Bioactive Electrospun Fibers of Poly(ε-Caprolactone) Incorporating α-Tocopherol for Food Packaging Applications

Antioxidant activity is an important feature for food contact materials such as packaging, aiming to preserve freshness and retard food spoilage. Common bioactive agents are highly susceptible to various forms of degradation; therefore, protection is required to maintain functionality and bioavailability. Poly(ε-caprolactone) (PCL), a biodegradable GRAS labeled polymer, was used in this study for encapsulation of α-tocopherol antioxidant, a major component of vitamin E, in the form of electrospun fibers. Rheological properties of the fiber forming solutions, which determine the electrospinning behavior, were correlated with the properties of electrospun fibers, e.g., morphology and surface properties. Interactions through hydrogen bonds were evidenced between the two components. These have strong effect on structuration of macromolecular chains, especially at low α-tocopherol amounts, decreasing viscosity and elastic modulus. Intra-molecular interactions in PCL strengthen at high α-tocopherol amounts due to decreased solvation, allowing good structural recovery after cease of mechanical stress. Morphologically homogeneous electrospun fibers were obtained, with ~6 μm average diameter. The obtained fibers were highly hydrophobic, with fast release in 95% ethanol as alternative simulant for fatty foods. This induced good in vitro antioxidant activity and significant in vivo reduction of microbial growth on cheese, as determined by respirometry. Therefore, the electrospun fibers from PCL entrapping α-tocopherol as bioactive agent showed potential use in food packaging materials.     

An alternative solvent system for the steady state electrospinning of polycaprolactone

Polycaprolactone (PCL) is a biocompatible aliphatic polyester with many possible applications in the medical field. PCL nanofibres, produced by electrospinning, could provide new characteristics that are of interest for these applications. However, a key prerequisite is the ability to obtain bead-free fibres with diameters in the nanoscale range. At present the most commonly used solvent for electrospinning PCL is chloroform, but this only leads to fibres in the microscale range. Therefore various solvent systems were examined in this study. The innovative solvent mixture formic acid/acetic acid was found to allow for nanofibres with a diameter 10 times smaller than the solvent chloroform. Moreover, steady state conditions could be obtained which thus allow electrospinning in a stable and reproducible way. Further it was noticed that the average fibre diameter decreased with decreasing polymer concentration while the diameter distribution decreased with increasing amount of formic acid. Also the humidity, an often overlooked yet important parameter, was noted to affect both diameter characteristics. Generally it can be concluded that the solvent system formic acid/acetic acid could fill the gap in electrospinning PCL since it is readily able to produce uniform fibres in the nanoscale range.     

Enzymatic degradation of poly(L-lactide) and poly(epsilon-caprolactone) electrospun fibers

Poly(L-lactide) (PLLA) and poly(epsilon-caprolactone) (PCL) ultrafine fibers were prepared by electrospinning. The influence of cationic and anionic surfactants on their enzymatic degradation behavior was investigated by measuring weight loss, molecular weight, crystallinity, and melting temperature of the fibers as a function of degradation time. Under the catalysis of proteinase K, the PLLA fibers containing the anionic surfactant sodium docecyl sulfate (SDS) exhibited a faster degradation rate than those containing cationic surfactant triethylbenzylammonium chloride (TEBAC), indicating that surface electric charge on the fibers is a critical factor for an enzymatic degradation. Similarly, TEBAC-containing PCL fibers exhibited a 47% weight loss within 8.5 h whereas SDS-containing PCL fibers showed little degradation in the presence of lipase PS. By analyzing the charge status of proteinase K and lipase PS under the experimental conditions, the importance of the surface charges of the fibers and their interactions with the charges on the enzymes were revealed. Consequently, a "two-step" degradation mechanism was proposed: (1) the enzyme approaches the fiber surface; (2) the enzyme initiates hydrolysis of the polymer. By means of differential scanning calorimetry and wide-angle X-ray diffraction, the crystallinity and orientation changes in the PLLA and PCL fibers during the enzymatic degradation were investigated, respectively.     

