ACS Applied Materials & Interfaces
·
2017
·
IF 7.504
Zhongxi Xie,Xiaoran Deng,Bei Liu,Shanshan Huang,Pingan Ma,Zhiyao Hou,Ziyong Cheng,Jun Lin,Shifang Luan
Photoinduced reversible addition–fragmentation chain transfer (RAFT) polymerization generally adopts high-energy ultraviolet (UV) or blue light. In combination with photoredox catalyst, the excitation light wavelength was extended to the visible and even near-infrared (NIR) region for photoinduced electron transfer RAFT polymerization. In this report, we introduce for the first time a surface NIR-light-initiated RAFT polymerization on upconversion nanoparticles (UCNPs) without adding any photocatalyst and construct a functional inorganic core/polymer shell nanohybrid for application in cancer theranostics. The multilayer core–shell UCNPs (NaYF4:Yb/Tm@NaYbF4:Gd@NaNdF4:Yb@NaYF4), with surface anchorings of chain transfer agents, can serve as efficient NIR-to-UV light transducers for initiating the RAFT polymerization. A hierarchical double block copolymer brush, consisting of poly(acrylic acid) (PAA) and poly(oligo(ethylene oxide)methacrylate-co-2-(2-methoxy-ethoxy)ethyl methacrylate) (PEG for short), was grafted from the surface in sequence. The targeting arginine–glycine–aspartic (RGD) peptide was modified at the end of the copolymer through the trithiolcarbonate end group. After loading of doxorubicin, the UCNPs@PAA-b-PEG-RGD exhibited an enhanced U87MG cancer cell uptake efficiency and cytotoxicity. Besides, the unique upconversion luminescence of the nanohybrids was used for the autofluoresence-free cell imaging and labeling. Therefore, our strategy verified that UCNPs could efficiently activate RAFT polymerization by NIR photoirradiation and construct the complex nanohybrids, exhibiting prospective biomedical applications due to the low phototoxicity and deep penetration of NIR light.
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PubMed
高影响因子
Polymer Chemistry
·
2017
·Vol. 8
·期 47
·7390-7399
·
IF 5.375
Ruming Jiang,Meiying Liu,Qiang Huang,Hongye Huang,Qing Wan,Yuanqing Wen,Jianwen Tian,Qian-yong Cao,Xiaoyong Zhang,Yen Wei
Fluorescent organic nanoparticles (FONs) based on an aggregation-induced emission (AIE) dye have recently received increasing interest owing to their unique optical properties, water dispersibility and biocompatibility. However, fabrication of multifunctional AIE-active FONs through a facile controlled free radical polymerization method has not been reported thus far. In this work, a novel photo-initiated reversible addition–fragmentation chain-transfer (RAFT) polymerization has been developed for the fabrication of AIE-active FONs for the first time. During this procedure, a new tetraphenylethene based dye (named TPE-DETC) was conjugated to a chain transfer agent, which could serve as the fluorescence signal and catalyst for RAFT polymerization. Styrene (SE) and itaconic acid (IA) were selected as the monomers to construct the final fluorescent copolymers (TPE-SE-IA). Due to the amphiphilicity and AIE properties of TPE-DETC, the TPE-SE-IA copolymers tend to self-assemble and form FONs. The physicochemical properties, drug loading and release behavior of TPE-SE-IA FONs towards cisplatin (CDDP), their biocompatibility as well as cell uptake behavior have been investigated in detail. The results verified that TPE-SE-IA FONs possess strong fluorescence, high water dispersibility, distinguished biocompatibility and highly efficient drug loading capability, making them promising candidates for biomedical applications. More importantly, the in situ photo-initiated RAFT polymerization strategy is an ideal method to be used for the preparation of functional polymeric materials owing to its fascinating features, such as environmental friendliness, mild reaction conditions, being catalyst-free and cost effectiveness.
