Acta Biomaterialia
·
2022
·
IF 10.633
Fangjun Liu,Dun Wang,Miao Zhang,Liwei Ma,Cui-Yun Yu,Hua Wei
Synthesis of polyfluorene (PF) based theranostic amphiphilic copolymers with simultaneously high drug loading efficiency and tumor microenvironment-specific responsiveness for promoted intracellular drug release and enhanced cancer therapy has been rarely reported likely due to the lack of efficient synthetic approaches to integrate these desirable properties. In this work, we recorded the successful preparation of well-defined theranostic amphiliphilic bottlebrush copolymers composing of fluorescent backbone of PF and tunable enzyme-degradable side chains of polytyrosine (PTyr) and POEGMA by integrating Suzuki coupling , NCA ROP and ATRP techniques. Notably, the resulting copolymer, PF 25 - g -(PTyr 26 - b -(POEGMA 28 ) 2 (P 4 ) with two branched POEGMA brushes tethered to one PTyr termini for each unit could form steady unimolecular micelles with higher fluorescence quantum yield of 18.3% in aqueous and greater entrapment efficiency (EE) of 91.0% for DOX ascribed to the efficient π–π stacking interactions between PTyr blocks and drug molecules and the unique structure of branched hydrophilic brushes with a moderate chain length. DOX@P 4 micelles revealed visualization of intracellular trafficking and accelerated drug release due to the enzyme-triggered degradation of PTyr blocks with proteinase K and subsequent deshielding of POEGMA corona for micelle destruction. In vitro and In vivo animal study further verified the intensive therapeutic efficiency with attenuated systematic toxicity. Taken together, we provided a universal strategy toward multifunctional polymeric delivery vehicles based on conjugated PF and biocompatible and degradable polypeptide by integratied Suzuki coupling and NCA ROP, and identified the branched structure of hydrophilic brushes for better performance of bottlebrush copolymers-based micelles for drug delivery applications. Statement of significance Synthesis of polyfluorene (PF)-based theranostic amphiphilic copolymers with simultaneously high drug loading efficiency and tumor microenvironment-specific responsiveness for promoted intracellular drug release and enhanced cancer therapy has been rarely reported likely due to the lack of efficient synthetic approaches to integrate these desirable properties. We reported herein successful preparation of enzyme-responsive theranostic amphiliphilic bottlebrush copolymers with simultaneously high drug loading efficiency and tumor microenvironment-specific responsiveness for enhanced chemotherapy in vivo . This study therefore not only developed a universal strategy for the construction of multifunction polymeric vehicles based on the conjugated polymer of PF and degradable polypeptide by integrated Suzuki coupling and NCA ROP, but also emphasized the better stability of micelles endowed by the branched hydrophilic brushes than linear ones.
研究领域:
高分子化学
·
生物医学工程
·
癌症治疗
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2017
·
IF 7.504
Haoquan Zhong,Chunchen Liu,Wenjiao Ge,Runcang Sun,Fei Huang,Xiaohui Wang
A fluorescent “turn-on” sensor for fast measurement of aliphatic biogenic amines (BAs) was developed based on fluorescent carboxylated polyfluorene (PFTBTCOOH)/chitosan-graft-oleic acid (CS-graft-OA) micelles. In this system, biobased CS-graft-OA micelles, prepared by graft modification of CS with OA, serve as the vector of the hydrophobic fluorescent probe. Bright turn-on fluorescence was achieved by the intermolecular fluorescence resonance energy transfer of the encapsulated PFTBTCOOH, driven by the formation of an electrostatic complex with aliphatic BAs, which facilitate visual identification. The peak intensity ratio of the PFTBTCOOH/CS-graft-OA micelles toward an increasing amount of aliphatic BAs was calibrated, giving a linear relationship. The fluorescence response of PFTBTCOOH/CS-graft-OA micelles to aliphatic BAs in milk and yogurt matrixes reaches a detection concentration as low as 10 μM, showing that the PFTBTCOOH/CS-graft-OA micelle solution is a potential chemosensor for fast and selective detection of trace aliphatic BAs, which is of great significance to public health and food safety.
