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1.
Schubert and co‐workers have performed a detailed investigation on ink‐jet printing of well‐defined dots of luminescent CdTe nanocrystals (NCs) embedded in a poly(vinyl alcohol) matrix, as reported on p. 23, and subsequently made studies of their morphology and photoluminescence. The inside cover shows a photograph of an ink‐jet‐printed combinatorial library of differently sized CdTe NCs emitting at different wavelengths, and a 3D profilometer image of an array of printed dots. Inkjet printing is used to produce well‐defined patterns of dots (with diameters of ca. 120 μm) that are composed of luminescent CdTe nanocrystals (NCs) embedded within a poly(vinylalcohol) (PVA) matrix. Addition of ethylene glycol (1–2 vol %) to the aqueous solution of CdTe NCs suppresses the well‐known ring‐formation effect in inkjet printing leading to exceptionally uniform dots. Atomic force microscopy characterization reveals that in the CdTe NC films the particle–particle interaction could be prevented using inert PVA as a matrix. Combinatorial libraries of CdTe NC–PVA composites with variable NC sizes and polymer/NC ratios are prepared using inkjet printing. These libraries are subsequently characterized using a UV/fluorescence plate reader to determine their luminescent properties. Energy transfer from green‐light‐emitting to red‐light‐emitting CdTe NCs in the composite containing green‐ (2.6 nm diameter) and red‐emitting (3.5 nm diameter) NCs are demonstrated.  相似文献   

2.
Biocompatible hydrogel inks with shear‐thinning, appropriate yield strength, and fast self‐healing are desired for 3D bioprinting. However, the lack of ideal 3D bioprinting inks with outstanding printability and high structural fidelity, as well as cell‐compatibility, has hindered the progress of extrusion‐based 3D bioprinting for tissue engineering. In this study, novel self‐healable pre‐cross‐linked hydrogel microparticles (pcHμPs) of chitosan methacrylate (CHMA) and polyvinyl alcohol (PVA) hybrid hydrogels are developed and used as bioinks for extrusion‐based 3D printing of scaffolds with high fidelity and biocompatibility. The pcHμPs display excellent shear thinning when injected through a syringe and subsequently self‐heal into gels as shear forces are removed. Numerical simulations indicate that the pcHμPs experience a plug flow in the nozzle with minimal disturbance, which favors a steady and continuous printing. Moreover, the pcHμPs show a self‐supportive yield strength (540 Pa), which is critical for the fidelity of printed constructs. A series of biomimetic constructs with very high aspect ratio and delicate fine structures are directly printed by using the pcHμP ink. The 3D printed scaffolds support the growth of bone‐marrow‐derived mesenchymal stem cells and formation of cell spheroids, which are most important for tissue engineering.  相似文献   

3.
Inkjet printing is used to produce well‐defined patterns of dots (with diameters of ca. 120 μm) that are composed of luminescent CdTe nanocrystals (NCs) embedded within a poly(vinylalcohol) (PVA) matrix. Addition of ethylene glycol (1–2 vol %) to the aqueous solution of CdTe NCs suppresses the well‐known ring‐formation effect in inkjet printing leading to exceptionally uniform dots. Atomic force microscopy characterization reveals that in the CdTe NC films the particle–particle interaction could be prevented using inert PVA as a matrix. Combinatorial libraries of CdTe NC–PVA composites with variable NC sizes and polymer/NC ratios are prepared using inkjet printing. These libraries are subsequently characterized using a UV/fluorescence plate reader to determine their luminescent properties. Energy transfer from green‐light‐emitting to red‐light‐emitting CdTe NCs in the composite containing green‐ (2.6 nm diameter) and red‐emitting (3.5 nm diameter) NCs are demonstrated.  相似文献   

