Ceramic 4D printing,which integrates dynamic deformation with additive manufacturing,demonstrates significant potential in intelligent manufacturing,on-demand shaping of complex structures,and multifunctional device d...Ceramic 4D printing,which integrates dynamic deformation with additive manufacturing,demonstrates significant potential in intelligent manufacturing,on-demand shaping of complex structures,and multifunctional device development.Its core advantage lies in endowing materials with environmentally responsive dynamic deformation capabilities.However,current technologies still face limitations in responsiveness,reversibility,and mechanical performance.To address these challenges,this study proposes a programmable ceramic precursor system based on synergistic reinforcement of phase-separating hydrogels and shape memory polymers,combined with a nano-ceramic particle enhancement strategy.Using stereolithography 3D printing,high-precision fabrication of complex structures was achieved.By adjusting precursor composition,programming time,and structural thickness,the phase-separation kinetics-driven delayed recovery mechanism was elucidated,enabling precise control over recovery onset time.Furthermore,the thermal response mechanism of the precursor materials is explored,along with their potential for multi-shape transformation in biomedical applications,which is further extended to shape memory polymer systems.By employing a layered printing strategy,the autonomous reversible deformation of ceramic precursors is realized,providing new possibilities for specific applications.展开更多
Wireless millirobots engineered to infiltrate intricate vascular networks within living organisms,particularly within constricted and confined spaces,hold immense promise for the future of medical treatments.However,w...Wireless millirobots engineered to infiltrate intricate vascular networks within living organisms,particularly within constricted and confined spaces,hold immense promise for the future of medical treatments.However,with their multifaceted and intricate designs,some robots often grapple with motion and functionality issues when confronted with tight spaces characterized by small cross-sectional dimensions.In this study,drawing inspiration from the high aspect ratio and undulating swimming patterns of snakes,a millimeter-scale,snake-like robot was designed and fabricated via a combination of extrusion-based four-dimensional(4D)printing and magnetic-responsive intelligent functional inks.A sophisticated motion control strategy was also developed,which enables the robots to perform various dynamic movements,such as undulating swimming,precise turns,graceful circular motions,and coordinated cluster movements,under diverse magnetic field variations.As a potential application,the snake robot can navigate and release drugs in a model coronary intervention vessel with tortuous channels and fluid filling.The novel design and promising applications of this snake robot are invaluable tools in future medical surgeries and interventions.展开更多
Liquid crystal elastomers(LCEs)exhibit exceptional reversible deformation and unique physical properties owing to their order-disorder phase transition under external stimuli.Among these deformations,helical structure...Liquid crystal elastomers(LCEs)exhibit exceptional reversible deformation and unique physical properties owing to their order-disorder phase transition under external stimuli.Among these deformations,helical structures have attracted attention owing to their distinctive configurations and promising applications in biomimetics and microelectronics.However,the helical deformation behavior of fiber actuators is critically influenced by their morphologies and alignments;yet,the underlying mechanisms are not fully understood.Through a two-step azaMichael addition reaction and direct ink writing(DIW)4D printing technology,fiber-based LCE actuators with a core-sheath alignment structure were fabricated and exhibited reversible helical deformation upon heating.By adjusting the printing parameters,the filament number,width,thickness,and core-sheath structure of the fiber actuators can be precisely controlled,resulting in deformation behaviors,such as contraction,bending,and helical twisting.Finite element simulations were performed to investigate the deformation behaviors of the fiber actuators,providing insights into the variations in stress and strain during the shape-changing process,which can be used to explain the shape-morphing mechanism.These findings demonstrate that the precise tuning of printing parameters enables the controllable construction of LCE actuator morphology and customization of their functional properties,paving the way for advanced applications in smart fabrics,biomedical engineering,and flexible electronics.展开更多