Synthesis and Characterization of Biodegradable Poly(ϵ-caprolactone)-b-Poly(L-lactide) and Study on Their Electrospun Scaffolds

A series of multi-block copolymers, poly(L-lactide)-b-poly (?-caprolactone) (PLLA-b-PCL) were synthesized. The first step of the synthesis consisted of the transesterification between the PLLA and 1,4-Butanediol, followed by the copolymerization of PLLA-diols and PCL, using isophorone diisocyanate (IPDI) as a coupling agent. The synthesized polymers were characterized by Fourier transform infrared (FTIR) spectra, differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WAXD). PLLA/PCL block copolymers were electrospun into ultrafine fibers. The morphology of the electrospun fibrous scaffolds were investigated by Scanning Electron Microscopy (SEM). Results showed that the morphology and diameter of the fibers were affected by the electrospinning solution concentrationan and different weight ratio of PLLA/PCL. These electrospun PLLA-b-PCL fibrous membranes exhibited good flexibility and deformability. In comparison with the electrospun PLLA membrane, the electrospun fibrous membranes of PLLA-b-PCL demonstrated an enhanced elongation with still high tensile strength and Young's modulus to be beneficial for tissue engineering scaffolds.     

Influence of solvents on the formation of ultrathin uniform poly(vinyl pyrrolidone) nanofibers with electrospinning

Although there have been many reports on the preparation and applications of various polymer nanofibers with the electrospinning technique, the understanding of synthetic parameters in electrospinning remains limited. In this article, we investigate experimentally the influence of solvents on the morphology of the poly(vinyl pyrrolidone) (PVP) micro/nanofibers prepared by electrospinning PVP solution in different solvents, including ethanol, dichloromethane (MC) and N,N‐dimethylformamide (DMF). Using 4 wt % PVP solutions, the PVP fibers prepared from MC and DMF solvents had a shape like a bead‐on‐a‐string. In contrast, smooth PVP nanofibers were obtained with ethanol as a solvent although the size distribution of the fibers was somewhat broadened. In an effort to prepare PVP nanofibers with small diameters and narrow size distributions, we developed a strategy of using mixed solvents. The experimental results showed that when the ratio of DMF to ethanol was 50:50 (w/w), regular cylindrical PVP nanofibers with a diameter of 20 nm were successfully prepared. The formation of these thinnest nanofibers could be attributed to the combined effects of ethanol and DMF solvents that optimize the solution viscosity and charge density of the polymer jet. In addition, an interesting helical‐shaped fiber was obtained from 20 wt % PVP solution in a 50:50 (w/w) mixed ethanol/DMF solvent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3721–3726, 2004     

Polycaprolactone composites with TiO(2) for potential nanobiomaterials: tunable properties using different phases

TiO(2) nanoparticles of different phases play a key role in property alteration of nanocomposite fibers. Polycaprolactone (PCL)/TiO(2) composite fibers were prepared using the electrospinning method. Pure anatase and rutile phases were synthesized using the sol-gel route for nanocomposite synthesis. The Effect of nanoparticle phases on crystallinity of fibers and interaction with polymer molecules have been studied using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, morphology through SEM, surface properties using BET method and wetting property of fibers commencing from contact angle measurement. Biocompatibility and biodegradation of hybrid materials have been studied in simulated body fluid (SBF) and phosphate buffer (PBS), respectively. The anatase phase with smaller particle dimensions exhibited significant improvement of most of the properties as compared to composites made of the rutile phase. Better interaction between polymer chain and anatase particle PCL-A nanocomposite fibers leads to better mechanical property and biocompatibility vis-à-vis PCL-R and pristine PCL fibers. Biocompatibility of PCL nanocomposite has been testified through proliferation of fibroblast cell and its adhesion; MTT (3-(4,5-dimethythiazol-2-yl)-2,5-diphenyl tetrazolium bromide) assay demonstrates good proliferation rate for cells on PCL-A nanocomposite fibres.     

