Elastomeric vitrimers with covalent adaptable networks are promising candidates to overcome the intrinsic drawbacks of conventional covalently-crosslinked elastomers;however, most elastomeric vitrimers show poor mecha...Elastomeric vitrimers with covalent adaptable networks are promising candidates to overcome the intrinsic drawbacks of conventional covalently-crosslinked elastomers;however, most elastomeric vitrimers show poor mechanical properties and require the addition of exogenous catalysts. Herein, we fabricate a catalyst-free and mechanically robust elastomeric vitrimer by constructing a segregated structure of sodium alginate (SA) in the continuous matrix of epoxidized natural rubber (ENR), and further crosslinking the composite by exchangeable hydroxyl ester bonds at the ENR-SA interfaces. The manufacturing process of the elastomeric vitrimer is facile and environmentally friendly without hazardous solvents or exogenous catalysts, as the abundant hydroxyl groups of the segregated SA phase can act as catalyst to activate the crosslinking reaction and promote the dynamic transesterification reaction. Interestingly, the segregated SA structure bears most of the load owing to its high modulus and small deformability, and thus ruptures preferentially upon deformation, leading to efficient energy dissipation.Moreover, the periodic stiffness fluctuation between rigid segregated SA phase and soft ENR matrix is beneficial to the crack-resisting. As a result,the elastomeric vitrimer manifests exceptional combination of catalyst-free, defect-tolerance, high tensile strength and toughness. In addition,the elastomeric vitrimer also exhibits multi-shape memory behavior which may further broaden its applications.展开更多
Poly(butylene adipate-co-terephthalate)(PBAT),a widely studied biodegradable material,has not effectively addressed the problem of plastic waste.Taking into consideration the cost-effectiveness,upcycling PBAT should t...Poly(butylene adipate-co-terephthalate)(PBAT),a widely studied biodegradable material,has not effectively addressed the problem of plastic waste.Taking into consideration the cost-effectiveness,upcycling PBAT should take precedence over direct composting degradation.The present work adopts a chain breaking-crosslinking strategy,upcycling PBAT into dual covalent adaptable networks(CANs).During the chainbreaking stage,the ammonolysis between PBAT and polyethyleneimine(PEI)established the primary crosslinked network.Subsequently,styrene maleic anhydride copolymer(SMA)reacted with the hydroxyl group,culminating in the formation of dual covalent adaptable networks.In contrast to PBAT,the PBAT-dual-CANs exhibited a notable Young's modulus of 239 MPa,alongside an inherent resistance to creep and solvents.Owing to catalysis from neighboring carboxyl group and excess hydroxyl groups,the PBAT-dual-CANs exhibited fast stress relaxation.Additionally,they could be recycled through extrusion and hot-press reprocessing,while retaining their biodegradability.This straightforward strategy offers a solution for dealing with plastic waste.展开更多
With the increasing consumption of non renewable resources such as oil,the traditional polymer manufacturing industry that relies on fossil resources is facing unprecedented challenges.The design,synthesis,and recycli...With the increasing consumption of non renewable resources such as oil,the traditional polymer manufacturing industry that relies on fossil resources is facing unprecedented challenges.The design,synthesis,and recycling of renewable and environmentally friendly bio-based polymers as alternatives to petroleum based polymers have become hot topics in research and industrial fields.Biomass has been used as a raw material to design and synthesize closed-loop recyclable polymers,which is of great significance in addressing the waste of resources and negative impact on the environment in the traditional polymer preparation process.This review summarized recent advances in the design,synthesis,and properties of closed-loop recyclable bio-based polymers,focusing on the sustainability and recyclability of bio-based materials,followed by a brief discussion of the potential applications of closed-loop recyclable bio-based polymers in emerging applications such as 3D printing and friction electric nanogenerators.In addition,perspectives and recommendations for future research on closedloop recyclable bio-based polymers were presented.展开更多