研究领域:
分析化学
·
食品安全
·
材料科学
✓ 已验证
DOI
PubMed
高影响因子
Science China-Chemistry
·
2011
·Vol. 55
·期 3
·352-358
·
IF 0
Liu Wei,Sun MingLiang,Wang Wei,Song LingXia,Ge HongLun,Sun Miao,Zhang QingJie
Polyfluorene (PF) film has been successfully electropolymerized at lower potential (0.91 V vs. Ag/AgCl) in the mixed electrolyte of boron trifluoride diethyl etherate and trifluoroacetic acid. The PF film is characterized to have about 10 repeat units and no presence of ketonic defect site. UV-vis and photoluminescent spectral studies indicate that the PF film is blue light emitting. From cyclic voltammetry and galvanostatic charge-discharge tests in 1 M lithium perchlorate/acetonitrile electrolyte, the polyfluorene/activated carbon electrode shows a specific capacitance of 227.1 F g −1 (per active layer mass) and reversible redox reaction at the potential of 1.4 V in a three electrode configuration. An asymmetric electrochemical capacitor based on this composite electrode and activated carbon electrode exhibits a specific energy of 14.7 Wh kg −1 (per active layer mass). These results indicate that electrochemically prepared polyfluorene could be used as energy storage component for electrochemical application.
研究领域:
材料科学
·
电化学
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产品关联
DOI
CHIRALITY
·
2017
·
IF 1.956
Yin Zhao,Lu Yin,Jingjing Liu,Hailing Chen,Wei Zhang
Conjugated homopolymer poly(9,9-bis(3-(( S )-2-methylbutylpropanoate))fluorene) (PSF) with chiral pendants was synthesized and characterized. Dissolution experiments show that PSF is well dissolved in racemic limonene at high temperature and begins aggregating upon sequential cooling treatment. The corresponding assemblies were transferred to quartz plate by the spin-coating method. Comparably, film casting from chloroform solution was also prepared. Upon annealing thermal treatments, these PSF films exhibited perfect mirror circular dichroism (CD) Cotton effects and dissymmetry ratios. Optical absorption spectroscopy (UV-vis), CD, and fluorescence spectroscopy results reveal that chiral side chains successfully induced M - and P -helical structures in aggregates and films, and this significant difference was ascribed to their differential supramolecular conformations.
研究领域:
高分子化学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
REACTIVE & FUNCTIONAL POLYMERS
·
2017
·
IF 3.151
Jingjing Liu,Yin Zhao,Hailing Chen,Zhengbiao Zhang,Wei Zhang,Xiulin Zhu
A novel circular dichroism (CD)-silent π -conjugated polyfluorene bearing the bulky crown ether pendant ( PF8C4 ) as the potassium ion binding site was successfully prepared by polymerization of the corresponding monomers with palladium catalyst. The polymer containing polar groups was found to form the eximious helical assembly by aggregating in chiral limonene at a lower temperature. The aggregates obtained from R - and S -limonene exhibited mirror-image CD peaks in the UV–vis region of polymer backbone. Therefore, the chirality of enantiopure limonene was successfully transferred to the optically inactive PF8C4 , and the relative P - and M -helical supramolecules were successfully prepared. Moreover, after appending K + ion to the helical supramolecules, the complexation between the K + ion and the crown ether pendant helped to strengthen the optical activity , and thus more stable optically active supramolecular structures were achieved.
研究领域:
材料科学
·
有机化学
✓ 已验证
产品关联
DOI
高影响因子
OPTICAL MATERIALS
·
2015
·
IF 1.981
Wei-Qiang Song,Yue-Zhi Cui,Fu-Rong Tao,Jin-Ku Xu,Tian-Duo Li,Ai-Qing Wang
Four conjugated polymers (P 1 , P 2 , P 3 and P 4 ) based on poly(fluorenylene ethynylene)s (PFEs) have been synthesized by introducing 9,9-diphenylfluorene units and/or thiophene units into the backbone of PFEs. These exotic units remarkably change the behaviors of polymer, such as the solubility, the peak wavelengths of the optical spectra , and the spectral red-shift of solid polymers, etc. As sensing materials for detecting nitroaromatics, all the four polymers show observable fluorescence quenching when DNT exists. For example, in DNT/THF solution, the quenching efficiencies ( η EP ) of P 2 and P 4 are 95% and 90% at quenching equilibrium respectively, which are much higher than those of P 1 (77%) and P 3 (72%). The high η EP of P 2 and P 4 may be ascribed to the electron-rich character of thiophenylene units which can facilitate the electron-transfer between polymer and DNT. However, in another case of polymer films in DNT vapor, P 3 shows higher quenching efficiency even than P 2 at quenching equilibrium, which may be attributed to the fact that the steric hinderance of 9,9-diphenylfluorene units in P 3 can improve the permeability of the film sensor. P 4 , which contains both thiophenylene and 9,9-diphenylfluorene units, shows the highest quenching efficiency of 91% in DNT vapor at quenching equilibrium.