Chain conformations of poly(gamma-benzyl-L-glutamate) pre and post an electrospinning process

In order to reveal mechanisms for the electrospinning of proteins, this study focuses on the polymer chain conformation, which is considered to be a critical factor for successful electrospinning. Poly(gamma-benzyl-L-glutamate) (PBLG) is employed and the relationships between the chain conformations of the pre-spun PBLG molecules and the morphologies of the post-spun PBLG fibers are investigated. By combining viscosity measurements, and circular dichroism and FT-IR spectroscopies, chain conformations of the pre- and post-spun PBLG are characterized. The chain conformations of the pre-spun PBLG changes from an alpha-helix to a random coil upon changing the solvent ratios of dichloromethane (CH(2)Cl(2)) and trifluoroacetic acid (CF(3)COOH) from 100:0 to 0:100. In an alpha-helix conformation, the morphology of PBLG fibers is relatively thick, while that of the random coil is thin and homogenous. The mean fiber diameters decrease when the chain conformations change from an alpha-helix to a random coil. FT-IR spectroscopy and wide-angle X-ray diffraction measurements reveal that electrospinning predominantly induces an alpha-helical conformation in post-spun PBLG fibers, and more highly crystallized fibers are generated as the alpha-helical content in the pre-spun solution increases.     

Effects of poly(ethylene oxide) and pH on the electrospinning of whey protein isolate

Poly(ethylene oxide) (PEO) is known for facilitating the electrospinning of biopolymer solutions, which are otherwise not electrospinnable. The objective of this study was to improve the understanding of the positive effects of PEO on the electrospinning of whey protein isolate (WPI) solutions under different pH conditions. Alterations in protein secondary structure and polymer solution properties (viscosity, conductivity, and dynamic surface tension), as induced by pH changes, significantly affected the electrospinning behavior of WPI/PEO (10% w/w: 0.4% w/w PEO) solutions. Acidic solutions resulted in smooth fibers (707 ± 105 nm) while neutral solutions produced spheres (2.0 ± 1.0 μm) linked with ultrafine fibers (138 ± 32 nm). In comparison, alkaline solutions produced fibers (191 ± 36 nm) that were embedded with spindle‐like beads (1.0 ± 0.5 μm). ¹³C NMR and FTIR spectroscopies showed that the increase in random coil and α‐helix secondary structures in WPI were the main contributors to the formation of bead‐less electrospun fibers. The electrospinning‐enabling properties of PEO on aqueous WPI solutions were attributed to physical chain entanglement between the two polymers, rather than specific polymer–polymer interactions. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Porous ultrafine fibers via a salt-induced electrospinning method

A salt-induced electrospinning method to produce porous polymer ultrafine fibers was reported in this work. Scanning electron microscopy, energy dispersive spectrometer, and BET surface area measurement were employed to evaluate the morphology, the element distribution, and the surface area of fibers, respectively. According to the investigation result, pores on the fiber were induced by water-soluble salt during electrospinning process in a humid spinning environment. There was no porous structure on the fiber surface when water-insoluble salt was used in a wet electrospinning environment or when water-soluble salt was used in a dry electrospinning environment. Compared with pure fibers, the average surface area of fibers containing salt increased significantly due to the porous structure. The possible mechanism of the porous structure induced by salt was proposed. Water-solubility salt and humid environment were considered as the key roles in the formation of porous structure. This method provided a new way to form porous structure during electrospinning.     

