Acta Biomaterialia
·
2014
·
IF 5.684
Junmin Qian,Minghui Xu,Aili Suo,Weijun Xu,Ting Liu,Xuefeng Liu,Yu Yao,Hongjie Wang
To minimize the side effects and enhance the efficiency of chemotherapy, a novel folate-decorated hydrophilic cationic star-block terpolymer , [poly( l -glutamic acid γ-hydrazide)- b -poly(N,N-dimethylaminopropyl methacrylamide)] 3 - g -poly(ethylene glycol) ((PGAH- b -PDMAPMA) 3 - g -PEG), with disulfide linkages between the PEG and PDMAPMA blocks, was developed for targeted co-delivery of doxorubicin and Bcl-2 small interfering RNA (siRNA) into breast cancer cells. The terpolymer was synthesized by a combination of ring-opening polymerization, reversible addition–fragmentation chain transfer polymerization, PEGylation and hydrazinolysis. The chemical structures of the polymers were confirmed by 1 H-NMR analysis. The terpolymer could conjugate doxorubicin via an acid-labile hydrazone linkage and simultaneously efficiently complex siRNA through electrostatic interaction at N/P ratios of ⩾4:1 to form “two-in-one” nanomicelleplexes, which displayed a spherical shape and had an average size of 101.3 nm. The doxorubicin loading efficiency and content were 61.0 and 13.23%, respectively. The cytotoxicity, drug release profile, targeting ability, cellular uptake and intracellular distribution of the nanomicelleplexes were evaluated in vitro. We found that the release behaviors of doxorubicin and siRNA had a pH/reduction dual dependency. They were released faster under reductive acidic conditions (pH 5.0, glutathione : 10 mM) than under physiological conditions (pH 7.4). The folate-decorated nanomicelleplexes could deliver doxorubicin and Bcl-2 siRNA more efficiently into the same MCF-7 cell and exhibited a higher cytotoxicity than non-targeted nanomicelleplexes. These results indicate that the terpolymer could act as an efficient vehicle for targeted intracellular co-delivery of doxorubicin and therapeutic siRNA in cancer therapy.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
RSC Advances
·
2013
·Vol. 4
·期 11
·5591-5597
·
IF 2.562
Zhao Hu,Xiao-dong Li,Wenjun Zhang,Aihui Liang,Dandan Ye,Zhitian Liu,Jing Liu,Yanjiao Liu,Junfeng Fang
Two novel star-shaped donor–acceptor small molecules, TPA–TBT–CN and TPA–TBT–R, with triphenylamine (TPA) as the core, benzothiadiazole (BT) as the arm, and alkyl cyanoacetate or 3-ethylrhodanine as the end-group are synthesized for application as donor materials in OSCs. The two small molecule films show broad absorption bands from 300 nm to 850 nm, narrow optical band gaps (1.5–1.7 eV), deep HOMO energy levels (−5.0 to −5.1 eV) and moderate hole mobilities. OSCs based on blends of the two donors and PC70BM acceptors exhibit power conversion efficiencies of 1.34% and 1.79%, respectively. Notably, TPA–TBT–R with 3-ethylrhodanine as the end-group displays a broader solar spectral coverage, a lower HOMO level, a higher hole mobility and higher photovoltaic properties. Our results indicate that 3-ethylrhodanine as the acceptor and end-group is a promising linker in constructing donor materials for high efficiency OSCs.
✓ 已验证
产品关联
DOI
高影响因子
MACROMOLECULAR BIOSCIENCE
·
2014
·Vol. 14
·期 10
·1415-1428
·
IF 3.65
Xiaoyu Ai,Jin Sun,Lu Zhong,Chunnuan Wu,Handong Niu,Tao Xu,He Lian,Xiaopeng Han,Guolian Ren,Wenya Ding,Jia Wang,Xiaohui Pu,Zhonggui He
A redox-responsive poly(ethylene glycol) (PEG)-sheddable copolymer of disulfide-linked PEG 5000-lysine-di-tocopherol succinate (P 5k SSLV) is developed which can self-assemble into nanomicelles in aqueous condition and trigger the rapid release of encapsulated drugs within tumor cells. The reduction-insensitive doxorubicin (DOX)-loaded P 5k LV (P 5k LV-DOX) nanomicelles are further prepared. Then head-to-head comparison of P 5k SSLV-DOX, P 5k LV-DOX and DOX-Sol is performed concerning in vitro release, cytotoxicity, cellular uptake and apoptosis. Results show that P 5k SSLV-DOX nanomicelles have a faster DOX release, a higher anti-tumor activity and more DOX concentrating in the nucleus than P 5k LV-DOX nanomicelles. In conclusion, the redox-responsive P 5k SSLV nanomicelles might hold a great potential to improve chemotherapy by tumor-triggering intracellular rapid release. The outcomes of this study also address the significance of such head-to-head comparison studies in translational research of nanomedicine.
