Cesium Lead Halide Perovskite Decorated Polyvinylidene Fluoride Nanofibers for Wearable Piezoelectric Nanogenerator Yarns.

Piezoelectric nanogenerators (PENGs) provide a viable solution to convert the mechanical energy generated by body movement to electricity. One-dimensional yarns offer a platform for flexible wearable textile PENGs, which can conform to body for comfort and efficient energy harvesting. In this context, we report a flexible piezoelectric yarn, assembled by one-step cocentric deposition of cesium lead halide perovskite decorated polyvinylidene fluoride (PVDF) nanofibers, on a stainless-steel yarn. Perovskite crystals were formed in situ during electrospinning. Our work demonstrates a nanofiber morphology in which perovskite crystals spread over the nanofiber, leading to a rough surface, and complementing piezoelectric nanocomposite formation with PVDF for superior stress excitation. We investigated how the halide anions of perovskite affect the piezoelectric performance of PENG yarns by comparing CsPbBr3 and CsPbI2Br. Effects of the perovskite concentration, annealing temperature, and deposition time on the piezoelectric properties of PENG yarns were investigated. Devices assembled with a single yarn of CsPbI2Br decorated PVDF nanofibers yield the optimal performance with an output voltage of 8.3 V and current of 1.91 µA in response to pressing from an actuator and used to charge capacitors for powering electronics. After aging in the ambient environment for 3 months, the device maintained its performance during 19,200 cycles of mechanical stresses. The excellent and stable electrical performance can be ascribed to the optimized crystallization of CsPbI2Br crystals, their complementing performance with PVDF, and formation of nanofibers with uniformity and strength. The flexibility of piezoelectric yarns enables them to be bent, twisted, braided, and woven for different textile integrations while harvesting energy from body movements, demonstrating the potential for wearable mechanical energy harvesting.

Electrospun pectin/modified copper-based metal-organic framework (MOF) nanofibers as a drug delivery system.

Pectin has been regarded as a drug carrier accelerating the healing process due to its bioactivities, abundance and lower cost of resources. However, a big challenge related to its practical application is its poor mechanical strength. In this study the modified Cu-based MOF containing Folic acid was synthesized and incorporated in the suitable pectin electrospun nanofibers which not only improved the copper ions release behavior but also made the fiber mat stronger, antibacterial and induce angiogenesis, fibroblast migration, and proliferation due to loaded copper ions and folic acid. The nanofibers composing of 75% pectin and 4000 kDa -PEO were chosen after morphological and mechanical characterization. Finally, the effect of MOF incorporation on the nanocomposite samples was characterized in terms of morphological, physiochemical and biological properties. The nanofibrous mats were evaluated by tensile testing, antibacterial and cytotoxicity. The release behavior of copper ions and folic acid was controlled and their burst release alleviated reducing cytotoxicity in vitro. It was found that the Young's moduli of the pectin nanofibers were improved to 19.13 MPa by the addition of Cu-based MOFs. Moreover, nanocomposite pectin nanofibers were found to be antibacterial and biocompatible. These results demonstrate that MOF-contained pectin nanofibers are promising for biomedical applications.

Biomimetically Mineralized Alginate Nanocomposite Fibers for Bone Tissue Engineering: Mechanical Properties and in Vitro Cellular Interactions.

We report herein the structural and mechanical properties and in vitro cellular response of hydroxyapatite (HAp)/alginate nanocomposite fibrous scaffolds mimicking the mineralized collagen fibrils of bone tissue. The biomimetically "engineered" nanocomposites, fabricated by electrospinning and in situ synthesis strategy, were compared with pure alginate nanofibers and micrometer-level HAp/alginate composite fibers. The tensile strength and elastic modulus of the nanocomposites increased by 79.3 and 158.4%, respectively, compared to those of alginate. The uniform nucleation and HAp nanocrystal growth on the alginate nanofibers resulted in such enhancement of the mechanical properties via a stress-transfer effect. Rat calvarial osteoblasts were stably attached and stretched more extensively on the nanocomposites' surface than on the pristine alginate. The controlled deposition of the HAp nanophase contributed to a much faster cell proliferation rate on the nanocomposites than on the others. The improved structural stability and osteoblast interactions suggest the fibrous nanocomposite scaffold's potential advantages for bone tissue regeneration.

