CD) in the single and binary systems were investigated. The adsorption amounts of both Cd2+ and SMT were pH-dependent, and the increase in the ionic strength of solutions resulted in significant decrease of their adsorption amounts. The adsorption of Cd2+ and SMT on MGO@poly(β-CD) was achieved by different mechanisms, respectively. The sorption of Cd2+ was related to complexation and electrostatic interactions, while the removal of SMT was realized by hydrogen bonding, host–guest supramolecular and π–π interactions. The synergetic adsorption of Cd2+ and SMT in the binary systems was attributed to interactions between loaded Cd2+ (SMT) and free SMT (Cd2+) in solutions. These results provided valuable information for designing novel adsorbents that can be used for synergetic adsorption of heavy metal ions and organic pollutants.

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MACROMOLECULAR CHEMISTRY AND PHYSICS · 2019 ·Vol. 220 ·期 9 ·1900022 · IF 2.622

Visible Light–Induced RAFT Polymerization of Methacrylate with 4-(N,N-diphenylamino)benzaldehyde as Organophotoredox Catalyst and the Effect of Temperature on the Polymerization

Wenxiu Zhang,Xianhong Zhang,Yuhong Ma,Dong Chen,Wantai Yang

With UV–vis absorption in the range of 270–435 nm, 4-( N , N -diphenylamino)benzaldehyde (DPAB) takes efficient photoreduction quench with 4-cynao-4-(phenylcarbonothioylthio)pentanoic acid (CTP). The polymerization rates of methyl methacrylate (MMA) are 0.019, 0.056, and 0.102 h −1 at 33, 40, and 50 °C, respectively, in the presence of DPAB and CTP under visible-light irradiation. Dark reaction produces no PMMA at 50 °C for 120 h. The living feature is demonstrated by linearly increasing M n with the monomer conversions and narrow polydispersity index (PDI), chain extension, and block polymerizations with benzyl methacrylate (BnMA) and poly(ethylene glycol) monomethyl ether methacrylate (PEGMA). With PMMA-CTP ( M n = 6800, PDI = 1.17), chain extension gives PMMA with M n = 15 900 and PDI = 1.15. With PMMA-CTP ( M n = 6000, PDI = 1.21) as macro-RAFT, PMMA- b -PBnMA of M n = 12 600 (PDI = 1.44) and M n = 18 500 (PDI = 1.31) are prepared. These results support that there is a positive synergistic effect between polymerization temperature and visible-light irradiation on the photo-RAFT without losing the living features.

CAS / MDL: 4181-05-9 9003-11-6
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EUROPEAN POLYMER JOURNAL · 2024 · IF 5.8

A high throughput strategy for synthesis of molecularly imprinted polymers microspheres via oxygen tolerant visible light-mediated RAFT polymerization for sweeteners sensing in sucrose

Xuewen Wu,Lingfeng Xia,Zhenfeng Luo,Kaikai Wu,Jinwen Lai,Yixiong Chen,Yan Xiong

Recently, the conventional oxygen-tolerant photo-activated reversible addition-fragmentation chain transfer (RAFT) polymerization has been fruitful. However, its application to the synthesis of molecularly imprinted polymers (MIPs) remains a challenge. Herein, we proposed a rapid, simple and reliable method to prepare MIPs microspheres by oxygen-tolerant visible light-mediated RAFT polymerization without additives, prior deoxygenation, or inert gas protection. The effects of various solvents, photo-initiator concentration, irradiation intensity of the visible light source, solids content of the functional monomer and crosslinker, RAFT agent content and light ON/OFF experiments on this oxygen tolerance photo-mediated RAFT precipitation polymerization was investigated using the real-time high throughput platform. Moreover, the multichannel sensor array based on the MIPs microspheres was attempted to recognize the sweeteners in sucrose. In summary, this photo-mediated RAFT precipitation polymerization would be one of the simple, rapid, efficient, and promising tools to synthesize MIPs materials and functional materials in glycol ether aqueous solvents under mild conditions. In addition, the MIPs sensor array also indicated favorable results in monitoring the sweeteners.

