Controllable Aligned Nanofiber Hybrid Yarns with Enhanced Bioproperties for Tissue Engineering

Electrospun nanofibers have large surface area, high porosity, and controllable orientation while conventional microfibers have appropriate mechanical properties such as stiffness, strength, and elasticity. Therefore, the combination of nanofibers and microfibers can provide building elements to engineer biomimetic scaffolds for tissue engineering. In this study, a core–shell structured fibrous structure with controllable surface topography is created by electrospinning polycaprolactone (PCL) nanofibers onto polyglycolic acid (PGA) microfibers. The surface morphology, surface wettability, and mechanical properties of the resultant core–shell structure are characterized. FE‐SEM images reveal that the orientation of PCL nanofibers on the yarn surface can be tuned by a fiber collector and rotating disks. Benefiting from the introduction of a shell of aligned PCL nanofibers on the core of PGA yarn, the uniaxially aligned PCL nanofiber–covered yarns (A‐PCLs) exhibit higher hydrophilicity, porosity, and mechanical properties than the core PGA yarns. Moreover, A‐PCLs promote the adhesion and proliferation of BALB/3T3 (mouse embryonic fibroblast cell line), and guide cell growth along the biotopographic cues of the PCL nanofibers with controllable alignment. The developed core–shell yarn having both the desired surface topography of PCL nanofibers and mechanical properties of PGA microfibers demonstrates great potential in constructing various tissue scaffolds.     

Influence of solution properties on the roller electrospinning of poly(vinyl alcohol)

In recent years, nanofiber production via electrospinning has gained importance because of superior properties of submicron fibers. In this study, the effect of molecular weight, concentration of solution, electric conductivity, surface tension and solution viscosity of the polymer solution on the roller electrospinning of PVA nanofibers was investigated. One nonspinnable and two spinnable polymer species were studied. The effect of polymer concentration and solution viscosity on the electrospinning process throughput, fiber diameters and quality of nanofiber layers was measured. According to the results there is a significant difference in rheological behavior of nonspinnable and spinnable polymer solutions. Electric conductivity and surface tension of the solutions did not influence both throughput and fiber diameter significantly. Whereas molecular weight has an important effect on the spinnability, concentration of the solutions has not. On the contrary, concentration influences the process throughput considerably and properties of nanofibers and nanofiber layers to some extent. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Comparison of prolonged antibacterial activity and release profile of propolis‐incorporated PVA nanofibrous mat,microfibrous mat,and film

Propolis as a natural antibacterial agent was incorporated into the poly(vinyl alcohol) (PVA) in different forms of nanofiber, microfiber, and film. The successful fabrication of uniform nanofibers with 85–314 nm diameters and microfibers with 2.02 μm diameter was proved by scanning electron microscopy. Structural analysis by Fourier transform infrared spectroscopy and X‐ray diffraction and swelling properties confirmed the formation PVA hydrogel and its H‐bonding to the propolis. Evaluation and comparison of antimicrobial properties of produced samples against Staphylococcus aureus strains revealed that nanofiber mat with 19 mm inhibition zone has 11.76 and 26.67% higher efficiency against bacteria than microfiber mat and film with 17 and 15 mm inhibition zone, respectively. Nanofibrous mat showed sustained release during 96 h by maintaining full antibacterial activity up to 51 h which is of great importance in burn wounds. These results confirm the advanced performance of natural propolis in the form of nanofiber substrate as wound dressing. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45794.     

Electrospinning and crosslinking of zein nanofiber mats

Electrospinning processing can be applied to fabricate fibrous polymer mats composed of fibers whose diameters range from several microns down to 100 nm or less. In this article, we describe how electrospinning was used to produce zein nanofiber mats and combined with crosslinking to improve the mechanical properties of the as‐spun mats. Aqueous ethanol solutions of zein were electrospun, and nanoparticles, nanofiber mats, or ribbonlike nanofiber mats were obtained. The effects of the electrospinning solvent and zein concentration on the morphology of the as‐spun nanofiber mats were investigated by scanning electron microscopy. The results showed that the morphologies of the electrospun products exhibited a zein‐dependent concentration. Optimizing conditions for zein produced nanofibers with a diameter of about 500 nm with fewer beads or ribbonlike nanofibers with a diameter of approximately 1–6 μm. Zein nanofiber mats were crosslinked by hexamethylene diisocyanate (HDI). The tensile strength of the crosslinked electrospun zein nanofiber mats was increased significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:380–385, 2007     

Conjugate electrospinning of continuous nanofiber yarn of poly(L‐lactide)/nanotricalcium phosphate nanocomposite