研究领域:
药剂学
·
肿瘤学
✓ 已验证
DOI
PubMed
高影响因子
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
·
2009
·Vol. 47
·期 24
·6962-6976
·
IF 3.821
Peng-Fei Gou,Wei-Pu Zhu,Ning Xu,Zhi-Quan Shen
Well-defined drug-conjugated amphiphilic A 2 B 2 miktoarm star copolymers [(PCL) 2 -(PEG) 2 -D] were prepared by the combination of controlled ring-opening polymerization (CROP) and “click” reaction strategy. First, bromide functionalized poly(ε-caprolactone) (PCL-Br) with double hydroxyl end groups was synthesized by the CROP of ε-caprolactone using 2,2-bis(bromomethyl)propane-1,3-diol as a difunctional initiator in the presence of Sn(Oct) 2 at 110 °C. Next, the bromide groups of PCL-Br were quantitatively converted to azide form by NaN 3 to give PCL-N 3 . Subsequently, the end hydroxyl groups of PCL-N 3 were capped with ibuprofen as a model drug at room temperature. Finally, copper(I)-catalyzed cycloaddition reaction between ibuprofen-conjugated PCL-N 3 and slightly excess alkyne-terminated poly(ethylene glycol) (A-PEG) led to ibuprofen-conjugated A 2 B 2 miktoarm star copolymer [(PCL) 2 -(PEG) 2 -D]. The excess A-PEG was removed by dialysis. 1 H NMR, FTIR and SEC analyzes confirmed the expected miktoarm star architecture. These amphiphilic miktoarm star copolymers could self-assemble into multimorphological aggregates in aqueous solution, which were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). In addition, the drug-loading capacity of these drug-conjugated miktoarm star copolymers as well as their nondrug-conjugated analogs were also investigated in detail. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009
✓ 已验证
DOI
高影响因子
DALTON TRANSACTIONS
·
2022
·Vol. 51
·期 29
·10930-10942
·
IF 4.569
Yixuan Wu,Dandan Zhao,Jinting Shang,Wenxin Huang,Zhanfen Chen
Polynuclear platinum(II) complexes represent a class of great prospective Pt-based antitumor drugs that may expand the antitumor spectrum and overcome the clinical problems of drug resistance and side effects of platinum-based drugs. Herein, a novel star-shaped trinuclear platinum(II) complex [Pt3(L–3H)Cl3] (1, L = 2,4,6-tris[(2-hydroxybenzyl)(2-pyridylmethyl)amine]-1,3,5-triazine) and its monomer [Pt(L′–H)Cl] (2, L′ = (2-hydroxybenzyl)(2-pyridylmethyl)amine) were synthesized and characterized. The in vitro antiproliferative activities of complexes 1 and 2 against a panel of human cancer cell lines including MDA-MB-231 (triple-negative breast cancer, TNBC), MCF-7 (breast), HepG-2 (liver), and A549 (lung) were investigated. The results revealed that 1 exhibited much higher antiproliferative properties than its monomer 2 against the tested cell lines. Importantly, 1 possessed 3.3-fold higher antiproliferative activity as compared with cisplatin against the TNBC cell line MDA-MB-231. Another TNBC cell line MDA-MB-468 is also sensitive to 1. The results indicated that 1 might have the potential to act as a candidate for the treatment of TNBC. Cellular uptake and distribution studies showed that 1 could pass through the membrane of cells and enter into cells and mainly accumulate in the nuclei and mitochondria. 1 could bind to DNA in a cooperative groove-electrostatic-platinating binding mode and induce stronger DNA double-strand breaks (DSBs) and damaging effects on MDA-MB-231 than cisplatin (upregulation of γ-H2AX). Moreover, the DNA damage could not be easily repaired (upregulation of p53), which would exert a much positive influence on the overcoming of drug resistance. Additionally, flow cytometry studies showed that 1 arrested the cell cycle in the G0/G1 phase, induced mitochondrial membrane depolarization, increased ROS generation, and induced cell apoptosis. The results demonstrated that 1 could target simultaneously mitochondria and nuclei that gave rise to mitochondrial injury and DNA damage and ultimately efficiently promote the apoptotic death of tumor cells. Further mechanistic studies showed that 1 induced MDA-MB-231 cell apoptosis via the p53-mediated mitochondrial pathway by upregulating Bax and cytochrome c and downregulating Bcl-2 proteins, leading to the activation of caspase-3 and upregulation of the cleaved-PARP level. Taken together, 1 with such a synergic mechanism has great potential to be an effective anticancer agent that can overcome treatment resistance in TNBC.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Polymers