This work develops a protein imprinted nanosphere with varied recognition specificity for bovine serum albumin(BSA)and lysozyme(Lyz)under different UV light through a gradient dual crosslinked imprinting strategy(i.e....This work develops a protein imprinted nanosphere with varied recognition specificity for bovine serum albumin(BSA)and lysozyme(Lyz)under different UV light through a gradient dual crosslinked imprinting strategy(i.e.,covalent crosslinking and dynamic reversible crosslinking).The imprinting cavities are initially constructed using irreversible covalent crosslinking to specifically recognize BSA,and then the coumarin residues in the imprinting cavities are crosslinked under 365 nm UV light to further imprint Lyz,because Lyz has smaller size than BSA.Since the photo-crosslinking of coumarin is a reversible reaction,the imprinting cavities of Lyz can be de-crosslinked under 254 nm UV light and restore the imprinting cavities of BSA.Moreover,the N-isopropyl acrylamide(NIPAM)and pyrrolidine residues copolymerized in the polymeric surface of the nanospheres are temperature-and p H-responsive respectively.Therefore,the protein rebinding and release behaviors of the nanospheres are controlled by external temperature and p H.As a result,the materials can selectively separate BSA from real bovine whole blood and Lyz from egg white under different UV light.This study may provide a new strategy for construction of protein imprinted materials with tunable specificity for different proteins.展开更多
Intracellular protein delivery is critical to the development of protein-based biopharmaceuticals and therapies.However,current delivery vectors often suffer from complicated syntheses,low generality among various pro...Intracellular protein delivery is critical to the development of protein-based biopharmaceuticals and therapies.However,current delivery vectors often suffer from complicated syntheses,low generality among various proteins,and insufficient serum stability.Herein,we developed an enlightened cytosolic protein delivery strategy by dynamically crosslinking epigallocatechin gallate(EGCG),low-molecular-weight polyethylenimine(PEI 1.8k),and 2-acetylphenylboric acid(2-APBA)on the protein surface,hence forming the EPP-protein nanocapsules(NCs).EGCG enhanced protein encapsulation via hydrogen bonding,and reduced the positive charge density of PEI to endow the NCs with high serum tolerance,thereby enabling effective cellular internalization in serum.The formation of reversible imine and boronate ester among 2-APBA,EGCG,and PEI 1.8k allowed acid-triggered dissociation of EPP-protein NCs in the endolysosomes,which triggered efficient intracellular release of the native proteins.Such strategy therefore showed high efficiency and universality for diversities of proteins with different molecular weights and isoelectric points,including enzyme,toxin,antibody,and CRISPR(clustered regularly interspaced short palindromic repeats)-Cas9 ribonucleoprotein(RNP),outperforming the commercial protein transduction reagent PULSin and RNP transfection reagent lipofectamine CMAX.Moreover,intravenously(i.v.)injected EPP-saporin NCs efficiently delivered saporin into 4T1 tumor cells to provoke robust antitumor effect.This simple,versatile,and robust cytosolic protein delivery system holds translational potentials for the development of protein-based therapeutics.展开更多
Patterning diversified properties and surface structure of polymer materials are of great importance toward their potential in biology,optics,and electronics.However,achieving both the patternability of stiffness and ...Patterning diversified properties and surface structure of polymer materials are of great importance toward their potential in biology,optics,and electronics.However,achieving both the patternability of stiffness and microstructure in a reconfigurable manner remains challenging.Here,we prepare amphigels crosslinked by dynamic disulfide bonds,which can be reversibly swollen by immiscible water or liquid paraffin.In the paraffingel form,the materials exhibited a high modulus of 130 MPa due to densified hydrogen bonds.Whereas swollen by water,the modulus fell over two orders of magnitude owing to the destruction of the hydrogen bonds.Via regionalized swelling of the solvents,well-controlled and rewritable soft/stiff mechanical patterns can be created.On the other hand,the dynamic exchange of the disulfide crosslinking enables mechanophoto patterning to fabricate sophisticated macrogeometries and microstructures.The reconfigurable stiffness-structure patterning can be manipulated orthogonally,which will create more application opportunities beyond conventional hydrogels and organogels.展开更多
Cutaneous nerve regeneration in diabetic wounds remains a challenge for current clinical treatment.Herein,a natural protein-based functional hydrogel is developed using keratin as the sole matrix,and protocatechuic al...Cutaneous nerve regeneration in diabetic wounds remains a challenge for current clinical treatment.Herein,a natural protein-based functional hydrogel is developed using keratin as the sole matrix,and protocatechuic aldehyde(PA)and zinc ions as the building blocks through dual-dynamic crosslinking reactions of thiol-aldehyde addition and catecholzinc ions coordination.The unique structural design endows the hydrogel with excellent injectability,skin adhesion,self-healing and antibacterial ability,and biocompatibility.In addition,this hydrogel acts as a drug carrier for the loading and sustained release of phellopterin(PP),a natural compound extracted from traditional Chinese medicine Angelica dahurica.Our findings demonstrate that the PP-loaded hydrogel promotes cutaneous nerve regeneration,angiogenesis and tissue remodeling in the full-thickness wounds in both db/db and streptozotocin-induced C57BL/6 diabetic mice,notably by the synergistic effect of zinc ions and PP,showing a great potential in diabetic wound therapy.展开更多