The continuous nanofiber yarns of poly(L ‐lactide) (PLLA)/nano‐β‐tricalcium phosphate (n‐TCP) composite are prepared from oppositely charged electrospun nanofibers by conjugate electrospinning with coupled spinnerets. The morphology and mechanical properties of PLLA/n‐TCP nanofiber yarns are characterized by scanning electron microscope, transmission electron microscope, and electronic fiber strength tester. The results show that PLLA/n‐TCP nanofibers are aligned well along the longitudinal axis of the yarn, and the concentration of PLLA plays a significant role on the diameter of the nanofibers. The thicker yarn of PLLA/n‐TCP composite with the weight ratio of 10/1 has been produced by multiple conjugate electrospinning using three pairs of spinnerets, and the yarn has tensile strength of 0.31cN/dtex. A preliminary study of cell biocompatibility suggests that PLLA/n‐TCP nanofiber yarns may be useable scaffold materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Densifying and strengthening of electrospun polyacrylonitrile‐based nanofibers by uniaxial two‐step stretching

The effects of alignment of polyacrylonitrile (PAN) nanofibers and a two‐step drawing process on the mechanical properties of the fibers were evaluated in the current study. The alignment was achieved using a high‐speed collector in electrospinning synthesis of the nanofibers. Under optimal two‐step drawing conditions (e.g., hot‐water and hot‐air stretching), the PAN nanofiber felts exhibited large improvements in both alignment and molecular chain‐orientation. Large increase in crystallinity, crystallite size, and molecular chain orientation were observed with increasing draw ratio. Optimally, stretched PAN‐based nanofibers exhibited 5.3 times higher tensile strength and 6.7 times higher tensile modulus than those of the pristine one. In addition, bulk density of the drawn PAN nanofibers increased from 0.19 to 0.33 g/cm³. Our results show that fully extended and oriented polymer chains are critical in achieving the highest mechanical properties of the electrospun PAN nanofibers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43945.     

Preparation of charged mosaic membrane of sodium polystyrene sulfonate and poly(4‐vinyl pyridine) by conjugate electrospinning

Conjugate electrospinning of two nozzles with opposite charges was used for the fabrication of charged mosaic membrane (CM membrane). Sodium polystyrene sulfonate (PNaSS) and poly(4‐vinyl pyridine) (P4VP) were selected as anionic and cationic exchange elements, respectively. Polyvinyl alcohol was used as the common matrix for the enhancement of mechanical properties by formaldehyde crosslinking. Scanning electron microscope (SEM), transmission electron microscope (TEM), and tensile testing for nanofiber were used for the characterizations of CM membrane. Using the conjugate electrospinning, a simple equation was established to predict the mean diameters of nanofibers. It was proved that the calculated diameters fit well with the experimental data using electrospinning parameters such as concentration of spun solution, collecting speed, rate of solution supply, and distance of two nozzles. TEM picture showed a PNaSS nanofiber was incorporated with a P4VP nanofiber. However, SEM photo indicated that the alignment of composite nanofibers in CM membrane was greatly affected by the concentration of polyelectrolyte. As the concentration of PNaSS increased, the alignment degree decreased. After crosslinking with formaldehyde for 20 h, the tensile strength and Young's modulus of CM membrane reached 11.3 and 24.8 MPa, respectively. The water content and water insolubility of CM membrane were also investigated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40716.     

In situ synthesis of iron oxide nanoparticles on poly(ethylene oxide) nanofibers through an electrospinning process

Iron oxide nanoparticle coated poly(ethylene oxide) nanofibers as organic–inorganic hybrids with 200–400‐nm diameters were prepared by the in situ synthesis of iron oxide nanoparticles on poly(ethylene oxide) nanofibers through the electrospinning of a poly(ethylene oxide) solution having Fe²⁺ and Fe³⁺ ions in a gaseous ammonia atmosphere. Transmission electron microscopy analysis proved the presence of iron oxide nanoparticles on the polymer nanofibers. The thermal properties of the nanofiber mat were also studied with differential scanning calorimetry and thermogravimetric analysis techniques. X‐ray diffraction showed that the formed iron oxide nanoparticles were maghemite nanoparticles. The results were compared with those of the electrospinning of a poly(ethylene oxide) solution having Fe²⁺ and Fe³⁺ ions and a pure poly(ethylene oxide) solution in an air atmosphere. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

A new approach for conductive network formation in electrospun poly(vinylidene fluoride) nanofibers

