Elastomeric Fibrous Hybrid Scaffold Supports In Vitro and In Vivo Tissue Formation

Biomimetic materials with biomechanical properties resembling those of native tissues while providing an environment for cell growth and tissue formation, are vital for tissue engineering (TE). Mechanical anisotropy is an important property of native cardiovascular tissues and directly influences tissue function. This study reports fabrication of anisotropic cell‐seeded constructs while retaining control over the construct's architecture and distribution of cells. Newly synthesized poly‐4‐hydroxybutyrate (P4HB) is fabricated with a dry spinning technique to create anelastomeric fibrous scaffold that allows control of fiber diameter, porosity, and rate ofdegradation. To allow cell and tissue ingrowth, hybrid scaffolds with mesenchymalstem cells (MSCs) encapsulated in a photocrosslinkable hydrogel were developed. Culturing the cellularized scaffolds in a cyclic stretch/flexure bioreactor resulted in tissue formation and confirmed the scaffold's performance under mechanical stimulation. In vivo experiments showed that the hybrid scaffold is capable of withstanding physiological pressures when implanted as a patch in the pulmonary artery. Aligned tissue formation occurred on the scaffold luminal surface without macroscopic thrombus formation. This combination of a novel, anisotropic fibrous scaffold and a tunable native‐like hydrogel for cellular encapsulation promoted formation of 3D tissue and provides a biologically functional composite scaffold for soft‐tissue engineering applications.     

Sensing of Damage Mechanisms in Fiber‐Reinforced Composites under Cyclic Loading using Carbon Nanotubes

The expanded use of advanced fiber‐reinforced composites in structural applications has brought attention to the need to monitor the health of these structures. It has been established that adding carbon nanotubes to fiber‐reinforced composites is a promising way to detect the formation of microscale damage. Because carbon nanotubes are three orders of magnitude smaller than traditional advanced fibers, it is possible for nanotubes to form an electrically conductive network in the polymer matrix surrounding the fibers. In this work, multi‐walled carbon nanotubes are dispersed into epoxy and infused into a glass‐fiber preform to form a network of in situ sensors. The resistance of the cross‐ply composite is measured in real‐time during incremental cyclic tensile loading tests to evaluate the damage evolution and failure mechanisms in the composite. Edge replication is conducted to evaluate the crack density after each cycle, and optical microscopy is utilized to study the crack mode and growth. The evolution of damage can be clearly identified through the damaged resistance parameter. Through analyzing the damaged resistance response curves with measurements of transverse crack density and strain, the transition between different failure modes can be identified. It is demonstrated that the integration of an electrically conducting network of carbon nanotubes in a glass fiber composite adds unique damage‐sensing functionality that can be utilized to track the nature and extent of microstructural damage in fiber composites.     

Strain‐Responsive Polyurethane/PEDOT:PSS Elastomeric Composite Fibers with High Electrical Conductivity

It is a challenge to retain the high stretchability of an elastomer when used in polymer composites. Likewise, the high conductivity of organic conductors is typically compromised when used as filler in composite systems. Here, it is possible to achieve elastomeric fiber composites with high electrical conductivity at relatively low loading of the conductor and, more importantly, to attain mechanical properties that are useful in strain‐sensing applications. The preparation of homogenous composite formulations from poly­urethane (PU) and poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) that are also processable by fiber wet‐spinning techniques are systematically evaluated. With increasing PEDOT:PSS loading in the fiber composites, the Young's modulus increases exponentially and the yield stress increases linearly. A model describing the effects of the reversible and irreversible deformations as a result of the re‐arrangement of PEDOT:PSS filler networks within PU and how this relates to the electromechanical properties of the fibers during the tensile and cyclic stretching is presented.     