CAS / MDL: 79-06-1 97-90-5
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MACROMOLECULAR CHEMISTRY AND PHYSICS · 2017 ·Vol. 218 ·期 19 ·1700141 · IF 2.5

Synthesis of Molecularly Imprinted Polymer via Visible Light Activated RAFT Polymerization in Aqueous Media at Room Temperature for Highly Selective Electrochemical Assay of Glucose

Qiankun Zhu,Xiaoming Li,Yonghua Xiao,Yan Xiong,Suiping Wang,Changli Xu,Jun Zhang,Xuewen Wu

The mild environment where most proteins and antibodies in living systems are prepared has inspired fascination among chemists. Herein, a new, rapid, low-cost, and environment-friendly method is proposed to synthesize molecularly imprinted polymers (MIPs) via visible light activated reversible addition–fragmentation chain transfer polymerization in aqueous media at room temperature for highly selective electrochemical assay of glucose. The MIPs with microsphere morphology, the better hydraulic distribution, large surface area, uniform large pore sizes, and high pore volume exhibit a significant adsorption efficiency compared with nonimprinted polymers for glucose. In addition, the MIP sensor recognizing the glucose significantly exceeds that of the other saccharide analogs, possesses regenerative ability, and presents high sensitivity by applying for the detection of glucose in human urine samples.

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SENSORS AND ACTUATORS B-CHEMICAL · 2016 · IF 4.758

One-side non-covalent modification of CVD graphene sheet using pyrene-terminated PNIPAAm generated via RAFT polymerization for the fabrication of thermo-responsive actuators

Degang Jiang,Huihui Zhu,Wenrong Yang,Liang Cui,Jingquan Liu

Thermo-responsive graphene-polymer films have been obtained by the modification of large CVD graphene films with pyrene-terminated poly( N -isopropylacrylamide) (PNIPAAm) via non-covalent π-π stacking interactions. Pyrene-terminated PNIPAAm was prepared by reversible addition fragmentation chain transfer (RAFT) polymerization using a pyrene-functionalized RAFT agent . Since PNIPAAm possesses a lower critical solution temperature (LCST) of 32   °C, the as-prepared graphene-PNIPAAm films could be reversibly deformed as a result of the morphology response of PNIPAAm to the environmental temperature variation. In addition, the thermo-triggered deformation of the graphene-PNIPAAm films was observed to be reversible and controllable by manipulation of the environmental temperature. Atomic force microscopy (AFM) and high-resolution SEM analysis evidenced the successful attachment of the PNIPAAm on the graphene surface. The thickness of the polymer was revealed by high-resolution scanning electron microscopy (SEM). The successful stepwise fabrication of the CVD graphene-polymer composite films was also characterized using Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). These thermo-responsive composite films would be highly desirable for a wide range of applications, such as thermo-responsive actuators, a thermo-responsive intelligent switch was fabricated using these thermo-responsive graphene composite films.

CAS / MDL: 538-75-0
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BIOSENSORS & BIOELECTRONICS · 2014 · IF 6.451

Preparation of surface-imprinted polymer grafted with water-compatible external layer via RAFT precipitation polymerization for highly selective and sensitive electrochemical determination of brucine

Lijuan Zhao,Faqiong Zhao,Baizhao Zeng

A novel brucine imprinted polymer was prepared on multi-walled carbon nanotubes by reversible addition–fragmentation chain transfer (RAFT) precipitation polymerization. The polymer was further grafted with hydrophilic poly(glycerol monomethacrylate) brushes to improve its water-compatibility. The obtained molecularly imprinted material showed enhanced accessibility to brucine and improved selective recognition property in water medium. When the material was supported on an ionic liquid functionalized graphene coated glassy carbon electrode for the electrochemical determination of brucine, the resulting electrochemical sensor presented good analytical performance. Under the optimized conditions, the peak current was linear to brucine concentration in the ranges of 0.006−0.6   μM and 0.6−5.0   μM with sensitivities of 15.3   μA/μM   mm 2 and 5.4   μA/μM mm 2 , respectively; the detection limit was 2   nM ( S / N =3). The sensor was successfully applied to the determination of brucine in practical samples and the recovery for the standards added was 94−104%.

CAS / MDL: 106-91-2
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RSC Advances · 2017 ·Vol. 7 ·期 46 ·28711-28722 · IF 3.108

Micellization and gelatinization in aqueous media of pH- and thermo-responsive amphiphilic ABC (PMMA82-b-PDMAEMA150-b-PNIPAM65) triblock copolymer synthesized by consecutive RAFT polymerization

Ye Huang,Ping Yong,Yan Chen,Yuting Gao,Weixiong Xu,Yongkang Lv,Liming Yang,Rui L. Reis,Rogério P. Pirraco,Jie Chen