Preparation of electrospun shape memory polyurethane fibers in optimized electrospinning conditions via response surface methodology

Herein, the electrospinning method, as an effective approach, was utilized to fabricate poly (ε‐caprolactone)‐based polyurethane (PCL‐based PU) fibers. PCL was synthesized by ring‐opening polymerization, and characterized by proton nuclear magnetic resonance (¹H NMR) and Fourier‐transform infrared (FTIR) spectroscopies. Afterward, PU was prepared by step‐growth polymerization. The effects of solution concentration and solvent type on fibers' diameter were investigated. Scanning electron microscopy (SEM) images revealed that the optimum solution was N, N‐dimethylformamide(DMF): chloroform with a ratio of 60:40. In addition, results showed that bead‐less nanofibers could be achieved by a concentration of 5 w/v% (polymer to solvent). Various optimum practical parameters, such as applied voltage, feeding rate, and needle‐to‐collector distance, were obtained and compared with the results of response surface methodology (RSM). On the other hand, the mechanical evaluations indicated that the porous structure of scaffolds caused them to possess lower mechanical properties, as well as shape fixity ratios than those of bulk samples.     

Centrifugally spun poly(ethylene oxide) fibers rival the properties of electrospun fibers

Centrifugal force spinning (CFS), also known as centrifugal spinning, forcespinning, or rotary jet spinning, provides considerably higher production rates than electrospinning (ES), but the more widespread use of CFS as an alternative depends on the ability to produce fibers with robust thermal and mechanical properties. Here, we report the CFS of poly(ethylene oxide) (PEO) fibers made using a spinning dope formulated with acetonitrile (AcN) as the volatile solvent, and we describe the thermal and mechanical properties of the centrifugally-spun fibers. Even though the formation, diameter, and morphology of electrospun and centrifugally-spun PEO fibers are relatively well-studied, the article presents three crucial contributions: the pioneering use of PEO solutions in AcN as spinning dope, characterization of crystallinity and mechanical properties of the centrifugally-spun PEO fibers, and a comparison with the corresponding properties of electrospun fibers. We find that fiber formation occurrs for the chosen CFS conditions if polymer concentration exceeds the entanglement concentration, determined from the measured specific viscosity. Most significantly, the centrifugally spun PEO fibers display crystallinity, modulus, elongation-at-break, and fiber diameter that rival the properties of electrospun PEO fibers reported in the literature.     

Large‐scale aligned fiber mats prepared by salt‐induced pulse electrospinning

In this article, a new large‐scale aligned fiber mats formation method called salt‐induced pulse electrospinning was developed. By electrospinning salted solution in a humid environment, traditional continuous electrospinning changed into pulse electrospinning and aligned fibers were thus formed. The possible mechanisms for the occurrence of salt‐induced pulse electrospinning and the formation of fiber alignment were studied. The continuous electrospinning changing into the pulse electrospinning was due to the change of viscosity and conductivity of salted polymer solution in a wet electrospinning condition. Fishing net‐shaped whipping region of the electrospinning jet during pulse electrospinning process was considered as the key factor for the formation of fiber alignment. The mechanical properties of the aligned fiber mat increased significantly compared with that of the random fiber mat. This aligned fiber preparation method only requires a very low rotating drum speed as the receiver and can produce large‐scale aligned fiber mats for many applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Poly(3-hexylthiophene)/Poly(methyl methacrylate) Core-Shell Electrospun Fibers for Sensory Applications

New electrospun (ES) sensory fibers consisted of poly(methyl methacrylate) (PMMA) core and poly(3-hexylthiophene-2,5-diyl) (P3HT) shell were successfully prepared using a two-fluid coaxial electrospinning process. Field-emission scanning electron microscope (FE-SEM) studies showed that the prepared ES fibers had diameters of 500–700 nm and worm-like surface structure of P3HT on the fiber. Red emission fibers were exhibited from the laser confocal microscope. Upon exposed to air under light for two weeks, significant blue-shifting on both absorption and luminescence spectra was found on the prepared ES fibers. It was probably due to the chain scission occurred in the P3HT and led to the reduced conjugated length. The sensitivity of the ES fibers was much better than that of the spin-coated P3HT film from the comparison on the variation of photophysical properties. Besides, the EPR result indicated the formation of the P3HT · O₂ charge transfer complex (CTC), leading to the fiber conductivity of 10⁻⁶ S/cm without an external doping. The present study demonstrates that conjugated polymer based ES core-shell fibers may have potential applications for oxygen-sensing devices.     