“Life”represents a distinctive attribute inherent to organisms in nature,evident in their capacity to actively adapt to changes in their environment.In contrast to the static and intricate constructs of additive man...“Life”represents a distinctive attribute inherent to organisms in nature,evident in their capacity to actively adapt to changes in their environment.In contrast to the static and intricate constructs of additive manufacturing(AM),the dynamic structure of 4D printing(4DP)adeptly integrates AM technology,responsive mechanisms,and external stimuli,imbuing it with a semblance of“life.”This fusion significantly broadens its functional applica-tions across biomedicine,actuators,and metamaterials.The escalating demand across diverse fields necessitates heightened criteria for 4DP,encompassing rapid response,multi-stimulus response,large shape change,and specific mechanical properties(e.g.,high strength,high modulus)capable of accommodating varying environ-mental conditions.In recent years,shape memory polymers(SMPs)have garnered increasing attention among 4DP researchers due to their ease of design and preprogramming at the molecular level,facilitating controlled transformations along predictable pathways.However,4DP of high-strength SMPs,as an indispensable part of the high-performance field,is full of challenges because the intrinsic properties of the raw materials are not well compatible with the printing principle and the printed configuration is not flexible enough.Consequently,this paper provides a concise overview of the response mechanisms and applications of five prominent high-strength SMPs utilized in 4DP:epoxy resin,poly(ether-ether-ketone),polyimide,polylactic acid,and polyurethane.Ad-ditionally,it delves into the associated challenges and prospects,offering researchers valuable insights into the potential value of high-strength SMPs within the domain of 4DP.展开更多
Three-dimensional(3D)-printed hydrogel scaffolds are widely used in spinal cord injury repair,with gelatin methacrylate being particularly favored owing to its excellent biocompatibility.However,traditional scaffolds ...Three-dimensional(3D)-printed hydrogel scaffolds are widely used in spinal cord injury repair,with gelatin methacrylate being particularly favored owing to its excellent biocompatibility.However,traditional scaffolds have a small contact area with tissues and lack the ability to regulate the inflammatory microenvironment.Therefore,there is a need to develop smart scaffolds with drug delivery and immune regulation functions.In this study,a 3D-printed gelatin methacrylate scaffold was developed to deliver interferon regulatory factor 4 in a targeted and sustained manner.The scaffold showed good mechanical properties,biocompatibility,and sustained interferon regulatory factor 4 release.The sustained-release interferon regulatory factor 4 competitively bound to myeloid differentiation factor 88 to inhibit the pro-inflammatory effects of interferon regulatory factor 5,and activated the signal transducer and activator of transcription 6 pathway to promote M2 macrophage polarization,thereby facilitating neural regeneration and recovery of spinal cord function.This indicates that the constructed interferon regulatory factor 4-loaded 3D-printed methyl acrylate-modified gelatin scaffold can regulate macrophage polarization through the interferon regulatory factor 4/5 axis,improve the inflammatory microenvironment after spinal cord injury,and thus provide a new target for promoting neural regeneration.展开更多
Abnormal wound scarring often leads to functional impairments and cosmetic deformities,primarily driven by the prolonged activation of the TGF-β/Smad signaling pathway.Addressing this challenge,we developed a biomime...Abnormal wound scarring often leads to functional impairments and cosmetic deformities,primarily driven by the prolonged activation of the TGF-β/Smad signaling pathway.Addressing this challenge,we developed a biomimetic scaffold aimed at facilitating rapid and scarless wound healing.This highly in-tegrated 3D-printed dermal scaffold comprised modified recombinant human type III collagen(rhCOLIII-MA),gelatin methacrylate(GelMA),and liposomes encapsulating SB431542 to target TGF-β1(Lip@SB).The rhCOLIII-MA/GelMA(CG)scaffold retained inherent biomaterial characteristics,exhibited tailored physicochemical properties,and demonstrated favorable biocompatibility.Moreover,the Lip@SB-loaded CG scaffold(CGL)effectively promoted in vitro wound healing,while enabling controlled release of SB431542 to inhibit pathological collagen deposition.In a full-thickness skin defect rat model,the CGL dermal scaffold combined with split-thickness skin graft(STSG)minimized scar contraction,stimulated functional neovascularization,and enhanced graft aesthetics comparable to normal skin.Remarkably,the performance of the CGL scaffold surpassed that of commercially available anti-scarring alternatives.This innovative strategy presents a straightforward approach toward scarless skin regeneration and holds promise in alleviating the prolonged,painful postoperative rehabilitation.展开更多
