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Nano Life · 2021 · IF 0

4D Printing of Self-Folding Hydrogel Tubes for Potential Tissue Engineering Applications

Yu-Dong Zhao,Jia-Hui Lai,Min Wang

In recent years, 4D printing has gained increasing attention in the tissue engineering field since this advanced manufacturing platform can create stimulus-responsive structures, which can change their shapes, functions, and/or properties when appropriate external stimulus/stimuli is/are applied. A number of hydrogels with swellable/shrinkable abilities have been explored for 4D printing to fabricate different shape-morphing structures for tissue engineering. Among them, gelatin methacryloyl (GelMA) has been 4D printed, which can self-fold into microtubular structures. Currently, the self-folding ability of 4D printed GelMA hydrogels is mainly based on the different cross-linking degrees (which control and govern the swelling degrees) across the thickness of hydrogels. However, this strategy alone can only form self-folding GelMA tubes with diameters at the micrometer level and cannot create self-folding GelMA tubes with diameters at the millimeter level, which is mainly due to the insufficient internal force generated in 4D printed GelMA hydrogels when they are exposed to water. To overcome this limitation, this study has investigated a new strategy to fabricate self-folding GelMA tubes with large diameters at the millimeter level for tissue engineering applications. The new strategy introduced a cross-linking degree gradient across the GelMA plane in addition to its thickness by printing a second layer of strips on the first 4D printed GelMA film. In the aqueous environment, under the current fabrication condition, such bilayer GelMA hydrogels could self-fold into tubes of larger diameters up to 6 mm. The in vitro release behavior of heparin incorporated into the 4D printed GelMA was also studied. It was shown that heparin release could be controlled by the GelMA concentration and heparin content in 4D printed GelMA. The 4D printed GelMA hydrogels with the improved self-folding ability and controlled release of a drug are promising for targeted tissue engineering applications.

研究领域: 生物医学工程 · 材料科学 · 组织工程
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Photo/thermal dual-responsive azobenzene-based photosensitive resin for 4D printing

Yuan Cao,Yao Wu,Yiming Huang,Hongping Xiang,Lanyue Zhang

4D printing, combining the advantages of 3D printing and stimuli-responsive materials, provides a precise and rapid fabrication method for complex-shaped smart objects. In this study, the photoisomerization characteristic of azobenzene is used to develop 4D printable resins composed of azobenzene-based acrylates (AZO) and other acrylate compounds, which can be UV-cured and 3D printed into objects with photo and thermal dual responsiveness. UV-curing kinetics reveal that AZO competes with the photoinitiator for photons during photopolymerization, reducing the generation of reactive oxygen species and subsequently affecting the mechanical properties of UV-cured resin. The optimum content of AZO in 4D printing resins is 0.5 wt%, producing 3D printed objects with excellent mechanical properties, including a maximum stress of 25.2 MPa and a strain of 100 %. This ensures the successful formation of complex-shaped objects in the 3D printing process. Moreover, the objects printed with this photosensitive resin demonstrate exceptional shape memory capabilities, achieving a 100 % shape recovery ratio over three cycles of thermal stimulation. The printed openwork spheroid with a concave shape can successfully revert to its original form after 48 s of irradiation with 365 nm UV light. The degree of shape recovery can be precisely controlled by adjusting the UV irradiation time and position. Therefore, these photo/thermal dual-responsive 4D objects show great application prospects in medical devices and smart materials.

研究领域: 材料科学 · 化学工程
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Lightweight and geometrically complex ceramics derived from 4D printed shape memory precursor with reconfigurability and programmability for sensing and actuation applications