The multi-stimuli-responsive amphiphilic ABC triblock copolymer of poly(methyl methacrylate)-block-poly[N,N-(dimethylamino) ethyl methacrylate]-block-poly(N-isopropylacrylamide) (PMMA-b-PDMAEMA-b-PNIPAM) was synthesized by sequential reversible addition–fragmentation chain transfer (RAFT) polymerizations. Due to the pH- and thermo-responsive blocks of PDMAEMA and thermo-responsive blocks of PNIPAM, the copolymer solution properties can be manipulated by changing the parameters such as temperature and pH, and it formed diverse nanostructures and had gel behavior in different conditions. In detail, when the pH was below 7.3, the pKa of DMAEMA, tertiary amino groups were protonated, the polymer micellar solution like weak gel changed into free-standing gel at around 40 °C even at a low concentration of 2 wt%. Further, the gel behavior and morphology of the system were studied by rheology, turbidimetry measurements, transmission electron microscopy (TEM) and scanning electron microscopy (SEM), respectively. When the pH was above the pKa, the triblock copolymer self-assembled into diverse micellar structures including shell–core, corona–shell–core and shell–shell–core nanoparticles as the temperature increased, but no free-standing gelation. The two-step thermo-responsive behavior, corresponding to the different LCSTs of PNIPAM block and DMAEMA block, was evidenced by turbidity analysis. The assembled structures rapidly collapsed due to the enhanced hydrophobic interaction when the temperature further increased. Dynamic light scattering (DLS) was used to confirm the transitions.

研究领域: 高分子科学 · 材料化学 · 软物质物理 · 纳米技术 · 刺激响应材料
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RSC Advances · 2020 ·Vol. 10 ·期 10 ·5704-5711 · IF 3.119

An acrylate AIE-active dye with a two-photon fluorescent switch for fluorescent nanoparticles by RAFT polymerization: synthesis, molecular structure and application in cell imaging

Zengfang Huang,Yali Chen,Runze Wang,Chaoyue Zhou,Xiaobo Liu,Liucheng Mao,Jinying Yuan,Lei Tao,Yen Wei

Recently, AIE-active fluorescent materials have attracted extensive investigation due to their significant applications in the fields of memory devices, photomodulation, information displays, sensors, and biological imaging. In this contribution, a novel acrylate AIE-active dye of TPMA was successfully synthesized by Suzuki coupling and acylation reaction, and belongs to the monoclinic crystal system and P21/c space group from the crystal structure analysis, and its fluorescence intensity was stronger with an obvious red shift of emission wavelength as compared with the reported TPB dye. Moreover, the obtained TPMA dye exhibits multi-stimuli-responsivity and a two-photon fluorescent switch with excellent reversibility in the solid state. Subsequently, the corresponding fluorescent polymers of PEG-TM were successfully fabricated via RAFT polymerization of TPMA and PEGMA with a molecular weight of about 25 000 (Mn) and narrow polydispersity index (PDI). From 1H NMR analysis, when the feeding ratio of TPMA increased to 32.2% from 19.2%, the molar fraction of TPMA in PEG-TM polymers accordingly increased to 32.8% from 19.5%. In water solution, the as-prepared PEG-TM1 polymers would self-assemble into fluorescent organic nanoparticles (FONs) with diameters ranging from 150 to 250 nm, and their maximum emission wavelength presented at 518 nm with obvious AIE phenomena. Moreover, the as-synthesized PEG-TM polymers have prospective application in biological imaging due to their good fluorescence, high water solubility and excellent biocompatibility.

研究领域: 材料化学 · 高分子科学 · 荧光材料 · 有机电子学 · 生物成像 · 纳米技术
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Materials Today Communications · 2023 · IF 3.8

Water soluble β-CD-PMAA/PMAm/PHEMA-Coumarin macromolecular fluorescent probes prepared via RAFT method and their sensing ability to Fe3+/Fe2+ and Cu2+ ions

Siyuan Zhang,Xinjian Cheng

Developing water-soluble fluorescent probes has important scientific and practical significance. In this work, coumarin derivatives bearing -OH were obtained through the classical Knoevenagel reaction firstly. Secondly, -C C- on allyl bromide was introduced into coumarin by Williamson ether formation method. Thirdly, hydrazine hydrate was added to the coumarin derivatives, a polymerizable small molecular coumarin fluorophore containing probe was obtained successfully. And, the -COOH on di-thioester underwent an esterification reaction with –OH groups on β-cyclodextrin(β-CD) to prepare oligomer based reversible addition-fragmentation chain transfer(RAFT) reagents. Finally, three copolymer probes β-CD-PMAA-Coumarin, β-CD-PMAm-Coumarin, and β-CD-PHEMA-Coumarin were prepared via RAFT polymerization , in which C C-coumarin was used as the functional monomer and methacrylamide(MAm)/methacrylic acid (MAA)/hydroxyethyl methacrylate (HEMA) as the main monomers. The MALDI-TOF mass tests showed that the macromolecular level probes were successfully prepared. These polymer probes have molecular weights up to 5.4 kDa and have narrow molecular weight distributions (PDI≤1.31). With the assistance of water-soluble long-chained PMAm/PMAA/PHEMA and hydrophilic β-CD, the coumarin containing macromolecular fluorescent probes could be dissolved in water readily. These water soluble polymer fluorescent probes could recognize Fe 3+ /Fe 2+ and Cu 2+ ions with high sensitivity. The detection limit of Fe 3+ could be as low as 0.34 μM. This study successfully developed a promising technique for producing highly selective, fully water-soluble fluorescent macromolecular probes.