In clinical applications,there is a lack of wound dressings that combine efficient resistance to drug-resistant bacteria with good self-healing properties.In this study,a series of adhesive self-healing conductive ant...In clinical applications,there is a lack of wound dressings that combine efficient resistance to drug-resistant bacteria with good self-healing properties.In this study,a series of adhesive self-healing conductive antibacterial hydrogel dressings based on oxidized sodium alginate-grafted dopamine/carboxymethyl chitosan/Fe3+(OSD/CMC/Fe hydrogel)/polydopamine-encapsulated poly(thiophene-3-acetic acid)(OSD/CMC/Fe/PA hydrogel)were prepared for the repair of infected wound.The Schiff base and Fe3+coordination bonds of the hydrogel structure are dynamic bonds that can be repaired automatically after the hydrogel network is disrupted.Macroscopically,the hydrogel exhibits self-healing properties,allowing the hydrogel dressing to adapt to complex wound surfaces.The OSD/CMC/Fe/PA hydrogel showed good conductivity and photothermal antibacterial properties under near-infrared(NIR)light irradiation.In addition,the hydrogels exhibit tunable rheological properties,suitable mechanical properties,antioxidant properties,tissue adhesion properties and hemostatic properties.Furthermore,all hydrogel dressings improved wound healing in the infected full-thickness defect skin wound repair test in mice.The wound size repaired by OSD/CMC/Fe/PA3 hydrogel+NIR was much smaller(12%)than the control group treated with Tegaderm™film after 14 days.In conclusion,the hydrogels have high antibacterial efficiency,suitable conductivity,great self-healing properties,good biocompatibility,hemostasis and antioxidant properties,making them promising candidates for wound healing dressings for the treatment of infected skin wounds.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 51873110 and 51790501)State Key Laboratory of Polymer Materials Engineering (No. sklpme2019-2-14)the Fundamental Research Funds for Central Universities。
文摘Elastomeric vitrimers with covalent adaptable networks are promising candidates to overcome the intrinsic drawbacks of conventional covalently-crosslinked elastomers;however, most elastomeric vitrimers show poor mechanical properties and require the addition of exogenous catalysts. Herein, we fabricate a catalyst-free and mechanically robust elastomeric vitrimer by constructing a segregated structure of sodium alginate (SA) in the continuous matrix of epoxidized natural rubber (ENR), and further crosslinking the composite by exchangeable hydroxyl ester bonds at the ENR-SA interfaces. The manufacturing process of the elastomeric vitrimer is facile and environmentally friendly without hazardous solvents or exogenous catalysts, as the abundant hydroxyl groups of the segregated SA phase can act as catalyst to activate the crosslinking reaction and promote the dynamic transesterification reaction. Interestingly, the segregated SA structure bears most of the load owing to its high modulus and small deformability, and thus ruptures preferentially upon deformation, leading to efficient energy dissipation.Moreover, the periodic stiffness fluctuation between rigid segregated SA phase and soft ENR matrix is beneficial to the crack-resisting. As a result,the elastomeric vitrimer manifests exceptional combination of catalyst-free, defect-tolerance, high tensile strength and toughness. In addition,the elastomeric vitrimer also exhibits multi-shape memory behavior which may further broaden its applications.
基金financially supported by the National Natural Science Foundation of China(Nos.52373007 and 52073296)Innovative Leading Talent of Taihu Lake Talent Plan in Wuxi City+1 种基金Zhejiang Ten Thousand Talent ProgramResearch startup fund from Jiangnan University。
文摘Poly(butylene adipate-co-terephthalate)(PBAT),a widely studied biodegradable material,has not effectively addressed the problem of plastic waste.Taking into consideration the cost-effectiveness,upcycling PBAT should take precedence over direct composting degradation.The present work adopts a chain breaking-crosslinking strategy,upcycling PBAT into dual covalent adaptable networks(CANs).During the chainbreaking stage,the ammonolysis between PBAT and polyethyleneimine(PEI)established the primary crosslinked network.Subsequently,styrene maleic anhydride copolymer(SMA)reacted with the hydroxyl group,culminating in the formation of dual covalent adaptable networks.In contrast to PBAT,the PBAT-dual-CANs exhibited a notable Young's modulus of 239 MPa,alongside an inherent resistance to creep and solvents.Owing to catalysis from neighboring carboxyl group and excess hydroxyl groups,the PBAT-dual-CANs exhibited fast stress relaxation.Additionally,they could be recycled through extrusion and hot-press reprocessing,while retaining their biodegradability.This straightforward strategy offers a solution for dealing with plastic waste.
