Amphiphilic diblock copolymers containing glycopolymer segments, polystyrene block poly[2 ( β D glucopyranosyloxy)ethylacrylate](PS b PGEA), were synthesized by atom transfer radical polymerization. The morphologies ...Amphiphilic diblock copolymers containing glycopolymer segments, polystyrene block poly[2 ( β D glucopyranosyloxy)ethylacrylate](PS b PGEA), were synthesized by atom transfer radical polymerization. The morphologies of the crew cut aggregates of PS b PGEA in water were studied by TEM. It has been found that for one specific diblock copolymer, the morphological transformation from spheres to vesicles was controllable by changing solvents. Spheres, rods and vesicles were found to be the dominant morphologies for PS 55 b PGEA 9 when the solvents were DMF, DMF/1,4 doxane and 1,4 dioxane respectively. When same solvent, e.g . 1,4 dioxane, was used, sphere to vesicle transition of crew cut aggregates was also obtainable by using diblock copolymers of different compositions. The copolymers with a higher hydrophilic segment content tend to form spheres, while those with a lower content yield predominated vesicles.展开更多
Despite the great potential of anti-PD-L1 antibodies for immunotherapy,their low response rate due to an immunosuppressive tumor microenvironment has hampered their application.To address this issue,we constructed a c...Despite the great potential of anti-PD-L1 antibodies for immunotherapy,their low response rate due to an immunosuppressive tumor microenvironment has hampered their application.To address this issue,we constructed a cell membrane-coated nanosystem(mB4S)to reverse an immunosuppressive microenvironment to an immuno-supportive one for strengthening the anti-tumor effect.In this system,Epirubicin(EPI)as an immunogenic cell death(ICD)inducer was coupled to a branched glycopolymer via hydrazone bonds and diABZI as a stimulator of interferon genes(STING)agonist was encapsulated into mB4S.After internalization of mB4S,EPI was acidic-responsively released to induce ICD,which was characterized by an increased level of calreticulin(CRT)exposure and enhanced ATP secretion.Meanwhile,diABZI effectively activated the STING pathway.Treatment with mB4S in combination with an anti-PD-L1 antibody elicited potent immune responses by increasing the ratio of matured dendritic cells(DCs)and CD8+T cells,promoting cytokines secretion,up-regulating M1-like tumor-associated macrophages(TAMs)and down-regulating immunosuppressive myeloid-derived suppressor cells(MDSCs).Therefore,this nanosystem for co-delivery of an ICD inducer and a STING agonist achieved promotion of DCs maturation and CD8+T cells infiltration,creating an immuno-supportive microenvironment,thus potentiating the therapy effect of the anti-PD-L1 antibody in both 4T1 breast and CT26 colon tumor mice.展开更多
Currently, conjugated polymer nanoparticles are widely used with many biological applications, especially bio-imaging and labeling. Thus their modification with different biomacromolecules becomes a crucial step befor...Currently, conjugated polymer nanoparticles are widely used with many biological applications, especially bio-imaging and labeling. Thus their modification with different biomacromolecules becomes a crucial step before various applications. In literature,this modification was normally performed via covalent bonds. To our best knowledge, modification based on inclusion complexation has not been reported. Herein, via host-guest interaction between cyclodextrin and adamantane, supramolecular modification to conjugated polyfluorene nanoparticles has been successfully achieved. The glycopolymer-modified conjugated polymer nanoparticles showed excellent binding ability to lectins, such as Galectin-3 and selective imaging behavior to Hep G2 cells.展开更多
The morphological transition of molecular assemblies in aqueous solutions for a new amphiphilic diblock copolymer induced by changing the initial solvent conditions was studied by transmission electron microscopy (TEM...The morphological transition of molecular assemblies in aqueous solutions for a new amphiphilic diblock copolymer induced by changing the initial solvent conditions was studied by transmission electron microscopy (TEM). The copolymer was polystyrene(77)-b-poly[2-(beta -D-glucopyranosyloxy)ethyl acrylate (6)] (PSt(77)-b-PGEA(6)) and the solvent was a mixture of DMF and THF. PSt(77)-b-PGEA(6) yields vesicles and tubules when it is initially dissolved in THF and DMF respectively. The morphological transition between vesicles and tubules can be achieved by simply varying the amounts of THF and DMF, or changing the temperature at which the aggregates were prepared.展开更多
A glycopolymer bearing glucose residues was tethered onto the surface of polypropylene microporous membrane by UV-induced graft polymerization ofα-allyl glucoside.Concanavalin A (Con A),a glucose recognizing lectin,c...A glycopolymer bearing glucose residues was tethered onto the surface of polypropylene microporous membrane by UV-induced graft polymerization ofα-allyl glucoside.Concanavalin A (Con A),a glucose recognizing lectin,could be specifically adsorbed to the membrane surface.On the other hand,the membrane surface showed no recognition ability to another lectin peanut agglutinin.Moreover,the recognition complex between the glycosylated membrane surface and Con A could be inhibited by glucose and mannose solution.T...展开更多