Molecular Orientation and Organization of Technical Lignin-Based Composite Nanofibers and Films.

Natural materials are highly anisotropic, maximizing performance of the polymeric structures while conserving mass and enhancing function. In synthetic materials, nanoscale fibers produced by electrospinning often contain molecular alignment of polymers along the fiber axis achieving some similarity to natural fibers. In this study, isolated softwood kraft lignin (SKL) was electrospun into aligned fibers utilizing a special collector. The molecular organization of lignin within the aligned nanofibers was investigated by polarized light optical microscopy. Furthermore, the functional groups that had preferred alignment along the fiber axis were identified with polarized Fourier transform infrared (FTIR) spectroscopy based on dichroism measurements. In addition, nanocrystalline cellulose (NCC) was added to the lignin solutions in order to create composite nanofibers. Both the orientation of NCC within the nanoscale fibers and the impact this component had on the degree of orientation of SKL within the aligned nanofibers were revealed by utilizing polarized FTIR. Finally, solvent cast lignin films were analyzed for their anisotropic polarizability, demonstrating birefringence with and without nanocrystalline cellulose. The work provided unique insight into both preferred orientation (fibers) and assembly (films) for technical lignin due to processing.

Impact of Thermal Oxidative Stabilization on the Performance of Lignin-Based Carbon Nanofiber Mats.

Lignin is a renewable biopolymer considered as a potential precursor for low-cost carbon materials. Thermal oxidative stabilization (TOS) is an important processing step to maintain fiber geometry during carbonization, yet the impact of  TOS on the properties of lignin-based carbon materials has not been clearly identified in the literature. Yield, change in fiber diameter/distribution, elemental composition, and mechanical properties were explored for both stabilized and carbonized lignin fibers. Vibrational spectroscopy and solid-state 13C nuclear magnetic resonance spectroscopy were used to analyze the changes in lignin molecular structure after exposure to various heating conditions during the TOS steps. Further, studies were focused on the effects of TOS conditions on the resulting carbon structure of fiber mats through Raman spectroscopy measurements and electrical conductivity analysis. Although TOS conditions influenced the properties of the oxidized lignin fiber mats, properties of the carbonized samples were invariant to the TOS procedures used in this study over most of the conditions. As a result, there was flexibility for the parameters (time and temperature) in the TOS process when conditioning softwood lignin materials for carbon fibers.

Palladium-Zeolite nanofiber as an effective recyclable catalyst membrane for water treatment.

Zeolite is an exciting natural material due to its unique capability of ammonium nitrogen (NH3N) adsorption in water. In this study, multifunctional hybrid composites of zeolite/palladium (Ze/Pd) on polymer nanofiber membranes were fabricated and explored for sustainable contaminant removal. SEM and XRD demonstrated that zeolite and palladium nanoparticles were uniformly distributed and deposited on the nanofibers. NH3N recovery rate was increased from 23 to 92% when palladium coated zeolite was embedded on the nanofiber. Multifunctional nanofibers of Ze/Pd membranes were able to adsorb NH3N on the zeolites placed on the surface of fibers and palladium catalysts were capable of selective oxidation of NH3N to N2 gas. The cycling of NH3N adsorption-oxidation, high flux, hydrophilicity, and flexibility of the membrane makes it a strong candidate for water treatment.

Three-dimensional (3D) palladium-zinc oxide nanowire nanofiber as photo-catalyst for water treatment.