The development of advanced information storage materials with spatiotemporal security features is critical to address the growing demand for high-level encryption and anti-counterfeiting protection.Herein,two types o...The development of advanced information storage materials with spatiotemporal security features is critical to address the growing demand for high-level encryption and anti-counterfeiting protection.Herein,two types of 4D-printed fluorescent hydrogels that exhibit time-gated hierarchical morphing and color-varying dual functions,driven solely by temperature,have been successfully developed.Specifically,for the first one,the target blooming state of Hydrogels A is realized under 365 nm UV light through synchronized hierarchical morphing and graded fluorescence color transition(orange→blue).For the second one,under 254 nm UV irradiation,doped Hydrogels B exhibit reversible hierarchical state switching between bloomed and closed configurations,accompanied by dynamic multicolor fluorescence modulation.These promising results originate from spatially gradient crosslinking networks precisely engineered via vat photopolymerization(VP)3D printing,and specially-designed luminescent chromophores,collectively enabling fluorescent hydrogels to achieve an all-in-one stimulus response integrating“shape morphing—multicolor fluorescence—information encryption”under thermal activation.Thus,a unique“codebook”—a time-dependent dual-parameter encryption system can be developed using these 4D-printed fluorescent hydrogels,by dynamically adjusting bending angles and fluorescence ratios,effectively enabling high-security spatiotemporal information protection.The integration of time-gated shape-shifting and multicolor fluorescence enhances encryption complexity through multi-layered protection.4D-printed fluorescent hydrogels enable this bimodal spatiotemporal strategy,preventing unautho-rized access while enabling novel secure storage approaches.展开更多
Digital light processing(DLP)is a crucial additive manufacturing(AM)technique for producing high-precision ceramic com-ponents.This study aims to optimize the formulation of Si_(3)N_(4)slurry to enhance both its perfo...Digital light processing(DLP)is a crucial additive manufacturing(AM)technique for producing high-precision ceramic com-ponents.This study aims to optimize the formulation of Si_(3)N_(4)slurry to enhance both its performance and manufacturability in the DLP process,and investigate key factors such as particle size distribution,photopolymer resin monomer ratios,and dispersant types to im-prove the slurry’s rheological properties.Through these optimizations,a photosensitive Si_(3)N_(4)slurry with 50vol%solid content was de-veloped,exhibiting excellent stability,and low viscosity(2.48 Pa·s at a shear rate of 12.8 s^(-1)).The effects of gas-pressure sintering on the material’s phase composition,microstructure,and mechanical properties were further explored,revealing that this technique significantly increases the flexural strength of the green sample from(109±10.24)to(618±42.15)MPa.The sintered ceramics exhibited high hard-ness((16.59±0.05)GPa)and improved fracture toughness((4.45±0.03)MPa·m^(1/2)).Crack trajectory analysis revealed that crack deflec-tion,crack bridging,and the pull-out of rod-likeβ-Si_(3)N_(4)grains,are the main toughening mechanisms,which could effectively mitigate crack propagation.Among these mechanisms,crack deflection and bridging were particularly influential,significantly enhancing the frac-ture toughness of the Si_(3)N_(4)matrix.Overall,this research highlights how monomer formulation and gas-pressure sintering strengthen the performance of Si_(3)N_(4)slurry in the DLP three-dimensional printing technique.This work is expected to provide new insights for fabricat-ing complex Si_(3)N_(4)ceramic components with superior mechanical properties.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.52025053 and 52235006)the Jilin Provincial Scientific and Technological Development Program(20220204119YY)the Natural Science Foundation of Shandong Province(ZR2023ME154)。
文摘Ceramic 4D printing,which integrates dynamic deformation with additive manufacturing,demonstrates significant potential in intelligent manufacturing,on-demand shaping of complex structures,and multifunctional device development.Its core advantage lies in endowing materials with environmentally responsive dynamic deformation capabilities.However,current technologies still face limitations in responsiveness,reversibility,and mechanical performance.To address these challenges,this study proposes a programmable ceramic precursor system based on synergistic reinforcement of phase-separating hydrogels and shape memory polymers,combined with a nano-ceramic particle enhancement strategy.Using stereolithography 3D printing,high-precision fabrication of complex structures was achieved.By adjusting precursor composition,programming time,and structural thickness,the phase-separation kinetics-driven delayed recovery mechanism was elucidated,enabling precise control over recovery onset time.Furthermore,the thermal response mechanism of the precursor materials is explored,along with their potential for multi-shape transformation in biomedical applications,which is further extended to shape memory polymer systems.By employing a layered printing strategy,the autonomous reversible deformation of ceramic precursors is realized,providing new possibilities for specific applications.