Herein, we designed a novel amphiphilic triblock glycopolymer poly（oligo（ethyleneglycol） methacry- late）-block-poly（maltopyranoside methacrylate）-block-polystyrene （POMA-b-PMal-b-PS） via the com- bination of r...Herein, we designed a novel amphiphilic triblock glycopolymer poly（oligo（ethyleneglycol） methacry- late）-block-poly（maltopyranoside methacrylate）-block-polystyrene （POMA-b-PMal-b-PS） via the com- bination of reversible addition-fragmentation chain transfer （RAFT） polymerization and post- polymerization modification. The micelles with core-shell-corona structures were prepared by direct self-assembly of this glycopolymer in water. We found that these micelles can be used in in situ formation and stabilization of AuNPs. By controlling the thickness of glyco-shell, we successfully obtained lanus particles and raspberry-like particles with AuNPs in the sugar shell.展开更多
The monomer 6-O-vinyladipoyl-D-glucopyranose( VAG)was synthesized by lipase catalyzed trans-esterification of divinyladipate with D-glucopyranose. A novel double hydrophilic glycopolymer poly( diethyleneglycol methacr...The monomer 6-O-vinyladipoyl-D-glucopyranose( VAG)was synthesized by lipase catalyzed trans-esterification of divinyladipate with D-glucopyranose. A novel double hydrophilic glycopolymer poly( diethyleneglycol methacrylate-co-6-Ovinyladipoyl-D-glucopyranose)( P( DEGMA-co-VAG)) with narrow polydispersity( PDI) and thermosensitivity was prepared by reversible addition-fragmentation chain transfer( RAFT)polymerization. P( DEGMA-co-VAG) was characterized by1 H NMR,FTIR and gel permeation chromatography( GPC). The characterization of UV-visible spectroscopy showed that the micelles from glycopolymer P( DEGMA-co-VAG) were thermo-responsive and the low critical solution temperature( LCST) could be controlled by the molar ratio of monomers. When the molar ratio of DEGMA and VAG was 2∶ 1,the LCST of P( DEGMA-co-VAG) was36 ℃ in aqueous solution,which could form nano micelles in the human body environment. It was found that P( DEGMA-co-VAG)was non-toxic at 0. 1-1 mg / m L concentrations when incubated with pig iliac endothelial cells( PIECs) for 24 h. Thus,the synthesized glycopolymers has great potential as drug delivery carriers.展开更多
文摘Amphiphilic diblock copolymers containing glycopolymer segments, polystyrene block poly[2 ( β D glucopyranosyloxy)ethylacrylate](PS b PGEA), were synthesized by atom transfer radical polymerization. The morphologies of the crew cut aggregates of PS b PGEA in water were studied by TEM. It has been found that for one specific diblock copolymer, the morphological transformation from spheres to vesicles was controllable by changing solvents. Spheres, rods and vesicles were found to be the dominant morphologies for PS 55 b PGEA 9 when the solvents were DMF, DMF/1,4 doxane and 1,4 dioxane respectively. When same solvent, e.g . 1,4 dioxane, was used, sphere to vesicle transition of crew cut aggregates was also obtainable by using diblock copolymers of different compositions. The copolymers with a higher hydrophilic segment content tend to form spheres, while those with a lower content yield predominated vesicles.
基金This work was supported by National Natural Science Foundation of China(32271445,52073193,and 82202322)National Science and Technology Major Project of China(2023YFB3810004)+2 种基金1·3·5 Project for Disciplines of Excellence,West China Hospital,Sichuan University(ZYJC21013,China)the Sichuan Science and Technology Program(2023NSFSC1592,China),the China Postdoctoral Science Foundation(2021M692255,China)the Post-Doctor Research Project,West China Hospital,Sichuan University(2020HXBH094,China).
文摘Despite the great potential of anti-PD-L1 antibodies for immunotherapy,their low response rate due to an immunosuppressive tumor microenvironment has hampered their application.To address this issue,we constructed a cell membrane-coated nanosystem(mB4S)to reverse an immunosuppressive microenvironment to an immuno-supportive one for strengthening the anti-tumor effect.In this system,Epirubicin(EPI)as an immunogenic cell death(ICD)inducer was coupled to a branched glycopolymer via hydrazone bonds and diABZI as a stimulator of interferon genes(STING)agonist was encapsulated into mB4S.After internalization of mB4S,EPI was acidic-responsively released to induce ICD,which was characterized by an increased level of calreticulin(CRT)exposure and enhanced ATP secretion.Meanwhile,diABZI effectively activated the STING pathway.Treatment with mB4S in combination with an anti-PD-L1 antibody elicited potent immune responses by increasing the ratio of matured dendritic cells(DCs)and CD8+T cells,promoting cytokines secretion,up-regulating M1-like tumor-associated macrophages(TAMs)and down-regulating immunosuppressive myeloid-derived suppressor cells(MDSCs).Therefore,this nanosystem for co-delivery of an ICD inducer and a STING agonist achieved promotion of DCs maturation and CD8+T cells infiltration,creating an immuno-supportive microenvironment,thus potentiating the therapy effect of the anti-PD-L1 antibody in both 4T1 breast and CT26 colon tumor mice.