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COLLOID AND POLYMER SCIENCE
·
2020
·Vol. 298
·期 8
·1053-1061
·
IF 1.536
Cai Shuwei,Gu Shiyu,Li Xian,Wan Songhan,Chen Songbo,He Xianru
A controlled grafting modification starch exhibited tunable phase transition temperature in aqueous solution was prepared via reversible addition–fragmentation chain transfer (RAFT) polymerization and esterification reaction under mild condition. P(AM/AN) copolymer was grafted onto the starch backbone and endowed the grafted copolymer thermosensitivity. The molecular structure and composition of P(AM/AN) copolymers were characterized by gel permeation chromatography (GPC), FTIR, and NMR, indicating a structurally controllable side chain of the grafted copolymer. Results of X-ray diffraction (XRD) demonstrate that the crystallinity of grafted copolymer decreases compared with starch due to side chains destruct the structural regularity of starch. Scanning electron microscopy (SEM) images show that grafted copolymer displays a rough, multilayer, and irregular morphology. Dynamic light scattering (DLS) and UV tests indicate that the grafted copolymer forms aggregates in aqueous solution and the UCST of the grafted copolymer is dependent on percent grafting (PG) and molecular interactions of side chains.
研究领域:
高分子化学
·
材料科学
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MOLECULES
·
2024
·Vol. 29
·期 10
·2377
·
IF 4.2
Zhilei Wang,Zipeng Zhang,Chenyu Wu,Zikuan Wang,Wenjian Liu
The photocatalyst (PC) zinc tetraphenylporphyrin (ZnTPP) is highly efficient for photoinduced electron/energy transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. However, ZnTPP suffers from poor absorbance of orange light by the so-called Q-band of the absorption spectrum (maximum absorption wavelengthλmax= 600 nm, at which molar extinction coefficientεmax=1.0×104L/(mol·cm)), hindering photo-curing applications that entail long light penetration paths. Over the past decade, there has not been any competing candidate in terms of efficiency, despite a myriad of efforts in PC design. By theoretical evaluation, here we rationally introduce a peripheral benzo moiety on each of the pyrrole rings of ZnTPP, giving zinc tetraphenyl tetrabenzoporphyrin (ZnTPTBP). This modification not only enlarges the conjugation length of the system, but also alters thea1uoccupiedπmolecular orbital energy level and breaks the accidental degeneracy between thea1uanda2uorbitals, which is responsible for the low absorption intensity of the Q-band. As a consequence, not only is there a pronounced hyperchromic and bathochromic effect (λmax= 655 nm andεmax=5.2×104L/(mol·cm)) of the Q-band, but the hyperchromic effect is achieved without increasing the intensity of the less useful, low wavelength absorption peaks of the PC. Remarkably, this strong 655 nm absorption takes advantage of deep-red (650–700 nm) light, a major component of solar light exhibiting good atmosphere penetration, exploited by the natural PC chlorophyll a as well. Compared with ZnTPP, ZnTPTBP displayed a 49% increase in PET-RAFT polymerization rate with good control, marking a significant leap in the area of photo-controlled polymerization.
研究领域:
材料科学
·
化学
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高影响因子
MACROMOLECULES
·
2025
·
IF 5.2
Ke Wang,Xiaofang Liu,Ziyan Li,Fan Zhao,Guiyan Liu,Yongfei Zeng
A new family of multistimuli-responsive acrylamide-based homopolymers with different end pendant substituents were prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization. They include three types of multistimuli-response: temperature/pH/CO2-response, temperature/pH/redox-response, and temperature/pH/light-response. When the terminal substituent was ethyl and tetrahydropyran, P(Et-N-AM) and P(THP-N-AM) exhibited lower critical solution temperature (LCST) behavior in water, which can be adjusted by degree of polymerization (DP) and concentration of polymer, additives, pH, and the injection of CO2/N2 to the solution. When the terminal substituents were phenyl, ferrocene, and azobenzene, P(Ph-N-AM), P(Fc-N-AM), and P(Azo-N-AM) were insoluble in water due to the increase of hydrophobicity, but the upper critical solution temperature (UCST) was exhibited in the mixed solution of nBuOH/water and can be adjusted by the addition of acid or base. P(Fc-N-AM) was also redox-responsive, and its UV/vis absorption peaks changed with the addition of FeCl3/VC. P(Azo-N-AM) was also light-responsive, and under UV/blue light radiation, the characteristic peaks of its UV/vis absorption spectrum changed reversibly. In addition, the three homopolymers were amphiphilic, which can self-assemble in solution, and the obtained micelles were also responsive. Finally, nile red (NR) was used as a hydrophobic drug model, and the controlled release behavior of NR-loaded micelles of P(Fc-N-AM) and P(Azo-N-AM) under different stimuli was investigated. This work has greatly enriched the family of multistimuli-responsive poly(N-substituted acrylamide)s, and the synthetic steps of homopolymers were simple; the responsive behavior was sensitive, and the species were rich. It provides a reference for the design of novel stimuli-responsive polymers and has a good application prospect in self-assembly, drug release, and other fields.