基金the National Natural Science Foundation of China(Nos.52105421 and 52373050)the Guangdong Provincial Natural Science Foundation,China(No.2022A1515011621)+1 种基金the Science and Technology Projects in Guangzhou,China(Nos.202102080330 and 2024A04J6446)the Fundamental Research Funds for the Central Universities,Sun Yat-sen University(No.22qntd0101).
文摘Wireless millirobots engineered to infiltrate intricate vascular networks within living organisms,particularly within constricted and confined spaces,hold immense promise for the future of medical treatments.However,with their multifaceted and intricate designs,some robots often grapple with motion and functionality issues when confronted with tight spaces characterized by small cross-sectional dimensions.In this study,drawing inspiration from the high aspect ratio and undulating swimming patterns of snakes,a millimeter-scale,snake-like robot was designed and fabricated via a combination of extrusion-based four-dimensional(4D)printing and magnetic-responsive intelligent functional inks.A sophisticated motion control strategy was also developed,which enables the robots to perform various dynamic movements,such as undulating swimming,precise turns,graceful circular motions,and coordinated cluster movements,under diverse magnetic field variations.As a potential application,the snake robot can navigate and release drugs in a model coronary intervention vessel with tortuous channels and fluid filling.The novel design and promising applications of this snake robot are invaluable tools in future medical surgeries and interventions.
基金financially supported by the National Natural Science Foundation of China(Nos.52103145 and 11832007)Science&Technology Department of Sichuan Province(No.2025ZNSFSC0352)State Key Laboratory of Polymer Materials Engineering(No.sklpme-2024-1-03)。
文摘Liquid crystal elastomers(LCEs)exhibit exceptional reversible deformation and unique physical properties owing to their order-disorder phase transition under external stimuli.Among these deformations,helical structures have attracted attention owing to their distinctive configurations and promising applications in biomimetics and microelectronics.However,the helical deformation behavior of fiber actuators is critically influenced by their morphologies and alignments;yet,the underlying mechanisms are not fully understood.Through a two-step azaMichael addition reaction and direct ink writing(DIW)4D printing technology,fiber-based LCE actuators with a core-sheath alignment structure were fabricated and exhibited reversible helical deformation upon heating.By adjusting the printing parameters,the filament number,width,thickness,and core-sheath structure of the fiber actuators can be precisely controlled,resulting in deformation behaviors,such as contraction,bending,and helical twisting.Finite element simulations were performed to investigate the deformation behaviors of the fiber actuators,providing insights into the variations in stress and strain during the shape-changing process,which can be used to explain the shape-morphing mechanism.These findings demonstrate that the precise tuning of printing parameters enables the controllable construction of LCE actuator morphology and customization of their functional properties,paving the way for advanced applications in smart fabrics,biomedical engineering,and flexible electronics.
基金supported by National Natural Science Foundation of China(Grant Nos.51935012,52005481)LICP Cooperation Foundation for Young Scholars(Grant No.HZJJ22-11)+1 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB0470303)Major Program of the Lanzhou Institute of Chemical Physics,CAS(Grant No.ZYFZFX-7).