Thermomechanical and structural characterization of polybutadiene/poly(ethylene oxide)/CNT stretchable electrospun fibrous membranes

It is difficult to produce rubbery polymer nanofibers, that is, polybutadiene, by the method of electrospinning, since during electrospinning rubbery polymer fibers join and entangles due to their low T_g. For this reason, it is not easy to achieve the fiber form out of these polymers. Homogeneously electrospun carbon nanotubes (CNT)‐filled polybutadiene (PBu) and poly(ethylene oxide) (PEO) composite elastomeric fibers exhibit distinctive physical features such as uniform fiber diameter and distribution with significant improvements in thermomechanical properties. Controlled hydrophilicity/hydrophobicity with the components allows to generate homogenous, thermally stable and stretchable bio‐composite scaffold, and fibrous antibacterial membrane scaffolds out of PBu/PEO/CNT composite. We have combined the exciting properties of PEO with high pore density with the rubber elasticity of PBu via dissolving them in a dichloromethane/ethyl acetate organic solvent, and subsequently producing electrospun woven fibers with different PBu/PEO ratios. Frequency‐dependent thermomechanical characterization via dynamic mechanical analysis reveals pronounced changes in the onset and extent of melting, as well as the storage and loss modulus values at the onset of melting, in particular when small amounts (1.25% by wt%) of CNTs are present. The characteristic bands were detected for the PBu/PEO and PBu/PEO/CNT samples by means of Raman and Fourier‐transform infrared spectroscopy. CNT addition increases the hydrophobicity via the increase in roughness as attained by atomic force microscopy.     

Fabrication and characterization of zein-based nanofibrous scaffolds by an electrospinning method

Electrospun zein membranes were prepared using DMF as solvent. By changing the solution concentration, the electrospinning voltage and the distance between the spinneret and collector, nanofibrous meshes without bead defects could be obtained. In order to improve the mechanical strength of the hydrated zein meshes, core-shell-structured nanofibrous membranes with PCL as the core material and zein forming the shell were prepared by coaxial electrospinning. The core-shell structure of the composite fibers was confirmed by SEM characterization of the fibers, either extracted with chloroform to remove the inner PCL, or elongated to expose their cross-section. The composition and average diameter of the composite fibers could be modulated by the feed rate of the inner PCL solution. It was found that the core-shell fibrous membranes have similar wettability to the electrospun zein mesh. The presence of PCL in the fibers could significantly improve the mechanical properties of the zein membrane.     

Production of aligned helical polymer nanofibers by electrospinning

A new and simple electrospinning method has been developed for producing aligned helical polymer nanofibers. Aligned helical polycaprolactone (PCL) nanofibers were prepared by this method. The helical fibers were collected by a tilted glass slide. The morphology and loop diameters of the helical structures are dependant on the PCL solution concentration and the loop diameters are in the range of 6.9-14.9 μm for the concentration range of 4.7%-10%. The three-dimensional helical structures were obtained at the high solution concentration of 10%. These helical structures were formed by jet buckling due to mechanical instability when hitting collector surface. Formation of the helical structures is dependent on the obliquity of the tilted glass slide and distance away from the syringe needle. The converging electrical field generated by a tip collector plays an important role in the alignment of the helical structures.     

Solvent and concentration effects on the properties of electrospun poly(ethylene terephthalate) nanofiber mats