·
2022
·Vol. 14
·期 9
·1695
·
IF 4.967
Yan Xue,Dan Huang,Xinyong Wang,Chunquan Zhang
A series of stimuli-responsive star-like block copolymers are synthesized via the combination of reversible addition, fragmentation chain transfer (RAFT) polymerization, and photo-initiated thiol-ene (PITE) click reaction. The controllable block ratio and block sequence, narrow distribution of molecular weight, and customized arm numbers of the star-shaped copolymers reveal the feasibility and benefits of combination of RAFT polymerization and PITE click reaction for synthesis of well-defined star-like (co)polymers. A clear insight into the relationship among the arm number, block sequence, and block ratio of the star-like block copolymers and their stimuli-responsive aggregation behavior was achieved via dynamic light scattering and UV-vis spectroscopy study. Notably, the star-like poly(acrylic acid)-b-poly(2-(dimethylamino) ethyl methacrylate) (star-PAA-b-PDMAEMA) shows higher lower critical solution temperature (LCST) compared to star-PDMAEMA-b-PAA with the same arm number and block ratio due to the inner charged PAA segments at pH > IEP. In addition, for star-like PAA-b-PDMAEMA, higher PAA content enhances the hydrophilicity of the polymer in basic solution and leads to the LCST increase, except for star-PAA1-b-PDMAEMA4at pH = 9.0 (≈IEP). For star-PDMAEMA-b-PAA, the PAA content shows minimal effect on their LCSTs, except for the polymer in solution with pH = 9.5, which is far from their IEP. The star-like block copolymers with well-defined structure and tunable composition, especially the facile-controlled block sequence, bring us a challenging opportunity to control the stimuli-responsive properties of star-like block copolymers.Keywords:reversible addition and fragmentation chain transfer (RAFT);star-like block copolymers;thiol-ene click reaction;dual-stimuli response
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Omega
·
2023
·
IF 4.1
Chunhua Zhao,Jian Zhang,Jianrong Lv,Bo Huang,Guang Yang,Engao Tang,Minggui Chen,Chenyu Xu,Yizhuo Ge
Injecting water with chemicals to generate emulsions in the reservoir is a promising method for enhancing heavy oil recovery because oil-in-water (O/W) emulsions significantly reduce oil viscosity. To enhance heavy oil recovery efficiency, we developed new star-like branched AM-SSS copolymers (SB-PAMs) with reduction in the viscosity of the heavy oil emulsion, which was synthesized by reversible addition–fragmentation chain transfer (RAFT) controlled radical polymerization. The core structure of the branched polymer was RAFT polymerization of acrylamide (AM) and N,N′-methylene bis-acrylamide (BisAM), in the presence of 3-(((benzylthio)carbonothioyl)thio)propanoic acid as a chain transfer agent, followed by chain extension with AM and SSS. The core structures were achieved by incorporation of total monomer ratios [BisAM]/[AM] of 1:11. The expansion of the core structures by copolymerization of AM and SSS resulted in star-like branched polymer SB-PAM-co-SSS with apparent molecular weights ranging from 240 to 2381 kDa. 1H-nuclear magnetic resonance (1H NMR) and Fourier transform infrared (FTIR) confirmed the synthesized polymer structure. The molecular weight was determined by gel permeation chromatography (GPC). The polydispersity coefficient was between 1 and 7, which has a broad molecular weight distribution. The polymer dissolves only 0.75 h in deionized water, faster than conventional polyacrylamide. At 50 °C, the viscosity of the 1000 mg/L SB-polymer solution can reach up to 45 mPa·s. First, heavy oil viscosity reduction by 800 mg/L SB polymer can reach 91.7%, at a water dehydration rate of 90.4%; second, with 0.6 PV injection, 800 mg/L SB polymer improved oil recovery up to 23.66% after water flooding; and third, SB-polymer-assisted hot water flooding shows that heavy oil recovery improved by 19.46% at 110 °C with 0.6 pore volume (PV) SB-polymer injection. This novel branched chain polymer with heavy oil emulsion capability will shed light on high-temperature polymer flooding and the development of a new candidate structure for heavy oil viscosity reduction.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2016
·Vol. 40
·期 5
·4761-4768
·
IF 3.277
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.