文摘“Life”represents a distinctive attribute inherent to organisms in nature,evident in their capacity to actively adapt to changes in their environment.In contrast to the static and intricate constructs of additive manufacturing(AM),the dynamic structure of 4D printing(4DP)adeptly integrates AM technology,responsive mechanisms,and external stimuli,imbuing it with a semblance of“life.”This fusion significantly broadens its functional applica-tions across biomedicine,actuators,and metamaterials.The escalating demand across diverse fields necessitates heightened criteria for 4DP,encompassing rapid response,multi-stimulus response,large shape change,and specific mechanical properties(e.g.,high strength,high modulus)capable of accommodating varying environ-mental conditions.In recent years,shape memory polymers(SMPs)have garnered increasing attention among 4DP researchers due to their ease of design and preprogramming at the molecular level,facilitating controlled transformations along predictable pathways.However,4DP of high-strength SMPs,as an indispensable part of the high-performance field,is full of challenges because the intrinsic properties of the raw materials are not well compatible with the printing principle and the printed configuration is not flexible enough.Consequently,this paper provides a concise overview of the response mechanisms and applications of five prominent high-strength SMPs utilized in 4DP:epoxy resin,poly(ether-ether-ketone),polyimide,polylactic acid,and polyurethane.Ad-ditionally,it delves into the associated challenges and prospects,offering researchers valuable insights into the potential value of high-strength SMPs within the domain of 4DP.
基金supported by the National Natural Science Foundation of China,Nos.81930070(to SF),82002309(to ZS)the Tianjin Key Medical Discipline(Specialty)Construct Project,No.TJYXZDXK-027A(to SF)a grant from Tianjin Institute of Orthopedic Innovation and Transformation(to SF).
文摘Three-dimensional(3D)-printed hydrogel scaffolds are widely used in spinal cord injury repair,with gelatin methacrylate being particularly favored owing to its excellent biocompatibility.However,traditional scaffolds have a small contact area with tissues and lack the ability to regulate the inflammatory microenvironment.Therefore,there is a need to develop smart scaffolds with drug delivery and immune regulation functions.In this study,a 3D-printed gelatin methacrylate scaffold was developed to deliver interferon regulatory factor 4 in a targeted and sustained manner.The scaffold showed good mechanical properties,biocompatibility,and sustained interferon regulatory factor 4 release.The sustained-release interferon regulatory factor 4 competitively bound to myeloid differentiation factor 88 to inhibit the pro-inflammatory effects of interferon regulatory factor 5,and activated the signal transducer and activator of transcription 6 pathway to promote M2 macrophage polarization,thereby facilitating neural regeneration and recovery of spinal cord function.This indicates that the constructed interferon regulatory factor 4-loaded 3D-printed methyl acrylate-modified gelatin scaffold can regulate macrophage polarization through the interferon regulatory factor 4/5 axis,improve the inflammatory microenvironment after spinal cord injury,and thus provide a new target for promoting neural regeneration.
基金supported by the National Natural Science Foundation of China(No.82272297).
文摘Abnormal wound scarring often leads to functional impairments and cosmetic deformities,primarily driven by the prolonged activation of the TGF-β/Smad signaling pathway.Addressing this challenge,we developed a biomimetic scaffold aimed at facilitating rapid and scarless wound healing.This highly in-tegrated 3D-printed dermal scaffold comprised modified recombinant human type III collagen(rhCOLIII-MA),gelatin methacrylate(GelMA),and liposomes encapsulating SB431542 to target TGF-β1(Lip@SB).The rhCOLIII-MA/GelMA(CG)scaffold retained inherent biomaterial characteristics,exhibited tailored physicochemical properties,and demonstrated favorable biocompatibility.Moreover,the Lip@SB-loaded CG scaffold(CGL)effectively promoted in vitro wound healing,while enabling controlled release of SB431542 to inhibit pathological collagen deposition.In a full-thickness skin defect rat model,the CGL dermal scaffold combined with split-thickness skin graft(STSG)minimized scar contraction,stimulated functional neovascularization,and enhanced graft aesthetics comparable to normal skin.Remarkably,the performance of the CGL scaffold surpassed that of commercially available anti-scarring alternatives.This innovative strategy presents a straightforward approach toward scarless skin regeneration and holds promise in alleviating the prolonged,painful postoperative rehabilitation.