研究领域:
高分子化学
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材料科学
·
药物递送
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高影响因子
JOURNAL OF VIROLOGY
·
2026
·
IF 4.1
Yingran Huang,Yinglin Qi,Junyong Guan,Ran Shao,Cankun Xi,Xing Liu,Dong Zhou,Shuhui Qi,Xin Yin
Bluetongue virus (BTV) is an economically important arbovirus of ruminants worldwide. The nonstructural glycoprotein NS3/NS3A contains a uniquely conserved N-linked glycosylation site at Asn150; yet, the functional consequences of this modification have remained unclear. Here, we characterize the Asn150-linked glycan and show that it predominantly comprises high-mannose structures that undergo maturation specifically in mammalian cells. Using a reverse-genetics system, we demonstrate that N-linked glycosylation is not required to maintain NS3/NS3A stability or its interaction with outer capsid proteins, but is essential for efficient virion egress. Ablation of this site (N150Q) markedly impaired plasma-membrane localization and reduced partitioning into detergent-resistant lipid raft microdomains. These defects resulted in reduced extracellular titers and attenuated multicycle spread. Together, these findings support a model in which the Asn150 glycan functions as a glycan-dependent targeting signal that biases NS3/NS3A toward plasma-membrane microdomains enriched in lipid rafts, thereby promoting productive virus release. In AG129 mice, the N150Q mutant exhibited attenuated virulence, characterized by reduced viremia, restricted tissue dissemination, and minimal pathology, in contrast to the severe systemic disease caused by the wild-type virus. The strict conservation of the Asn150 motif across BTV serotypes underscores its functional importance and highlights NS3/NS3A glycosylation as a potential target for broad-spectrum antivirals or vaccine strategies.
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高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2025
·
IF 2.8
Longyun Dong,Fengming Bi,Ze Li,Yu Kuai
A high-solid-content emulsion system exhibiting pH-responsive reversible coagulation and redispersion behavior was successfully developed through reversible addition–fragmentation chain transfer (RAFT) polymerization. The system was constructed using amphiphilic macro-RAFT copolymers comprising poly(acrylic acid) (PAA) as the hydrophilic block and poly(methyl methacrylate) (PMMA) as the hydrophobic segment. These block copolymers were precisely designed with hydrophilic–lipophilic balance (HLB) values optimized for effective oil-in-water (O/W) emulsion stabilization. The influence of the hydrophilic-to-hydrophobic ratio in macro-RAFT copolymers on the stability, rheological properties, and reversible coagulation–redispersion behavior of the resulting emulsions was systematically investigated. Rotational viscometry, gel permeation chromatography (GPC), dynamic light scattering (DLS), and zeta potential measurements revealed that the macro-RAFT copolymers, when effectively anchored at the oil–water interface, significantly enhanced emulsion stability while maintaining low viscosity and exhibiting excellent reversible solid–liquid transition behavior upon pH modulation. Emulsions stabilized by macro-RAFT copolymers with extended hydrophilic segments demonstrated remarkably low viscosities (~700 mPa·s) even at a high solid content of 60 wt.%. These emulsions exhibited excellent colloidal stability, as evidenced by zeta potentials consistently maintained below −34.0 mV after five consecutive coagulation–redispersion cycles. Furthermore, the variations in particle size and particle size distribution (PSD) remained within 20% and 10%, respectively, highlighting the system's robust reversibility and structural integrity.
