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NEW JOURNAL OF CHEMISTRY · 2016 ·Vol. 40 ·期 5 ·4761-4768 · IF 3.277

Synthesis and self-assembly behavior of thermo-responsive star-shaped POSS–(PCL–P(MEO2MA-co-PEGMA))16 inorganic/organic hybrid block copolymers with tunable lower critical solution temperature

Lei Li,Beibei Lu,Jianning Wu,Qikui Fan,Xuhong Guo,Zhiyong Liu

In this work, we report that well-defined amphiphilic star-shaped polyhedral oligomeric silsesquioxane (POSS)-based inorganic/organic hybrid block copolymers of poly(ε-caprolactone)–poly(2-(2-methoxyethoxy)ethyl methacrylate)-co-poly(ethylene glycol) methacrylate (POSS–(PCL–P(MEO2MA-co-PEGMA))16) were synthesized via click chemistry, ring opening polymerization (ROP) and atom transfer radical polymerization (ATRP), and their synthesis was confirmed by Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (1H NMR), gel permeation chromatography (GPC) and X-ray photoelectron spectroscopy (XPS). The obtained polymers could self-assemble into ellipsoidal aggregates with a moderately uniform size, owing to the amphiphilic properties of the hydrophobic inorganic POSS and PCL cores and the hydrophilic P(MEO2MA-co-PEGMA) segments. These thermo-responsive organic/inorganic hybrid polymeric micelles exhibited critical phase transition temperatures in water, which could be finely tuned by changing the feed ratios of PEGMA and MEO2MA. The lower critical solution temperature (LCST) of star-shaped POSS–(PCL–P(MEO2MA-co-PEGMA))16 increased from 34 to 57 °C with the increase of PEGMA content. The results were investigated by ultraviolet-visible (UV-vis) spectroscopy, dynamic light scattering (DLS), and transmission electron microscopy (TEM). When the temperature was higher than the corresponding LCSTs, the micelles started to associate and form spherical nanoparticles. Therefore, POSS–(PCL–P(MEO2MA-co-PEGMA))16 block copolymers, a class of novel organic/inorganic hybrid materials with advantageous properties, are amphiphilic hybrid polymers with potential applications as nano-carriers, nano-reactors, and smart materials and in the biomedical field.

CAS / MDL: 78-67-1
研究领域: 材料科学 · 高分子化学 · 生物医药
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2018 · IF 5.091

Surface PEGylation and biological imaging of fluorescent Tb3+-doped layered double hydroxides through the photoinduced RAFT polymerization

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

Tb 3+ -doped layered double hydroxides (LDHs) exhibit excellent optical characteristics , uniform size and uniform morphologies when synthesized through a hydrothermal method . However, due to their lack of functional groups and poor dispersibility, applications of these fluorescent Tb 3+ -doped LDHs have been largely impeded especially in the biomedical fields. In this work, a novel strategy was developed for the surface modification of these fluorescent Tb 3+ -doped LDHs using photoinduced surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization with hydrophilic poly(ethylene glycol) methacrylate (PEGMA) as the monomer . The final products were obtained via the metal free surface-initiated RAFT polymerization with light irradiation . Successful preparation of these fluorescent LDHs polymer composites (LDH-PEG) was confirmed by a number of analytical technologies, such as transmission electron microscopy , Fourier transformed infrared spectroscopy , X-ray photoelectron spectroscopy and thermogravimetric analysis . In addition, laser scanning confocal microscope was employed to examine the cell uptake behavior of the LDH-PEG composites and evaluate their potential for biomedical applications. We demonstrated that the hydrophilic monomer PEGMA could be facilely grafted on the surface of Tb 3+ -doped LDHs through metal free photoinduced surface-initiated RAFT polymerization. The resultant LDH-PEG composites displayed high water dispersibility, strong fluorescence, low cytotoxicity and a desirable cell uptake performance. These features of the LDH-PEG composites indicated their great potential for biomedical applications. More importantly, photoinduced RAFT polymerization has the advantages of a conventional controlled living radical polymerization , which could overcome drawbacks such as toxicity, the fluorescence quenching effects of metal catalysts and the complex synthesis of chain transfer agents. Therefore, this method could be an alternative tool for the surface modification of materials and fabrication of multifunctional fluorescent nanomaterials based polymer composites.