4.
Direct ink writing (DIW) provides programmable and customizable platforms to engineer hierarchically organized constructs. However, one‐step, facile synthesis of such architectures via DIW has been challenging. This study introduces inks based on two‐phase emulgels for direct printing and in situ formation of protecting layers enveloping multicomponent cores, mimicking skin‐bearing biological systems. The emulgel consists of a Pickering emulsion with an organic, internal phase containing poly(lactic acid) stabilized by chitin/cellulose nanofibers and a continuous, cross‐linkable hydrogel containing cellulose nanofibers and any of the given solid particles. The shear during ink extrusion through nozzles of low surface energy facilitates the generation of the enveloped structures via fast and spontaneous phase separation of the emulgel. The skin‐bearing architectures enable control of mass transport as a novel configuration for cargo release. As a demonstration, a hydrophilic molecule is loaded in the hydrogel, which is released through the core and skin, enabling regulation of diffusion and permeation phenomena. This 3D‐printed functional material allows independent control of strength owing to the hierarchical construction. The new method of fabrication is proposed as a simple way to achieve protection, regulation, and sensation, taking the example of the functions of skins and cuticles, which are ubiquitous in nature.  相似文献   

5.
Engineering colloidal gel inks with suitable features for fabricating robust supraparticle architectures through 3D printing may overcome the challenges of precisely controlling nanoparticles spatial distribution across multiple scales. Herein, oppositely charged proteinaceous-polymeric nanoparticles are combined to generate multi-component colloidal gel (COGEL) inks for fabricating supraparticle volumetric architectures. Leveraging on different nano-functional units, double-interlinked supraparticle assemblies are established via electrostatic interactions and on-demand covalent photocrosslinking. The COGEL inks are readily processable through in-air extrusion 3D printing, forming stable colloidal filaments. 3D printing yielded architecturally defined and robust supraparticle constructs that supported human stem cells attachment and cytoskeletal spreading. Owing to double interparticle interlinks the fabricated supraparticle constructs remained stable under physiological conditions and high/low shear stress, improving over the lower mechanical stability of single-interlinked platforms. Double-interlinked COGELs are processable via suspension 3D printing, unlocking the freeform volumetric writing of nanoparticle inks in protein-based hydrogels volume. The dual-interlinked COGEL technology opens new possibilities for generating user-defined supraparticle architectures with precise volumetric distribution of nanoparticles, both in-air and in-hydrogel platforms. The freedom to select modular multi-particle combinations, as well as the rapid 3D programming of COGEL inks, broadens the range of modular colloidal materials that can be fabricated for a variety of biomedical applications.  相似文献   

6.
Despite recent advances in clinical procedures, the repair of soft tissue remains a reconstructive challenge. Current technologies such as synthetic implants and dermal flap autografting result in inefficient shape retention and unpredictable aesthetic outcomes. 3D printing, however, can be leveraged to produce superior soft tissue grafts that allow enhanced host integration and volume retention. Here, a novel dual bioink 3D printing strategy is presented that utilizes synthetic and natural materials to create stable, biomimetic soft tissue constructs. A double network ink composed of covalently cross‐linked poly(ethylene) glycol and ionically cross‐linked alginate acts as a physical support network that promotes cell growth and enables long‐term graft shape retention. This is coupled with a cell‐laden, biodegradable gelatin methacrylate bioink in a hybrid printing technique, and the composite scaffolds are evaluated in their mechanical properties, shape retention, and cytotoxicity. Additionally, a new shape analysis technique utilizing CloudCompare software is developed that expands the available toolbox for assessing scaffold aesthetic properties. With this dynamic 3D bioprinting strategy, complex geometries with robust internal structures can be easily modulated by varying the print ratio of nondegradable to sacrificial strands. The versatility of this hybrid printing fabrication platform can inspire the design of future multimaterial regenerative implants.  相似文献   

7.
A new class of thermoplastic elastomers has been created by introducing nanoscale‐dispersed lignin (a biomass‐derived phenolic oligomer) into nitrile rubber. Temperature‐induced controlled miscibility between the lignin and the rubber during high shear melt‐phase synthesis allows tuning the material's morphology and performance. The sustainable product has unprecedented yield stress (15–45 MPa), strain hardens at large deformation, and has outstanding recyclability. The multiphase polymers developed from an equal‐mass mixture of a melt‐stable lignin fraction and nitrile rubber with optimal acrylonitrile content, using the method described here, show 5–100 nm lignin lamellae with a high‐modulus rubbery interphase. Molded or printed elastomeric products prepared from the lignin‐nitrile material offer an additional revenue stream to pulping mills and biorefineries.  相似文献   