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高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2021
·
IF 4.539
Caiyu Zhang,Jiawei Li,Niuniu Cui,Xiaofei Yan,Ziwen Xie,Dongming Qi
By using organic pigment-based ink-jet inks, the digital ink-jet printing of textiles is one kind of environmentally friendly technology for cleaner dyeing. Due to the shortcomings of easy agglomeration and poor water dispersion stability of organic nanoparticles , however, the encapsulation and dispersion of organic pigment nanoparticles are also hot and difficult research problems. In this work, we report the reversible addition-fragmentation chain transfer (RAFT) polymerization technology was used to synthesize random copolymer of 2-(dimethylamino) ethyl methacrylate (DMAEMA), poly(ethylene glycol) methyl ether methacrylate (PEGA), and methyl methacrylate (MMA) or butyl acrylate (BA) with a trithiocarbonate reactive end-group. These cationic macromolecular RAFT agents (macro-RAFT) with a pH of 5 were subsequently adsorbed at the surface of size-monodisperse colloidal Pigment Red 170 particles. The absorbed macro-RAFT agents were considered to be the living points to mediate the RAFT polymerization of monomers (MMA and BA) by starved feed emulsion polymerization . TEM results shown that the resulting hybrid latexes synthesized in presence of the tri-copolymer macro-RAFT agents resulted in the formation of individually encapsulated pigment particles. In addition, the dynamic light scattering (DLS), zeta potential and stability tests found that the macro-RAFT agent participated in the growing latex stabilization which is the key to obtaining the stable and uniform core-shell hybrid latex. More importantly, the preparation of film-forming copolymer/pigment hybrid latex in this study shown that the high potential of the P(DMAEMA- co -PEGA- co -MMA or BA) macro-RAFT agent for the development of polymer-pigment hybrid latexes which has good application properties.
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高影响因子
PROGRESS IN ORGANIC COATINGS
·
2026
·
IF 7.9
Xing-Yu Lei,Liang Ma,Qi Xu,Hui-Jing Li,Yan-Chao Wu
Biofouling poses a great challenge to marine facilities and causes serious economic losses, making the development of green and non-toxic anti-fouling coatings a high priority. In this study, leveraging the broad-spectrum bacteriostatic and economic properties of the natural product curcumin (Cur), it was chemically grafted onto the surface of xanthate-functionalized silica nanoparticles with the hydrophilic monomer vinylpyrrolidone (NVP) using a reversible addition-fragmentation chain transfer (RAFT) polymerization strategy. The resulting modified particles were incorporated as active fillers into a terminal hydroxy-polydimethylsiloxane (PDMS) matrix, successfully constructing a functional coating labeled PDMS/SiO 2 -X. This coating exhibits a synergistic antifouling mechanism combining self-polishing, static antifouling agent mitigation and dynamic fouling release. The presence of modified silica significantly improves the mechanical properties of the coating. The low surface energy surface imparts excellent fouling-release characteristics, while the hydrolysis of ester bond enables the sustained release of Cur to achieve efficient bacterial inhibition. Additionally, NVP effectively resists protein adhesion by forming a hydration layer. A 180-day real-sea field test verifies the long-lasting and stable antifouling performance of the coating. This work provides a new idea for developing highly efficient and environmentally friendly marine antifouling coatings.
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高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2023
·Vol. 140
·期 39
·e54462
·
IF 3
Jia Liu,Zhengchun Cai,Yongxin Ji
The synthesis of bio-based modified amphoteric epoxy modified acrylate sizing emulsion based on reversible addition fragmentation chain transfer (RAFT) polymerization and its application in paper sizing were studied. A macromolecular chain transfer agent for RAFT polymerization was synthesized by the esterification of epoxy resin E-51 with RAFT agent to eliminate the active groups on RAFT agent. Amphoteric polymer emulsifiers with good emulsification and dispersion effects in acidic and alkaline media were successfully prepared by RAFT polymerization. After neutralization, other monomers were polymerized to access cationic sizing emulsion (acid neutralization) and anionic sizing emulsion (alkali neutralization). The effects of bio-based monomer content, hydrophilic monomer dimethylaminoethyl methacrylate (DM) content and degree of quaternization on the properties of sizing emulsion and sizing paper were further explored. In addition to the particle size and polymer dispersion index (PDI) of latex particles in different experimental groups, the water resistance, folding resistance, bursting strength, tensile strength and surface roughness of sized paper were analyzed and evaluated. Based on these results, a better sizing emulsion formulation was established. It was confirmed that the addition of bio-based monomers can improve the sizing performance of paper.
