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Polymer Chemistry · 2020 ·Vol. 11 ·期 41 ·6650-6657 · IF 5.342

A fluorescent sensor for intracellular Zn2+ based on cylindrical molecular brushes of poly(2-oxazoline) through ion-induced emission

Shanshan Chen,Tingting Sun,Zhigang Xie,Dewen Dong,Ning Zhang

Mobile divalent zinc, Zn(II), is an essential cofactor involved in mammalian biological processes. To understand the intrinsic action mechanism of mobile zinc, the development of a Zn2+-selective fluorescent probe that can detect mobile zinc via biological imaging is of great significance. We present here a novel Zn2+-selective fluorescent sensor based on poly(2-oxazoline) (POx) cylindrical molecular brushes with good water solubility and biocompatibility. The POx molecular brushes were end-capped by a Zn2+-responsive functionality, which can give efficient blue emission upon coordination with zinc ions. Fluorescence investigation indicates that the POx molecular brushes exhibit superior selectivity toward Zn2+ in comparison with most competitive heavy and transition metal ions. Due to the ease of cellular uptake that results from their unique molecular contour, POx molecular brushes are capable of detecting intracellular Zn2+ ions as demonstrated by living cell fluorescence studies.

研究领域: 生物化学 · 材料科学 · 分析化学
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Journal of Materials Chemistry B · 2019 ·Vol. 7 ·期 36 ·5520-5527 · IF 5.047

Intelligent antibacterial surface based on ionic liquid molecular brushes for bacterial killing and release

Lunqiang Jin,Zhenqiang Shi,Xiang Zhang,Xiaoling Liu,Huiling Li,Jingxia Wang,Feng Liang,Weifeng Zhao,Changsheng Zhao

The prevention of bacteria-induced infections has been increasing in importance in both clinical surgery and biomedical engineering. Although great attention has been paid to designing intelligent antibacterial surfaces, the fabrication processes are still not facile and universal enough, and the antibacterial efficiencies of these surfaces are also not ideal. Herein, ionic liquid (IL) molecules of 3-(12-mercaptododecyl)-1-methyl-1H-imidazol-3-ium bromide (IL(Br)) were synthesized with the minimum inhibitory concentrations as low as 4 and 8 μg mL−1 against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli), respectively. By simply immersing a polymeric substrate into the IL(Br) solution, an antibacterial surface with high killing efficiency of 99% against S. aureus (94% against E. coli) was achieved via a mussel-inspired approach. Subsequently, 97% S. aureus and 95% E. coli on the substrate could be released by simple ion-exchange of Br− with (CF3SO2)2N− due to the ion sensitivity of the IL molecular brushes. Thus, the proposed facile strategy towards a superior efficiency surface could be potentially used in intelligent antibacterial fields.

研究领域: 生物医学工程 · 材料科学 · 微生物学
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LANGMUIR · 2025 · IF 3.9

Flow Interface Regulates Charge and Reactivity of Bulk Liquid

Yunlong Yu,Zixuan Song,Boran Xu,Yunxin Tang,Qiangqiang Sun,Shaobing Zhou

Flow alters the charge distribution at the solid–liquid interface. However, the property change in bulk liquids in the flow has received little attention. In this article, we show that the charge separation between liquid and solid surfaces is controllable, and interfacial chemistry is changed to make electrostatically charged and reactive water. We designed a pipeline with unequal cross-sectional diameters at both ends to enhance the pressure difference between the two ends of the pipeline. By adjusting the flow rate, pipeline length, and cross-sectional diameter of the conical port, we achieved flexible control of the amount of liquid charge. To further regulate the liquid charge, we grafted charged molecular brushes onto the inner wall of the pipeline. In particular, the polarity of liquid charges is opposite to the polarity of the pipeline’s inner wall surface. Finally, we demonstrated the chemical activity of charged water through oxidative degradation of methylene blue and reduction of chloroauric acid.

CAS / MDL: 31098-21-2 75-65-0
研究领域: 物理化学 · 材料科学 · 界面科学
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DESALINATION · 2023 · IF 9.9

Construction of tunable “silica molecular brush” on the polyamide membrane surface for enhancing water permeability and antifouling performance

