Chitosan/PEO nanofibers electrospun on metallized track-etched membranes: fabrication and characterization

The development of next-generation adsorption, separation, and filtration materials is growing with an increased research focus on polymer composites. In this study, a novel blend of chitosan (CS) and polyethylene oxide (PEO) nanofiber mats was electrospun on titanium (Ti)-coated polyethylene terephthalate (PET) track-etched membranes (TMs) with after-treatment by glutaraldehyde in the vapor phase for enhancing the nanofiber stability by crosslinking. The prepared composite, titanium-coated track-etched nanofiber membrane (TTM-CPnf) was characterized by Fourier transform infra-red (FTIR), water contact angle, and scanning electron microscopy (SEM) analyses. Smooth and uniform CS nanofibers with an average fiber diameter of 156.55 nm were produced from a 70/30 CS/PEO blend solution prepared from 92 wt. % acetic acid and electrospun at 15 cm needle to collector distance with 0.5 mL/h flow rate and an applied voltage of 30 kV on the TTM-CPnf. Short (15 min) and long (72 h)-term solubility tests showed that after 3 h, crosslinked nanofibers were stable in acidic (pH = 3), basic (pH = 13), and neutral (pH = 7) solutions. The crosslinked TTM-CPnf material was biocompatible based on the low mortality of freshwater crustaceans Daphnia magna. The composite membranes comprised of electrospun nanofiber and TMs proved to be biocompatible and may thus be suitable for diverse applications such as dual adsorption–filtration systems in water treatment.     

Chitosan as green kinetic inhibitors for gas hydrate formation

The kinetic inhibiting effect of a number of chitosans on hydrate formation was investigated using methane and methane/ethane gas mixtures.The results indicated that chitosan was a good kinetic inhibitor.The induction time of gas hydrate formation evidently increased with the degree of deacetylation(DD),however,when DD was higher than 80%,the effect of DD on the induction time was negligible.Moreover,it was found that the molecular weight(MW)of chitosan and the addition of polyethylene oxide(PEO)had little effect on the induction time.The optimal concentration of chitosan was found to be 0.6wt%.Finally,the mechanisms of the kinetic inhibitor on the hydrate formation were discussed.     

Electrospinning of cyclodextrin functionalized polyethylene oxide (PEO) nanofibers

By means of the electrospinning technique we have successfully synthesized cyclodextrin (CD) functionalized polyethylene oxide (PEO) nanofibers (PEO/CD) with the ultimate goal to develop functional nanowebs. Three different types of CDs; α-CD, β-CD and γ-CD are incorporated individually in electrospun PEO nanofibers. The aqueous solutions containing different amount of PEO (3%, 3.5% and 4% (w/v), with respect to solvent) and CDs (25% and 50% (w/w), with respect to PEO) are electrospun and bead-free nanofibers are obtained. The presence of the CDs in the PEO solutions is found to facilitate the electrospinning of bead-free nanofibers from the lower polymer concentrations and this behavior is attributed to the high conductivity and viscosity of the PEO/CD solutions. The presence of CDs in the electrospun PEO nanofibers is confirmed by Fourier transform infrared (FTIR) spectroscopy studies. The 2-D X-ray diffraction (XRD) spectra of PEO/CD nanowebs did not show any significant diffraction peaks for CDs indicating that the CD molecules are distributed within the polymer matrix without any phase separated crystalline aggregates.     

Atmospheric plasma treatment of pre‐electrospinning polymer solution: A feasible method to improve electrospinnability

The electrospinnability of polyethylene oxide (PEO) was manipulated by atmospheric plasma treatment of pre‐electrospinning solutions. Conductivity, viscosity, and surface tension of PEO solutions increased after plasma treatment, and the plasma effect remained longer when the solution concentrate increased. Both untreated and treated solutions were then electrospun, and the morphology of the resultant nanofibers was observed by SEM. Atmospheric plasma treatment improved the electrospinnability of PEO solutions and led to less beads and finer diameter distribution in the resultant nanofibers. Additionally, plasma treatment of the pre‐electrospinning solutions affected the crystal structure of resultant nanofibers. These results suggest that atmospheric plasma treatment is a feasible approach to improve the electrospinnability of polymer solutions and can used to control the structure of electrospun nanofibers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Cyclodextrin short-nanofibers using sacrificial electrospun polymeric matrix for VOC removal

Cyclodextrins (CD) are cyclic oligosaccharides that can form noncovalent host–guest inclusion complexes to yield intriguing supramolecular structures. Electrospinning of nanofibers from CD is challenging since they are small molecules, nonetheless, electrospun nanofibers from CD would be particularly attractive because of the distinctive properties obtained by combining the very large surface area of nanofibers along with the inclusion complexation capability of CD. Herein, we performed the electrospinning of native CD type (i.e. γ-CD) using a minimal amount of carrier polymeric matrix (polyethylene oxide (PEO)). Once, the uniform nanofibers were electrospun from γ-CD/PEO systems, the polymeric carrier matrix was selectively removed by simple washing procedure, at the end, γ-CD short-nanofibers were obtained. We observed that γ-CD short-nanofibers could remove volatile organic compounds (VOC) (i.e. aniline) due to the inclusion complexation capability whereas pristine γ-CD powder could not have the capability for the VOC removal.     