基金Natural Science Foundation of China(Grant Nos.32471815 and 32401528)Natural Science Foundation of Jiangsu Province of China(Grant Nos.BK20241745 and BK20240294).
文摘With the increasing consumption of non renewable resources such as oil,the traditional polymer manufacturing industry that relies on fossil resources is facing unprecedented challenges.The design,synthesis,and recycling of renewable and environmentally friendly bio-based polymers as alternatives to petroleum based polymers have become hot topics in research and industrial fields.Biomass has been used as a raw material to design and synthesize closed-loop recyclable polymers,which is of great significance in addressing the waste of resources and negative impact on the environment in the traditional polymer preparation process.This review summarized recent advances in the design,synthesis,and properties of closed-loop recyclable bio-based polymers,focusing on the sustainability and recyclability of bio-based materials,followed by a brief discussion of the potential applications of closed-loop recyclable bio-based polymers in emerging applications such as 3D printing and friction electric nanogenerators.In addition,perspectives and recommendations for future research on closedloop recyclable bio-based polymers were presented.
基金financial support from the National Natural Science Foundation of China(No.22275148)National Key R&D Program of China(No.2018YFB1900201)for Qiuyu Zhang+2 种基金the National Natural Science Foundation of China(No.22271232)Fundamental Research Funds for the Central Universities(No.D5000230114)for Shixin Fathe Fundamental Research Funds for the Central Universities(No.D5000220339)for Qing Liu。
文摘This work develops a protein imprinted nanosphere with varied recognition specificity for bovine serum albumin(BSA)and lysozyme(Lyz)under different UV light through a gradient dual crosslinked imprinting strategy(i.e.,covalent crosslinking and dynamic reversible crosslinking).The imprinting cavities are initially constructed using irreversible covalent crosslinking to specifically recognize BSA,and then the coumarin residues in the imprinting cavities are crosslinked under 365 nm UV light to further imprint Lyz,because Lyz has smaller size than BSA.Since the photo-crosslinking of coumarin is a reversible reaction,the imprinting cavities of Lyz can be de-crosslinked under 254 nm UV light and restore the imprinting cavities of BSA.Moreover,the N-isopropyl acrylamide(NIPAM)and pyrrolidine residues copolymerized in the polymeric surface of the nanospheres are temperature-and p H-responsive respectively.Therefore,the protein rebinding and release behaviors of the nanospheres are controlled by external temperature and p H.As a result,the materials can selectively separate BSA from real bovine whole blood and Lyz from egg white under different UV light.This study may provide a new strategy for construction of protein imprinted materials with tunable specificity for different proteins.
基金supported by the Natural Science Foundation of Jiangsu Province(No.BK20220245)the National Natural Science Foundation of China(Nos.52273144 and 82241008)Collaborative Innovation Center of Suzhou Nano Science&Technology,the 111 project,Suzhou Key Laboratory of Nanotechnology and Biomedicine,and Joint International Research Laboratory of Carbon-Based Functional Materials and Devices.
文摘Intracellular protein delivery is critical to the development of protein-based biopharmaceuticals and therapies.However,current delivery vectors often suffer from complicated syntheses,low generality among various proteins,and insufficient serum stability.Herein,we developed an enlightened cytosolic protein delivery strategy by dynamically crosslinking epigallocatechin gallate(EGCG),low-molecular-weight polyethylenimine(PEI 1.8k),and 2-acetylphenylboric acid(2-APBA)on the protein surface,hence forming the EPP-protein nanocapsules(NCs).EGCG enhanced protein encapsulation via hydrogen bonding,and reduced the positive charge density of PEI to endow the NCs with high serum tolerance,thereby enabling effective cellular internalization in serum.The formation of reversible imine and boronate ester among 2-APBA,EGCG,and PEI 1.8k allowed acid-triggered dissociation of EPP-protein NCs in the endolysosomes,which triggered efficient intracellular release of the native proteins.Such strategy therefore showed high efficiency and universality for diversities of proteins with different molecular weights and isoelectric points,including enzyme,toxin,antibody,and CRISPR(clustered regularly interspaced short palindromic repeats)-Cas9 ribonucleoprotein(RNP),outperforming the commercial protein transduction reagent PULSin and RNP transfection reagent lipofectamine CMAX.Moreover,intravenously(i.v.)injected EPP-saporin NCs efficiently delivered saporin into 4T1 tumor cells to provoke robust antitumor effect.This simple,versatile,and robust cytosolic protein delivery system holds translational potentials for the development of protein-based therapeutics.
基金supported by the National Natural Science Foundation of China (Nos.22105167,U20A6001,and 52273112).
