Charge measurement of electrospun polyvinylidene fluoride fibers using a custom-made Faraday bucket.

Electrical charges on fabrics, films, and membrane materials are of scientific interest for material development and performance. In many applications, available instruments do not have sufficient sensitivity to detect variations in charge needed for scientific investigations. This paper discusses the design and construction of a custom-made Faraday bucket for measuring the charge of electrospun polyvinylidene fluoride fiber mats of sizes 3 × 3 cm2 and 4 × 4 cm2. An electrometer directly measured the change in the voltage potentials of the inner conductor of the Faraday bucket due to the insertion of fiber mat samples. The measured potentials were converted to electrical charge by modeling the Faraday bucket as a source-free resistance-capacitance circuit. The results show that the Faraday bucket was sufficiently sensitive and measured differences in the potential and charge of the fiber mats due to variations in sample size (or mass), and it detected differences in charge depending on whether the sample was taken from the center or the edges of the electrospun fiber mats.

Pilot Mouse Study of 1 mm Inner Diameter (ID) Vascular Graft Using Electrospun Poly(ester urea) Nanofibers.

An off-the-shelf, small diameter tissue engineered vascular graft (TEVG) would be transformative to surgeons in multiple subspecialties. Herein, the results of a small diameter (ID ≈ 1 mm) vascular graft constructed from resorbable, amino acid-based poly(ester urea) (PEU) are reported. Electrospun PEU grafts of two different wall thicknesses (type A: 250 µm; type B: 350 µm) are implanted as abdominal infra-renal aortic grafts in a severe combined immune deficient/beige mouse model and evaluated for vessel remodeling over one year. Significantly, the small diameter TEVG does not rupture or lead to acute thrombogenic events during the intervals tested. The pilot TEVG in vivo shows long-term patency and extensive tissue remodeling with type A grafts. Extensive tissue remodeling in type A grafts leads to the development of well-circumscribed neovessels with an endothelial inner lining, a neointima containing smooth muscle cells. However, due to slow degradation of the PEU scaffold materials in vivo, the grafts remain after one year. The type B grafts, which have 350 µm thick walls, experience occlusion over the one year interval due to intimal hyperplasia. This study affords significant findings that will guide the design of future generations of small diameter vascular grafts.

Polyvinylidene fluoride molecules in nanofibers, imaged at atomic scale by aberration corrected electron microscopy.

Atomic scale features of polyvinylidene fluoride molecules (PVDF) were observed with aberration corrected transmission electron microscopy. Thin, self-supporting PVDF nanofibers were used to create images that show conformations and relative locations of atoms in segments of polymer molecules, particularly segments near the surface of the nanofiber. Rows of CF2 atomic groups, at 0.25 nm intervals, which marked the paths of segments of the PVDF molecules, were seen. The fact that an electron microscope image of a segment of a PVDF molecule depended upon the particular azimuthal direction, along which the segment was viewed, enabled observation of twist around the molecular axis. The 0.2 nm side-by-side distance between the two fluorine atoms attached to the same carbon atom was clearly resolved. Morphological and chemical changes produced by energetic electrons, ranging from no change to fiber scission, over many orders of magnitude of electrons per unit area, promise quantitative new insights into radiation chemistry. Relative movements of segments of molecules were observed. Promising synergism between high resolution electron microscopy and molecular dynamic modeling was demonstrated. This paper is at the threshold of growing usefulness of electron microscopy to the science and engineering of polymer and other molecules.

Fabrication, Polarization of Electrospun Polyvinylidene Fluoride Electret Fibers and Effect on Capturing Nanoscale Solid Aerosols.

Electrospun polyvinylidene fluoride (PVDF) fiber mats with average fiber diameters (≈200 nm, ≈2000 nm) were fabricated by controlled electrospinning conditions. These fiber mats were polarized using a custom-made device to enhance the formation of the electret ß-phase ferroelectric property of the fibers by simultaneous uniaxial stretching of the fiber mat and heating the mat to the Curie temperature of the PVDF polymer in a strong electric field of 2.5 kV/cm. Scanning electron microscopy, Fourier transform infrared spectroscopy, thermal gravimetric analysis, differential scanning calorimetry and Brunauer-Emmett-Teller (BET) surface area analyses were performed to characterize both the internal and external morphologies of the fiber mat samples to study polarization-associated changes. MATLAB simulations revealed the changes in the paths of the electric fields and the magnetic flux inside the polarization field with inclusion of the ferroelectric fiber mats. Both polarized and unpolarized fiber mats were challenged as filters against NaCl particles with average particle diameters of about 150 nm using a TSI 8130 to study capture efficiencies and relative pressure drops. Twelve filter experiments were conducted on each sample at one month time intervals between experiments to evaluate the reduction of the polarization enhancement over time. The results showed negligible polarization loss for the 200-nm fiber sample. The polarized mats had the highest filter efficiencies and lowest pressure drops.