Self‐healing Fibers: Autonomic Recovery of Fiber/Matrix Interfacial Bond Strength in a Model Composite (Adv. Funct. Mater. 20/2010)

Autonomic self‐healing of interfacial damage in a model single‐fiber composite is achieved through sequestration of ca. 1.5 μm diameter dicyclopentadiene (DCPD) healing‐agent‐filled capsules and recrystallized Grubbs’ catalyst to the fiber/matrix interface. When damage initiates at the fiber/matrix interface, the capsules on the fiber surface rupture, and healing agent is released into the crack plane where it contacts the catalyst, initiating polymerization. A protocol for characterizing the efficiency of interfacial healing for the single‐fiber system is established. Interfacial shear strength (IFSS), a measure of the bond strength between the fiber and matrix, is evaluated for microbond specimens consisting of a single self‐healing functionalized fiber embedded in a microdroplet of epoxy. The initial (virgin) IFSS is equivalent or enhanced by the addition of capsules and catalyst to the interface and up to 44% average recovery of IFSS is achieved in self‐healing samples after full interfacial debonding. Examination of the fracture interfaces by scanning electron microscopy reveals further evidence of a polyDCPD film in self‐healing samples. Recovery of IFSS is dictated by the bond strength of polyDCPD to the surrounding epoxy matrix.     

Autonomic Recovery of Fiber/Matrix Interfacial Bond Strength in a Model Composite

Autonomic self‐healing of interfacial damage in a model single‐fiber composite is achieved through sequestration of ca. 1.5 μm diameter dicyclopentadiene (DCPD) healing‐agent‐filled capsules and recrystallized Grubbs’ catalyst to the fiber/matrix interface. When damage initiates at the fiber/matrix interface, the capsules on the fiber surface rupture, and healing agent is released into the crack plane where it contacts the catalyst, initiating polymerization. A protocol for characterizing the efficiency of interfacial healing for the single‐fiber system is established. Interfacial shear strength (IFSS), a measure of the bond strength between the fiber and matrix, is evaluated for microbond specimens consisting of a single self‐healing functionalized fiber embedded in a microdroplet of epoxy. The initial (virgin) IFSS is equivalent or enhanced by the addition of capsules and catalyst to the interface and up to 44% average recovery of IFSS is achieved in self‐healing samples after full interfacial debonding. Examination of the fracture interfaces by scanning electron microscopy reveals further evidence of a polyDCPD film in self‐healing samples. Recovery of IFSS is dictated by the bond strength of polyDCPD to the surrounding epoxy matrix.     

Self‐Assembled Hydrogel Fiber Bundles from Oppositely Charged Polyelectrolytes Mimic Micro‐/Nanoscale Hierarchy of Collagen

Fiber bundles are present in many tissues throughout the body. In most cases, collagen subunits spontaneously self‐assemble into a fibrilar structure that provides ductility to bone and constitutes the basis of muscle contraction. Translating these natural architectural features into a biomimetic scaffold still remains a great challenge. Here, a simple strategy is proposed to engineer biomimetic fiber bundles that replicate the self‐assembly and hierarchy of natural collagen fibers. The electrostatic interaction of methacrylated gellan gum with a countercharged chitosan polymer leads to the complexation of the polyelectrolytes. When directed through a polydimethylsiloxane channel, the polyelectrolytes form a hierarchical fibrous hydrogel demonstrating nanoscale periodic light/dark bands similar to D‐periodic bands in native collagen and align parallel fibrils at microscale. Importantly, collagen‐mimicking hydrogel fibers exhibit robust mechanical properties (MPa scale) at a single fiber bundle level and enable encapsulation of cells inside the fibers under cell‐friendly mild conditions. Presence of carboxyl‐ (in gellan gum) or amino‐ (in chitosan) functionalities further enables controlled peptide functionalization such as Arginylglycylaspartic acid (RGD) for biochemical mimicry (cell adhesion sites) of native collagen. This biomimetic‐aligned fibrous hydrogel system can potentially be used as a scaffold for tissue engineering as well as a drug/gene delivery vehicle.     