Zinc Oxide Nano Wires (ZNWs) has been considered as a promising material for purification and disinfection of water and remediation of hazardous waste owing to its high activity and lower cost. In this study, three-dimensional (3D) structured palladium (Pd)/ZNWs were synthesized on the fabricated electrospun nanofibers and explored for enhancement of organic matter (OM) removal efficiency in water by suppressing electron-hole recombination during photocatalytic activity and increased surface area. The densely populated ZNWs were fabricated on the electrospun nanofiber by electroless plating (EP) and hydrothermal synthesis. In order to improve photocatalytic efficiency, a thin layer of Pd was coated prior to ZNWs growth to induce suppression of electron hole recombination produced during catalyst activity. The creation of a highly porous network of nanofibers decorated with ZNWs resulted in an increase of specific removal rate (SRR) of OM from 0.0249 to 0.0377 mg CODCr removed/mg ZNWs-hr when ZNW were grown on a Pd layer. It is believed that the demonstration of OM removal in the water through Pd/ZNWs membrane and enhanced photocatalytic activity under UV irradiation from layered structure can broaden potential applicability of Pd/ZNWs membranes for various photo catalytic water treatment.

Effects of emulsion droplet size on the structure of electrospun ultrafine biocomposite fibers with cellulose nanocrystals.

Electrospinning of cellulose nanocrystals (CNC)/poly(lactic acid) (PLA) emulsions has been demonstrated to be an effective dispersion and alignment method to control assembly of CNC into continuous composite ultrafine fibers. CNC-PLA nanocomposite random-fiber mats and aligned-fiber yarns were prepared by emulsion electrospinning. A dispersed phase of CNC aqueous suspension and an immiscible continuous phase of PLA solution comprised the CNC-PLA water-in-oil (W/O) emulsion system. Under a set of specific conditions, the as-spun composite ultrafine fibers assumed core-shell or hollow structures. In these structures, CNCs were aligned along the core in the core-shell case, or on the wall of the hollow cylinder in the hollow fiber case. CNCs act as nucleating agents influencing PLA crystallinity, and improve the strength and stiffness of electrospun composite fibers. The effects of emulsion droplet size on fiber structural formation and CNC distribution within the electrospun fibers have been carefully examined.

Emulsion electrospinning of a collagen-like protein/PLGA fibrous scaffold: empirical modeling and preliminary release assessment of encapsulated protein.

The effectiveness of a multifunctional scaffold produced by the electrospinning of emulsions composed of organic PLGA and aqueous collagen-like protein (denoted as Fol-8Col) solutions is demonstrated. The resultant Fol-8Col/PLGA fibrous scaffolds with homogeneous morphology have mean fiber diameters from 600 to 2,000 nm. A uniform distribution of encapsulated Fol-8Col in the fibers is observed by fluorescence microscopy. TEM is used to clarify the representative core/sheath structure of emulsion electrospun Fol-8Col/PLGA fibers. Preliminary release assessment of encapsulated Fol-8Col shows results of sustained release for more than one month from the Fol-8Col/PLGA fibrous mats. The cytocompatibility of fibroblast cell line L929 with the fibrous composite seems promosing.

Microfabricated formaldehyde gas sensors.

Formaldehyde is a volatile organic compound that is widely used in textiles, paper, wood composites, and household materials. Formaldehyde will continuously outgas from manufactured wood products such as furniture, with adverse health effects resulting from prolonged low-level exposure. New, microfabricated sensors for formaldehyde have been developed to meet the need for portable, low-power gas detection. This paper reviews recent work including silicon microhotplates for metal oxide-based detection, enzyme-based electrochemical sensors, and nanowire-based sensors. This paper also investigates the promise of polymer-based sensors for low-temperature, low-power operation.

Co-electrospun poly(lactide-co-glycolide), gelatin, and elastin blends for tissue engineering scaffolds.

