Control crosslink network and chain connectivity are essential to develop shape memory polymers(SMPs)with high shape memory capabilities,adjustable response temperature,and satisfying mechanistical properties.In this ...Control crosslink network and chain connectivity are essential to develop shape memory polymers(SMPs)with high shape memory capabilities,adjustable response temperature,and satisfying mechanistical properties.In this study,novel poly(ε-caprolactone)(PCL)-poly(2-vinyl)ethylene glycol(PVEG)copolymers bearing multi-pendant vinyl groups is synthesized by branched-selective allylic etherification polymerization of vinylethylene carbonate(VEC)with linear and tetra-arm PCLs under a synergistic catalysis of palladium complex and boron reagent.Facile thiol-ene photo-click reaction of PCL-PVEG copolymers with multifunctional thiols can rapidly access a serious crosslinked SMPs with high shape memory performance.The thermal properties,mechanical properties and response temperature of the obtained SMPs are tunable by the variation of PCL prepolymers,vinyl contents and functionality of thiols.Moreover,high elastic modulus in the rubbery plateau region can be maintained effectively owing to high-density topological networks of the PCL materials.In addition,the utility of the present SMPs is further demonstrated by the post-functionalization via thiol-ene photo-click chemistry.展开更多
Crosslinking is one of the effective routes for improving the orientation stability of poled polymer films. The derivative of polyvinyl alcohol containing 4-nitro-4'-alkoxystilbene and photo-crosslinkable cinnamyl...Crosslinking is one of the effective routes for improving the orientation stability of poled polymer films. The derivative of polyvinyl alcohol containing 4-nitro-4'-alkoxystilbene and photo-crosslinkable cinnamyl groups as side chains has been synthesized. The in-situ simultaneous photo-crosslinking poling of synthesized polymer films has teen performed, The second order nonlinear optical coefficient d(33) of poled film is 11 pm/V. The SHG measurements show that the break-over temperature of SHG signal is raised obviously after irradiation, its orientation stability is doubled as compared with that of non-crosslinking samples.展开更多
The immature state of in vitro engineered cartilage(IVEC)hinders its clinical translation,highlighting the need for optimized scaffold platforms and cultivation models.Our previous work demonstrated that Wharton's...The immature state of in vitro engineered cartilage(IVEC)hinders its clinical translation,highlighting the need for optimized scaffold platforms and cultivation models.Our previous work demonstrated that Wharton's jelly(WJ)contains an extracellular matrix(ECM)whose composition closely resembles that of native cartilage and includes several bioactive factors that promote chondrogenic induction.Furthermore,earlier studies have shown that photo-crosslinkable hydrogels are ideal carrier scaffolds for cartilage tissue engineering and that bioreactors improve nutrient and waste exchange between scaffolds and the culture medium.Based on these findings,we employed a dynamic bioreactor in combination with a WJ-derived photocrosslinkable hydrogel to enhance IVEC maturity.Our results indicate that the decellularized WJ matrix(DWJM)effectively retains its native chondrogenic ECM components and bioactive factors.The photo-crosslinkable ADWJM hydrogel—produced by modifying DWJM with methacrylate anhydride—demonstrated excellent gelation capacity as well as tunable rheological properties,swelling ratios and degradation rates across different DWJM concentrations.In addition,the ADWJM hydrogel exhibited outstanding biocompatibility by providing a favorable 3D microenvironment for chondrocyte survival and proliferation.Most importantly,the dynamic bioreactor markedly promoted IVEC maturation.Constructs cultured under dynamic conditions displayed increased thickness,wet weight and volume;enhanced mechanical strength;more typical lacunae structures;and uniform deposition of cartilagespecific ECM compared to constructs maintained in static conditions or within a static bioreactor.Moreover,in vivo subcutaneous implantation of IVEC in goats further validated these findings,as the implanted constructs exhibited cartilage components and mechanical properties closely resembling those of natural cartilage.These results offer a promising approach for enhancing IVEC maturity and support its future clinical translation.展开更多