8.
Dielectric elastomers are progressively emerging as one of the best‐performing classes of electroactive polymers for electromechanical transduction. They are used for actuation devices driven by the so‐called Maxwell stress effect. At present, the need for high‐driving electric fields limits the use of these transduction materials in some areas of potential application, especially in the case of biomedical disciplines. A reduction of the driving fields may be achieved with new elastomers offering intrinsically superior electromechanical properties. So far, most attempts in this direction have been focused on the development of composites between elastomer matrixes and high‐permittivity ceramic fillers, yielding limited results. In this work, a different approach was adopted for increasing the electromechanical response of a common type of dielectric elastomer. The technique consisted in blending, rather than loading, the elastomer (poly(dimethylsiloxane)) with a highly polarizable conjugated polymer (undoped poly(3‐hexylthiophene)). The resulting material was characterised by dielectric spectroscopy, scanning electron microscopy, tensile mechanical analysis, and electromechanical transduction tests. Very low percentages (1–6 wt %) of poly(3‐hexylthiophene) yielded both an increase of the relative dielectric permittivity and an unexpected reduction of the tensile elastic modulus. Both these factors synergetically contributed to a remarkable increase of the electromechanical response, which reached a maximum at 1 wt % content of conjugated polymer. Estimations based on a simple linear model were compared with the experimental electromechanical data and a good agreement was found up to 1 wt %. This approach may lead to the development of new types of materials suitable for several types of applications requiring elastomers with improved electromechanical properties.  相似文献   

9.
3D printing permits the construction of objects by layer‐by‐layer deposition of material, resulting in precise control of the dimensions and properties of complex printed structures. Although 3D printing fabricates inanimate objects, the emerging technology of 4D printing allows for animated structures that change their shape, function, or properties over time when exposed to specific external stimuli after fabrication. Among the materials used in 4D printing, hydrogels have attracted growing interest due to the availability of various smart hydrogels. The reversible shape‐morphing in 4D printed hydrogel structures is driven by a stress mismatch arising from the different swelling degrees in the parts of the structure upon application of a stimulus. This review provides the state‐of‐the‐art of 4D printing of hydrogels from the materials perspective. First, the main 3D printing technologies employed are briefly depicted, and, for each one, the required physico‐chemical properties of the precursor material. Then, the hydrogels that have been printed are described, including stimuli‐responsive hydrogels, non‐responsive hydrogels that are sensitive to solvent absorption/desorption, and multimaterial structures that are totally hydrogel‐based. Finally, the current and future applications of this technology are presented, and the requisites and avenues of improvement in terms of material properties are discussed.  相似文献   

10.
The fabrication of functional multilayered conjugated‐polymer structures with well‐defined organic‐organic interfaces for optoelectronic‐device applications is constrained by the common solubility of many polymers in most organic solvents. Here, we report a simple, low‐cost, large‐area transfer‐printing technique for the deposition and patterning of conjugated‐polymer thin films. This method utilises a planar poly(dimethylsiloxane) (PDMS) stamp, along with a water‐soluble sacrificial layer, to pick up an organic thin film (~20 nm to 1 µm) from a substrate and subsequently deliver this film to a target substrate. We demonstrate the versatility of this transfer‐printing technique and its applicability to optoelectronic devices by fabricating bilayer structures of poly(9,9‐di‐n‐octylfluorene‐alt‐(1,4‐phenylene‐((4‐sec‐butylphenyl)imino)‐1,4‐phenylene))/poly(9,9‐di‐n‐octylfluorene‐alt‐benzothiadiazole) (TFB/F8BT) and poly(3‐hexylthiophene)/methanofullerene([6,6]‐phenyl C61 butyric acid methyl ester) (P3HT/PCBM), and incorporating them into light‐emitting diodes (LEDs) and photovoltaic (PV) cells, respectively. For both types of device, bilayer devices fabricated with this transfer‐printing technique show equal, if not superior, performance to either blend devices or bilayer devices fabricated by other techniques. This indicates well‐controlled organic‐organic interfaces achieved by the transfer‐printing technique. Furthermore, this transfer‐printing technique allows us to study the nature of the excited states and the transport of charge carriers across well‐defined organic interfaces, which are of great importance to organic electronics.  相似文献   

