Naturally Derived Maleic Chitosan/Thiolated Sodium Hyaluronate Hydrogels as Potential 3D Printing Tissue Engineering Materials

3D printing is an attractive method to accurately construct artificial organs or alternative materials with complicated structures and functional performance. Naturally derived hydrogels have emerged as promising materials for the preparation of biomimetic 3D organization or scaffolds by 3D printing due to their good biocompatibility, high water content, and fascinating 3D network. However, the poor printing properties and weak structural stability of naturally derived hydrogels limit their applications. In this study, photopolymerizable hydrogels are designed based on maleic chitosan (MCS) and thiolated sodium hyaluronate (SHHA). The Michael addition between MCS and SHHA improves the viscosity of the mixed solution. Moreover, it benefits the 3D printing process, followed by photopolymerization (acrylate-thiol step-chain polymerization and acrylate–acrylate chain polymerization) to form a stable covalent network rapidly. The rheological property, swelling behaviors, microstructure, and in vitro degradation are tuned by adjusting the molar ratio of the thiol group and acrylate group. In addition, MCS/SHHA hydrogel scaffolds with good accuracy and enhanced structural stability are prepared using extrusion-based 3D printing and photopolymerization technology. The hydrogels display excellent cytocompatibility and can support adherence of L929 cells, which can be used as prospective materials for tissue engineering applications.     

Highly stretchable hydrogels for sensitive pressure sensor and programmable surface patterning by thermal bubble inkjet technology

Hydrogels with tough strength, programmable deformation are crucial for their practical applications. In this work, we reported the preparation and the programmable shape deformations of highly stretchable hydrogel. The graphene oxide/polyacrylamide/sodium alginate composite hydrogel was prepared, its microstructure and mechanical properties were studied. An aqueous calcium solution was selectively printed onto the hydrogel surfaces using an inkjet printer, resulting in programmable deformation of the composite hydrogel by creating regions of swelling/deswelling when subjected to external stimulations. Next, we fabricated a pressure-capacitance hydrogel sensor to demonstrate its application. Furthermore, the deformation rate and extent of the hydrogels can be controlled by adjusting the printing pattern position, number, length, and calcium solution concentration. Finally, several complex 2D and 3D shapes were fabricated by printing appropriate patterns on one or both surfaces of the hydrogel sheets.     

Self-assembly and metal ions-assisted one step fabrication of recoverable gelatin hydrogel with high mechanical strength

ABSTRACT

Gelatin hydrogel has been widely applied in bio-applications due to their good biocompatibility and high water content. However, poor mechanical properties of gelatin hydrogel greatly limit their application. Here we present a facile one-step soaking method to fabricate a recoverable gelatin hydrogel with high mechanical property, which is based on hydrogen bonds and metal ionic interaction. The mechanical properties of gelatin hydrogels can be tuned with different metal ions, temperatures and soaking times. Especially, gelatin-Fe³⁺ hydrogel can reach to 65 MPa compression stress with the compressive strain over 99% and possess good fatigue resistance under cyclic loadings. Besides, hydrogels crosslinked with metal ions show better antibacterial ability against Escherichia coli and Staphylococcus aureus. This work suggested an alternative for the design of tough gelatin-based hydrogels with desirable properties, which may hold promising for potential bio-applications under physiological conditions.     

Photolithographically patterned smart hydrogel based bilayer actuators

We describe the fabrication of photopatterned actuators, composed of stimuli-responsive hydrogel bilayers made from N-isopropyl-acrylamide (NIPAm), acrylic acid (AAc), and poly-ethylene oxide diacrylate (PEODA). The hydrogels were deposited by spin coating and casting and were patterned by non-contact photolithography. We investigated the swelling behavior of the individual photopatterned hydrogels in aqueous solutions of varying pH and ionic strength (IS). By combining materials with optimal swelling responses, bilayer structures were triggered via changes in pH and IS to actuate into three dimensional (3D) structures. We also used these hydrogel bilayers as hinges to actuate integrated structures composed of rigid polymeric SU-8 panels, patterned to resemble the shape of a Venus Flytrap. This system provides a straightforward way to design and fabricate actuator hinges composed entirely of polymers.     