文摘Patterning diversified properties and surface structure of polymer materials are of great importance toward their potential in biology,optics,and electronics.However,achieving both the patternability of stiffness and microstructure in a reconfigurable manner remains challenging.Here,we prepare amphigels crosslinked by dynamic disulfide bonds,which can be reversibly swollen by immiscible water or liquid paraffin.In the paraffingel form,the materials exhibited a high modulus of 130 MPa due to densified hydrogen bonds.Whereas swollen by water,the modulus fell over two orders of magnitude owing to the destruction of the hydrogen bonds.Via regionalized swelling of the solvents,well-controlled and rewritable soft/stiff mechanical patterns can be created.On the other hand,the dynamic exchange of the disulfide crosslinking enables mechanophoto patterning to fabricate sophisticated macrogeometries and microstructures.The reconfigurable stiffness-structure patterning can be manipulated orthogonally,which will create more application opportunities beyond conventional hydrogels and organogels.
基金supported by grants from the National Natural Science Foundation of China(Nos.82474515 and 82074428)Highlevel Chinese Medicine Key Discipline Construction Project(Integrative Chinese and Western Medicine Clinic)of National Administration of TCM(No.zyyzdxk-2023065)+1 种基金Young Qi-Huang Scholar of National Administration of Traditional Chinese Medicine,Evidence-Based Capacity Building for TCM Specialty Therapies for Skin Diseases of National Administration of TCM,and Innovative Team Projects of Shanghai Municipal Commission of Health(No.2022CX011)to Fulun Lithe National Natural Science Foundation of China(No.32371413)to Guang Yang.
文摘Cutaneous nerve regeneration in diabetic wounds remains a challenge for current clinical treatment.Herein,a natural protein-based functional hydrogel is developed using keratin as the sole matrix,and protocatechuic aldehyde(PA)and zinc ions as the building blocks through dual-dynamic crosslinking reactions of thiol-aldehyde addition and catecholzinc ions coordination.The unique structural design endows the hydrogel with excellent injectability,skin adhesion,self-healing and antibacterial ability,and biocompatibility.In addition,this hydrogel acts as a drug carrier for the loading and sustained release of phellopterin(PP),a natural compound extracted from traditional Chinese medicine Angelica dahurica.Our findings demonstrate that the PP-loaded hydrogel promotes cutaneous nerve regeneration,angiogenesis and tissue remodeling in the full-thickness wounds in both db/db and streptozotocin-induced C57BL/6 diabetic mice,notably by the synergistic effect of zinc ions and PP,showing a great potential in diabetic wound therapy.
基金Deanship of Scientific Research at Najran University for funding this work,under the Research Groups Funding Program grant code(NU/RG/MRC/12/5)the National Natural Science Foundation of China(grant numbers:51973172,52273149)+2 种基金Supported by 111 Project 2.0(BPO618008)the Natural Science Foundation of Shaanxi Province(No.2020JC-03)State Key Laboratory for Mechanical Behavior of Materials,and the World-Class Universities(Disciplines)and the Characteristic Development Guidance Funds for the Central Universities.
文摘In clinical applications,there is a lack of wound dressings that combine efficient resistance to drug-resistant bacteria with good self-healing properties.In this study,a series of adhesive self-healing conductive antibacterial hydrogel dressings based on oxidized sodium alginate-grafted dopamine/carboxymethyl chitosan/Fe3+(OSD/CMC/Fe hydrogel)/polydopamine-encapsulated poly(thiophene-3-acetic acid)(OSD/CMC/Fe/PA hydrogel)were prepared for the repair of infected wound.The Schiff base and Fe3+coordination bonds of the hydrogel structure are dynamic bonds that can be repaired automatically after the hydrogel network is disrupted.Macroscopically,the hydrogel exhibits self-healing properties,allowing the hydrogel dressing to adapt to complex wound surfaces.The OSD/CMC/Fe/PA hydrogel showed good conductivity and photothermal antibacterial properties under near-infrared(NIR)light irradiation.In addition,the hydrogels exhibit tunable rheological properties,suitable mechanical properties,antioxidant properties,tissue adhesion properties and hemostatic properties.Furthermore,all hydrogel dressings improved wound healing in the infected full-thickness defect skin wound repair test in mice.The wound size repaired by OSD/CMC/Fe/PA3 hydrogel+NIR was much smaller(12%)than the control group treated with Tegaderm™film after 14 days.In conclusion,the hydrogels have high antibacterial efficiency,suitable conductivity,great self-healing properties,good biocompatibility,hemostasis and antioxidant properties,making them promising candidates for wound healing dressings for the treatment of infected skin wounds.