基金supported by the National Natural Science Foundation of China(21474020,91227203,51322306 and91527305)the State Key Laboratory of Molecular Engineering of Polymers Program(K2016-17)the Innovation Program of the Shanghai Municipal Education Commission
文摘Currently, conjugated polymer nanoparticles are widely used with many biological applications, especially bio-imaging and labeling. Thus their modification with different biomacromolecules becomes a crucial step before various applications. In literature,this modification was normally performed via covalent bonds. To our best knowledge, modification based on inclusion complexation has not been reported. Herein, via host-guest interaction between cyclodextrin and adamantane, supramolecular modification to conjugated polyfluorene nanoparticles has been successfully achieved. The glycopolymer-modified conjugated polymer nanoparticles showed excellent binding ability to lectins, such as Galectin-3 and selective imaging behavior to Hep G2 cells.
基金This work was partially supported by the National Natural Science Foundation of China (No. 29995648-4 and 59603004).
文摘The morphological transition of molecular assemblies in aqueous solutions for a new amphiphilic diblock copolymer induced by changing the initial solvent conditions was studied by transmission electron microscopy (TEM). The copolymer was polystyrene(77)-b-poly[2-(beta -D-glucopyranosyloxy)ethyl acrylate (6)] (PSt(77)-b-PGEA(6)) and the solvent was a mixture of DMF and THF. PSt(77)-b-PGEA(6) yields vesicles and tubules when it is initially dissolved in THF and DMF respectively. The morphological transition between vesicles and tubules can be achieved by simply varying the amounts of THF and DMF, or changing the temperature at which the aggregates were prepared.
基金the National Natural Science Foundation of China (No.20474054)the National Natural Science Foundation of China for Distinguished Young Scholars (No.50625309).
文摘A glycopolymer bearing glucose residues was tethered onto the surface of polypropylene microporous membrane by UV-induced graft polymerization ofα-allyl glucoside.Concanavalin A (Con A),a glucose recognizing lectin,could be specifically adsorbed to the membrane surface.On the other hand,the membrane surface showed no recognition ability to another lectin peanut agglutinin.Moreover,the recognition complex between the glycosylated membrane surface and Con A could be inhibited by glucose and mannose solution.T...
基金Ministry of Science and Technology of China (No. 2011CB932503332)National Natural Science Foundation of China (No. 91227203, 21474020 and 51322306)the Shanghai Rising-Star Program (No. 13QA1400600) are acknowledged for their financial support
文摘Herein, we designed a novel amphiphilic triblock glycopolymer poly（oligo（ethyleneglycol） methacry- late）-block-poly（maltopyranoside methacrylate）-block-polystyrene （POMA-b-PMal-b-PS） via the com- bination of reversible addition-fragmentation chain transfer （RAFT） polymerization and post- polymerization modification. The micelles with core-shell-corona structures were prepared by direct self-assembly of this glycopolymer in water. We found that these micelles can be used in in situ formation and stabilization of AuNPs. By controlling the thickness of glyco-shell, we successfully obtained lanus particles and raspberry-like particles with AuNPs in the sugar shell.
基金National Natural Science Foundation of China(No.21303014)
文摘The monomer 6-O-vinyladipoyl-D-glucopyranose( VAG)was synthesized by lipase catalyzed trans-esterification of divinyladipate with D-glucopyranose. A novel double hydrophilic glycopolymer poly( diethyleneglycol methacrylate-co-6-Ovinyladipoyl-D-glucopyranose)( P( DEGMA-co-VAG)) with narrow polydispersity( PDI) and thermosensitivity was prepared by reversible addition-fragmentation chain transfer( RAFT)polymerization. P( DEGMA-co-VAG) was characterized by1 H NMR,FTIR and gel permeation chromatography( GPC). The characterization of UV-visible spectroscopy showed that the micelles from glycopolymer P( DEGMA-co-VAG) were thermo-responsive and the low critical solution temperature( LCST) could be controlled by the molar ratio of monomers. When the molar ratio of DEGMA and VAG was 2∶ 1,the LCST of P( DEGMA-co-VAG) was36 ℃ in aqueous solution,which could form nano micelles in the human body environment. It was found that P( DEGMA-co-VAG)was non-toxic at 0. 1-1 mg / m L concentrations when incubated with pig iliac endothelial cells( PIECs) for 24 h. Thus,the synthesized glycopolymers has great potential as drug delivery carriers.