Siyao Chen,Jinping Li,Haofan Shi,Xuliang Chen,Guo Liu,Songhe Meng,Jian Lu

There is growing interest in additive manufacturing (AM) of ceramics due to the feasibility of achieving geometrically complex shapes for various engineering applications. Polymer-derived ceramics (PDCs), pyrolyzed from polymeric ceramic precursors, act as a competitive material for ceramic AM with advantages such as easy processability, flexible designability, and relatively low sintering temperature. However, the functionality of preceramic polymers is far from being fully exploited, thus restricting the development and applications of 3D printed ceramics. Herein, a novel multifunctional preceramic polymer composite with reconfigurability and shape memory effect is synthesized. By tuning the material compositions, the precursor inks suitable for 4D printing are pyrolyzed into lightweight self-shaping ceramics, allowing complex geometries to be fabricated. The preceramic polymers undergo a stepwise partial-to-full crosslinking process to form interpenetrating polymer networks , resulting in reconfigurability where the as-printed parts can be transformed into shapes with higher complexity. Unlike traditional precursors with static shapes, the precursor here possesses shape memory capability ( T g  ∼ 95 °C). During the sintering process, the 3D printed precursor could successively undergo programmable active shape transformation with a high recovery ratio (∼100 %) and pyrolysis conversion into lightweight ceramics (1.05 g/cm 3 ). By exploring the semiconducting behavior of resulting ceramics, temperature sensors leveraging the advantages of reshaping are designed to detect the surface over a wide range (25–750 °C) with good conformability. The development of 4D printed reconfigurable and programmable precursors for the construction of complex ceramics enriches both the complexity and self-shaping capability of ceramics, allowing them to be applied as smart thermistors and deployable structures.

CAS / MDL: 1675-54-3 19438-60-9
研究领域: 材料科学 · 智能材料 · 增材制造
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BIOMACROMOLECULES · 2022 · IF 6.978

Structurally Dynamic Gelatin-Based Hydrogels with Self-Healing, Shape Memory, and Cytocompatible Properties for 4D Printing

Ziyan Wang,Jieyu Gu,Difei Zhang,Yan Zhang,Jinghua Chen

Three-dimensional (3D) printable hydrogels with a shape memory effect have emerged as a new class of 4D printing materials recently and found wide applications in various fields. However, synergistically endowing such materials with good mechanical strength and biocompatibility for biomedical uses remains challenging. In this study, a series of multiresponsive hydrogels have been prepared through a dynamic covalent imine/Diels–Alder network from biocompatible starting materials of modified gelatin and poly(ethylene glycol)-based polymers. By further secondary crosslinking with a hyperbranched triethoxysilane reagent (HPASi) that contains multiple supramolecular hydrogen bonding, the hydrogels presented a strengthened self-healing and temperature-responsive shape memory effect. With the additional features of superior stretchability (elongation at break up to 523%), good cytocompatibility, and 3D printable properties, these multifunctional hydrogels showed great potential for broad biomedical applications.

CAS / MDL: 9000-70-8
研究领域: 生物材料学 · 组织工程 · 再生医学
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Small · 2023 ·Vol. 19 ·期 42 ·2302656 · IF 13.3

A 4D-Printing Inverse Design Strategy for Micromachines with Customized Shape-Morphing

Jingang Wang,Yuzhao Zhang,Jianchen Zheng,Xiubao Zhao,Hongji Guo,Ye Qiu,Xiaoduo Wang,Lianqing Liu,Haibo Yu

An active heterostructure with smart-response material used as “muscle” and inactive material as “skeleton” can deform over time to respond to external stimuli. 4D printing integrated with two-photon polymerization technology and smart material allows the material or characteristic distribution of active heterostructures to be defined directly at the microscale, providing a huge programmable space. However, the high degree of design freedom and the microscale pose a challenge to the construction of micromachines with customized shape morphing. Here, a reverse design strategy based on multi-material stepwise 4D printing is proposed to guide the structural design of biomimetic micromachines. Inspired by the piecewise constant curvature model of soft robot, a reverse design algorithm based on the Timoshenko model is developed. The algorithm can approximate 2D features to a constant-curvature model and determine an acceptable material distribution within the explored printing range. Three Chinese “Long” (Chinese dragon heralds of good fortune) designed by the strategy can deform to the customized shape. In addition, a microcrawler printed using this method can imitate a real inchworm gait. These results demonstrate that this method can be an efficient tool for the action or shape design of bionic soft microrobots or micromachines with predetermined functions.

研究领域: 材料科学 · 生物仿生学 · 微纳米技术
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Nano-Micro Letters · 2024 ·Vol. 17 ·期 1 ·1-14 · IF 31.6

Nanograting-Based Dynamic Structural Colors Using Heterogeneous Materials

Wang Jingang,Yu Haibo,Zheng Jianchen,Zhang Yuzhao,Guo Hongji,Qiu Ye,Wang Xiaoduo,Yang Yongliang,Liu Lianqing

A 2.5-dimensional dynamic structural color based on nanogratings of heterogeneous materials was proposed by interweaving a pH-responsive hydrogel with IP-L photoresist. The nanogrid structures exhibit brilliant tuneable structural color, high sensitivity, and ultrafast recovery speeds in response to pH. The 4D printing-based grayscale design approach was proposed for the patterned encoding and array printing of dynamic structural colors, promoting their application in patterned printing, information encryption, and microfluidic chip sensing.