Reactive Spinning of Cyanate Ester Fibers Reinforced with Aligned Amino‐Functionalized Single Wall Carbon Nanotubes

We report a new approach of reactive spinning to fabricate thermosetting cyanate ester micro‐scale diameter fibers with aligned single walled carbon nanotubes (SWNTs). The composite fibers were produced by first dispersing the SWNTs (1 wt %) in cyanate ester (CE) via solvent blending, followed by pre‐polymerization, spinning and then multiple‐stage curing. The pre‐polymerization, spinning and post‐spinning cure temperatures were carefully controlled to achieve good spun crosslinked fibers. Both pristine and amino‐functionalized SWNTs were used for the reinforced fiber spinning. Amino‐functionalized SWNTs (f‐SWNTs) were prepared by reacting acid‐treated SWNTs with toluene 2,4‐diisocyanate and then ethylenediamine (EDA). FTIR, optical microscopy and scanning electron microscopy (SEM) showed that the amino‐functionalized SWNTs were covalently and uniformly dispersed into the cyanate ester matrix and aligned along the fiber axis. The alignment was further confirmed using polarized Raman spectroscopy. The composite fibers with aligned amino‐functionalized SWNTs possess improved tensile properties with respect to neat CE fibers, showing 85, 140, and 420% increase in tensile strength, elongation and stress‐strain curve area (i.e., toughness), respectively. NH₂‐functionalization of SWNTs improves their dispersibility, alignment and interfacial strength and hence tensile properties of composite spun fibers. Fiber spinning to align SWNTs using thermosetting resin is novel. Others have reported fiber spinning to align SWNTs in thermoplastics. However, thermosetting CE resins offer the advantages of low and controllable viscosity during spinning and reactivity with amino functional groups to enable f‐SWNT/CE covalent bonding.     

Increased Interface Strength in Carbon Fiber Composites through a ZnO Nanowire Interphase

One of the most important factors in the design of a fiber reinforced composite is the quality of the fiber/matrix interface. Recently carbon nanotubes and silicon carbide whiskers have been used to enhance the interfacial properties of composites; however, the high growth temperature degrade the fiber strength and significantly reduce the composite's in‐plane properties. Here, a novel method for enhancing the fiber/matrix interfacial strength that does not degrade the mechanical properties of the fiber is demonstrated. The composite is fabricated using low‐temperature solution‐based growth of ZnO nanowires on the surface of the reinforcing fiber. Experimental testing shows the growth does not adversely affect fiber strength, interfacial shear strength can be significantly increased by 113%, and the lamina shear strength and modulus can be increased by 37.8% and 38.8%, respectively. This novel interface could also provide embedded functionality through the piezoelectric and semiconductive properties of ZnO.     

基于BOTDA的OPGW应变性能研究

为研究长期运行光纤复合架空地线(OPGW)的应变性能,使用高精度的分布式光纤传感监测设备布里渊光时域分析仪(BOTDA)对新缆和不同覆冰环境下的旧缆进行应变监测,对比分析了OPGW光缆内光纤的布里渊频率在长期外界环境作用下的变化.试验结果表明,运行时间和覆冰等级是影响OPGW光缆内光纤应变性能的主要因素.     

Ag Nanowire Reinforced Highly Stretchable Conductive Fibers for Wearable Electronics

Stretchable conductive fibers have received significant attention due to their possibility of being utilized in wearable and foldable electronics. Here, highly stretchable conductive fiber composed of silver nanowires (AgNWs) and silver nanoparticles (AgNPs) embedded in a styrene–butadiene–styrene (SBS) elastomeric matrix is fabricated. An AgNW‐embedded SBS fiber is fabricated by a simple wet spinning method. Then, the AgNPs are formed on both the surface and inner region of the AgNW‐embedded fiber via repeated cycles of silver precursor absorption and reduction processes. The AgNW‐embedded conductive fiber exhibits superior initial electrical conductivity (σ₀ = 2450 S cm^?1) and elongation at break (900% strain) due to the high weight percentage of the conductive fillers and the use of a highly stretchable SBS elastomer matrix. During the stretching, the embedded AgNWs act as conducting bridges between AgNPs, resulting in the preservation of electrical conductivity under high strain (the rate of conductivity degradation, σ/σ₀ = 4.4% at 100% strain). The AgNW‐embedded conductive fibers show the strain‐sensing behavior with a broad range of applied tensile strain. The AgNW reinforced highly stretchable conductive fibers can be embedded into a smart glove for detecting sign language by integrating five composite fibers in the glove, which can successfully perceive human motions.     