In this study, we describe composite scaffolds composed of synthetic and natural materials with physicochemical properties suitable for tissue engineering applications. Fibrous scaffolds were co-electrospun from a blend of a synthetic biodegradable polymer (poly(lactic-co-glycolic acid), PLGA, 10% solution) and two natural proteins, gelatin (denatured collagen, 8% solution) and alpha-elastin (20% solution) at ratios of 3:1:2 and 2:2:2 (v/v/v). The resulting PLGA-gelatin-elastin (PGE) fibers were homogeneous in appearance with an average diameter of 380 +/- 80 nm, which was considerably smaller than fibers made under identical conditions from the starting materials (PLGA, 780 +/- 200 nm; gelatin, 447 +/- 123 nm; elastin, 1060 +/- 170 nm). Upon hydration, PGE fibers swelled to an average fiber diameter of 963 +/- 132 nm, but did not disintegrate. Importantly, PGE scaffolds were stable in an aqueous environment without crosslinking and were more elastic than those made of pure elastin fibers. To investigate the cytocompatibility of PGE, we cultured H9c2 rat cardiac myoblasts and rat bone marrow stromal cells (BMSCs) on fibrous PGE scaffolds. We found that myoblasts grew equally as well or slightly better on the scaffolds than on tissue-culture plastic. Microscopic evaluation confirmed that myoblasts reached confluence on the scaffold surfaces while simultaneously growing into the scaffolds. Histological characterization of the PGE constructs indicated that BMSCs penetrated into the center of scaffolds and began proliferating shortly after seeding. Our results suggest that fibrous scaffolds made of PGE and similar biomimetic blends of natural and synthetic polymers may be useful for engineering soft tissues, such as heart, lung, and blood vessels.

Evaluation of the anterior cruciate ligament, medial collateral ligament, achilles tendon and patellar tendon as cell sources for tissue-engineered ligament.

This study investigated four different connective tissue cell types to determine which cell type should be the source for seeding a tissue-engineered anterior cruciate ligament (ACL) replacement. Cells derived from the ACL, medial collateral ligament (MCL), achilles tendon (AT), and patellar tendon (PT) of New Zealand White rabbits were isolated and cultured. Each cell type was cultured in vitro after seeding on three-dimensional (3-D) braided polymer scaffolds and on tissue culture polystyrene that served as a control. Samples were evaluated and compared for their morphology, proliferation, and gene expression of fibronectin, type I and type III collagen. Scanning electron microscopy (SEM) photomicrographs verified cell attachment of all four types of connective tissue fibroblasts to the scaffolds. Preliminary results comparing proliferation indicate that cells obtained from the PT and AT have the fastest proliferation. Whereas gene expression of the phenotypic markers measured using real-time reverse transcription polymerase chain reaction (RT-PCR) indicates ACL cells have the highest gene expression for the matrix markers. This leads to the question of which cell type should be the cell source for tissue-engineering of ligament, the highly proliferating cells or the differentiated matrix producing cells. This study would suggest that ACL differentiated matrix producing cells are the most suitable cells for further study and development of a tissue-engineered ligament.

Electrospun protein fibers as matrices for tissue engineering.

Electrospinning has recently emerged as a leading technique for generating biomimetic scaffolds made of synthetic and natural polymers for tissue engineering applications. In this study, we compared collagen, gelatin (denatured collagen), solubilized alpha-elastin, and, as a first, recombinant human tropoelastin as biopolymeric materials for fabricating tissue engineered scaffolds by electrospinning. In extending previous studies, we optimized the shape and size (diameter or width) of the ensuing electrospun fibers by varying important parameters of the electrospinning process, such as solute concentration and delivery rate of the polymers. Our results indicate that the average diameter of gelatin and collagen fibers could be scaled down to 200-500 nm without any beads, while the alpha-elastin and tropoelastin fibers were several microns in width. Importantly, and contrary to any hitherto reported structures of electrospun polymers, fibers composed of alpha-elastin, especially tropoelastin, exhibited "quasi-elastic" wave-like patterns at increased solution delivery rates. The periodicity of these wave-like tropoelastin fibers was partly affected by the delivery rate. Atomic force microscopy was utilized to profile the topography of individual electrospun fibers and microtensile testing was performed to measure their mechanical properties. Cell culture studies confirmed that the electrospun engineered protein scaffolds support attachment and growth of human embryonic palatal mesenchymal (HEPM) cells.