Conductive nanofibers of poly(vinylidene fluoride) (PVDF) filled with polyaniline (PANi)‐coated multi‐wall carbon nanotubes (MWCNTs) were fabricated using the electrospinning technique. PANi is an intrinsically conductive polymer. The addition of PANi‐coated MWCNTs to PVDF created short conductive strands on the surface of the nanofibers, facilitating the formation of a conductive network in the transverse direction of the nanofibers. Piezoelectricity along with electric conductivity makes these PVDF nanofibers promising for applications such as sensors and actuators. Electrospun PVDF nanofiber mats had higher piezoelectricity than melt‐processed samples produced using traditional polymer processing techniques, such as compression molding. Spectroscopic imaging techniques were employed to study the effects of the filler and processing conditions on the nanofiber structure. X‐ray diffraction, Fourier transform infrared spectroscopy and differential scanning calorimetry results indicated a large increase in the β‐phase crystals of the PVDF nanofibers. This higher content of β‐phase crystals enhanced the piezoelectricity of the nanofibers. © 2015 Society of Chemical Industry     

Fabrication of aligned electrospun nanofibers by inclined gap method

A high‐performance of uniaxial alignment of electrospun nanofibers was realized by introducing an inclined gap into dual collectors that consisted of two conductive strips. Because the two strips that were configured horizontally and vertically had a height difference from the inclined gap, the electrospun nanofibers were sequentially suspended across the edges of strips in a well‐aligned and regularly distributed form. Some parameters, such as concentration of solution, applied voltage, and spinning distance were considered for the successful suspension and formation of the aligned electrospun fibers. The method could improve the properties of nanofiber alignment and allow for easy transfer onto other solid substrates or devices. The alignment technique used polycaprolactone, which resulted in continuous and well‐aligned nanofibers with diameters ranging from 500 to 700 nm. Furthermore, it is suggested that repetitive transfer be used to achieve a higher density of aligned nanofiber arrays. This would enlarge the applicability of nanofibers, especially for the tissue engineering field. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Tensile fatigue behavior of polyamide 66 nanofiber yarns

Nanofiber yarns with twisted and continuous structures have potential applications in fabrication of complicated structures such as surgical suture yarns, artificial blood vessels, and tissue scaffolds. The objective of this article is to characterize the tensile fatigue behavior of continuous Polyamide 66 (PA66) nanofiber yarns produced by electrospinning with three different twist levels. Morphology and tensile properties of yarns were obtained under static tensile loading and after fatigue loading. Results showed that tensile properties and yarn diameter were dependent on the twist level. Yarns had nonlinear time‐independent stress–strain behavior under the monotonic loading rates between 10 and 50 mm/min. Applying cyclic loading also positively affected the tensile properties of nanofiber yarns and changed their stress–strain behavior. Fatigue loading increased the crystallinity and alignment of nanofibers within the yarn structure, which could be interpreted as improved tensile strength and elastic modulus. POLYM. ENG. SCI., 55:1805–1811, 2015. © 2014 Society of Plastics Engineers     

One‐dimensional polymer nanofiber arrays with high aspect ratio obtained by thermal nanoimprint method

Polymer surface modification that mimicks natural behaviors has been a subject of great interest. Fabrication of polymer nanofiber arrays with various applications has been studied intensively. Avoidance of chemical solvents, reduction of processing time, improvement of the nanofiber size distribution and aspect ratios, and improvement of reproducibility have been sought for industrial value creation. This study examines an alternative fabrication methods for polymer nanofiber arrays using a combination of anodic aluminum oxide (AAO) nanoporous template and thermal nanoimprinting lithography for simple, precise processing. Based on those results, nanofiber arrays were fabricated with 40‐µm‐thick film and 50–100 nm fiber diameter polystyrene (PS) and polypropylene (PP). For this study, 50‐nm diameter PS nanofibers with 50 µm maximum length and a maximum aspect ratio of 1,000 were produced in addition to PP nanofibers having 130 µm maximum length and an aspect ratio of 2,600. The nanofiber lengths were affected considerably by molten polymer flow related to imprint processing conditions, polymer properties, AAO properties, and surface wettability between AAO and molten polymers. Moreover, AAO nanoconfinement demonstrated molecular orientation alignment of polymers that affect thermal properties, crystallinity, and mechanical properties of the obtained polymer nanofiber arrays. POLYM. ENG. SCI., 57:214–223, 2017. © 2016 Society of Plastics Engineers     