Development of a Zeolite/Polymer-Based Hydrogel Composite through Photopolymerization for 3D Printing Application

In recent years, hydrogels have been widely applied in daily life and industry. More and more fillers have been combined with hydrogel to broaden their fields of application and improve their mechanical properties. However, there are few works about zeolite-based hydrogel composites via photopolymerization. Hence, in this work, it is reported that the fabrication of hydrogel composites containing zeolite (FAU-13X ≈ 40 wt%) under mild photopolymerization conditions (visible LED light irradiation, at room temperature, under air, and without any monomer purification). Markedly, compared to pure hydrogel, the elastic modulus (G′) of hydrogel composite contains 10% FAU-13X increased by more than 100%. When the zeolite content reached 40%, the water swelling ratio in mass reached 120%, and that in volume remained at 150%. In addition, 3D patterns with flat surface are obtained through direct laser write as a lithography technique. This means these hydrogel composites can be applied in the field of water absorption materials and 3D printing.     

Fabrication of Photothermally Responsive Nanocomposite Hydrogel through 3D Printing

The responsive hydrogels have received great attention in many fields. However, the molding method and response mode of such hydrogels are criticized when it comes to real applications. In this work, a novel class of poly(N‐isopropyl acrylamide)/graphene oxide (PNIPAm/GO) nanocomposite hydrogel through self‐assembly three‐dimensional (3D) printing via ultraviolet light polymerization. The precursor is ordinarily constituted by NIPAm monomer, crosslinker, and water mixed with a photoinitiator, besides the introduction of nanoclay adjusts the shear thinning properties to an optimal level, which is important for the 3D printing precision. Then, the graphite oxide as infrared light absorber endows the hydrogel fast photothermal excited responsivity instead of conventional temperature response. The shrinkage and swelling of the composite hydrogel can be controlled by turning the near‐infrared light on or off. Meanwhile, the reversible behavior of as‐prepared hydrogel is easily regulated by altering the content of GO and illumination time of near‐infrared light. Additionally, a round tube is obtained based on the as‐prepared hydrogel, which can be driven to get a pencil, indicating their potential applications in actuator and other functional program.     

Material Design for 3D Multifunctional Hydrogel Structure Preparation

Hydrogels are recognized as one of the most promising materials for e-skin devices because of their unique applicable functionalities such as flexibility, stretchability, biocompatibility, and conductivity. Beyond the excellent sensing functionalities, the e-skin devices further need to secure a target-oriented 3D structure to be applied onto various body parts having complex 3D shapes. However, most e-skin devices are still fabricated in simple 2D film-type devices, and it is an intriguing issue to fabricate complex 3D e-skin devices resembling target body parts via 3D printing. Here, a material design guideline is provided to prepare multifunctional hydrogels and their target-oriented 3D structures based on extrusion-based 3D printing. The material design parameters to realize target-oriented 3D structures via 3D printing are systematically derived from the correlation between material design of hydrogels and their gelation characteristics, rheological properties, and 3D printing processability for extrusion-based 3D printing. Based on the suggested material design window, ion conductive self-healable hydrogels are designed and successfully applied to extrusion-based 3D printing to realize various 3D shapes.     

Nanogrooved carbon microtubes for wet three‐dimensional printing of conductive composite structures

Recent advances in three‐dimensional (3D) printing have enabled the fabrication of interesting structures which are not achievable using traditional fabrication approaches. The 3D printing of carbon microtube composite inks allows fabrication of conductive structures for practical applications in soft robotics and tissue engineering. However, it is challenging to achieve 3D printed structures from solution‐based composite inks, which requires an additional process to solidify the ink. Here, we introduce a wet 3D printing technique which uses a coagulation bath to fabricate carbon microtube composite structures. We show that through a facile nanogrooving approach which introduces cavitation and channels on carbon microtubes, enhanced interfacial interactions with a chitosan polymer matrix are achieved. Consequently, the mechanical properties of the 3D printed composites improve when nanogrooved carbon microtubes are used, compared to untreated microtubes. We show that by carefully controlling the coagulation bath, extrusion pressure, printing distance and printed line distance, we can 3D print composite lattices which are composed of well‐defined and separated printed lines. The conductive composite 3D structures with highly customised design presented in this work provide a suitable platform for applications ranging from soft robotics to smart tissue engineering scaffolds. © 2019 Society of Chemical Industry     

Hydrogels for Engineering of Perfusable Vascular Networks

Hydrogels are commonly used biomaterials for tissue engineering. With their high-water content, good biocompatibility and biodegradability they resemble the natural extracellular environment and have been widely used as scaffolds for 3D cell culture and studies of cell biology. The possible size of such hydrogel constructs with embedded cells is limited by the cellular demand for oxygen and nutrients. For the fabrication of large and complex tissue constructs, vascular structures become necessary within the hydrogels to supply the encapsulated cells. In this review, we discuss the types of hydrogels that are currently used for the fabrication of constructs with embedded vascular networks, the key properties of hydrogels needed for this purpose and current techniques to engineer perfusable vascular structures into these hydrogels. We then discuss directions for future research aimed at engineering of vascularized tissue for implantation.     