基金supported by National Natural Science Foundation of China(12304482)Guizhou Provincial Basic Research Program(Natural Science,ZK[2022]Major Project 029 and ZD[2025]025)Fund Project of Guizhou Minzu University(4D Printing Smart Materials Technological Innovative Talents Team,GZMUZK[2023]CXTD01).
文摘The development of advanced information storage materials with spatiotemporal security features is critical to address the growing demand for high-level encryption and anti-counterfeiting protection.Herein,two types of 4D-printed fluorescent hydrogels that exhibit time-gated hierarchical morphing and color-varying dual functions,driven solely by temperature,have been successfully developed.Specifically,for the first one,the target blooming state of Hydrogels A is realized under 365 nm UV light through synchronized hierarchical morphing and graded fluorescence color transition(orange→blue).For the second one,under 254 nm UV irradiation,doped Hydrogels B exhibit reversible hierarchical state switching between bloomed and closed configurations,accompanied by dynamic multicolor fluorescence modulation.These promising results originate from spatially gradient crosslinking networks precisely engineered via vat photopolymerization(VP)3D printing,and specially-designed luminescent chromophores,collectively enabling fluorescent hydrogels to achieve an all-in-one stimulus response integrating“shape morphing—multicolor fluorescence—information encryption”under thermal activation.Thus,a unique“codebook”—a time-dependent dual-parameter encryption system can be developed using these 4D-printed fluorescent hydrogels,by dynamically adjusting bending angles and fluorescence ratios,effectively enabling high-security spatiotemporal information protection.The integration of time-gated shape-shifting and multicolor fluorescence enhances encryption complexity through multi-layered protection.4D-printed fluorescent hydrogels enable this bimodal spatiotemporal strategy,preventing unautho-rized access while enabling novel secure storage approaches.
基金supported in part by the National Natural Science Foundation of China.(Nos.62461160259,92360307 and 92267103).
文摘Digital light processing(DLP)is a crucial additive manufacturing(AM)technique for producing high-precision ceramic com-ponents.This study aims to optimize the formulation of Si_(3)N_(4)slurry to enhance both its performance and manufacturability in the DLP process,and investigate key factors such as particle size distribution,photopolymer resin monomer ratios,and dispersant types to im-prove the slurry’s rheological properties.Through these optimizations,a photosensitive Si_(3)N_(4)slurry with 50vol%solid content was de-veloped,exhibiting excellent stability,and low viscosity(2.48 Pa·s at a shear rate of 12.8 s^(-1)).The effects of gas-pressure sintering on the material’s phase composition,microstructure,and mechanical properties were further explored,revealing that this technique significantly increases the flexural strength of the green sample from(109±10.24)to(618±42.15)MPa.The sintered ceramics exhibited high hard-ness((16.59±0.05)GPa)and improved fracture toughness((4.45±0.03)MPa·m^(1/2)).Crack trajectory analysis revealed that crack deflec-tion,crack bridging,and the pull-out of rod-likeβ-Si_(3)N_(4)grains,are the main toughening mechanisms,which could effectively mitigate crack propagation.Among these mechanisms,crack deflection and bridging were particularly influential,significantly enhancing the frac-ture toughness of the Si_(3)N_(4)matrix.Overall,this research highlights how monomer formulation and gas-pressure sintering strengthen the performance of Si_(3)N_(4)slurry in the DLP three-dimensional printing technique.This work is expected to provide new insights for fabricat-ing complex Si_(3)N_(4)ceramic components with superior mechanical properties.