研究领域: 材料科学 · 纳米技术 · 生物医学工程 · 高分子化学
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RSC Advances · 2016 ·Vol. 6 ·期 66 ·61630-61640 · IF 3.289

Synthesis and self-assembly behavior of pH-responsive star-shaped POSS-(PCL-P(DMAEMA-co-PEGMA))16 inorganic/organic hybrid block copolymer for the controlled intracellular delivery of doxorubicin

Lei Li,Beibei Lu,Qikui Fan,Jianning Wu,Lulu Wei,Jun Hou,Xuhong Guo,Zhiyong Liu

In this work, well-defined amphiphilic polyhedral oligomeric silsesquioxane (POSS) star-shaped inorganic/organic hybrid block copolymers with poly(ε-caprolactone)-poly(2-(dimethylamino)ethyl methacrylate)-co-poly(ethylene glycol) methacrylate (POSS-PCL-P(DMAEMA-co-PEGMA))16 were synthesized with different PCL segments via thiol-ene click reaction, ring opening polymerization (ROP) and atom transfer radical polymerization (ATRP), which were confirmed by Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance (1H NMR), gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). Subsequently, the polymers could self-assemble into micelles in aqueous solution, which were investigated by dynamic light scattering (DLS), ultraviolet-visible spectroscopy (UV-vis) and transmission electron microscopy (TEM). The pH-responsive self-assembly behavior of these triblock copolymers in water was investigated at different pH values of 5.0 and 7.4 for controlled doxorubicin release; the results indicated that the release rate of DOX could be effectively controlled by altering the pH and the release of drug loading efficiency (DLE) was up to 82% (w/w). Furthermore, CCK-8 assays and confocal laser scanning microscopy (CLSM) against HeLa cells indicated that the micelles had no associated cytotoxicity, possessed good biodegradability and biocompatibility, and identified the location of the DOX in HeLa cells. The DOX-loaded micelles could easily enter the cells and produce the desired pharmacological action, and minimize the side effects of free DOX. Moreover, these flexible micelles with on-off switched drug release may offer a promising method to deliver a wide variety of hydrophobic payloads to tumor cells for cancer therapy.

CAS / MDL: 78-67-1
研究领域: 高分子科学 · 纳米技术 · 药学 · 生物医学工程 · 材料科学
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LANGMUIR · 2024 · IF 3.7

Poly(Photosensitizer-Prodrug) Unimolecular Micelles for Chemo-Photodynamic Synergistic Therapy of Antitumor and Antibacteria

Jieheng Zhang,Jianchang Xu,Jiaying Zhang,Yibin Lin,Jiaxin Li,Duoqu Chen,Wenjing Lin,Chufen Yang,Guobin Yi

It is crucial to use simple methods to prepare stable polymeric micelles with multiple functions for cancer treatment. Herein, via a “bottom-up” strategy, we reported the fabrication of β-CD-(PEOSMA-PCPTMA-PPEGMA)21 (βPECP) unimolecular micelles that could simultaneously treat tumors and bacteria with chemotherapy and photodynamic therapy (PDT). The unimolecular micelles consisted of a 21-arm β-cyclodextrin (β-CD) core as a macromolecular initiator, photosensitizer eosin Y (EOS-Y) monomer EOSMA, anticancer drug camptothecin (CPT) monomer, and a hydrophilic shell PEGMA. Camptothecin monomer (CPTMA) could achieve controlled release of the CPT due to the presence of responsively broken disulfide bonds. PEGMA enhanced the biocompatibility of micelles as a hydrophilic shell. Two βPECP with different lengths were synthesized by modulating reaction conditions and the proportion of monomers, which both were self-assembled to unimolecular micelles in water. βPECP unimolecular micelles with higher EOS-Y/CPT content exhibited more excellent 1O2 production, in vitro drug release efficiency, higher cytotoxicity, and superior antibacterial activity. Also, we carried out simulations of the self-assembly and CPT release process of micelles, which agreed with the experiments. This nanosystem, which combines antimicrobial and antitumor functions, provides new ideas for bacteria-mediated tumor clinical chemoresistance.