研究领域: 材料科学 · 光学 · 生物医学工程
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ADVANCED FUNCTIONAL MATERIALS · 2025 · IF 19

Dynamic Boronate Ester Chemistry Facilitating 3D Printing Interlayer Adhesion and Modular 4D Printing of Polylactic Acid

Wenjun Peng,Hanxin Xia,Jingjun Wu,Zizheng Fang,Xianming Zhang

3D printing, such as fused deposition modeling (FDM), is an advanced 3D shaping technology, employing a layer-by-layer process to construct 3D objects. However, the weak interlayer bonding restricts the performance and functionality of FDM-fabricated parts. Herein, boronate bond exchange is utilized to enhance interlayer mechanical strength and enable modular 4D printing of polylactic acid (PLA). Blending the dynamic system endows PLA with improved interlayer adhesion and welding capabilities. The blended filaments demonstrate excellent printability, with a 150% enhancement in Z-axis interlayer strength, while nearly unchanged along the X-axis. Moreover, this enhanced interlayer bonding facilitates the modular assembly of intricate structures, eliminating the need for traditional 3D-printed supports. Combined with shape memory effects, diverse modular 4D printing possibilities are demonstrated. This strategy highlights the potential of dynamic covalent bonds in 3D printing, enhancing not only material performance but also intelligent designs.

CAS / MDL: 4612-26-4
研究领域: 材料科学 · 化学工程 · 智能制造
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ADVANCED FUNCTIONAL MATERIALS · 2025 · IF 19

4D Printed Cardiac Occlusion Device with Efficient Anticoagulation, Proendothelialization, and Precise Localization

Mengjiao Yang,Yingjie Xu,Xiaozhou Xin,Chengjun Zeng,Yuanshi Li,Cheng Lin,Yanju Liu,Yuanyuan Guo,Jinsong Leng

Congenital heart defects (CHDs) are one of the most common congenital malformations, accounting for ≈30% of all congenital malformations. Interventional implantation of occlusion devices is becoming the preferred treatment for CHDs. However, current occlusion devices suffer from serious problems, such as thrombosis, slow endothelialization, imprecise localization, abrasion, displacement, etc. Here, a multifunctional drug-carrying fiber platform with structural similar to the extracellular matrix is innovatively designed to develop 4D printed cardiac occlusion devices, with characteristics of efficient anticoagulation, proendothelialization, and precise localization. Biomimetic ligament structures are designed to achieve a similar mechanical response to myocardial tissue, which helps to synergize deformation and reduce tissue wear. A structural design method for biomimetic personalized multilevel occlusion devices is proposed, facilitating further improvement of sealing reliability. The radiopaque 4D printed shape memory composites are developed, realizing the complete visualization and precise localization of the device in vivo. The novel 4D printed cardiac occlusion device provides an effective way to reduce the risk of complications and contributes to versatility. It is expected to be a next-generation multifunctional repair device for personalized treatment of CHDs.

CAS / MDL: 25322-68-3
研究领域: 生物医学工程 · 心血管病学
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Matter · 2020 · IF 0

Modular 4D Printing via Interfacial Welding of Digital Light-Controllable Dynamic Covalent Polymer Networks

Zizheng Fang,Huijie Song,Yue Zhang,Binjie Jin,Jingjun Wu,Qian Zhao,Tao Xie

Summary Advanced multifunctional devices increasingly rely on challenging complex shapes for their functions. 3D printing offers a solution but is often limited by the fabrication speed and/or material diversity. 4D printing based on digitally controlled 2D-to-3D transformation is advantageous in speed, but the accessible shapes are limited and integration of multiple materials is difficult. We report herein a concept that significantly extends the technological scope by combining 4D printing with modular assembly. Specifically, 4D photo-printed structures based on dynamically crosslinked polymers can be assembled in a modular fashion by interfacial bond exchange. Complex 3D objects with tailorable multiple materials can consequently be produced. This allows the fabrication of sophisticated shape-memory devices including a 3D Miura-patterned structure with zero Poisson's ratio and a Kresling-patterned cylindrical structure with superior mechanical stability. Our approach extends the possibilities for the future development of multifunctional devices with seamless integration of material, structure, and function.