Anterior cruciate ligament regeneration using braided biodegradable scaffolds: in vitro optimization studies.

The anterior cruciate ligament (ACL) is the most commonly injured intra-articular ligament of the knee, and limitations in existing reconstruction grafts have prompted an interest in tissue engineered solutions. Previously, we reported on a tissue-engineered ACL scaffold fabricated using a novel, three-dimensional braiding technology. A critical factor in determining cellular response to such a graft is material selection. The objective of this in vitro study was to optimize the braided scaffold, focusing on material composition and the identification of an appropriate polymer. The selection criteria are based on cellular response, construct degradation, and the associated mechanical properties. Three compositions of poly-alpha-hydroxyester fibers, namely polyglycolic acid (PGA), poly-L-lactic acid (PLLA), and polylactic-co-glycolic acid 82:18 (PLAGA) were examined. The effects of polymer composition on scaffold mechanical properties and degradation were evaluated in physiologically relevant solutions. Prior to culturing with primary rabbit ACL cells, scaffolds were pre-coated with fibronectin (Fn, PGA-Fn, PLAGA-Fn, PLLA-Fn), an important protein which is upregulated during ligament healing. Cell attachment and growth were examined as a function of time and polymer composition. While PGA scaffolds measured the highest tensile strength followed by PLLA and PLAGA, its rapid degradation in vitro resulted in matrix disruption and cell death over time. PLLA-based scaffolds maintained their structural integrity and exhibited superior mechanical properties over time. The response of ACL cells was found to be dependent on polymer composition, with the highest cell number measured on PLLA-Fn scaffolds. Surface modification of polymer scaffolds with Fn improved cell attachment efficiency and effected the long-term matrix production by ACL cells on PLLA and PLAGA scaffolds. Therefore based on the overall cellular response and its temporal mechanical and degradation properties in vitro, the PLLA braided scaffold pre-coated with Fn was found to be the most suitable substrate for ACL tissue engineering.

Fiber-based tissue-engineered scaffold for ligament replacement: design considerations and in vitro evaluation.

The anterior cruciate ligament (ACL) is the major intraarticular ligamentous structure of the knee, which functions as a joint stabilizer. It is the most commonly injured ligament of the knee, with over 150,000 ACL surgeries performed annually in the United States. Due to limitations associated with current grafts for ACL reconstruction, there is a significant demand for alternative graft systems. We report here the development of a biodegradable, tissue-engineered ACL graft. Several design parameters including construct architecture, porosity, degradability, and cell source were examined. This graft system is based on polymeric fibers of polylactide-co-glycolide 10:90, and it was fabricated using a novel, three-dimensional braiding technology. The resultant micro-porous scaffold exhibited optimal pore diameters (175-233 microm) for ligament tissue ingrowth, and initial mechanical properties of the construct approximate those of the native ligament.

Position of single amino acid substitutions in the collagen triple helix determines their effect on structure of collagen fibrils.

Collagen II fibrils are a critical structural component of the extracellular matrix of cartilage providing the tissue with its unique biomechanical properties. The self-assembly of collagen molecules into fibrils is a spontaneous process that depends on site-specific binding between specific domains belonging to interacting molecules. These interactions can be altered by mutations in the COL2A1 gene found in patients with a variety of heritable cartilage disorders known as chondrodysplasias. Employing recombinant procollagen II, we studied the effects of R75C or R789C mutations on fibril formation. We determined that both R75C and R789C mutants were incorporated into collagen assemblies. The effects of the R75C and R789C substitutions on fibril formation differed significantly. The R75C substitution located in the thermolabile region of collagen II had no major effect on the fibril formation process or the morphology of fibrils. In contrast, the R789C substitution located in the thermostable region of collagen II caused profound changes in the morphology of collagen assemblies. These results provide a basis for identifying pathways leading from single amino acid substitutions in collagen II to changes in the structure of individual fibrils and in the organization of collagenous matrices.