Electrospinning of Nanofibers Based on Chitosan/Gelatin Blend for Antibacterial Uses

Chitosan/gelatin blend nanofibers were electrospun and the focus of this study was on the chitosan and gelatin concretions and on morphology of resulting nanofibers. The morphology of electrospun chitosan/gelatin blend nanofibers were characterized using scanning electron microscope (SEM). The miscibility of blend was determined using a SEM and Fourier transform infrared spectrometer/attenuated total reflectance (FTIR/ATR). Antibacterial property and stability of samples was also investigated. Water contact angle measurement (WCA) was employed to investigate the wettability of nanofibers.     

Processing-structure-property relationships of electrospun PLA-PEO membranes reinforced with enzymatic cellulose nanofibers

Three different solvent mixtures were used to prepare electrospun membranes based on polylactic acid (PLA), polyethylene oxide (PEO) and enzymatic cellulose nanofibers (CNF). The materials were characterized from a morphological, spectroscopic, mechanical and rheological point of view. Furthermore, swelling test were performed in order to assess the water uptake of each sample.The results put into evidence that the choice of the solvents affects the structure and the properties of the membranes. Among the protocols tested, using chloroform/acetone/ethanol mixture was found to allow a high degree of CNF dispersion and a good electrospinnability of polymer solutions. These features led to membranes with impressive improvement of mechanical properties (+350% in stiffness, +350% in tensile strength and +500% in toughness) with respect to those of PLA/PEO and dramatically increased the water uptake of these materials (up to +350% within 120 min).     

Enhanced orientation of PEO polymer chains induced by nanoclays in electrospun PEO/clay composite nanofibers

Polymer fibers composed of poly(ethylene oxide) (PEO) and nanoclay were fabricated by electrospinning. The morphology of the composite nanofibers was characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM), which showed aligned nanoclays in the fibers. Polarized Fourier transform infrared (FT-IR) spectroscopy revealed that the PEO chains in the composite fibers exhibit a higher degree of orientation than that in PEO nanofibers containing no nanoclay. It is believed that spatial confinement is present in the electrospun nanofibers, which results in the enforcement of the mutual restriction. The anisotropic hierarchical nanostructure may have potential applications in optics, mechanical materials, and biomedical materials for cell culture.     

Electrospun poly(ethylene oxide)/chitosan nanofibers with cellulose nanocrystals as support for cell culture of 3T3 fibroblasts

Chitosan/poly(ethylene oxide) (PEO) (5:1) nanofibers with cellulose nanocrystals (CNCs) were produced using an electrospinning technique. The addition of CNCs to the chitosan/PEO solutions allowed the production of uniform fibers (without beads) with a high proportion of chitosan. The fiber diameters were influenced by the concentration of CNCs in the chitosan/PEO solutions. The solutions containing 10% (w/w) of CNCs produced thinner fibers compared to solutions containing 5% (w/w) of CNCs. Thermogravimetric analysis indicated that the nanofibers were thermally stable, despite the CNCs having an effect on the PEO decomposition. Results from the cell assay in cultures of 3T3 fibroblasts indicated that the chitosan/PEO nanofibers (with 10% CNCs) promoted cell attachment with changes in the cytoskeletal organization. The results obtained in this work highlight the favorable effect of CNCs in electrospinning of chitosan/PEO. As expected, the influence of nanofibers on 3T3 fibroblasts F-actin and β-tubulin network revealed alterations in cytoskeleton, leading to changes in cell morphology and spreading.     

Fabrication of Electrically Conducting Polypyrrole‐Poly(ethylene oxide) Composite Nanofibers

Summary: Electrically conducting polypyrrole‐poly(ethylene oxide) (PPy‐PEO) composite nanofibers are fabricated via a two‐step process. First, FeCl₃‐containing PEO nanofibers are produced by electrospinning. Second, the PEO‐FeCl₃ electrospun fibers are exposed to pyrrole vapor for the synthesis of polypyrrole. The vapor phase polymerization occurs through the diffusion of pyrrole monomer into the nanofibers. The collected non‐woven fiber mat is composed of 96 ± 30 nm diameter PPy‐PEO nanofibers. FT‐IR, XPS, and conductivity measurements confirm polypyrrole synthesis in the nanofiber.