研究领域: 纳米技术 · 药学 · 生物医学工程 · 癌症研究 · 微生物学
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POWDER TECHNOLOGY · 2023 · IF 5.2

Fabrication and evaluation of novel amphiphilic star block copolymers for increasing free water content in lignite to make coal water slurries

Xuan Liu,Jie Gong,Kai Jiang,Xiaojuan Lai,Yu Tian,Kang Zhang

In order to reduce the apparent viscosity of lignite coal water slurries (CWSs) and improve its static stability, a series of three-arm amphiphilic block copolymers have been prepared through RAFT polymerization by using poly(ethylene glycol) methyl ether acrylate (PEGMA) and sodium 4-vinylbenzenesulfonate (SSNa) as hydrophilic monomers and styrene (St) as hydrophobic monomer. The chemical structure of the copolymers has been investigated, and the impact of relative molecular weight, hydrophilic/hydrophobic ratio, and ionic group content on the pulping performance of three-arm amphiphilic block copolymers has been examined. The lignite coal water slurries (CWSs) prepared from the block copolymer tri -P(St 50 - s -SSNa 50 ) 10K - b -PPEGMA 10K exhibit a remarkably low apparent viscosity of 395 mPa·s and excellent static stability when the coal content is at 55 wt% and dispersant content is at 0.5 wt%. Moreover, these CWSs can achieve a maximum pulping concentration of up to 59 wt%. Additionally, the thermogravimetric test reveals insights into the water occurrence in CWSs, indicating that higher levels of free water content correspond to lower apparent viscosities. Suitable hydrophobicity facilitates the removal of internal water from lignite by dispersants, disrupting its flocculation structure and promoting CWSs formation. Meanwhile, the presence of ionic groups enhances the static stability of the resulting CWSs. Furthermore, the adsorption behavior of the three-arm amphiphilic block copolymer dispersant in lignite has been analyzed through XPS testing to elucidate its dispersion mechanism. The use of three-arm amphiphilic block copolymers in preparing lignite CWSs results in lower apparent viscosity and improved static stability, attributed to the amphiphilic and steric hindrance effects of dispersants. This not only expands the application range of lignite CWSs but also highlights the significant potential of this type of dispersant.

研究领域: 聚合物化学 · 材料科学 · 能源工程 · 化工工程
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2018 · IF 5.091

Facile fabrication of organic dyed polymer nanoparticles with aggregation-induced emission using an ultrasound-assisted multicomponent reaction and their biological imaging

Ruming Jiang,Meiying Liu,Hongye Huang,Liucheng Mao,Qiang Huang,Yuanqing Wen,Qian-yong Cao,Jianwen Tian,Xiaoyong Zhang,Yen Wei

Ultrasound as a powerful technique has increasingly been used in both industry and academia in recent years. Herein, an efficient approach to the ultrafast preparation of cross-linked fluorescent copolymers (PEGMA-AEMA-TPE) with aggregation-induced emission (AIE) via an ultrasound-assisted multicomponent reaction (MCR) is described. A number of characterization techniques were carried out to certify the successful preparation of these AIE-active copolymers. Due to the introduction of a hydrophilic PEG fragment and a hydrophobic AIE-active dye, the obtained fluorescent copolymers showed amphiphilic properties and could assemble into organic dyed polymer nanoparticles (ODPNs) with great water dispersibility. The final PEGMA-AEMA-TPE ODPNs demonstrated intense fluorescence, strong photostability, a low critical micelle concentration (CMC) of 0.007 mg mL −1 and high biocompatibility. More importantly, the PEGMA-AEMA-TPE ODPNs show obvious AIE characteristics, which could elegantly overcome the quenching effect caused by the aggregation of ODPNs based on conventional organic dyes. Considered the above results, we believe that these AIE-active ODPNs should be promising candidates for biological imaging and other biomedical applications.