Post-Electrospinning "Triclick" Functionalization of Degradable Polymer Nanofibers.

4-Dibenzocyclooctynol (DIBO) was used as an initiator for the ring-opening copolymerization of ε-caprolactone and 1,4,8-trioxaspiro[4.6]-9-undecanone (TOSUO) resulting in a series of DIBO end-functionalized copolymers. Following deprotection of the ketone group, the polymers were derivatized with aminooxyl-containing compounds by oxime ligation. Mixtures of keto- and alkyne-derivatized polymers were co-electrospun into well-defined nanofibers containing three separate chemical handles. Strain-promoted azide alkyne cycloaddition (SPAAC), oxime ligation, and copper-catalyzed azide alkyne cycloaddition (CuAAC) were used to sequentially functionalize the nanofibers first with fluorescent reporters and then separately with bioactive Gly-Arg-Gly-Asp-Ser (GRGDS), BMP-2 peptide, and dopamine. This translationally relevant approach facilitates the straightforward derivatization of diverse bioactive molecules that can be controllably tethered to the surface of nanofibers.

Enhanced Schwann cell attachment and alignment using one-pot "dual click" GRGDS and YIGSR derivatized nanofibers.

Using metal-free click chemistry and oxime condensation methodologies, GRGDS and YIGSR peptides were coupled to random and aligned degradable nanofiber networks postelectrospinning in a one-pot reaction. The bound peptides are bioactive, as demonstrated by Schwann cell attachment and proliferation, and the inclusion of YIGSR with GRGDS alters the expression of the receptor for YIGSR. Additionally, aligned nanofibers act as a potential guidance cue by increasing the aspect ratio and aligning the actin filaments, which suggest that peptide-functionalized scaffolds would be useful to direct SCs for peripheral nerve regeneration.

A tough and high-performance transparent electrode from a scalable and transfer-free method.

Conductive metal films are patterned into transparent metal nanowire networks by using electrospun fibers as a mask. Both the transmittance and sheet resistance (6 Ω/□ at 83% transmittance and 24 Ω/□ at 92% transmittance) of the metal nanowire-based electrode out-perform commercial indium doped tin oxide (ITO) electrodes. The metal nanowire-based transparent electrodes were fabricated on both rigid glass and flexible polyethylene terephthalate (PET) substrates. In addition to state of art performance, the transparent electrodes also exhibit outstanding toughness. They can withstand repeated scotch tape peeling and various bending tests. The method for making the metal nanowire is scalable, and a touch screen on flexible substrate is demonstrated.

Directed differentiation and neurite extension of mouse embryonic stem cell on aligned poly(lactide) nanofibers functionalized with YIGSR peptide.

End-functional PLLA nanofibers were fabricated into mats of random or aligned fibers and functionalized post-spinning using metal-free "click chemistry" with the peptide Tyr-Ile-Gly-Ser-Arg (YIGSR). Fibers that were both aligned and functionalized with YIGSR were found to significantly increase the fraction of mouse embryonic stem cells (mESC) expressing neuron-specific class III beta-tubulin (TUJ1), the level of neurite extension and gene expression for neural markers compared to mESC cultured on random fiber mats and unfunctionalized matrices. Precise functionalization of degradable polymers with bioactive peptides created translationally-relevant materials that capitalize on the advantages of both synthetic and natural systems, while mitigating the classic limitations of each.

Post-assembly derivatization of electrospun nanofibers via strain-promoted azide alkyne cycloaddition.

A primary amine-derivatized 4-dibenzocyclooctynol (DIBO) was used to initiate the ring-opening polymerization of poly(γ-benzyl-L-glutamate) (DIBO-PBLG). This initiator yields well-defined PBLG polymers functionalized with DIBO at the chain termini. The DIBO end group further survives an electrospinning process that yields nanofibers that were then derivatized post-assembly with azide-functionalized gold nanoparticles. The availability of DIBO on the surface of the fibers is substantiated by fluorescence, SEM, and TEM measurements. Post-assembly functionalization of nanofiber constructs with bioactive groups can be facilitated easily using this process.

Nanofibers from Scalable Gas Jet Process.

A new, simple, and effective method is reported for production of polymer fibers ranging from a few tens of nanometers to a few micrometers from polymer solutions. The method capitalizes on a high velocity expanding gas jet to turn polymer solutions streaming from nozzles into fibers with smooth or wrinkled fiber surface morphology and with core-shell and side-by-side arrangements. The polymer solution is brought in contact with the gas jet on a flat surface, at the tip of a circular needle, and at the surface a pendant drop. The fiber diameter bears relationship with capillary number of the liquid jet and polymer concentration in the solution. Several levels of fiber conglutination are observed as function of collection distance from the nozzle set up.

Highly hydrophobic electrospun fiber mats from polyisobutylene-based thermoplastic elastomers.