11.
Additive manufacturing, i.e., 3D printing, is being increasingly utilized to fabricate a variety of complex‐shaped electronics and energy devices (e.g., batteries, supercapacitors, and solar cells) due to its excellent process flexibility, good geometry controllability, as well as cost and material waste reduction. In this review, the recent advances in 3D printing of emerging batteries are emphasized and discussed. The recent progress in fabricating 3D‐printed batteries through the major 3D‐printing methods, including lithography‐based 3D printing, template‐assisted electrodeposition‐based 3D printing, inkjet printing, direct ink writing, fused deposition modeling, and aerosol jet printing, are first summarized. Then, the significant achievements made in the development and printing of battery electrodes and electrolytes are highlighted. Finally, major challenges are discussed and potential research frontiers in developing 3D‐printed batteries are proposed. It is expected that with the continuous development of printing techniques and materials, 3D‐printed batteries with long‐term durability, favorable safety as well as high energy and power density will eventually be widely used in many fields.  相似文献   

12.
4D printing has attracted tremendous interest since its first conceptualization in 2013. 4D printing derived from the fast growth and interdisciplinary research of smart materials, 3D printer, and design. Compared with the static objects created by 3D printing, 4D printing allows a 3D printed structure to change its configuration or function with time in response to external stimuli such as temperature, light, water, etc., which makes 3D printing alive. Herein, the material systems used in 4D printing are reviewed, with emphasis on mechanisms and potential applications. After a brief overview of the definition, history, and basic elements of 4D printing, the state‐of‐the‐art advances in 4D printing for shape‐shifting materials are reviewed in detail. Both single material and multiple materials using different mechanisms for shape changing are summarized. In addition, 4D printing of multifunctional materials, such as 4D bioprinting, is briefly introduced. Finally, the trend of 4D printing and the perspectives for this exciting new field are highlighted.  相似文献   

13.
The development of transparent, conducting, and stretchable poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)‐based electrodes using a combination of a polyethylene oxide (PEO) polymer network and the surfactant Zonyl is reported. The latter improves the ductility of PEDOT:PSS and enables its deposition on hydrophobic surfaces such as polydimethylsiloxane (PDMS) elastomers, while the presence of a 3D matrix offers high electrical conductivity, elasticity, and mechanical recoverability. The resulting electrode exhibits attractive properties such as high electrical conductivity of up to 1230 S cm?1 while maintaining high transparency of 95% at 550 nm. The potential of the electrode technology is demonstrated in indium‐tin‐oxide (ITO)‐free solar cells using the PBDB‐T‐2F:IT‐4F blend with a power conversion efficiency of 12.5%. The impact of repeated stretch‐and‐release cycles on the electrical resistance is also examined in the effort to evaluate the properties of the electrodes. The interpenetrated morphology of the PEDOT:PSS and polyethylene oxide network is found to exhibit beneficial synergetic effects resulting in excellent mechanical stretchability and high electrical conductivity. By carefully tuning the amount of additives, the ability to detect small changes in electrical resistance as a function of mechanical deformation is demonstrated, which enables the demonstration of stretchable and resilient on‐skin strain sensors capable of detecting small motions of the finger.  相似文献   