Physiological repair of large-sized bone defects is great challenging in clinic due to a lack of ideal grafts suitable for bone regeneration.Decalcified bone matrix(DBM)is considered as an ideal bone regeneration scaf...Physiological repair of large-sized bone defects is great challenging in clinic due to a lack of ideal grafts suitable for bone regeneration.Decalcified bone matrix(DBM)is considered as an ideal bone regeneration scaffold,but low cell seeding efficiency and a poor osteoinductive microenvironment greatly restrict its application in large-sized bone regeneration.To address these problems,we proposed a novel strategy of bone regeneration units(BRUs)based on microgels produced by photo-crosslinkable and microfluidic techniques,containing both the osteogenic ingredient DBM and vascular endothelial growth factor(VEGF)for accurate biomimic of an osteoinductive microenvironment.The physicochemical properties of microgels could be precisely controlled and the microgels effectively promoted adhesion,proliferation,and osteogenic differentiation of bone marrow mesenchymal stem cells(BMSCs)in vitro.BRUs were successfully constructed by seeding BMSCs onto microgels,which achieved reliable bone regeneration in vivo.Finally,by integrating the advantages of BRUs in bone regeneration and the advantages of DBM scaffolds in 3D morphology and mechanical strength,a BRU-loaded DBM framework successfully regenerated bone tissue with the desired 3D morphology and effectively repaired a large-sized bone defect of rabbit tibia.The current study developed an ideal bone biomimetic microcarrier and provided a novel strategy for bone regeneration and large-sized bone defect repair.展开更多
The distribution of photo-crosslinkable moieties onto a protein backbone can affect a biomaterial’s crosslinking behavior, and therefore also its mechanical and biological properties. A profound insight in this respe...The distribution of photo-crosslinkable moieties onto a protein backbone can affect a biomaterial’s crosslinking behavior, and therefore also its mechanical and biological properties. A profound insight in this respect is essential for biomaterials exploited in tissue engineering and regenerative medicine. In the present work, photo-crosslinkable moieties have been introduced on the primary amine groups of: (i) a recombinant collagen peptide (RCPhC1) with a known amino acid (AA) sequence, and (ii) bovine skin collagen (COL BS) with an unknown AA sequence. The degree of substitution (DS) was quantified with two conventional techniques: an ortho-phthalic dialdehyde (OPA) assay and ^(1)H NMR spectroscopy. However, neither of both provides information on the exact type and location of the modified AAs. Therefore, for the first time, proteomic analysis was evaluated herein as a tool to identify functionalized AAs as well as the exact position of photo-crosslinkable moieties along the AA sequence, thereby enabling an in-depth, unprecedented characterization of functionalized photo-crosslinkable biopolymers. Moreover, our strategy enabled to visualize the spatial distribution of the modifications within the overall structure of the protein. Proteomics has proven to provide unprecedented insight in the distribution of photo-crosslinkable moieties along the protein backbone, undoubtedly contributing to superior functional biomaterial design to serve regenerative medicine.展开更多
Elastomeric scaffolds, individually customized to mimic the structural and mechanical properties of natural tissues have been used for tissue regeneration. In this regard, polyester elastic scaffolds with tunable mech...Elastomeric scaffolds, individually customized to mimic the structural and mechanical properties of natural tissues have been used for tissue regeneration. In this regard, polyester elastic scaffolds with tunable mechanical properties and exceptional biological properties have been reported to provide mechanical support and structural integrity for tissue repair. Herein, poly(4-methyl-ε-caprolactone) (PMCL) was first double-terminated by alkynylation (PMCL-DY) as a liquid precursor at room temperature. Subsequently, three-dimensional porous scaffolds with custom shapes were fabricated from PMCL-DY via thiol-yne photocrosslinking using a practical salt template method. By manipulating the Mn of the precursor, the modulus of compression of the scaffold was easily adjusted. As evidenced by the complete recovery from 90% compression, the rapid recovery rate