A biopolymer‐based 3D printable hydrogel for toxic metal adsorption from water

Herein, we describe a 3D printable hydrogel that is capable of removing toxic metal pollutants from aqueous solution. To achieve this, shear‐thinning hydrogels were prepared by blending chitosan with diacrylated Pluronic F‐127 which allows for UV curing after printing. Several hydrogel compositions were tested for their ability to absorb common metal pollutants such as lead, copper, cadmium and mercury, as well as for their printability. These hydrogels displayed excellent metal adsorption with some examples capable of up to 95% metal removal within 30 min. We show that 3D printed hydrogel structures that would be difficult to fabricate by conventional manufacturing methods can adsorb metal ions significantly faster than solid objects, owing to their higher accessible surface areas. © 2019 Society of Chemical Industry     

Reversibly highly stretchable and self-healable zwitterion-containing polyelectrolyte hydrogel with high ionic conductivity for high-performance flexible and cold-resistant supercapacitor

It remains challenging to develop stretchable and self-healable polymer electrolytes with improved ion-conductive nature for high-performance multifunctional flexible supercapacitors. Herein, a P(AM-SBMA-AMPS)-SiO₂ zwitterion-containing polyelectrolyte hydrogel is fabricated via copolymerization of acrylamide (AM), sulfobetaine methacrylate (SBMA) zwitterionic monomer, and 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) anionic monomer grafted from the surface of vinyl silica nanoparticles (VSNPs). The hydrogen bonding among polymer chains and the high-density dynamic ionic interactions between SBMA and AMPS work as reversible “sacrificial bonds” to toughen hydrogel, while the VSNPs function as multifunctional crosslinkers and stress transfer centers, which makes these hydrogels tough (fracture energy 2.7 MJ m⁻³), stretchable (fracture strain 4,016%), and self-healable (fracture strain of healable sample 775%). More importantly, this zwitterion-containing polyelectrolyte hydrogel exhibits high ionic conductivities (3.4 S m⁻¹) owing to the highly hydration capacity of the zwitterionic polyelectrolyte copolymer which produced efficient ion migration channels for ion transport. Accordingly, a flexible supercapacitor based on this multifunctional hydrogel as electrolyte demonstrates a high electric double-layer capacitive capacitance of 60.6 F g⁻¹ at 0.5 A g⁻¹ and excellent capacitance retention of ~98% over 1,000 cycles as well as encouraging electrochemical properties at subzero temperature. This work provides new insights into the synthesis of highly conductive and multifunctional polyelectrolyte hydrogels for high-performance flexible supercapacitors. © 2020 Wiley Periodicals, Inc.     

Site‐Specific Oxidation‐Induced Stiffening and Shape Morphing of Soft Tough Hydrogels

Living biological tissues are made of structures with properly defined mechanical properties (toughness and stiffness) toward specific biological functions. Herein, a chemical manipulation strategy is developed to locally vary the oxidation state of Fe ions from divalent to trivalent in the tough hydrogels. The resultant trivalent ionically cross‐linked networks become less flexible and lead to a significant enhancement of the stiffness of the tough hydrogels. The mechanical strengthening of Fe²⁺/Ca²⁺‐alginate/polyacrylamide tough hydrogels is demonstrated by the oxidation with ammonium persulfate (APS). Moreover, by applying surface patterning, the mechanical properties of the tough hydrogels are spatially stiffened and thus can serve as anisotropic elements to guide the shape morphing of tough hydrogels into complex 3D structures. This method opens up a simple strategy not only to dynamically vary the mechanics of tough hydrogels, both in bulk and locally from prefabricated soft tough hydrogels, but also toward their shape morphing behaviors on demand.     