14.
The limited range of mechanical responses achievable by materials compatible with additive manufacturing hinders the 3D printing of continuum soft robots with programmed motion. This paper describes the rapid design and fabrication of low‐density, 3D‐architected soft machines (ASMs) by combining Voronoi tessellation and additive manufacturing. On tendon‐based actuation, ASMs deform according to the topologically encoded buckling of their structure to produce a wide range of motions (contraction, twisting, bending, and cyclic motion). ASMs exhibiting densities as low as 0.094 g cm?3 (≈8% of bulk polymer) can be rapidly built by the stereolithographic 3D printing of flexible photopolymers or the injection molding of elastomers. The buckling of ASMs can be programmed by inducing gradients in the thickness of their flexible beams or by the localized enlargement of the Voronoi cells to generate complex motions such as multi‐finger gripping or quadrupedal locomotion. The topological architecture of these low‐density soft robots confers them with the stiffness necessary to recover their original shape even after ultrahigh compression (400%) and extension (500%). ASMs expand the range of mechanical properties currently achievable by 3D printed or molded materials to enable the fabrication of soft machines with auxetic mechanical metamaterial properties.  相似文献   

15.
Tissue engineering benefits from advances in 3D printing and multi-material assembly to attain certain functional benefits over existing man-made materials. Multilayered tissue engineering constructs might unlock a unique combination of properties, but their fabrication remains challenging. Herein, a facile process is reported to manufacture biomaterials with an engineered multilayer architecture, via a combination of co-extrusion and 3D printing. Polymer filaments containing 5, 17, or 129 alternating layers of poly(lactic acid)/thermoplastic polyurethane (PLA/TPU) are produced, and explored for their use in fused deposition modeling (FDM) to fabricate scaffolds for cardiomyocyte culture. The co-extruded filaments exhibit a layered architecture in their cross-section with a continuous interface, and the integrity and alignment of the layers are preserved after 3D printing. The 17 alternating layers PLA/TPU composites exhibit excellent mechanical properties. It is envisaged that the multilayered architecture of the fabricated scaffolds can be beneficial for aligning cardiomyocytes in culture. It is found that the 17 alternating layers PLA/TPU significantly improve cardiomyocyte morphology and functionality compared to single phase materials. It is believed that this biomaterials fabrication scheme, combining a top-down and bottom-up approach, offers tremendous flexibility in producing a broad class of novel-architectured materials with tunable structural design for tissue engineering applications and beyond.  相似文献   

16.
3D printing of renewable building blocks like cellulose nanocrystals offers an attractive pathway for fabricating sustainable structures. Here, viscoelastic inks composed of anisotropic cellulose nanocrystals (CNC) that enable patterning of 3D objects by direct ink writing are designed and formulated. These concentrated inks are composed of CNC particles suspended in either water or a photopolymerizable monomer solution. The shear‐induced alignment of these anisotropic building blocks during printing is quantified by atomic force microscopy, polarized light microscopy, and 2D wide‐angle X‐ray scattering measurements. Akin to the microreinforcing effect in plant cell walls, the alignment of CNC particles during direct writing yields textured composites with enhanced stiffness along the printing direction. The observations serve as an important step forward toward the development of sustainable materials for 3D printing of cellular architectures with tailored mechanical properties.  相似文献   

17.
Stimuli‐responsive materials have the potential to enable the generation of new bioinspired devices with unique physicochemical properties and cell‐instructive ability. Enhancing biocompatibility while simplifying the production methodologies, as well as enabling the creation of complex constructs, i.e., via 3D (bio)printing technologies, remains key challenge in the field. Here, a novel method is presented to biofabricate cellularized anisotropic hybrid hydrogel through a mild and biocompatible process driven by multiple external stimuli: magnetic field, temperature, and light. A low‐intensity magnetic field is used to align mosaic iron oxide nanoparticles (IOPs) into filaments with tunable size within a gelatin methacryloyl matrix. Cells seeded on top or embedded within the hydrogel align to the same axes of the IOPs filaments. Furthermore, in 3D, C2C12 skeletal myoblasts differentiate toward myotubes even in the absence of differentiation media. 3D printing of the nanocomposite hydrogel is achieved and creation of complex heterogeneous structures that respond to magnetic field is demonstrated. By combining the advanced, stimuli‐responsive hydrogel with the architectural control provided by bioprinting technologies, 3D constructs can also be created that, although inspired by nature, express functionalities beyond those of native tissue, which have important application in soft robotics, bioactuators, and bionic devices.  相似文献   