of >500 mm min 1, the extremely low energy loss coefficient of <0.1, and the superior fatigue resistance, the PMCL20-DY porous scaffold was confirmed to harbor excellent elastic properties. In addition, the high resilience of the scaffold was confirmed to endow it with a minimally invasive application potential. In vitro testing revealed that the 3D porous scaffold was biocompatible with rat bone marrow stromal cells (BMSCs), inducing BMSCs to differentiate into chondrogenic cells. In addition, the elastic porous scaffold demonstrated good regenerative efficiency in a 12-week rabbit cartilage defect model. Thus, the novel polyester scaffold with adaptable mechanical properties may have extensive applications in soft tissue regeneration.展开更多
Artificial sensory systems,designed to emulate human senses like sight,touch,and hearing,have garnered significant attention for their potential to enhance human capabilities,improve human-machine interactions,and ena...Artificial sensory systems,designed to emulate human senses like sight,touch,and hearing,have garnered significant attention for their potential to enhance human capabilities,improve human-machine interactions,and enable autonomous systems to better perceive their surroundings.Hydrogels,with their biocompatibility,flexibility,and water-rich polymer structure,are increasingly recognized as crucial materials in the development of these systems,especially in applications such as wearable sensors,artificial skin,and neural interfaces.This review explores various hydrogel fabrication techniques,including 3D bioprinting,electro spinning,and photopolymerization,which allow for the precise control of hydrogel properties like mechanical strength,flexibility,and conductivity.By tailoring these properties to mimic natural tissues,hydrogels offer transformative benefits in the creation of advanced,biocompatible,and durable sensory systems.We emphasize the importance of selecting appropriate fabrication methods to meet the specific functional requirements of artificial sensory applications,such as sensitivity to stimuli,durability,and ease of integration.This review further highlights the pivotal role of hydrogels in advancing future artificial sensory technologies and their broad potential in fields ranging from robotics to biomedical devices.展开更多
基金financially supported by the National Natural Science Foundation of China(No.22171182)Sichuan Tianfu Emei Plan.
文摘Control crosslink network and chain connectivity are essential to develop shape memory polymers(SMPs)with high shape memory capabilities,adjustable response temperature,and satisfying mechanistical properties.In this study,novel poly(ε-caprolactone)(PCL)-poly(2-vinyl)ethylene glycol(PVEG)copolymers bearing multi-pendant vinyl groups is synthesized by branched-selective allylic etherification polymerization of vinylethylene carbonate(VEC)with linear and tetra-arm PCLs under a synergistic catalysis of palladium complex and boron reagent.Facile thiol-ene photo-click reaction of PCL-PVEG copolymers with multifunctional thiols can rapidly access a serious crosslinked SMPs with high shape memory performance.The thermal properties,mechanical properties and response temperature of the obtained SMPs are tunable by the variation of PCL prepolymers,vinyl contents and functionality of thiols.Moreover,high elastic modulus in the rubbery plateau region can be maintained effectively owing to high-density topological networks of the PCL materials.In addition,the utility of the present SMPs is further demonstrated by the post-functionalization via thiol-ene photo-click chemistry.
基金This work was supported by the National Natural Science Foundation of China
文摘Crosslinking is one of the effective routes for improving the orientation stability of poled polymer films. The derivative of polyvinyl alcohol containing 4-nitro-4'-alkoxystilbene and photo-crosslinkable cinnamyl groups as side chains has been synthesized. The in-situ simultaneous photo-crosslinking poling of synthesized polymer films has teen performed, The second order nonlinear optical coefficient d(33) of poled film is 11 pm/V. The SHG measurements show that the break-over temperature of SHG signal is raised obviously after irradiation, its orientation stability is doubled as compared with that of non-crosslinking samples.
基金supported by Hainan Province Clinical Medical Center,Hainan Provincial Natural Science Foundation(ZDYF2020130)Natural Science Foundation of China(82360560).