3D gel printing of magnetic hydrogel scaffolds assisted by in-situ gelation in a water level-controlled crosslinker bath

Polyvinylalcohol/chitosan (PVA/CS) is an excellent dual-network hydrogel material, but some significant challenges remain in fabricating composites with specific structures. In this study, 3D gel printing (3DGP) combined with a water-level controlled crosslinker bath was proposed for the rapid in-situ prototyping of PVA/CS/Fe₃O₄ magnetic hydrogel scaffolds. Specifically, the PVA/CS/Fe₃O₄ hydrogels were extruded into the crosslinker water to achieve rapid in-situ gelation, improving the printability of hydrogel scaffolds. The effect of the PVA/CS ratio on the rheological and mechanical properties of dual-network magnetic hydrogels was evaluated. The printing parameters were systematically optimized to facilitate the coordination between the crosslinking water bath and printer. The different crosslinking water baths were investigated to improve the printability of PVA/CS/Fe₃O₄ hydrogels. The results showed that the printability of the sodium hydroxide (NaOH) crosslinker was significantly better than that of sodium tripolyphosphate (TPP). The magnetic hydrogels (PVA: CS= 1: 1) crosslinked by NaOH had better compressive strength, swelling rate, and saturation magnetization of 1.17 MPa, 92.43%, and 22.19 emu/g, respectively. The MC3T3-E1 cell culture results showed that the PVA/CS/Fe₃O₄ scaffolds promoted cell adhesion and proliferation, and the scaffolds crosslinked by NaOH had superior cytocompatibility. 3DGP combined with a water-level controlled crosslinker bath offers a promising approach to preparing magnetic hydrogel materials.     

Low-temperature assembling of naturally driven copper ferrite starch nanocomposites hydrogel with magnetic and antibacterial activities

Most hydrogels are prepared with using synthetic polymers that are nonecofriendly materials. Also, hydrogel nanocomposites are mostly prepared in the multi-step processing through costly techniques. Here, starch as a natural, biodegradable, hydrophilic, and inexpensive material was used for fabrication of a copper ferrite starch nanocomposites hydrogel. This was synthesized using alkali starch solution along with copper and iron salts through coprecipitation method at low-temperature led to the one-step gelatinization and retrogradation. The various characteristics of the nanocomposites hydrogel were examined including morphology and chemical structure besides magnetic, antimicrobial, and swelling behaviors. Further, the remaining ashes were considered as a simple method to estimate organic matter and inorganic nanoparticles content of hydrogel nanocomposite. The results indicated successful fabrication of a green hydrogel with magnetic and antibacterial features through a very simple method. The obtained ecofriendly hydrogel can be used in various applications such as controlled drug delivery, cancer hyperthermia, waste-water treatment, and many others. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48961.     

Fabrication of 3D Polypyrrole/Graphene Oxide Composite Hydrogels with High Performance Swelling Properties

The polypyrrole (PPy)/graphene oxide (GO) composite hydrogels with hierarchical porous structures were fabricated by one-step self-assembly method. The static oxidation polymerization of pyrrole monomer in GO aqueous solution resulted in the formation of three-dimensional (3D) PPy/GO composite hydrogels, which consisted of one-dimensional PPy nanofibers and two-dimensional GO nanosheets. The as-prepared composite hydrogels exhibited shrinking–swelling behavior with cycles of suction and water-supplying. The effects of GO nanosheets content on the swelling properties were investigated. Results showed that the well-dispersed GO nanosheets in the hydrogel networks resulted in a significant improvement in water absorbencies of the hydrogels. PPy/GO composite hydrogels exhibited unobvious variation in the water absorbency even in saline solutions. Such excellent properties in water absorbencies endow the conducting 3D PPy/GO composite hydrogels with great potential applications in electrochemical sensors or controlled release.     

Macroporous hydrogel beads of high toughness and superfast responsivity

Macroporous hydrogel beads based on the monomers acrylamide and 2-acrylamido-2-methylpropane sulfonic acid sodium salt were prepared by dropwise addition of the monomer solution into the paraffin oil as the continuous phase at subzero temperatures. The beads prepared between ?15 and ?20 °C have irregular large pores of 1–10 μm in diameter, typical for macroporous networks created by the cryogelation technique, while nonporous hydrogels were obtained at room temperature. Swelling measurements show that the low temperature beads swell within seconds to attain their equilibrium states in water. The beads formed at subzero temperatures were very tough and can be compressed up to 94% strain without any crack development while those formed at room temperature were fragile and broke at a strain of about 40%. The results indicate that the tough hydrogel beads formed at subzero temperatures can be used in separation processes in which the separated compounds can easily be recovered by compression of the beads under a piston.     