研究领域:
材料科学
·
化学
✓ 已验证
DOI
高影响因子
ACS Applied Polymer Materials
·
2022
·
IF 4.855
Liangliang Zhu,Zejian He,Yifan Zhang,Moontarij Jahan Orvy,Jintao Yang,Mi Zhou,Dong Zhang
Herein, a zwitterionic PF-based copolymer, polyfluorene-a-polybenzothiadiazole-g-polycaprolactone-b-poly[3-dimethyl(methacryloxyethyl)-propaneammoniumsulfonate] [PF-a-PBTH-g-(PCL-b-PDMAPS)], was synthesized by combining multiple polymerization techniques and further quaternization. The resultant copolymer with optimized structures (P5) was able to form stabilized unimolecular micelles in an aqueous solution with a diameter of approximately 110 nm. The unique donor–acceptor structure between fluorene and benzothiadiazole group along the conjugated main chains endows copolymers with yellow-green fluorescence, while the PDMAPS chains with a unique zwitterionic nature enabled not only to enhance water solubility, drug loading efficiency (DLE), and drug loading capacity (DLC) of the whole copolymers but also to present promising antifouling property by preventing nonspecific protein/bacteria adhesion. Further in vivo and in vitro experiments demonstrate that the resultant P5 micelles also present lower cytotoxicity and efficient cellular uptake with the incubation of HeLa and HUVEC cells, which tends to prolong the circulation time of drugs. Our work not only provides a rational combination of zwitterions and polyfluorenes to significantly enhance the water solubility of hydrophobic fluorophores but also exhibits the potential of promising bioimaging for dual stimuli-responsive micelles in vitro (simulated body fluids) and in vivo (open).
研究领域:
材料科学
·
生物医学工程
·
药剂学
✓ 已验证
DOI
高影响因子
RSC Advances
·
2014
·Vol. 4
·期 38
·19869-19877
·
IF 3.708
Jin-Jin Li,Jian-Jian Wang,Yin-Ning Zhou,Zheng-Hong Luo
The origin of the low-energy emission of fluorene-based rod-coil block copolymers still remains controversial. In this work, a series of polyfluorene-based rod-coil block copolymers having different coil segments, i.e., poly[2,7-(9,9-dihexylfluorene)]-block-poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate, (PF-b-PHFBMA), PF-b-poly(butylmethacrylate) (PF-b-PBMA), PF-b-poly(2-hydroxyethyl methacrylate) (PF-b-PHEMA) and PF-b-poly(acrylic acid) (PF-b-PAA), were synthesized using the ATRP technique. The optical and surface properties and thermal behaviors of these copolymers were systematically investigated. In particular, different thermal treatment conditions, including annealing temperature, annealing time and annealing atmosphere were introduced to study the effect of coil segment on the copolymer spectral stability. The incorporation of PBMA, PHEMA and PAA segments to PF could indeed improve the copolymer spectral stability, while the PHFBMA block brought undesirable low-energy emission. In addition, water contact angle (WCA) measurements of the copolymer films before and after annealing further demonstrated that the low-energy emission of PF-based rod-coil block copolymers was attributed to the molecular aggregation rather than the formation of fluorenone defects.
研究领域:
材料科学
·
光学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2018
·
IF 4.439
Kai Yang,Lei Zhong,Ruiteng Guan,Min Xiao,Dongmei Han,Shuanjin Wang,Yuezhong Meng
Lithium-sulfur (Li-S) batteries have remarkably high theoretical specific capacity as promising candidates for next-generation energy storage. However, the “polysulfides shuttle” effect hampers its commercial application. Here, we use a kind of rice paper as a raw material to get inorganic oxides doping carbon felt by the facile carbonization method, and then modified by a simple coating process using poly (fluorenyl ether ketone) and Super P slurry. The special structure of the carbon felt derived from rice paper and its modified layer endow the final electronic conductive interlayer with inherent polysulfides absorbents and ion Coulombic repulsion functions, respectively, which show synergistic effect for trapping polysulfides. As an interlayer of Li-S batteries, the obtained carbon felt/poly (fluorenyl ether ketone)& Super P (CFSS) interlayer shows excellent electrochemical performance in improving specific capacity and decreasing polarization. The batteries with CFSS interlayer exhibit a high capacity of 837 mA h g −1 at 2.0 C and a high initial capacity of 1073.4 mA h g −1 and good capacity retention of 824.5 mA h g −1 after 500 cycles at 0.5 C. CFSS interlayer also shows excellent anti-self-discharge performance. Therefore, the simple and economical CFSS interlayer can be considered as a promising component for high performance Li-S batteries.