A Synthetic Hydrogel Composite with the Mechanical Behavior and Durability of Cartilage

This article reports the first hydrogel with the strength and modulus of cartilage in both tension and compression, and the first to exhibit cartilage‐equivalent tensile fatigue strength at 100 000 cycles. These properties are achieved by infiltrating a bacterial cellulose (BC) nanofiber network with a poly(vinyl alcohol) (PVA)–poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid sodium salt) (PAMPS) double network hydrogel. The BC provides tensile strength in a manner analogous to collagen in cartilage, while the PAMPS provides a fixed negative charge and osmotic restoring force similar to the role of aggrecan in cartilage. The hydrogel has the same aggregate modulus and permeability as cartilage, resulting in the same time‐dependent deformation under confined compression. The hydrogel is not cytotoxic, has a coefficient of friction 45% lower than cartilage, and is 4.4 times more wear‐resistant than a PVA hydrogel. The properties of this hydrogel make it an excellent candidate material for replacement of damaged cartilage.     

Magnetic Electrospun Fibers for Cancer Therapy

Iron oxide nanoparticles (IONPs) for magnetic hyperthermia in cancer treatment have recently gained substantial interest. Unfortunately, the use of free IONPs still faces major challenges such as poor tumor targetability, high variability in the amount of IONPs taken up by the tumor and the IONP leakage from dead cancer cells into the surrounding healthy tissues. The present work reports on electrospun fiber webs, heavily loaded with 50 nm sized IONPs. The high loading capacity of the fibers enables significant heating of the environment upon applying an alternating magnetic field. Furthermore, magnetic fibers can be repeatedly heated without loss of heating capacity or release of IONPs. Upon functionalization of the fiber surface with collagen, human SKOV‐3 ovarian cancer cells attached well to the fibers. Applying an alternating magnetic field during 10 minutes to the fiber webs killed all fiber‐associated cancer cells. Killing the cells using this method seemed more efficient compared to the use of a warm water bath. As the fiber webs can be i) loaded with a well‐controlled amount of IONPs and ii) localized in the body by Magnetic Resonance Imaging, magnetic electrospun fibers may become promising materials for a highly reproducible (repeated) heating of cancer tissues in vivo.     

ZnO/PVA Macroscopic Fibers Bearing Anisotropic Photonic Properties

Composite PVA/ZnO‐nanorods fibers, synthesized through co‐axial flux extrusion exhibit higher anisotropic photonic properties, both in absorption and emission, as a result of the collective alignment of the ZnO nanorods along the main axis of the PVA fiber. This photonic anisotropy is triggered by a synergistic interaction between the PVA matrix, stretched above the glass transition temperature (Tg), and cooled down under strain. Compared with non‐elongated fibers that present an isotropic emission, composite fibers previously submitted to a tensile stress absorb selectively UV emission when the polarized laser beam is parallel to the main axis of the fiber. In addition, their photolumincescence is also anisotropic, with a waveguide behavior along the main axis of the fiber. Mechanical properties of these composite fibers are also drastically improved, compared with pure PVA fibers: the longitudinal Young modulus of these fibers is increased from 2 to 6 GPa upon ZnO addition, a value similar to those already observed for composite fibers, prepared either with carbon nanotubes, or V₂O₅ macroscopic fibers.     

Efficient Load Transfer to Polymer‐Grafted Multiwalled Carbon Nanotubes in Polymer Composites

Multiwalled carbon nanotubes (MWNTs) grafted with poly(methyl methacrylate) (PMMA) were synthesized by emulsion reactions and used as a reinforcement for commercial PMMA. Both scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that the applied tensile load on the composites was transferred to the PMMA‐grafted MWNTs, leading to a strain failure of the MWNTs rather than an adhesive failure between the MWNTs and the matrix. Dynamic mechanical analysis (DMA) data showed that the storage modulus at 20 °C of the PMMA composite containing 20 wt.‐% of the PMMA‐grafted MWNTs was significantly enhanced by ～ 29 GPa (or by ～ 1100 %) as compared with commercial PMMA.     