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COLLOID AND POLYMER SCIENCE · 2020 ·Vol. 299 ·期 4 ·663-674 · IF 1.536

Preparation of zwitterionic microspheres of PDMAEMA-b-PMAA by RAFT dispersion polymerization in alcohol, their pH-sensitivity in water, and self-assembly in KCl solution

Xia Yunfei,Xu Xiuhang,Yu Haihua,Zhou Chuan,Nie Zhenzhou,Yang Jianfeng,Qian Jiajia,Ni Henmei

Zwitterionic microspheres of poly2-(dimethylamino) ethyl methacrylate (PDMAEMA) block polymethacrylic acid (MAA) were prepared by RAFT dispersion polymerization in alcohols. 4-Cyano-4-(phenylcarbonothioylthio) pentanoic acid (CPDB) was used as the RAFT agent. 2,2′-Azobis(2,4-dimethyl) valeronitrile (V65) was used as the initiator, and PDMAEMA-CPDB was used as the macro-chain transfer agent (CTA). 1 HNMR was applied to determine the polymerization degrees of both PDMAEMA-CTA and PDMAEMA-b-PMAA. SEM, dynamic light scattering (DLS), and small-angle X-ray diffraction (SAX) were employed to characterize the microspheres. It was observed that the polarity of alcohols impacted the partition of MAA and V65 between the mini-droplets of PDMAEMA-CTA/MAA complexes and the continuous phase, thereby affected on the diameters of microspheres, the total conversion of MAA, and the polymerization degree of PMAA in the copolymers. For example, in methanol, the smallest diameter and polymerization degree of PMAA in the block copolymers were obtained, whereas the total conversion of MAA of the RAFT polymerization system was the highest. Most of RAFT polymerization of MAA occurred nearby PDMAEMA-CTA chains; thus, PDMAEMA-CTA acted as a template to regulate the length of PMAA in the copolymers. pH-sensitive characteristics of microspheres were dependent to the extra length of PDMAEMA-CTA, i.e., the difference of lengths between two blocks. When the length of PMAA was too short, e.g., PDMAEMA 600 -b-PMAA 87 , or the length of PMAA was closed to that of PDMAEMA, e.g., PDMAEMA 79 -b-PMAA 93 and PDMAEMA 102 -b-PMAA 131 , the amphoteric characteristics of microspheres disappeared. The self-assembly behavior of diblock copolymers in KCl alcohol-water solution was also determined by the extra length of PDMAEMA. Microspheres turned into nanofibers or nano-ribbons, but for PDMAEMA 600 -b-PMAA 87 , the microspheres maintained their original spheric morphology. These results indicated that the charge-screening effects of salts played the key roles in the self-assembly. Graphical abstract

CAS / MDL: 79-41-4
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ACS Applied Polymer Materials · 2025 · IF 4.7

Diblock Copolymer Nanoparticles Bearing Phenols: Potential Stimuli-Responsive Pickering Emulsifiers with Antioxidant and Antibacterial Activities

Jiani Peng,Yong Gao

Core–shell structure diblock copolymer nanoparticles carrying phenolic groups in the core domain were prepared through the combination of RAFT-mediated dispersion polymerization and the hydrolysis of postpolymerization in this study. Poly(2-(dimethylamino)ethyl methacrylate)23 (PDMAEMA23) was first synthesized through RAFT-mediated solution polymerization, which was then utilized as macro-CTA to mediate the dispersion polymerization of 4-tert-butoxystyrene (tBOS) in isopropanol/water (8:2, v/v) mixtures. PDMAEMA23-PtBOSx diblock copolymer nanoparticles with different morphologies, including spheres, worms, and vesicles, were produced. Subsequently, the selected PDMAEMA23-PtBOS490 vesicles underwent hydrolysis in an acidic environment. During the hydrolysis, tBOS repeat units were partially converted into 4-vinylphenols (VPl), affording polymer nanoparticles bearing phenolic groups in the core domain, accompanied with a gradual morphological transition from vesicles to spheres. The content of VPl units in the core domain could be flexibly adjusted by varying the hydrolysis time. The as-prepared diblock copolymer spheres demonstrated a unique combination of stimuli-responsive emulsifying performances and intrinsic antioxidant activity, as well as antibacterial effectiveness.

CAS / MDL: 2867-47-2 95418-58-9
研究领域: 聚合物化学 · 材料科学 · 纳米技术 · 胶体科学
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