✓ 已验证
产品关联
DOI
高影响因子
BIOMACROMOLECULES
·
2010
·
IF 4.502
Peng-Fei Gou,Wei-Pu Zhu,Zhi-Quan Shen
Novel drug-conjugated amphiphilic A14B7 miktoarm star copolymers composed of 14 poly(ε-caprolactone) (PCL) arms and 7 poly(ethylene glycol) (PEG) arms with β-cyclodextrin (β-CD) as core moiety were synthesized by the combination of controlled ring-opening polymerization (CROP) and “click” chemistry. 1H NMR, FT-IR, and SEC-MALLS analyses confirmed the well-defined A14B7 miktoarm star architecture. These amphiphilic miktoarm star copolymers could self-assemble into multimorphological aggregates in aqueous solution, which were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). Moreover, the drug-loading efficiency and drug-encapsulation efficiency of the drug-conjugated miktoarm star copolymers were higher than those of the corresponding non-drug-conjugated miktoarm star copolymers.
✓ 已验证
DOI
PubMed
高影响因子
Polymer Chemistry
·
2010
·Vol. 1
·期 8
·1205-1214
·
IF 0
Peng-Fei Gou,Wei-Pu Zhu,Zhi-Quan Shen
Novel well-defined drug-grafted seven-arm amphiphilic star poly(ε-caprolactone-co-carbonate)-b-poly(ethylene glycol)s based on a β-CD core [CDS-P(CL-co-DTC)-D-b-PEG] have been synthesized by the combination of controlled ring-opening polymerization (CROP), esterification coupling reactions and “click” reactions. First, 5,5-dibromomethyl-trimethylene carbonate (DBTC) bearing two bromide pendent groups was synthesized and used to copolymerize with CL to prepare seven-arm star random copolymers [CDS-P(CL-co-DBTC)] in the presence of per-2,3-acetyl-β-cyclodextrin and Sn(Oct)2. Second, esterification coupling reaction between CDS-P(CL-co-DBTC) and carboxyl-terminated mPEG led to amphiphilic seven-arm star copolymers [CDS-P(CL-co-DBTC)-b-PEG]. Subsequently, the bromide pendent groups on CDS-P(CL-co-DBTC)-b-PEG had been converted into azide groups by treating with NaN3. Finally, alkyne functionalized ibuprofen had been grafted onto the hydrophobic block of the star copolymers by copper(I)-catalyzed “click” reaction. 1H NMR, FT-IR and SEC analyses confirmed the well-defined drug grafted star architecture. These copolymers could self-assemble into multi-morphological aggregates in water, which were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM).
✓ 已验证
产品关联
DOI
RSC Advances
·
2016
·Vol. 6
·期 66
·61630-61640
·
IF 3.289
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.
✓ 已验证
产品关联
DOI
高影响因子
POLYMER DEGRADATION AND STABILITY
·
2026
·
IF 8.1
Haopeng Li,Xinbo Dong,Jiahui Huang,Zheng Zhao,Xigao Jian,Cheng Liu
Conventional toughening of bismaleimide (BMI) resin with linear thermoplastic faces a critical compromise: enhanced toughness often compromises thermal properties and elevates melt viscosity, severely limitations for their application in extreme environments. To overcome this long-standing challenge, a novel strategy was pioneered by designing and synthesizing a unique class of hyperbranched poly(carbazole-type bisphthalazinone sulfone)s (h-PCBPSs) with tailored reactive groups (propenyl or allyl), with the trifunctional monomer 4,4′-(9H-carbazole-2,7-diyl)bis(phthalazin-1(2H)-one) (CZ-BDHPZ) employed as the building block via a two-step procedure for the modification of BMI resin. h-PCBPSs exhibited high thermal resistance, with glass transition temperatures ( T g ) ranging from 308 to 355°C. The rheological behavior of the h-PCBPSs/BMI blends was characterized. The temperature range corresponding to the processing window, defined by a viscosity below 0.2 Pa·s, was broadened up to 140.1-185.5°C. The formation mechanisms of sea-island, single-phase, and star-shaped morphologies were elucidated, and the effects of these three distinct morphological structures on the thermal and mechanical properties of the BMI were systematically analyzed. The T g , unnotched impact strength, and flexural strength reached 293°C, 33.5 kJ/m², and 190 MPa, respectively. Compared with the cured product of the neat BMI, these values increased by 5.4%, 196.5%, and 36.7%, respectively. The thermo-oxidative aging resistance mechanism of BMI modified by h-PCBPS-A was elucidated. After 7 days of aging at 250°C, the impact strength retention rate and flexural strength retention rate of h-PCBPS-A-10phr/BMI reached 36.3% and 88.9%, respectively. This work provides a new design strategy for BMI toughening agents and promotes the application of BMI resin in extreme environments.
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）