Energy‐Dissipative Matrices Enable Synergistic Toughening in Fiber Reinforced Soft Composites

Tough hydrogels have shown strong potential as structural biomaterials. These hydrogels alone, however, possess limited mechanical properties (such as low modulus) when compared to some load‐bearing tissues, e.g., ligaments and tendons. Developing both strong and tough soft materials is still a challenge. To overcome this obstacle, a new material design strategy has been recently introduced by combining tough hydrogels with woven fiber fabric to create fiber reinforced soft composites (FRSCs). The new FRSCs exhibit extremely high toughness and tensile properties, far superior to those of the neat components, indicating a synergistic effect. Here, focus is on understanding the role of energy dissipation of the soft matrix in the synergistic toughening of FRSCs. By selecting a range of soft matrix materials, from tough hydrogels to weak hydrogels and even a commercially available elastomer, the toughness of the matrix is determined to play a critical role in achieving extremely tough FRSCs. This work provides a good guide toward the universal design of soft composites with extraordinary fracture resistance capacity.     

A Printable Photopolymerizable Thermosensitive p(HPMAm‐lactate)‐PEG Hydrogel for Tissue Engineering

Bioprinting is a new technology in regenerative medicine that allows the engineering of tissues by specific placement of cells in biomaterials. Importantly, the porosity and the relatively small dimensions of the fibers allow rapid diffusion of nutrients and metabolites. This technology requires the availability of hydrogels that ensure viability of encapsulated cells and have adequate mechanical properties for the preparation of structurally stable and well‐defined three‐dimensional constructs. The aim of this study is to evaluate the suitability of a biodegradable, photopolymerizable and thermosensitive A–B–A triblock copolymer hydrogel as a synthetic extracellular matrix for engineering tissues by means of three dimensional fiber deposition. The polymer is composed of poly(N‐(2‐hydroxypropyl)methacrylamide lactate) A‐blocks, partly derivatized with methacrylate groups, and hydrophilic poly(ethylene glycol) B‐blocks of a molecular weight of 10 kDa. Gels are obtained by thermal gelation and stabilized with additional chemical cross‐links by photopolymerization of the methacrylate groups coupled to the polymer. A power law dependence of the storage plateau modulus of the studied hydrogels on polymer concentration is observed for both thermally and chemically cross‐linked hydrogels. The hydrogels demonstrated mechanical characteristics similar to natural semi‐flexible polymers, including collagen. Moreover, the hydrogel shows suitable mechanical properties for bioprinting, allowing subsequent layer‐by‐layer deposition of gel fibers to form stable constructs up to at least 0.6 cm (height) with different patterns and strand spacing. The resulting constructs have reproducible vertical porosity and the ability to maintain separate localization of encapsulated fluorescent microspheres. Moreover, the constructs show an elastic modulus of 119 kPa (25 wt% polymer content) and a degradation time of approximately 190 days. Furthermore, high viability is observed for encapsulated chondrocytes after 1 and 3 days of culture. In summary, we conclude that the evaluated hydrogel is an interesting candidate for bioprinting applications.     

Hierarchical Intrafibrillar Nanocarbonated Apatite Assembly Improves the Nanomechanics and Cytocompatibility of Mineralized Collagen