Qianqian Zhao,Shiyu Yu,Yan Zhang,Shaolu Li,Genghao Gong,Yunxia Hu

Surface modification has been widely applied for improvement permeability and antifouling performance of polyamide (PA) reverse osmosis (RO) membrane. A low-cost and easily obtained organoalkoxysilane, γ-Aminopropyl triethoxysilane (APTES), was grafted on PA RO membrane surface via a second interfacial polymerization (SIP) process combined with the activation effect of n-decane solvent, thus to form an antifouling PA surface with different silica brush-like structures, which can effectively weaken the attractive forces between the membrane surface and organic foulants. Meanwhile, n-decane solvent during the SIP process plays a dual function, which can not only minimize hydrolysis of both APTES monomers and unreacted acyl chloride groups on PA surface but also enhance microporosity of the nascent PA (solvent activation of PA), thereby grafting APTES on PA surface via amidation reaction can achieve maximization, and the water permeability of APTES modified PA (APTES-PA) membranes is improved. These APTES-PA membranes showed high water permeability (above 3.47 LMH/bar) with competitive NaCl rejection (above 98.75%), as well as excellent stability during 70 h of cross-flow test. Moreover, the existence of silica brush-like structures via grafting APTES molecules on PA layer can significantly elevate the antifouling performance of membranes against both negatively and positively charged foulants.

研究领域: 材料科学 · 环境工程
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Anti-fogging/dry-dust transparent superhydrophobic surfaces based on liquid-like molecule brush modified nanofiber cluster structures

Yingying Dou,Chengjiao Wu,Yue Fan,Yingke Wang,Zhe Sun,Shilin Huang,Yabin Yang,Xuelin Tian

Transparent protective coatings capable of preventing fog and dust accumulation have broad application prospect in photovoltaic systems , optical devices and consumer electronics. Although a number of superhydrophobic coatings have been developed for self-cleaning purpose over the past three decades, there is still a lack of surfaces that can simultaneously possess high transparency, remarkable superhydrophobicity, and excellent fog and dust resistance. In this study, we have prepared surfaces featuring sub-wavelength nanofiber cluster structures through a facile plasma etching method, and further modified the surface with liquid-like perfluoropolyether (PFPE) brushes. The prepared PFPE modified nanofibrous surface (PFPE-NS) exhibits superior optical transparency (transmittance 90.4 % ± 0.7 %) and water repellency , with a water contact angle as high as 171.0° ± 0.6° and sliding angle down to 0.5° ± 0.1° (5 µL). More importantly, benefitted from the nanofiber cluster structures and the slippery liquid-like surface chemistry, the adhesion and accumulation of fog droplets and dust particles on PFPE-NS is greatly inhibited. As a consequence, PFPE-NS can keep excellent optical clearness after 2 h fogging test and maintain an average transmittance above 87 % after 24 h dusting test. Our study provides a promising strategy through constructing liquid-like nanofibrous coating for optical protection that could be applicable in practical rainy, foggy, and dusty environments.

研究领域: 材料科学 · 光学工程
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Journal of Materials Chemistry B · 2015 ·Vol. 3 ·期 41 ·8170-8179 · IF 4.726

A supramolecular brush polymer via the self-assembly of bridged tris(β-cyclodextrin) with a porphyrin derivative and its magnetic resonance imaging

Mo Sun,Heng-Yi Zhang,Qian Zhao,Xin-Yue Hu,Li-Hua Wang,Bo-Wen Liu,Yu Liu

Accurate imaging of soft tissues is one of the ultimate goals in biomedical imaging. Different imaging modalities can improve their disadvantages, and promote the imaging ability. However, once an imaging agent has been prepared, it is usually hard to adjust it according to the actual needs. Herein, we developed a supramolecular brush polymer (SBP) as a versatile imaging agent platform. The SBP platform (SBPP) is constructed by the intermolecular inclusion complexation of bridged tris(β-cyclodextrin) (1) with Mn(III)-porphyrin-bearing poly(ethylene glycol) (PEG) side chains (Mn(III)-TPP), and can further bind other functional groups by host–guest interactions of cyclodextrin and adamantine. The SBPP is characterized by UV/vis absorption spectroscopy, NMR, dynamic light scattering (DLS), atomic force microscopy (AFM) and transmission electron microscopy (TEM). We demonstrated that this SBPP not only has no cellular toxicity against NIH 3T3 cells in in vitro cell experiments, but it also shows an efficient enhanced T1 relaxivity in in vitro MR imaging experiments. When used as multifunctional imaging agents, different imaging probes and/or targeting agents can be introduced to this SBPP as needed through simple host–guest interactions. In in vitro imaging experiments, it shows accurate imaging of different kinds of cancer cells by choosing on-demand targeting agents. These results suggest a promising strategy for engineering multifunctional imaging agents with SBPs.