文摘The immature state of in vitro engineered cartilage(IVEC)hinders its clinical translation,highlighting the need for optimized scaffold platforms and cultivation models.Our previous work demonstrated that Wharton's jelly(WJ)contains an extracellular matrix(ECM)whose composition closely resembles that of native cartilage and includes several bioactive factors that promote chondrogenic induction.Furthermore,earlier studies have shown that photo-crosslinkable hydrogels are ideal carrier scaffolds for cartilage tissue engineering and that bioreactors improve nutrient and waste exchange between scaffolds and the culture medium.Based on these findings,we employed a dynamic bioreactor in combination with a WJ-derived photocrosslinkable hydrogel to enhance IVEC maturity.Our results indicate that the decellularized WJ matrix(DWJM)effectively retains its native chondrogenic ECM components and bioactive factors.The photo-crosslinkable ADWJM hydrogel—produced by modifying DWJM with methacrylate anhydride—demonstrated excellent gelation capacity as well as tunable rheological properties,swelling ratios and degradation rates across different DWJM concentrations.In addition,the ADWJM hydrogel exhibited outstanding biocompatibility by providing a favorable 3D microenvironment for chondrocyte survival and proliferation.Most importantly,the dynamic bioreactor markedly promoted IVEC maturation.Constructs cultured under dynamic conditions displayed increased thickness,wet weight and volume;enhanced mechanical strength;more typical lacunae structures;and uniform deposition of cartilagespecific ECM compared to constructs maintained in static conditions or within a static bioreactor.Moreover,in vivo subcutaneous implantation of IVEC in goats further validated these findings,as the implanted constructs exhibited cartilage components and mechanical properties closely resembling those of natural cartilage.These results offer a promising approach for enhancing IVEC maturity and support its future clinical translation.
基金financially supported by the National Key Research and Development Program of China(2017YFC1103900)the National Natural Science Foundation of China(81871502,81701843,and 81671837)+3 种基金the Shanghai Excellent Technical Leader(18XD1421500)the Program of Shanghai Academic/Technology Research Leader(19XD1431100)the Shanghai Collaborative Innovation Program on Regenerative Medicine and Stem Cell Research(2019CXJQ01)the Clinical Research Plan of SHDC(No.SHDC2020CR2045B).
文摘Physiological repair of large-sized bone defects is great challenging in clinic due to a lack of ideal grafts suitable for bone regeneration.Decalcified bone matrix(DBM)is considered as an ideal bone regeneration scaffold,but low cell seeding efficiency and a poor osteoinductive microenvironment greatly restrict its application in large-sized bone regeneration.To address these problems,we proposed a novel strategy of bone regeneration units(BRUs)based on microgels produced by photo-crosslinkable and microfluidic techniques,containing both the osteogenic ingredient DBM and vascular endothelial growth factor(VEGF)for accurate biomimic of an osteoinductive microenvironment.The physicochemical properties of microgels could be precisely controlled and the microgels effectively promoted adhesion,proliferation,and osteogenic differentiation of bone marrow mesenchymal stem cells(BMSCs)in vitro.BRUs were successfully constructed by seeding BMSCs onto microgels,which achieved reliable bone regeneration in vivo.Finally,by integrating the advantages of BRUs in bone regeneration and the advantages of DBM scaffolds in 3D morphology and mechanical strength,a BRU-loaded DBM framework successfully regenerated bone tissue with the desired 3D morphology and effectively repaired a large-sized bone defect of rabbit tibia.The current study developed an ideal bone biomimetic microcarrier and provided a novel strategy for bone regeneration and large-sized bone defect repair.
基金The authors acknowledge the IBiSA network for financial support of the USR 3290(MSAP)proteomics facility TOP_OMICS.The mass spec-trometers were funded by the University of Lille,the CNRS,the Region Hauts-de-France and the European Regional Development Fund (ERDF).