18.
Direct graphene transfer is an attractive candidate to prevent graphene damage, which is a critical problem of the conventional wet transfer method. Direct graphene transfer can fabricate the transferred graphene film with fewer defects by using a polymeric carrier. Here a unique direct transfer method is proposed using a 300 nm thick copper carrier as a suspended film and a transfer printing process by using the polydimethylsiloxane (PDMS) stamp under controlled peeling rate and modulus. Single and multilayer graphene are transferred to flat and curved PDMS target substrate directly. With the transfer printing process, the transfer yield of a trilayer graphene with 1000 µm s?1 peeling rate is 68.6% of that with 1 µm s?1 peeling rate. It is revealed that the graphene transfer yield is highly related to the storage modulus of the PDMS stamp: graphene transfer yield decreases when the storage modulus of the PDMS stamp is lower than a specific threshold value. The relationship between the graphene transfer yield and the interfacial shear strain of the PDMS stamp is studied by finite‐element method simulation and digital image correlation.  相似文献   

19.
Biodegradable biomaterials with intrinsically multifunctional properties such as high strength, photoluminescent ability (bioimaging monitoring), and antimicrobial activity (anti‐infection), as well as high osteoblastic differentiation ability, play a critical role in successful bone tissue regeneration. However, fabricating a biomaterial containing all these functions is still a challenge. Here, urethane cross‐linked intrinsically multifunctional silica‐poly(citrate) (CMSPC)‐based hybrid elastomers are developed by first one‐step polymerization and further chemical crosslinked using isocyanate. CMSPC hybrid elastomers demonstrate a high modulus of 976 ± 15 MPa, which is superior compared with most conventional poly(citrate)‐based elastomers. Hybrid elastomers show strong and stable intrinsic photoluminescent ability (emission 400–600 nm) due to the incorporation of silica phase. All elastomers exhibit high inherent antibacterial properties against Staphylococcus aureus. In addition, CMSPC hybrid elastomers significantly enhance the proliferation and metabolic activity of osteoblasts (MC3T3‐E1). CMSPC hybrid elastomers significantly promote the osteogenic differentiation of MC3T3‐E1 by improving alkaline phosphatase activity and calcium biomineralization deposits, as well as expressions of osteoblastic genes. These hybrid elastomers also show a minimal inflammatory response indicated by subcutaneous transplantation in vivo. These optimized structure and multifunctional properties make this hybrid elastomer highly promising for bone tissue regeneration and antiinfection and bioimaging applications.  相似文献   

20.
Mechanotransduction is the fundamental process by which cells detect and respond to their mechanical environment, and is critical for tissue homeostasis. Understanding mechanotransduction mechanisms will provide insights into disease processes and injuries, and may support novel tissue engineering research. Although there has been extensive research in mechanotransduction, many pathways remain unclear, due to the complexity of the signaling mechanisms and loading environments involved. This study describes the development of a novel hydrogel‐based fiber composite material for investigating mechanotransduction in fibrous tissues. By encapsulating poly(2‐hydroxyethyl methacrylate) rods in a bulk poly(ethylene glycol) matrix, it aims to create a micromechanical environment more representative of that seen in vivo. Results demonstrated that collagen‐coated rods enable localized cell attachment, and cells are successfully cultured for one week within the composite. Mechanical analysis of the composite indicates that gross mechanical properties and local strain environments could be manipulated by altering the fabrication process. Allowing diffusion between the rods and surrounding matrix creates an interpenetrating network whereby the relationships between shear and tension are altered. Increasing diffusion enhances the shear bond strength between rods and matrix and the levels of local tension along the rods. Preliminary investigation into fibroblast mechanotransduction illustrates that the fiber composite upregulates collagen I expression, the main protein in fibrous tissues, in response to cyclic tensile strains when compared to less complex 2D and 3D environments. In summary, the ability to create and manipulate a strain environment surrounding the fibers, where combined tensile and shear forces uniquely impact cell functions, is demonstrated.  相似文献   

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