研究领域: 材料科学 · 纳米技术 · 生物医学工程 · 化学
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Journal of Materials Chemistry B · 2015 ·Vol. 3 ·期 20 ·4170-4180 · IF 4.726

One-pot cross-linked copolymerization for the construction of robust antifouling and antibacterial composite membranes

Chong Cheng,Ai He,Chuanxiong Nie,Yi Xia,Chao He,Lang Ma,Changsheng Zhao

This study reports a highly efficient, convenient and universal protocol for the fabrication of robust antifouling and antibacterial polymeric membranes via one-pot cross-linked copolymerization of methyl acryloyloxygen ethyl trimethyl ammonium chloride (DMC) and poly(ethylene glycol) methyl ether methacrylate (PEGMA). The infrared testing and X-ray photoelectron spectroscopy gave obvious evidence that abundant DMC and PEGMA chains had enriched on the membrane surface. The surface and cross-sectional SEM images indicated that the addition of DMC and PEGMA had a little effect on the membrane roughness and inner structure. Meanwhile, the systematic investigations into the water contact angle, protein adsorption, ultrafiltration and bacterial inhibition indicated that the composite membranes showed improved hydrophilicity, decreased protein adsorption, increased water flux and antifouling property, as well as greatly enhanced antibacterial ability. Furthermore, it was found that the cross-linked copolymerization could further endow the composite membrane with multi-chemical properties, for instance the charged interface. As a model system, Ag nanoparticle-PDMC multilayers were coated onto the positively charged PES–DMC6 membranes via layer by layer assembly, and the successful surface coating confirmed their versatile ability and also provided a more effective and durable antibacterial coating to the composite membranes. All these results suggest that the robust antifouling and antibacterial composite membranes can be prepared via the proposed one-pot cross-linked copolymerization, and it is believed that this approach has great potential to be applied in various biomedical or industrial fields where antifouling and antibacterial properties are highly demanded.

研究领域: 材料科学 · 化学工程 · 生物医学工程 · 高分子科学
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EUROPEAN POLYMER JOURNAL · 2022 · IF 5.546

Fabrication of patterned polymer brushes using programmable modulated light-excited controllable radical polymerization

Haili Zhao,Hao Gao,Tao Chen,Linsheng Xie,Yulu Ma,Jin Sha

In the present work, programmable light pattern produced by digital micro-mirror device (DMD) spatial light modulator was employed to initiate the atom transfer radial polymerization (ATRP) for fabricating the patterned polymer brushes on the silicon substrate surface. Results from a series of characterization methods such as optical microscopy, 3D optical surface profiler, and X-ray photoelectron spectroscopy proved the poly (ethylene glycol) methyl acrylate (PEGMA) brushes with complex structures were successfully generated. The thickness of PEGMA brushes could be regulated by adjusting the DMD light modulation parameter including pattern size, gray value and exposure time. The contact angle measurements showed the PEGMA brushes could improve the hydrophilicity property of substrate surface. The antifouling property of the patterned surfaces with different shapes were tested, and the results indicated that the PEGMA brushes could effectively resist the adhesion of bovine serum albumin (BSA) protein, leading to the selective arrangement of protein. The reported method for generating the polymer brush patterns shows great potential for the manipulation of surface property in facilitating a range amount of applications from anti-biofouling coating, interface lubrication to biomimetic and smart surfaces.

CAS / MDL: 1344-28-1
研究领域: 材料科学 · 高分子化学 · 表面科学 · 生物医学工程
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EUROPEAN POLYMER JOURNAL · 2023 · IF 6

Multifunctional hydrogels simultaneously featuring ultrahigh stretchability, remarkable tearing resistance, and reusable fluorescence for information encoding–decoding and smart anticounterfeiting