CAS / MDL: 6066-82-6 134-03-2
研究领域: 生物医学工程 · 材料科学 · 医学影像学
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Polymer Chemistry · 2018 ·Vol. 9 ·期 45 ·5470-5475 · IF 4.927

Facile synthesis of cylindrical molecular brushes via Lewis pair-mediated polymerization

Shanshan Chen,Liman Hou,Qiliao Wang,Dewen Dong,Ning Zhang

We demonstrate the first application of Lewis pair-mediated polymerization (LPP) in the efficient synthesis of cylindrical molecular brushes bearing poly(methyl methacrylate) and polylactone side chains. Poly(N-heterocyclic olefin) (poly(NHO)) as a macroinitiator precursor was firstly prepared by the reversible addition–fragmentation chain transfer (RAFT) polymerization of N-vinylimidazolium iodide and successive deprotonation in the presence of a strong base. Poly(NHO) together with Al(C6F5)3 can jointly promote the polymerization of methyl methacrylate and δ-valerolactone, leading to the formation of PMMA and polylactone side chains along the backbone via the grafting-from approach. NMR, GPC, AFM characterization and polymerization dynamic investigation indicate the successful formation of side chains and the resulting stretched conformation of the polymer backbone. DSC characterization reveals that molecular brushes have a higher glass transition temperature than their linear counterpart because of the branched architecture of molecular brushes. The current strategy represents a new avenue for the application of LPP and provides potential in the synthesis of polymers with well-defined topological structures.

CAS / MDL: 9011-14-7
研究领域: 高分子化学 · 材料科学
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RSC Advances · 2012 ·Vol. 2 ·期 31 ·11953-11962 · IF 0

Salt/pH dual-responsive supramolecular brush copolymer micelles with molecular recognition of nucleobases for drug delivery

Dali Wang,Xiuying Huan,Lijuan Zhu,Jinyao Liu,Feng Qiu,Deyue Yan,Xinyuan Zhu

A new type of salt/pH dual-responsive micelles based on supramolecular amphiphilic brush copolymers, poly(2-hydroxyethyl metharylate)-g-(poly(ε-caprolactone)-adenine:uracil-poly(ethylene glycol)) (PHEMA-g-(PCL-A:U-PEG)) was developed for the anticancer drug delivery owing to the fact that the tumor tissues show low pH and high salt concentration. The supramolecular structure of brush copolymer was confirmed by variable-temperature 1H NMR and Fourier transform infrared spectroscopy (FTIR). Doxorubicin (DOX) as a model anticancer drug was efficiently loaded into the supramolecular micelles (up to 70%) due to the compact structure of brush polymer. The cumulative release profile of the DOX-loaded micelles showed a low level of drug release (about 20 wt% in 25 h) at pH 7.4 with a low salt concentration, and was significantly accelerated at a lower pH (5.0) and a high salt concentration (over 70 wt% in 6 h), exhibiting an salt/pH dual-responsive controlled drug release capability. Methyl tetrazolium (MTT) assay showed that DOX-loaded micelles had high anticancer efficacy against Hela cancer cells and blank micelles had a very low cytotoxicity. These supramolecular brush copolymer micelles possess many favorable traits, such as low cytotoxicity and excellent biodegradability, adequate drug loading capacity, and rapid drug release in response to the intracellular level of pH and salt concentration, which endow them as a promise candidate for delivering anticancer drugs.

研究领域: 高分子化学 · 药剂学 · 肿瘤学
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NEW CARBON MATERIALS · 2022 · IF 3.7

Controllable fabrication of superhierarchical carbon nanonetworks from 2D molecular brushes and their use in electrodes of flexible supercapacitors

Yu-heng Lu,You-chen Tang,Ke-han Tang,Ding-cai Wu,Qian Ma

Three-dimensional carbon nanonetworks (3D CNNs) have interconnected conductive skeletons and accessible pore structures, which provide multi-level transport channels and thus have promising applications in many areas. However, the physical stacking of these network units to form long-range conductive paths is hard to accomplish, and the introduction of micropores and small mesopores is usually difficult. We report a simple yet efficient strategy to construct CNNs with a nitrogen-doped micro-meso-macroporous carbon nanonetwork using Schiff-base gelation followed by carbonization. Using a polyacrolein-grafted graphene oxide molecular brush as the building block and tetrakis (4-aminophenyl) methane as the crosslinking agent, the obtained molecular brush nanonetworks have a high carbon yield and largely retain the original morphology, leading to the formation of a 3D continuous nanonetwork after carbonization. The materials have a micro-meso-macroporous structure with a high surface area and a highly conductive N-doped carbon backbone. This unique structure has a large number of exposed active sites and excellent charge/mass transfer ability. When loaded on carbon cloth and used as the electrodes of a flexible supercapacitor, the CNN has a specific capacitance of 180 F g −1 at 1 A g −1 and a high capacitance retention of 91.4% after 10 000 cycles at 8 A g −1 .