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高影响因子
MACROMOLECULAR CHEMISTRY AND PHYSICS
·
2021
·Vol. 223
·期 3
·2100340
·
IF 2.527
Jianxiong Zhang,Junjin Duan,Dong Chen,Yuhong Ma,Wantai Yang
A direct photolysis reversible addition-fragmentation chain transfer (RAFT) polymerization of (meth)acrylates is developed with 2-cyano-2-propyldodecyl trithiocarbonate (TTP), which plays the dual role as photoinitiator and chain transfer agent. The polymerizations can be efficiently activated by blue light while maintaining a linear increase in M n versus conversion. With poly(methyl methacrylate)-TTP (PMMA-TTP, M n = 6700 g mol –1 , Ð = 1.29) as precursor, a higher molecular weight PMMA ( M n = 14 600 g mol –1 , Ð = 1.67) by chain extension, and a series of block copolymers, including poly(methyl methacryalte)- b -poly(glycidyl methacrylate), poly(methyl methacrylate)- b -poly(tert-butyl methacrylate), and poly(methyl methacrylate)- b -poly(benzyl meacrylate)(PMMA- b -PBnMA), are prepared. The M n,NMR = 14 900 g mol –1 of PMMA- b -PBnMA measured by NMR is very close to M n,GPC = 14 200 g mol –1 determined by gel permeation chromatography. Furthermore, the polymerization of acrylates exhibits higher controllability in regarding to dispersity ( Ð < 1.20) compared to those of polymethacrylates ( Ð = 1.10–1.80). With poly(methyl acrylate) (PMA-TTP, M n = 11 900 g mol –1 , Ð = 1.09) as macro-RAFT agent, a higher molecular weight PMA ( M n = 23 500 g mol –1 , Ð = 1.28) by chain extension, and PMA- b -PBnA ( M n = 26 500 g mol –1 , Ð = 1.19) are also prepared. A positive synergic effect is demonstrated by enhanced apparent polymerization rates at elevated temperature. For example, the apparent polymerization rates of MA increases from 0.0860 to 0.115 h –1 with temperature rising from 32 to 50 °C.
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Polymer Chemistry
·
2021
·Vol. 12
·期 39
·5574-5582
·
IF 5.582
Qianqian Ge,Guangzu Wang,Xiang Zhu,Weisheng Yu,Jiahui Zhou,Bin Wu,Yahua Liu,Zhengzhi Zheng,Zhengjin Yang,Jiasheng Qian
Polyolefin-based anion exchange membranes have recently been increasingly studied, but obtaining polyolefins with controllable molecular weights and high chemical stability under facile and metal-free conditions remains a critical challenge. Here, we demonstrate a novel strategy of exploiting visible light-induced reversible addition–fragmentation chain transfer polymerization (Vis-RAFT) for the preparation of poly(2-chloroethyl vinyl ether) (PCEVE), which exhibits high alkaline stability. With this strategy, we can control the molecular weight of PCEVE by an “on/off” light procedure. The quaternization of PCEVE yields quaternized poly(2-chloroethyl vinyl ether) (PQEVE) membranes with a well-defined microphase-separated morphology, a high chloride conductivity of 26.1 mS cm−1 at 30 °C, and a significantly reduced water swelling of 1.2% at 80 °C. We anticipate that this strategy can be a potent alternative to metal-catalysed coordination polymerization or metathesis polymerization in preparing high molecular weight polyolefins for membrane applications.
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