Nanoscale replication of the hierarchical organization of minerals in biogenic mineralized tissues is believed to contribute to the better mechanical properties of biomimetic collagen scaffolds. Here, an intrafibrillar nanocarbonated apatite assembly is reported, which has a bone‐like hierarchy, and which improves the mechanical and biological properties of the collagen matrix derived from fibril‐apatite aggregates. A modified biomimetic approach is used, which based on the combination of poly(acrylic acid) as sequestration and sodium tripolyphosphate as templating matrix‐protein analogs. With this modified dual‐analog‐based biomimetic approach, the hierarchical association between collagen and the mineral phase is discerned at the molecular and nanoscale levels during the process of intrafibrillar collagen mineralization. It is demonstrated by nanomechanical testing, that intrafibrillarly mineralized collagen features a significantly increased Young's modulus of 13.7 ± 2.6 GPa, compared with pure collagen (2.2 ± 1.7 GPa) and extrafibrillarly‐mineralized collagen (7.1 ± 1.9 GPa). Furthermore, the hierarchy of the nanocarbonated apatite assembly within the collagen fibril is critical to the collagen matrix's ability to confer key biological properties, specifically cell proliferation, differentiation, focal adhesion, and cytoskeletal arrangement. The availability of the mineralized collagen matrix with improved nanomechanics and cytocompatibility may eventually result in novel biomaterials for bone grafting and tissue‐engineering applications.     

Highly Stretchable Conducting SIBS‐P3HT Fibers

Poly(styrene‐β‐isobutylene‐β‐styrene)‐poly(3‐hexylthiophene) (SIBS‐P3HT) conducting composite fibers are successfully produced using a continuous flow approach. Composite fibers are stiffer than SIBS fibers and able to withstand strains of up 975% before breaking. These composite fibers exhibit interesting reversible mechanical and electrical characteristics, which are applied to demonstrate their strain gauging capabilities. This will facilitate their potential applications in strain sensing or elastic electrodes. Here, the fabrication and characterization of highly stretchable electrically conducting SIBS‐P3HT fibers using a solvent/non‐solvent wet‐spinning technique is reported. This fabrication method combines the processability of conducting SIBS‐P3HT blends with wet‐spinning, resulting in fibers that could be easily spun up to several meters long. The resulting composite fiber materials exhibit an increased stiffness (higher Young’s modulus) but lower ductility compared to SIBS fibers. The fibers’ reversible mechanical and electrical characteristics are applied to demonstrate their strain gauging capabilities.     

Ultrahigh‐Strength Ultrahigh Molecular Weight Polyethylene (UHMWPE)‐Based Fiber Electrode for High Performance Flexible Supercapacitors

Flexible fiber‐based supercapacitor (FSC) with excellent electrochemical performance and high tensile strength and modulus is strongly desired for some special circumstances, such as load‐bearing, abrasion resistant, and anticutting fabrics. Here, a series of ultrahigh‐strength fiber electrodes are prepared for flexible FSCs based on ultrahigh molecular weight polyethylene fibers, on which the polydopamine, Ag, and poly (3,4‐ethylene dioxythiophene): poly(styrenesulfonate) are deposited in sequence. The modified fiber‐based electrode exhibits superhigh strength up to 3.72 GPa, which is the highest among fiber‐based electrodes reported to date. In addition, FSCs fabricated with the optimized fiber electrode shows a specific areal capacity as high as 563 mF cm^?2 at 0.17 mA cm^?2, which corresponds to a high areal energy density of ≈50.1 µWh cm^?2 at a power density of ≈124 µW cm^?2. The specific areal capacity only decrease 8% after 1000 times bending test, indicating the outstanding bending performance of this composite fiber electrode. Furthermore, several FSCs can be connected in series or in parallel to get higher working voltage or higher capacity respectively, which demonstrates its potential for broad applications in flexible devices.     

Directed Motility of Hygroresponsive Biomimetic Actuators

The capability of cellulose microfibrils to elicit directionality by anisotropically restricting the deformation of amorphous biogenic matrices is central to the motility of many plants as motoric and shape‐restoring elements. Herein, an approach is described to control directionality of artificial composite actuators that mimic the hygroinduced motion of composite plant tissues such as the opening of seed pods, winding of plant tendrils, and burial of seed awns. The actuators are designed as bilayer structures where single or double networks of buried parallel glass fibers reinforce the composite. By anisotropically restricting the expansion along certain directions they also effectively direct the mechanical reconfiguration, thereby determining the mechanical effect. A mathematical model is developed to quantify the kinematic response of fiber‐reinforced actuators. Within a broader context, the results of this study provide means for control over mechanical deformation of artificial dynamic elements that mimic the oriented fibrous architectures in biogenic motoric elements.