文摘The distribution of photo-crosslinkable moieties onto a protein backbone can affect a biomaterial’s crosslinking behavior, and therefore also its mechanical and biological properties. A profound insight in this respect is essential for biomaterials exploited in tissue engineering and regenerative medicine. In the present work, photo-crosslinkable moieties have been introduced on the primary amine groups of: (i) a recombinant collagen peptide (RCPhC1) with a known amino acid (AA) sequence, and (ii) bovine skin collagen (COL BS) with an unknown AA sequence. The degree of substitution (DS) was quantified with two conventional techniques: an ortho-phthalic dialdehyde (OPA) assay and ^(1)H NMR spectroscopy. However, neither of both provides information on the exact type and location of the modified AAs. Therefore, for the first time, proteomic analysis was evaluated herein as a tool to identify functionalized AAs as well as the exact position of photo-crosslinkable moieties along the AA sequence, thereby enabling an in-depth, unprecedented characterization of functionalized photo-crosslinkable biopolymers. Moreover, our strategy enabled to visualize the spatial distribution of the modifications within the overall structure of the protein. Proteomics has proven to provide unprecedented insight in the distribution of photo-crosslinkable moieties along the protein backbone, undoubtedly contributing to superior functional biomaterial design to serve regenerative medicine.
基金support by the National Key Research and Development Program(2021YFB3800800)the National Natural Science Foundation of China(52273009)+1 种基金the National Natural Science Foundation of China(82271038)the Interdisciplinary Program of Shanghai JiaoTong University(YG2022QN050).
文摘Elastomeric scaffolds, individually customized to mimic the structural and mechanical properties of natural tissues have been used for tissue regeneration. In this regard, polyester elastic scaffolds with tunable mechanical properties and exceptional biological properties have been reported to provide mechanical support and structural integrity for tissue repair. Herein, poly(4-methyl-ε-caprolactone) (PMCL) was first double-terminated by alkynylation (PMCL-DY) as a liquid precursor at room temperature. Subsequently, three-dimensional porous scaffolds with custom shapes were fabricated from PMCL-DY via thiol-yne photocrosslinking using a practical salt template method. By manipulating the Mn of the precursor, the modulus of compression of the scaffold was easily adjusted. As evidenced by the complete recovery from 90% compression, the rapid recovery rate of >500 mm min 1, the extremely low energy loss coefficient of <0.1, and the superior fatigue resistance, the PMCL20-DY porous scaffold was confirmed to harbor excellent elastic properties. In addition, the high resilience of the scaffold was confirmed to endow it with a minimally invasive application potential. In vitro testing revealed that the 3D porous scaffold was biocompatible with rat bone marrow stromal cells (BMSCs), inducing BMSCs to differentiate into chondrogenic cells. In addition, the elastic porous scaffold demonstrated good regenerative efficiency in a 12-week rabbit cartilage defect model. Thus, the novel polyester scaffold with adaptable mechanical properties may have extensive applications in soft tissue regeneration.
基金supported by the National Research Foundation of Korea(NRF)Grants funded by the Korea government(MSIT)(Nos.RS-2023-00213047 and RS-2024-00405818)。
文摘Artificial sensory systems,designed to emulate human senses like sight,touch,and hearing,have garnered significant attention for their potential to enhance human capabilities,improve human-machine interactions,and enable autonomous systems to better perceive their surroundings.Hydrogels,with their biocompatibility,flexibility,and water-rich polymer structure,are increasingly recognized as crucial materials in the development of these systems,especially in applications such as wearable sensors,artificial skin,and neural interfaces.This review explores various hydrogel fabrication techniques,including 3D bioprinting,electro spinning,and photopolymerization,which allow for the precise control of hydrogel properties like mechanical strength,flexibility,and conductivity.By tailoring these properties to mimic natural tissues,hydrogels offer transformative benefits in the creation of advanced,biocompatible,and durable sensory systems.We emphasize the importance of selecting appropriate fabrication methods to meet the specific functional requirements of artificial sensory applications,such as sensitivity to stimuli,durability,and ease of integration.This review further highlights the pivotal role of hydrogels in advancing future artificial sensory technologies and their broad potential in fields ranging from robotics to biomedical devices.