Bioresorbable nanofiber-based systems for wound healing and drug delivery: optimization of fabrication parameters.

Wound healing is a complex process that often requires treatment with antibiotics. This article reports the initial development of a biodegradable polymeric nanofiber-based antibiotic delivery system. The functions of such a system would be (a) to serve as a biodegradable gauze, and (b) to serve as an antibiotic delivery system. The polymer used in this study was poly(lactide-co-glycolide) (PLAGA), and nanofibers of PLAGA were fabricated with the use of the electrospinning process. The objective of this study was to determine the effect of fabrication parameters: orifice diameter (needle gauge), polymer solution concentration, and voltage per unit length, on the morphology and diameter of electrospun nanofibers. The needle gauges studied were 16 (1.19 mm), 18 (0.84 mm), and 20 (0.58 mm), and the range of polymer solution concentration studied was from 0.10 g/mL to 0.30 g/mL. The effect of voltage was determined by varying the voltage per unit electrospinning distance, and the range studied was from 0.375 kV/cm to 1.5 kV/cm. In addition, the mass per unit area of the electrospun nanofibers as a function of time was determined and the feasibility of antibiotic (cefazolin) loading into the nanofibers was also studied. The results indicate that the diameter of nanofibers decreased with an increase in needle gauge (decrease in orifice diameter), and increased with an increase in the concentration of the polymer solution. The voltage study demonstrated that the average diameter of the nanofibers decreased with an increase in voltage. However, the effect of voltage on fiber diameter was less pronounced as compared to polymer solution concentration. The results of the areal density study indicated that the mass per unit area of the electrospun nanofibers increased linearly with time. Feasibility of drug incorporation into the nanofibers was demonstrated with the use of cefazolin, a broad-spectrum antibiotic. Overall, these studies demonstrated that PLAGA nanofibers can be tailored to desired diameters through modifications in processing parameters, and that antibiotics such as cefazolin can be incorporated into these nanofibers. Therefore, PLAGA nanofibers show potential as antibiotic delivery systems for the treatment of wounds.

Modeling of mechanical properties and structural design of spider web.

With a unique combination of strength and toughness among materials, spider silk is the model for engineering materials. This paper presents the stress-strain behavior of Nephila clavipes spider silk under tension, transverse compression, and torsional deformation obtained by a battery of micro testing equipment. The experimental results showed significantly higher toughness than the state-of-the-art fibers in tension and in transverse compression. Higher shear modulus was also observed for the spider silk comparing to other liquid crystalline fibers such as aramid fibers. On the basis of the experimental results finite element analysis is used to simulate static and dynamic properties of spider web and to explore the role of both material properties and architectural design in its structural integrity and mechanical performance.

Electrospun nanofibrous structure: a novel scaffold for tissue engineering.

The architecture of an engineered tissue substitute plays an important role in modulating tissue growth. A novel poly(D,L-lactide-co-glycolide) (PLGA) structure with a unique architecture produced by an electrospinning process has been developed for tissue-engineering applications. Electrospinning is a process whereby ultra-fine fibers are formed in a high-voltage electrostatic field. The electrospun structure, composed of PLGA fibers ranging from 500 to 800 nm in diameter, features a morphologic similarity to the extracellular matrix (ECM) of natural tissue, which is characterized by a wide range of pore diameter distribution, high porosity, and effective mechanical properties. Such a structure meets the essential design criteria of an ideal engineered scaffold. The favorable cell-matrix interaction within the cellular construct supports the active biocompatibility of the structure. The electrospun nanofibrous structure is capable of supporting cell attachment and proliferation. Cells seeded on this structure tend to maintain phenotypic shape and guided growth according to nanofiber orientation. This novel biodegradable scaffold has potential applications for tissue engineering based upon its unique architecture, which acts to support and guide cell growth.