Acidic poly(ionic liquid)s(PILs)with swelling ability were synthesized by free radical copolymerization of N-vinylimidazolium ionic liquids,divinylbenzene(DVB)and sodium acrylate(NaAA),and further acidification by sul...Acidic poly(ionic liquid)s(PILs)with swelling ability were synthesized by free radical copolymerization of N-vinylimidazolium ionic liquids,divinylbenzene(DVB)and sodium acrylate(NaAA),and further acidification by sulfuric acid.The swelling ability of acidic PILs was greatly affected by cross-linker content and chain length of 3-alkyl-substituents on imidazolium.Cross-linked network structures could be observed from the cryogenic scanning electron microscopy(cryo-SEM)images of the swollen acidic PILs in formic acid.Acidic PILs with network structures in swollen state exhibited excellent activities in the esterification of cyclohexene and formic acid,and the catalytic activities were in positive correlation with their swelling abilities.Acidic PIL with 3-octyl-substituent and 2.5 mol%DVB(PIL-C8-2.5DVB-HSO4)had the highest swelling ability in formic acid and exhibited comparable catalytic activities with homogeneous catalysts such as sulfuric acid and p-toluenesulfonic acid.展开更多
Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(te...Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.展开更多
A novel AB3-type monomer was prepared from gallic acid and DL-2-aminobutyric acid, and used for the synthesis of the biocompatible hyperbranched poly(ester-amide)s by self-polycondensation. The polymers were character...A novel AB3-type monomer was prepared from gallic acid and DL-2-aminobutyric acid, and used for the synthesis of the biocompatible hyperbranched poly(ester-amide)s by self-polycondensation. The polymers were characterized via FTIR and NMR spectroscopy and thermal analysis, and the average degree of branching of the polymers was estimated to be 0.75. The polymers with abundant acetyl end groups were found to be amorphous with lower intrinsic viscosity, better thermal stability and excellent solubility.展开更多
The synthesis and characterization of a series of novel poly(aryl amide imide)s based on o diphenyltrimellitic anhydride are described.The poly(aryl amide imide)s having inherent viscosities of 0.39-1.43dL/g in N m...The synthesis and characterization of a series of novel poly(aryl amide imide)s based on o diphenyltrimellitic anhydride are described.The poly(aryl amide imide)s having inherent viscosities of 0.39-1.43dL/g in N methyl 2 pyrrolidinone at 30℃,were prepared by polymerization with aromatic diamines in N,N-dimethylacetamide and subsequent chemical imidization.All the polymers were amorphous,readily soluble in aprotic polar solvents such as DMAC,NMP,DMF,DMSO,and m cresol,and could be cast to form flexible and tough films.The glass trsanition temperatures were in the range of 284-336℃,and the temperatures for 5% weight loss in nitrogen were above 468℃.展开更多
As a potent anticancer drug,gambogic acid(GA)suffers from its poor water solubility and low chemical stability and shows a limited clinical outcome.To address this problem,we report here a simple and effective strateg...As a potent anticancer drug,gambogic acid(GA)suffers from its poor water solubility and low chemical stability and shows a limited clinical outcome.To address this problem,we report here a simple and effective strategy to immobilize and deliver GA using a reducible diblock poly(amino acid)as a model.The electrostatic interaction between GA and polymer enables a high drug loading content up to 53.6%.Moreover,the drug complexation induces a micelle-to-vesicle transformation,combined with a conformation tra nsition from random coil to a-helix.The hierarchically assembled drug nanocomplexes can serve as a smart carrier for efficient cell internalization and triggered release of multiple drugs under intracellular acidic and reductive conditions,resulting in a synergistic antitumor efficacy in vitro.This work provides a new insight into the drug-carrier interaction and a facile nanoplatform for drug delivery applications.展开更多
As one of the top global health problems,the effective treatment of cancer is one of the most urgent clinical challenges.Currently,the main treatments for cancer include surgery,chemotherapy,radiotherapy,and gene ther...As one of the top global health problems,the effective treatment of cancer is one of the most urgent clinical challenges.Currently,the main treatments for cancer include surgery,chemotherapy,radiotherapy,and gene therapy etc.Chemotherapy is one of the most commonly used treatments,however it has limitations such as highly toxic side effects and low drug utilization rate that limit its application.Gene therapy,as an emerging cancer treatment,has limitations such as drug instability,off-target effects and low internalization efficiency.Poly(amino acid)s carriers with good biocompatibility,degradability and multifunctionality as drug carriers have received much attention,as they can reduce the toxic side effects of chemotherapy,improve drug utilization,and enhance the internalization efficiency and utilization of gene drugs.However,little attention has been paid to the nature of the carriers themselves.This paper reviews the immunomodulatory,anti-inflammatory,antioxidant,internalization-promoting and apoptosispromoting functions of poly(amino acid)s drug carriers in tumor therapy to provide a theoretical basis for different carrier-drug-adapted synergistic therapies.展开更多
基金This work was supported by the National Natural Science Foundation of China(21773068,21811530273,21573072)the National Key Research and Development Program of China(2017YFA0403102)Shanghai Leading Academic Discipline Project(B409).