基于浆料形态的陶瓷3D打印技术的浆料体系研究进展

3D打印技术因其操作简单便捷、成型快速灵活、可制备复杂结构的器件等优点,在精密陶瓷零件制造方面具有广泛应用。本文根据3D打印陶瓷的材料形态综述不同3D打印技术在陶瓷制备方面的特点,重点介绍了陶瓷3D打印成型技术中直写式3D打印、光固化3D打印、喷墨3D打印等技术所涉及的粘结剂、分散剂等组分的应用及作用机理,并对水基和非水基两种类型的添加剂组分进行总结和探讨,以期为3D打印技术制备高性能陶瓷样件提供参考。     

Enhanced Regeneration of Vascularized Adipose Tissue with Dual 3D-Printed Elastic Polymer/dECM Hydrogel Complex

A flexible and bioactive scaffold for adipose tissue engineering was fabricated and evaluated by dual nozzle three-dimensional printing. A highly elastic poly (L-lactide-co-ε-caprolactone) (PLCL) copolymer, which acted as the main scaffolding, and human adipose tissue derived decellularized extracellular matrix (dECM) hydrogels were used as the printing inks to form the scaffolds. To prepare the three-dimensional (3D) scaffolds, the PLCL co-polymer was printed with a hot melting extruder system while retaining its physical character, similar to adipose tissue, which is beneficial for regeneration. Moreover, to promote adipogenic differentiation and angiogenesis, adipose tissue-derived dECM was used. To optimize the printability of the hydrogel inks, a mixture of collagen type I and dECM hydrogels was used. Furthermore, we examined the adipose tissue formation and angiogenesis of the PLCL/dECM complex scaffold. From in vivo experiments, it was observed that the matured adipose-like tissue structures were abundant, and the number of matured capillaries was remarkably higher in the hydrogel–PLCL group than in the PLCL-only group. Moreover, a higher expression of M2 macrophages, which are known to be involved in the remodeling and regeneration of tissues, was detected in the hydrogel–PLCL group by immunofluorescence analysis. Based on these results, we suggest that our PLCL/dECM fabricated by a dual 3D printing system will be useful for the treatment of large volume fat tissue regeneration.     

Ultrastretchable,Super Tough,and Rapidly Recoverable Nanocomposite Double‐Network Hydrogels by Dual Physically Hydrogen Bond and Vinyl‐Functionalized Silica Nanoparticles Macro‐Crosslinking

It remains a challenge to develop tough hydrogels with recoverable or healable properties after damage. Herein, a new nanocomposite double‐network hydrogel (NC‐DN) consisting of first agar network and a homogeneous vinyl‐functionalized silica nanoparticles (VSNPs) macro‐crosslinked polyacrylamide (PAM) second network is reported. VSNPs are prepared via sol‐gel process using vinyltriethoxysilane as a silicon source. Then, Agar/PAM‐SiO₂ NC‐DN hydrogels are fabricated by dual physically hydrogen bonds and VSNPs macro‐crosslinking. Under deformation, the reversible hydrogen bonds in agar network and PAM nanocomposite network successively break to dissipate energy and then recombine to recover the network, while VSNPs in the second network could effectively transfer stress to the network chains grafted on their surfaces and maintain the gel network. As a result, the optimal NC‐DN hydrogels exhibit ultrastretchable (fracture strain 7822%), super tough (fracture toughness 18.22 MJ m^‐3, tensile strength 431 kPa), rapidly recoverable (≈92% toughness recovery after 5 min resting at room temperature), and self‐healable (can be stretched to 1331% after healing) properties. The newly designed Agar/PAM‐SiO₂ NC‐DN hydrogels with tunable network structure and mechanical properties by multi‐bond crosslinking provide a new avenue to better understand the fundamental structure‐property relationship of DN hydrogels and broaden the current hydrogel research and applications.     

A Novel Polymeric Substrate with Dual-Porous Structures for High-Performance Inkjet-Printed Flexible Electronic Devices

Inkjet printing has emerged as a promising low-cost and high-performance method for manufacturing printing-based devices. However, the development of optimized substrates for inkjet printing using novel materials is limited. In this study, a novel polymeric substrate optimized for flexible electronic devices is fabricated using thin-film processing and phase inversion of polyethersulfone (PES). The PES film consists of two layers of pores; the upper layer has nano-sized pores that filter the nanoparticles in the conductive ink and allow for high-density aggregation on the substrate, while the lower layer contains micro-scale pores that quickly absorb and drain the ink solvent. The two porous structures lead to higher conductivity and high-resolution printed patterns by minimizing solvent lateral diffusion. Additionally, the PES printing substrate can undergo high-temperature curing of metal nanoparticles, enabling high-resolution pattern printing with low resistance. The PES substrate is highly transparent and flexible, allowing for the fabrication of various printed electronic patterns and the production of high-performance flexible electronic devices.