研究领域: 材料科学 · 先进制造 · 高分子化学 · 机械工程
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Additive Manufacturing · 2024 · IF 10.3

Breaking the limitation of terahertz resonances in ferrites through 4D printing of metamaterials

Xinxi Zeng,Pingfan Jia,Desheng Pan,Yunlong Guo,Xiaoqing Xi,Peipei Li,Lingyun Qian,Chaoyang Sun,Ying Li,Bo Li,Ji Zhou

4D printing allows the creation of 3D-printed structures with a variety of new functionalities that respond to external stimuli, including electromagnetic properties, for which research is limited, such as terahertz resonances in ferrite materials; and therefore holding great promise for a wide range of applications. However, the limited physical properties of ferrite materials, including their anisotropic properties and limited material manipulation space, pose significant challenges to the development of ferrite materials designed for progressively increasing terahertz frequencies. Therefore, this paper proposes a platform for overcoming the limitations of terahertz resonance in ferrites through the 4D printing of metamaterials. Both the elastic and viscous moduli of the slurry are sensitive to the applied shear stress; as this stress increases, these moduli sharply decrease by several orders of magnitude, resulting in the transformation of the slurry into a fluid state similar to the liquefaction of ink. Electromagnetic coupling modes between electric dipoles and magnetic dipoles endow these ferrite metamaterials with induction and switching of terahertz resonances due to orientation stimulation. Our work sheds light on the creation of electromagnetic properties and their control by 4D printing.

CAS / MDL: 1309-37-1
研究领域: 材料科学 · 电磁学 · 物理学
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Additive Manufacturing · 2024 · IF 10.3

4D-Printed micro-tentacles exhibiting wide-spectrum deformability

Jingang Wang,Yuzhao Zhang,Jianchen Zheng,Hongji Guo,Ye Qiu,Xiaoduo Wang,Lianqing Liu,Haibo Yu

It has been widely reported that untethered micro-robots can access hard-to-reach regions within the body to perform a range of medical procedures. However, the narrow operating space limits the ability of such micro-robots to interact with the external environment. Here, inspired by chameleons, we propose a prehensile micro-tentacle with wide-spectral deformability using the micro four-dimensional (4D)-printing technology. The design procedure includes programmable design material distribution and the integration of pH-responsive hydrogels and photoresists via the two-photon polymerization (TPP) process to build pH-responsive actuated joints . The resulting micro-tentacles were able to wrap objects located within a range of >12 times their own volume, wherein the theoretical size range of these entangled objects was found to range from 6.5 to 40 µm. Furthermore, we demonstrate the cell-capturing characteristics of micro-tentacles and confirm their ability to anchor onto specific objects. Such micro-tentacles with a large graspable space and an excellent shape adaptability could be easily integrated into untethered micro-robots in the future, paving the way for their medical application in complex biological environments.

研究领域: 生物医学工程 · 材料科学 · 微纳米技术
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JOURNAL OF FOOD ENGINEERING · 2024 · IF 5.3

4D printing of Pickering emulsion: Temperature-driven color changes

Ziang Guo,Bingxue Yang,Nini Liang,Xiaowei Huang,Jiyong Shi,Zhihua Li,Paraskevi Paximada,Zou Xiaobo

Pickering emulsion inks were employed to demonstrate the temperature-driven 4D printing method. The Pickering emulsion consisted of water phase containing NaHCO 3 and oil phase containing curcumin. Upon heating, the movement of pigment molecules was induced, resulting in color changes. The formation mechanism, rheological properties, printing properties and color changes of Pickering emulsion as well as the release kinetic mechanism of curcumin were investigated. The results indicated that relationships were also established between quantified color values (L*, a*, b*) and heating time. Moreover, the release of the curcumin in the Pickering emulsion, which was designated as a swelling process, followed the non-Fickian mechanism due to the occurrence of diffusion and erosion. The Hixson-Crowell model exhibited the highest linearity (R 2 : 0.9430 to 0.9825) of Pickering emulsions. In conclusion, the research offers a new perspective for the development of personalized Pickering emulsion food with bright colors.

CAS / MDL: 9004-32-4
研究领域: 食品科学 · 材料科学
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