This study describes the preparation and characterization of nanofibrous mats obtained by electrospinning poly(ethylene terephthalate) (PET) solutions in trifluoroacetic acid/dichloromethane (TFA/DCM). Special attention was paid to the effect of polymer concentration and solvent properties on the morphology, structure, and mechanical and thermal properties of the electrospun nonwovens. The results show that the spinnable concentration of PET solution in TFA/DCM solvents is above 10 wt %. Mats have nanofibrous morphology with fibers having an average diameter in the range of 200–700 nm (depending on polymer concentration and solvent composition) and an interconnected pore structure. Higher solution concentration favors the formation of uniform fibers without beads and with higher diameter. Morphology and fiber assembly changed with the solvent properties. Solvent mixtures rich in TFA, i.e., those with higher dielectric constant and lower surface tension, originated fibers with small diameter. However, due to the lower volatility, those solvent mixtures also produced more branched and crosslinking fibers, with less morphologic uniformity. Mechanical properties (Young's modulus, ultimate strength, and elongation at break) and thermal properties (glass transition, crystallization, and melting) have been studied for the PET electrospun nanomats and compared with those of the original polymer. Solvent effect on fiber crystallinity was not significant, but a complex effect was observed on the mechanical properties of the electrospun mats, as a consequence of the different structural organization of the fibers within the mat network. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 460–471, 2008     

Electrospinning of ultra-thin polymer fibers

The electrospinning technique was used to spin ultra-thin fibers from several polymer/solvent systems. The diameter of the electrospun fibers ranged from 16 nm to 2 μm. The morphology of these fibers was investigated with an atomic force microscope (AFM) and an optical microscope. Polyethylene oxide) (PEO) dissolved in water or chloroform was studied in greater detail. PEO fibers spun from aqueous solution show a “beads on a string” morphology. An AFM study showed that the surface of these fibers is highly ordered. The “beads on a string” morphology can be avoided if PEO is spun from solution in chloroform; the resulting fibers show a lamellar morphology. Polyvinylalcohol (PVA) dissolved in water and cellulose acetate dissolved in acetone were additional polymer/solvent systems which were investigated. Furthermore, the electrospinning process was studied: different experimental lay-outs were tested, electrostatic fields were simulated, and voltage - current characteristics of the electrospinning process were recorded.     

Human serum albumin in electrospun PCL fibers: structure,release, and exposure on fiber surface

Human serum albumin (HSA) introduced to the fibers produced by electrospinning from HSA and polycaprolactone (PCL) solutions in hexafluoroisopropanol has been studied in terms of its structure, release from the fibers, stability of interaction with basic polymer, accessibility for protease attack, and cellular receptors, as well as dependence of the studied parameters on the protein concentration in fibers. A limited part of the protein leaves the fibers right after soaking with water, whereas the remaining protein stays tightly bound to fibers for a long time because protein nanoparticles are tightly integrated with PCL, as shown by small‐angle X‐ray scattering. As has been demonstrated, the proteins leave the fibers in complexes with PCL. X‐ray photoelectron spectroscopy demonstrates that the protein concentration on the fiber surface is higher than the concentration in electrospinning solution. The surface‐exposed protein is recognized by cell receptors and is partially hydrolyzed by proteinase K. The data on pulse protein release, presence of PCL in the protein released from matrixes, overrepresentation of the protein on the fiber surface, and tight interaction of protein with PCL may be useful for rational design of electrospun scaffolds intended for drug delivery and tissue engineering. Copyright © 2016 John Wiley & Sons, Ltd.     

Grafting of wheat straw fibers with poly (ε‐caprolactone) via ring‐opening polymerization for poly(lactic acid) reinforcement

The use of natural materials has grown in the last years in the plastics industry. Natural lignocellulose fibers derived from agricultural waste present potential to be used as a replacement for glass fibers for polymer reinforcement, leading to lower CO₂ footprint products. This work focuses on the modification of the cellulose fibers in order to improve the compatibility with poly(lactic acid) (PLA). The scoured wheat straw fibers were grafted with polycaprolactone (PCL) through ring opening polymerization. Thermal stability of the wheat straw fibers improved after chemical modifications enabling higher processing temperatures. Flexural and tensile moduli were improved by 23% and 15%, respectively, compared with neat PLA, using 20 wt% modified fibers. An improvement of 20% in the impact strength was obtained using PCL grafted fibers because of entanglements and molecular interactions between PCL grafted on the wheat straw fibers and PLA molecules. Copyright © 2015 John Wiley & Sons, Ltd.