研究领域:
材料科学
·
能源存储技术
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF POLYMER SCIENCE
·
2015
·Vol. 34
·期 2
·229-241
·
IF 1.835
Zhang Hui,Zhang Ge,Xu Jing-kun,Wen Yang-ping,Ding Wan-chuan,Zhang Jie,Ming Shou-li,Zhen Shi-jie
An amino acid side chain functionalized polyfluorene derivative poly[ N -(9-fluorenylmethoxycarbonyl)-glycine] (P9FG) was facilely electrosynthesized and characterized, and the structure, properties and optical sensing application of the obtained polymer were described and discussed. The electropolymerization occurred at C 2 and C 7 positions of fluorene units, and amino acid side chain groups were not cleaved from polyfluorene backbone in mixed electrolytes of boron trifluoride diethyl etherate and dichloromethane. Thermal analysis demonstrated good thermal stability of P9FG. Fluorescent spectra indicated that P9FG was a good blue light emitting material that could be employed as optical sensors. The soluble P9FG as a turn-off fluorescent sensor could realize the detection of Fe 3+ , Cu 2+ and Cr 2 O 7
2- , respectively. In addition, P9FG as a turn-off ultraviolet sensor could realize the detection of Cu 2+ while as turn-on ultraviolet sensors could also realize the determination of Fe 3+ and Cr 2 O 7
2- , respectively. All results indicate that P9FG is a promising candidate for optical sensing.
研究领域:
材料科学
·
分析化学
✓ 已验证
产品关联
DOI
高影响因子
Small Methods
·
2021
·Vol. 5
·期 10
·2100839
·
IF 14.188
Shiming Chen,Zhibo Song,Yuchen Ji,Kai Yang,Jianjun Fang,Lu Wang,Zijian Wang,Yan Zhao,Yunlong Zhao,Luyi Yang,Feng Pan
Exhibiting high specific energy and low cost, lithium–sulfur batteries are considered promising candidates for the next-generation battery. However, its wide applications are limited by the insulating nature of the sulfur, dissolution of polysulfide species, and large volume change of the sulfur cathode. In this work, a conductive binder, crosslinked polyfluorene (C-PF) is synthesized and employed in Li–S batteries to enhance the overall electrochemical performance from the following three aspects: 1) possessing high electronic conductivity, C-PF facilitates lowered areal resistance for the sulfur electrode and leads to an improved rate capability; 2) owing to the cross-linked polymer structure, favorable mechanical properties of the electrode can be achieved, hence the well-preserved electrode integrity; 3) forming strong binding with various polysulfide species, C-PF manages to trap them from diffusing to the Li anode, which greatly improves the cycling stability of Li–S cells. Through designing a multifunctional binder to comprehensively enhance the Li–S cathode, this proposed approach could be broadly applied to fully harness the energy from S redox in addition to cathode material modifications.
研究领域:
材料科学
·
能源存储技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
MACROMOLECULES
·
2012
·
IF 5.167
Aiguo Sui,Xincui Shi,Shupeng Wu,Hongkun Tian,Yanhou Geng,Fosong Wang
A new catalyst system, i.e., nickel acetylacetonate/1,3-bis(diphenylphosphino)propane (Ni(acac)2/dppp), was explored to catalyze the Kumada catalyst transfer polycondensation (KCTP) of three fluorene monomers with different substituents at 9-position. The “living” nature of the polymerization was confirmed by polymerization kinetic studies, “monomer addition” experiment and block copolymerizations. As a result, poly(9,9-dioctylfluorene)s (PF8s) with the number-average molecular weights (Mns) in the range 2.8–62.2 kDa and polydispersity indices (PDIs) of ∼1.20 were successfully synthesized in a controlled manner. The syntheses of fluorene-fluorene and fluorene-thiophene diblock copolymers with Mns up to 46 kDa were also demonstrated. A complex, i.e. Ni(dppp)(acac)2, with an octahedral coordination geometry was isolated and confirmed by X-ray crystallographic analysis. The polymerization experiments indicated that the in situ formed Ni(dppp)(acac)2 should be the active catalyst. To the best of our knowledge, this is the first report on the controlled synthesis of polyfluorenes (PFs) via KCTP.
研究领域:
材料科学
·
高分子化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）