An SEM image of the PPy‐PEO composite nanofibers. The scale bar in the image is 500 nm.     

Polymer decoration study in chain folding behavior of solution-grown poly(ethylene oxide) crystals

The polymer decoration method based on the vaporization and condensation-crystallization of polyethylene (PE) upon the fold surface of polymer crystals has been widely used to study the chain folding behavior of the crystals. When this method was utilized to study solution-grown high molecular weight poly (ethylene oxide) (PEO) lamellar crystals, the highly anisotropic, low molecular weight fragment PE decorated become oriented parallel to the fold direction and form rods, which can be observed by transmission electron microscopy (TEM) and electron diffraction (ED). The growth sectors were clearly observed. From the ED patterns the {200} planes of the orthorhombic low molecular weight PE rod crystals can be observed, and the c-axis of these crystals is aligned parallel to the {120} growth planes of the PEO crystals. The decoration results indicate that the major fold orientation of high molecular weight PEO single crystals grown from dilute solution is along the {120} planes. © 1995 John Wiley & Sons, Inc.     

Single-walled carbon nanotubes embedded in oriented polymeric nanofibers by electrospinning

The electrospinning process was used successfully to embed single-walled carbon nanotubes (SWCNTs) in a poly(ethylene oxide) (PEO) matrix, forming composite nanofibers. Initial dispersion of SWCNTs in water was achieved by the use of an amphiphilic alternating copolymer of styrene and sodium maleate. The resulting dispersions were stable, having a dark, smooth, ink-like appearance. For electrospinning, the dispersions were mixed with PEO solution in an ethanol/water mixture. The distribution and conformation of the nanotubes in the nanofibers were studied by transmission electron microscopy (TEM). Oxygen plasma etching was used to expose the nanotubes within the nanofibers to facilitate direct observation. Nanotube alignment within the nanofibers was shown to depend strongly on the quality of the initial dispersions. Well-dispersed and separated nanotubes were embedded in a straight and aligned form, while entangled nonseparated nanotubes were incorporated as dense aggregates. X-ray diffraction demonstrated a high degree of orientation of the PEO crystals in the electrospun nanofibers with embedded SWCNTs. This result is in pronounced distinction to the detrimental effect of incorporation of multiwalled carbon nanotubes on polymer orientation in electrospun nanofibers, as reported previously.     

Homogeneous dispersion of chitin nanofibers in polylactic acid with different pretreatment methods

Chitin nanofibers extracted from crab shell were used to reinforce polylactic acid (PLA) by extrusion molding. The dispersion problem of nanofibers in PLA matrix was solved by three pretreatment methods, including water pretreatment, polyethylene glycol (PEG) pretreatment, and polyethylene oxide (PEO) pretreatment. The results demonstrated that chitin nanofibers were distributed uniformly on the fracture surface of the PLA matrix with three different pretreatment methods. However, the aspect ratio of nanofibers with was reduced with the PEG and PEO pretreatment methods. Therefore, the bending modulus (MOE), bending strength (MOR) and impact toughness of the chitin nanofibers/PLA composites prepared by the water pretreatment method were much higher than those of the composites prepared by the PEG and the PEO pretreatment method. Furthermore, the reinforcing effect with the PEG method is slightly better than that with the PEO method. Although it was found that both PEG and PEO were good interfacial compatibilizers for nanofibers and PLA, the reinforcing effect of the composites prepared by PEG and PEO pretreat methods was suppressed due to the decrease of the aspect ratio for chitin nanofibers.     

Electrospun Hybrid Nanofibers Based on Chitosan or N‐Carboxyethylchitosan and Silver Nanoparticles

Hybrid nanofibers from chitosan or N‐carboxyethylchitosan (CECh) and silver nanoparticles (AgNPs) were prepared by electrospinning using HCOOH as a solvent. AgNPs were synthesized in situ in the spinning solution. HCOOH slowed down the cross‐linking of the polysaccharides with GA enabling the reactive electrospinning in the presence of poly(ethylene oxide) (PEO). EDX analyses showed that AgNPs are uniformly dispersed in the nanofibers. Since AgNPs hampered the cross‐linking of chitosan and CECh with GA in the hybrid fibers, the imparting of water insolubility to the fibers was achieved at a second stage using GA vapors. The surface of chitosan/PEO/AgNPs nanofibers was enriched in chitosan and 15 wt.‐% of the incorporated AgNPs were on the fiber surface as evidenced by XPS.