Transparent poly(methyl methacrylate‐co‐butyl acrylate) nanofibers

Nanofibers of n‐Butyl Acrylate/Methyl Methacrylate copolymer [P(BA‐co‐MMA)] were produced by electrospinning in this study. P(BA‐co‐MMA) was synthesized by emulsion polymerization. The structural and thermal properties of copolymers and electrospun P(BA‐co‐MMA) nanofibers were analyzed using Fourier transform infrared spectroscopy–Attenuated total reflectance (FTIR–ATR), Nuclear magnetic spectroscopy (NMR), and Differential scanning calorimetry (DSC). FTIR–ATR spectra and NMR spectrum revealed that BA and MMA had effectively participated in polymerization. The morphology of the resulting nanofibers was investigated by scanning electron microscopy, indicating that the diameters of P(BA‐co‐MMA) nanofibers were strongly dependent on the polymer solution dielectric constant, and concentration of solution and flow rate. Homogeneous electrospun P(BA‐co‐MMA) fibers as small as 390 ± 30 nm were successfully produced. The dielectric properties of polymer solution strongly affected the diameter and morphology of electrospun polymer fibers. The bending instability of the electrospinning jet increased with higher dielectric constant. The charges inside the polymer jet tended to repel each other so as to stretch and reduce the diameter of the polymer fibers by the presence of high dielectric environment of the solvent. The extent to which the choice of solvent affects the nanofiber characteristics were well illustrated in the electrospinning of [P(BA‐co‐MMA)] from solvents and mixed solvents. Nanofiber mats showed relatively high hydrophobicity with intrinsic water contact angle up to 120°. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4264–4272, 2013     

Three-dimensional coating of nanofibers on surfaces of poorly conductive objects

Rectangular-shaped, poorly conductive synthetic polymer scaffolds composed of a mixture of polycaprolactone and poly-L-lactic acid (PCL/PLLA, 75:25) were coated directly with nanofibers composed of PLLA using an electrospinning technique having a modified design for the electrically grounded collector. The design modification consisted of mounting each scaffold onto a fine-point needle which was attached directly to the ground electrode of the electrospinning unit. Nanofibers were collected on all six surfaces of each scaffold. The coated scaffolds were then dried at ambient temperature overnight before sterilization by immersion in 100% ethanol to assess and ensure adherence between the scaffold and nanofibers. Photomicrographs from scanning electron microscopy illustrate nanofiber coverage over all six surfaces of the polymer scaffold. The design in this manner for three-dimensional coating of poorly conductive objects advances electrospinning capability for numerous new applications.     

Magnetic‐field‐assisted electrospinning highly aligned composite nanofibers containing well‐aligned multiwalled carbon nanotubes

Composite nanofiber meshes of well‐aligned polyacrylonitrile (PAN)/polyvinylpyrrolidone (PVP) nanofibers containing multiwalled carbon nanotubes (MWCNTs) were successfully fabricated by a magnetic‐field‐assisted electrospinning (MFAES) technology, which was confirmed to be a favorable method for preparation of aligned composite nanofibers in this article. The MFAES experiments showed that the diameters of composite nanofibers decreased first and then increased with the increase of voltage and MWCNTs content. With the increase of voltage, the degree of alignment of the composite nanofibers decreased, whereas it increased with increasing MWCNTs concentration. Transmission electron microscopy observation showed that MWCNTs were parallel and oriented along the axes of the nanofibers under the low concentration. A maximum enhancement of 178% in tensile strength was manifested by adding 2 wt % MWCNTs in well‐aligned composite nanofibers. In addition, the storage modulus of PAN/PVP/MWCNTs composite nanofibers was significantly higher than that of the PAN/PVP nanofibers. Besides, due to the highly ordered alignment structure, the composite nanofiber meshes showed large anisotropic surface resistance, that is, the surface resistance of the composite nanofiber films along the fiber axis was about 10 times smaller than that perpendicular to the axis direction. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41995.     

Continuous polymer nanofiber yarns prepared by self-bundling electrospinning method

Continuous polymer nanofiber yarns were manufactured by self-bundling electrospinning method. Compared with typical electrospinning setup, the special difference in this method was that a grounded needle tip was used to induce the self-bundling of polymer nanofibers at the beginning of electrospinning process. Four kinds of polymer self-bundling yarns, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), polyacrylonitrile (PAN), poly(l-lactic acid) (PLLA) and poly(m-phenylene isophthalamide) (PMIA), were prepared successfully by using this self-bundling electrospinning method. Good alignment of polymer nanofibers in self-bundled yarns was confirmed by SEM observation. It was found out that the conductivity of the polymer solution was crucial to achieve stably continuous self-bundled fiber yarns. A possible mechanism for the self-bundling formation of align nanofiber yarn was proposed.     