Haojie Qian,Xiaowen Xu

Fluorescent hydrogels with fluorescent dyes are widely used for anti-counterfeiting encryption. However, developing highly stretchable and remarkable tear-resistant hydrogels with reusable fluorescence for anti-counterfeiting purposes remains challenging. In this study, we fabricated and characterized double network (DN) hydrogels comprising polyvinyl alcohol-borax (PVA-borax) as the first network and poly(methacrylamide- co -polyethylene glycol- co -pyrenylmethyl acrylate) (P(MAM- co -PEGMA- co -PyMA)) as the second network with varying MAM to PEGMA ratios. SEM images showed the hydrogels had 3D porous structures. FT-IR and thermal properties analysis (DSC and TGA) indicated the presence of hydrogen bonds between PVA-borax and P(MAM- co -PEGMA- co -PyMA) without any chemical bonds. The red shift in characteristic absorption bands at 841 and 710 cm −1 further confirmed the presence of π-π* interactions between pyrene moieties. XRD analysis revealed no significant changes in crystalline phase of the hydrogels, which facilitated the formation of a 3D network due to abundant hydrogen bond presence. When the MAM to PEGMA ratio was adjusted to 9:2, the resulting hydrogels exhibited remarkable properties such as ultra-high stretchability (strain over 3300 %), excellent notch-insensitivity, and exceptional tear resistance (tearing energy over 3.25 × 10 5 J/m 2 ). Importantly, the hydrogel's fluorescence intensity could be reversibly changed by alternatively adding Fe 3+ and EDTA-2Na. It could be reused more than 10 times while maintaining a fluorescence intensity of around 80 %, demonstrating its reliability as a versatile hydrogel probe for Fe 3+ detection with “ON-OFF-ON” fluorescence behavior. Furthermore, the hydrogels demonstrated exceptional 2D encryption and decryption capabilities, highlighting their potential applications in information storage and data security. To improve the level of anti-counterfeiting, multiple encryption approaches such as QR codes and ASCII binary codes were rationally designed. Overall, this study successfully developed a universal DN hydrogel platform with ultra-high stretchability and remarkable tear resistance, capable of rapid encoding and decoding of complex information for smart anti-counterfeiting.

CAS / MDL: 9002-89-5 1303-96-4
研究领域: 材料科学 · 化学 · 纳米技术 · 防伪技术
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Energy Technology · 2018 ·Vol. 7 ·期 1 ·122-130 · IF 3.175

Nanocomposite All-Solid-State Polymer Electrolyte for High-Performance Lithium Batteries

Shi Wang,Hao Xu,Ailian Wang,Xu Liu,Jie Chen,Zhinan Wang,Di Feng,Qinghui Zeng,Liaoyun Zhang

An inorganic-polymeric hybrid all-solid-state electrolyte (SSE) composed of chemically modified nano-silica, linear poly(trifluoroethyl methacrylate)-co-poly(poly(ethylene glycol) methyl ether methacrylate copolymer (PTFEMA-co-PPEGMA or LCP) and lithium salt is prepared and used in lithium-ion batteries (LIBs) for the first time. Nano-silica is transformed to SiO 2 -SH via esterification reaction. Then, SiO 2 -PEGMA is synthesized through click chemistry of SiO 2 -SH and PEGMA. The compatibility of the nano-SiO 2 and the LCP can be effectively improved due to the excellent dispersibility of the chemically modified nano-SiO 2 in the polymer matrix. As a result, the hybrid SSE has good thermal stability, excellent film-forming ability. Furthermore, the hybrid SSE shows superior comprehensive electrochemical properties, which makes the corresponding LiFePO 4 /Li cells have good cycling performance (the discharge capacity reaches 144 mAh g −1 at 0.3 C) and rate capability (90 mAh g −1 is reached at 1 C). Thus, the hybrid electrolyte can be a powerful SSE for high-safety and high-performance LIBs.

研究领域: 材料科学 · 电化学 · 能源存储
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TALANTA · 2021 · IF 6.057

Synthesis of water-soluble europium-containing nanoprobes via polymerization-induced self-assembly and their cellular imaging applications

Yicheng Wang,Dongliang Yang,Yaqin Hu,Yuxin Wang,Wen Jing Yang,Lianhui Wang

Lanthanide nanoprobes have attracted extensive attention for applications in cellular imaging and biological sensing. Herein, water-dispersible europium (III)-based (Eu(III)-based) nanoprobes were prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly (PISA) of hydrophobic monomers (Eu(III)-containing monomer and methyl methacrylate (MMA)) using hydrophilic macro-chain transfer agent poly(PEGMA)-CTA. The resulted poly(PMEu) nanoprobes showed spherical in shape in good monodispersity with average diameters of around 210 nm. The poly(PMEu) nanoprobles excellent aqueous dispersity, high aqueous stability and good luminescence properties with quantum yields of 37.21% and fluorescence lifetime of 312.4 μs. Moreover, the poly(PMEu) nanoprobes exhibited good cellular biocompatibility with cell viabilities of 88.2% and high fluorescence intensity for in vitro cellular imaging. The present approach provides a facile strategy for fabrication of luminescent Eu(III)-based nanoprobes with great potential applications for biological imaging.

研究领域: 材料科学 · 纳米技术 · 生物医学工程 · 细胞生物学
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