CAS / MDL: 107-02-8
研究领域: 材料科学 · 能源存储与转换
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Polymer Chemistry · 2013 ·Vol. 4 ·期 19 ·5074-5085 · IF 5.231

Surface-initiated RAFT polymerization of sulfobetaine from cellulose membranes to improve hemocompatibility and antibiofouling property

Jiang Yuan,Xiaobo Huang,Pengfei Li,Li Li,Jian Shen

Two major complications generally occur in blood-contacting devices, namely thrombus formation and microbial invasion and infection. Therefore, hemocompatible and antibiofouling surfaces, which function as barriers to bacterial and cell adhesion, are essential. Herein, we report the successful grafting of zwitterionic polysulfobetaine brushes onto a cellulose membrane (CM) via surface-initiated reversible addition–fragmentation chain-transfer (SI-RAFT) polymerization for improving hemocompatibility and antibiofouling property. Both pristine and polysulfobetaine brush-modified CM substrates were characterized by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), water contact angle measurements (WCA), X-ray photoelectron spectroscopy analysis (XPS), and atomic force microscopy (AFM). Experimental observations demonstrated the successful grafting of polysulfobetaine brushes, where brush thicknesses were found to increase gradually with polymerization time and monomer concentrations. Tests conducted by investigating platelet adhesion, hemolytic rates and protein adsorption indicated that polysulfobetaine brush-grafted CMs had excellent hemocompatibility featuring lower platelet adhesion and protein adsorption properties without causing hemolysis. E. coli adhesion and HeLa cell adhesion tests showed that grafted CMs had superior antibacterial adhesion properties and long-term cell adhesion resistance for up to four days. The functionalized cellulose substrate described holds great potential for use in biomedical applications.

研究领域: 材料科学 · 生物医学工程
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ACS Applied Materials & Interfaces · 2019 · IF 8.456

Fabrication of Porous Nanonetwork-Structured Carbons from Well-Defined Cylindrical Molecular Bottlebrushes

Xidong Lin,Guojun Xie,Shaohong Liu,Michael R. Martinez,Zelin Wang,He Lou,Ruowen Fu,Dingcai Wu,Krzysztof Matyjaszewski

Atom transfer radical polymerization was utilized to prepare well-defined cylindrical molecular bottlebrushes which were employed as building blocks and transformed into porous nanonetwork-structured carbons (PNSCs) via hypercross-linking chemistry and shape-regulated carbonization. The as-prepared PNSCs exhibited a unique nanomorphology-tunable characteristic by simply varying carbonization conditions. Because of their three-dimensional network nanomorphologies with well-developed hierarchical porous structures and conductive carbon framework, the PNSCs demonstrated excellent electrochemical performance in lithium–sulfur batteries.

研究领域: 高分子化学 · 纳米材料科学 · 电化学 · 能源材料 · 功能材料
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Polymer Chemistry · 2013 ·Vol. 4 ·期 16 ·4450-4460 · IF 5.231

Dendritic molecular brushes: synthesis via sequential RAFT polymerization and cage effect for fluorophores

Sipei Li,Chao Gao

Multifunctional dendritic molecular brushes (DMBs) with pendent poly(glycidyl methacrylate) (PGMA) chains were synthesized via a sequential reversible addition–fragmentation chain transfer (RAFT) polymerization approach. By controlling the kinetics of the polymerization, DMBs with a high number-averaged molecular weight (Mn) of ∼1.4 × 106 g mol−1 and narrow polydispersity index (PDI) of 1.50 were obtained. DMBs were reacted with sodium azide, giving rise to giant macromolecules with a high density of hydroxyl and azide bifunctional groups. Pyrene moieties (with a conventional chromophore) were efficiently attached to the DMBs by esterification, affording solution-emissive blue-light DMBs. Ultrahigh excimer emission at 475 nm was achieved for these fluorescent DMBs at a very low concentration of pyrene (∼10−7 mol L−1). Alternatively, tetraphenylethylene (TPE, with an aggregation-induced emission (AIE) chromophore) units were attached to DBMs with a conversion of 100% by copper-catalyzed alkyne–azide click chemistry. The solid-state-emissive blue-light TPE-functionalized DMBs exhibited typical AIE (rather than aggregation enhanced emission, AEE) effect which was rarely observed for dendritic scaffolds and its quantum yield at aggregated state is two times higher than that of fluorophore monomer. Such topology-induced unusual emission phenomena were attributed to the cage effect of DMBs.

研究领域: 高分子化学 · 材料科学 · 光化学
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