Biocompatibility of braided poly(L‐lactic acid) nanofiber wires applied as tissue sutures

Almost all sutures in current usage only play one role, i.e. to mechanically tie wound tissues together. Drug‐loaded composite nanofibers obtained through coaxial electrospinning can initiate the development of a new type of biodegradable sutures with drug release. In this work, electrospun poly(L ‐lactic acid) (PLLA) nanofibers with uniaxial alignment were made into braided wires and were coated with chitosan and applied as tissue sutures. Toxicity evaluation on cells for the chitosan‐coated PLLA braided wires was carried out using the MTT (3‐(4,5‐dimethylthiazol‐2‐yl)‐5‐(3‐carboxymethoxyphenyl)‐2‐(4‐sulfophenyl)‐2H‐tetrazolium) test, and an in vivo study was conducted by implanting the braided wires into muscle tissues of rats. The inflammation responses were examined at 3, 7, 14, 21 and 28 days after implanting. Experimental results indicated that the braided PLLA nanofiber wires coated with chitosan exhibited comparable tensile and knot strengths to those of a commercial suture, could tie wounded tissues for a complete healing without any breakage, had no cellular toxicity and could promote cell growth well. The chitosan‐coated PLLA sutures showed better histological compatibility than a silk suture in the in vivo study. Braided PLLA nanofiber wires fabricated using an electrospinning process followed by a braiding technique and coated with chitosan are applicable for uses within the body. Copyright © 2009 Society of Chemical Industry     

Effect of air blowing on the morphology and nanofiber properties of blowing‐assisted electrospun polycarbonates

Polycarbonate (PC) nanofibers are prepared using the air blowing‐assisted electrospinning process. The effects of air blowing pressure and PC solution concentration on the physical properties of fibers and the filtration performance of the nanofiber web are investigated. The air blowing‐assisted electrospinning process produces fewer beads and smaller nanofiber diameters compared with those obtained without air blowing. Uniform PC nanofibers with an average fiber diameter of about 0.170 μm are obtained using an applied voltage of 40 kV, an air blowing pressure of 0.3 MPa, a PC solution concentration of 16%, and a tip‐to‐collection‐screen distance (TCD) of 25 cm. The filtration efficiency improvement of the air blowing‐assisted electrospun web can be attributed to the narrow distribution of fiber diameter and small mean flow pore size of the electrospun web. Performance results show that the air blowing‐assisted electrospinning process can be applied to produce PC nanofiber mats with high‐quality filtration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of electrospun ultrafine polyamide‐6 nanofibers

We report on the preparation and characterization of ultrafine polyamide‐6 nanofibers by the electrospinning technique. The effect of electrospinning on the formation of ultrafine polyamide‐6 nanofiber structure was examined. The morphological and structural characterizations and thermal properties of the ultrafine polyamide‐6 nanofibers were investigated in comparison with bulk polyamide‐6 pellets. In order to accurately characterize the ultrafine polyamide‐6 nanofiber structure by direct identification of mass resolved components, we performed matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectrometry. Field emission scanning electron microscopy images revealed the presence of ultrafine polyamide‐6 nanofibers bound between the main fibers. The diameter of the polyamide‐6 nanofibers was observed to be in the range 75–110 nm, whereas the ultrafine structures consisted of regularly distributed very fine nanofibers with diameters of about 9–28 nm. The MALDI‐TOF spectra showed the presence of protonated and sodiated ions that were assigned to polyamide‐6 chains. Copyright © 2011 Society of Chemical Industry     

Fabrication and characterization of 3-dimensional PLGA nanofiber/microfiber composite scaffolds

Novel three-dimensional (3-D) nano-/microfibrous poly(lactic-co-glycolic acid) (PLGA) scaffolds were fabricated by hybrid electrospinning, involving a combination of solution electrospinning and melt electrospinning. The scaffolds consisted of a randomly oriented structure of PLGA microfibers (average fiber diameter = 28 μm) and PLGA nanofibers (average fiber diameter = 530 nm). From mercury porosimetry, the PLGA nano-/microfiber (10/90) scaffolds were found to have similar pore parameters to the PLGA microfiber scaffolds. PLGA nano-/microfibrous scaffolds were examined and compared with the PLGA microfiber scaffolds in terms of the attachment, spreading and infiltration of normal human epidermal keratinocytes (NHEK) and fibroblasts (NHEF). The cell attachment and spreading of both cell types were several times higher in the nano-/microfiber composite scaffolds than in the microfibrous scaffolds without nanofibers. This shows that the presence of nanofibers enhanced the attachment and spreading of the cells on the nano-/microfiber composite scaffolds. Moreover, the nanofibers helped the cells infiltrate easily into the scaffolds. Overall, this novel nano-/microfiber structures has great potential for the 3-D organization and guidance of cells provided for tissue engineering.