     

Controlled Nanofiber Composed of Multi‐Wall Carbon Nanotube/Poly(Ethylene Oxide)

We have successfully fabricated poly(ethylene oxide) (PEO) nanofibers containing embedded multi‐wall carbon nanotubes (MWCNTs). An initial dispersion of the MWCNTs in distilled water was achieved using sodium dodecyl sulfate. Subsequently, the dispersion was decanted into a PEO solution, which enabled separation of the MWCNTs and their individual incorporation into the PEO nanofibers on subsequent electrospinning. Initially, the carbon nanotube (CNT) rods were randomly oriented, but owing to the sink‐like flow in the electrospinning wedge, they became gradually oriented along the streaming direction, in order that oriented CNTs were obtained on entering the electrospun jet. Individual MWCNTs became embedded in the nanofibers, and were mostly aligned along the fiber axis. Evidence of load transfer to the nanotubes in the composite nanofiber was observed from the field‐emission scanning electron microscopy, transmission electron microscopy and conductivity data.     

过氧化氢在乙酸均相体系中对壳聚糖的降解

为制备分子量较低的可溶于水的壳低聚糖,研究了在乙酸均相体系中过氧化氢氧化降解壳聚糖的过程,采用凝胶渗透色谱法跟踪测定了壳聚糖氧化降解过程中分子量及其分布的变化,探索制备不同分子量壳低聚糖的适宜条件。     

Core–shell structure PEO/CS nanofibers based on electric field induced phase separation via electrospinning and its application

Core–shell structured PEO‐chitosan nanofibers have been produced from electric field inducing phase separation. Chitosan, a positive charged polymer, was dissolved in 50 wt % aqueous acetic acid and the amino group on polycation would protonize, which would endow chitosan electrical properties. Chitosan molecules would move along the direction of the electric field under the electrostatic force and formed the shell layer of nanofibers. Preparation process of core – shell structure is quite simple and efficient without any post‐treatment. The core–shell structure and existence of chitosan on the shell layer were confirmed before and after post‐treatment by TEM and further supported by SEM, FTIR, XRD, DSC, and XPS studies. Blending ratio of PEO and chitosan, molecular weight of chitosan for the mobility of chitosan are thought to be the key influence factors on formation of core–shell structure. Drug release studies show that the prepared core–shell structure nanofibers has a potential application in the biomedical fields involving drug delivery. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2298–2311     

Dual-syringe reactive electrospinning of cross-linked hyaluronic acid hydrogel nanofibers for tissue engineering applications

A facile fabrication of a cross-linked hyaluronic acid (HA) hydrogel nanofibers by a reactive electrospinning method is described. A thiolated HA derivative, 3,3'-dithiobis(propanoic dihydrazide)-modified HA (HA-DTPH), and poly(ethylene glycol) diacrylate (PEGDA) are selected as the cross-linking system. The cross-linking reaction occurs simultaneously during the electrospinning process using a dual-syringe mixing technique. Poly(ethylene oxide) (PEO) is added into the spinning solution as a viscosity modifier to facilitate the fiber formation and is selectively removed with water after the electrospinning process. The nanofibrous structure of the electrospun HA scaffold is well preserved after hydration with an average fiber diameter of 110 nm. A cell morphology study on fibronectin (FN)-adsorbed HA nanofibrous scaffolds shows that the NIH 3T3 fibroblasts migrate into the scaffold through the nanofibrous network, and demonstrate an elaborate three-dimensional dendritic morphology within the scaffold, which reflects the dimensions of the electrospun HA nanofibers. These results suggest the application of electrospun HA nanofibrous scaffolds as a potential material for wound healing and tissue regeneration. [image: see text] Laser scanning confocal microscopy demonstrates that the NIH3T3 fibroblast develops an extended 3D dendritic morphology within the fibronectin-adsorbed electrospun HA nanofibrous scaffold.     

Melting of water/poly(ethylene oxide) systems

The transition temperatures of poly(ethylene oxide) (PEO)/water systems were studied over the temperature range from ?90 to 110°C by differential scanning calorimetry. The composition of the systems and the average molecular weight of the PEO were varied over a wide range. The systems under study tend to supercool and become partially or completely glassy depending on the cooling rate, composition, and PEO molecular weight. The glassy phases crystallize on being heated above their glass transition temperature. Systems containing about 60 wt % of PEO are most readily super cooled without crystallization. The dependence of melting temperatures and enthalpies on composition was studied and their isobar phase diagrams were drawn. They show that at a definite polymer content (about 50 wt %), which is molecular weight dependent, the systems behave as binary eutectic mixtures. The results confirm the idea that PEO forms quite stable molecular complexes with water.     

低分子量壳聚糖制备与应用研究进展

低分子量壳聚糖因具有特殊的生物活性而日益受到人们的关注。本文概要介绍了近5年来国内外低分子量壳聚糖的研究进展,包括低分子量壳聚糖的制备方法,如酶降解法、酸水解法、氧化降解法、物理法等,以及低分子量壳聚糖在农业、医药、抗菌、化妆品、食品等方面的应用。