文摘Acidic poly(ionic liquid)s(PILs)with swelling ability were synthesized by free radical copolymerization of N-vinylimidazolium ionic liquids,divinylbenzene(DVB)and sodium acrylate(NaAA),and further acidification by sulfuric acid.The swelling ability of acidic PILs was greatly affected by cross-linker content and chain length of 3-alkyl-substituents on imidazolium.Cross-linked network structures could be observed from the cryogenic scanning electron microscopy(cryo-SEM)images of the swollen acidic PILs in formic acid.Acidic PILs with network structures in swollen state exhibited excellent activities in the esterification of cyclohexene and formic acid,and the catalytic activities were in positive correlation with their swelling abilities.Acidic PIL with 3-octyl-substituent and 2.5 mol%DVB(PIL-C8-2.5DVB-HSO4)had the highest swelling ability in formic acid and exhibited comparable catalytic activities with homogeneous catalysts such as sulfuric acid and p-toluenesulfonic acid.
基金supported by The National Key Research and Development Program of China(2021YFB4001204)National Natural Science Foundation of China(22379143)。
文摘Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.
文摘A novel AB3-type monomer was prepared from gallic acid and DL-2-aminobutyric acid, and used for the synthesis of the biocompatible hyperbranched poly(ester-amide)s by self-polycondensation. The polymers were characterized via FTIR and NMR spectroscopy and thermal analysis, and the average degree of branching of the polymers was estimated to be 0.75. The polymers with abundant acetyl end groups were found to be amorphous with lower intrinsic viscosity, better thermal stability and excellent solubility.
文摘The synthesis and characterization of a series of novel poly(aryl amide imide)s based on o diphenyltrimellitic anhydride are described.The poly(aryl amide imide)s having inherent viscosities of 0.39-1.43dL/g in N methyl 2 pyrrolidinone at 30℃,were prepared by polymerization with aromatic diamines in N,N-dimethylacetamide and subsequent chemical imidization.All the polymers were amorphous,readily soluble in aprotic polar solvents such as DMAC,NMP,DMF,DMSO,and m cresol,and could be cast to form flexible and tough films.The glass trsanition temperatures were in the range of 284-336℃,and the temperatures for 5% weight loss in nitrogen were above 468℃.
基金supported by the National Natural Science Foundation of China(Nos.51873118,21474064,52022062)the KeyResearch and Development Program of Science and Technology Department of Sichuan Province(No.2019YFS0514)+2 种基金Science and Technology Project of Chengdu(No.2019-YF05-00784-SN)the Project of State Key Laboratory of Polymer Materials Engineering(No.sklpme2020-2-03)the Fundamental Research Funds for Central Universities。
文摘As a potent anticancer drug,gambogic acid(GA)suffers from its poor water solubility and low chemical stability and shows a limited clinical outcome.To address this problem,we report here a simple and effective strategy to immobilize and deliver GA using a reducible diblock poly(amino acid)as a model.The electrostatic interaction between GA and polymer enables a high drug loading content up to 53.6%.Moreover,the drug complexation induces a micelle-to-vesicle transformation,combined with a conformation tra nsition from random coil to a-helix.The hierarchically assembled drug nanocomplexes can serve as a smart carrier for efficient cell internalization and triggered release of multiple drugs under intracellular acidic and reductive conditions,resulting in a synergistic antitumor efficacy in vitro.This work provides a new insight into the drug-carrier interaction and a facile nanoplatform for drug delivery applications.
基金supported by the National Natural Science Foundation of China(Nos.51973243 and 52173150)the Shenzhen Basic Research Project(No.JCYJ20190807155801657)the International Cooperation and Exchange of the National Natural Science Foundation of China(No.51820105004)。
文摘As one of the top global health problems,the effective treatment of cancer is one of the most urgent clinical challenges.Currently,the main treatments for cancer include surgery,chemotherapy,radiotherapy,and gene therapy etc.Chemotherapy is one of the most commonly used treatments,however it has limitations such as highly toxic side effects and low drug utilization rate that limit its application.Gene therapy,as an emerging cancer treatment,has limitations such as drug instability,off-target effects and low internalization efficiency.Poly(amino acid)s carriers with good biocompatibility,degradability and multifunctionality as drug carriers have received much attention,as they can reduce the toxic side effects of chemotherapy,improve drug utilization,and enhance the internalization efficiency and utilization of gene drugs.However,little attention has been paid to the nature of the carriers themselves.This paper reviews the immunomodulatory,anti-inflammatory,antioxidant,internalization-promoting and apoptosispromoting functions of poly(amino acid)s drug carriers in tumor therapy to provide a theoretical basis for different carrier-drug-adapted synergistic therapies.