This paper is the first report of electrospinning neat polyisobutylene-based thermoplastic elastomers. Two generations of these materials are investigated: a linear poly(styrene-b-isobutylene-b-styrene) (L_SIBS) triblock copolymer and a dendritic poly(isobutylene-b-p-methylstyrene) (D_IB-MS), also a candidate for biomedical applications. Cross-polarized optical microscopy shows birefringence, indicating orientation in the electrospun fibers, which undergo large elongation and shear during electrospinning. In contrast to the circular cross section of L_SIBS fibers, D_IB-MS yields dumbbell-shaped fiber cross sections for the combination of processing conditions, molecular weight, and architecture. Hydrophobic surfaces with a water contact angle as high as 146 ± 3° were obtained with D_IB-MS that had the noncircular fiber cross section and a hierarchical arrangement of nano- to micrometer-sized fibers in the mat. These highly water repellent fiber mats were found to serve as an excellent scaffold for bovine chondrocytes to produce cartilage tissue.

Growth of carbon nanostructures on carbonized electrospun nanofibers with palladium nanoparticles.

This paper studies the mechanism of the formation of carbon nanostructures on carbon nanofibers with Pd nanoparticles by using different carbon sources. The carbon nanofibers with Pd nanoparticles were produced by carbonizing electrospun polyacrylonitrile (PAN) nanofibers including Pd(Ac)(2). Such PAN-based carbon nanofibers were then used as substrates to grow hierarchical carbon nanostructures. Toluene, pyridine and chlorobenzine were employed as carbon sources for the carbon nanostructures. With the Pd nanoparticles embedded in the carbonized PAN nanofibers acting as catalysts, molecules of toluene, pyridine or chlorobenzine were decomposed into carbon species which were dissolved into the Pd nanoparticles and consequently grew into straight carbon nanotubes, Y-shaped carbon nanotubes or carbon nano-ribbons on the carbon nanofiber substrates. X-ray diffraction analysis and transmission electron microscopy (TEM) were utilized to capture the mechanism of formation of Pd nanoparticles, regular carbon nanotubes, Y-shaped carbon nanotubes and carbon nano-ribbons. It was observed that the Y-shaped carbon nanotubes and carbon nano-ribbons were formed on carbonized PAN nanofibers containing Pd-nanoparticle catalyst, and the carbon sources played a crucial role in the formation of different hierarchical carbon nanostructures.

Electrospun polymer nanofibres with small diameters.

Nylon-4,6 nanofibres with diameters ranging from about 1 µm down to 1 nm were prepared by electrospinning. The fibre diameter was varied by adjusting the concentration of the polymer solution. Electrospinning of a concentrated solution of as high as 20% nylon-4,6 by weight in formic acid produced a ribbon-like electrospun fibre with a ribbon width of about 850 nm. A semi-dilute concentration of 2% nylon-4,6 by weight produced the thinnest nylon-4,6 nanofibres with diameters of 1.6 nm or less. A small amount of pyridine was added to the electrospinning solution to avoid the formation of beaded nanofibres in the course of electrospinning at low concentrations. Scanning and transmission electron microscopy were used to characterize the size of the nanofibres. An ultra-thin nylon-4,6 nanofibre of 1.2 nm diameter might contain six or seven nylon-4,6 molecules in a typical cross-section of the fibre.

Silver(I)-imidazole cyclophane gem-diol complexes encapsulated by electrospun tecophilic nanofibers: formation of nanosilver particles and antimicrobial activity.

Silver(I)-imidazole cyclophane gem-diol complex, 3 [Ag2C36 N10(O)4](2+)2(x)-, where x = OH- or CO3(2-), was synthesized and well characterized. The minimum inhibition concentration tests showed that the aqueous form of 3 is 2 times less effective as an antibiotic than 0.5% AgNO3, with about the same amount of silver. The antimicrobial activity of 3 was enhanced when encapsulated into Tecophilic polymer by electrospinning to obtain mats made of nano-fibers. The fiber mats released nanosilver particles, which in turn sustained the antimicrobial activity of the mats over a long period of time. The rate of bactericidal activity of 3 was greatly improved by encapsulation, and the amount of silver used was much reduced. The amount of silver contained in the fiber mat of 3, with 75% of 3 and 25% Tecophilic, was 8 times less than that in 0.5% AgNO3 and 5 times lower than that in silver sulfadiazine cream 1%. The fiber mat was found to kill S. aureus at the same rate as 0.5% AgNO3, with zero colonies on an agar plate, and about 6 times faster than silver sulfadiazine cream. The silver mats were found effective against E. coli, P. aeruginosa, S. aureus, C. albicans, A. niger, and S. cerevisiae. Transmission electron microscopy and scanning electron microscopy were used to characterize the fiber mats. The acute toxicity of the ligand (imidazolium cyclophane gem-diol dichloride) was assessed by intravenous administration to rats, with an LD 50 of 100 mg/kg of rat.

Assembly of well-aligned multiwalled carbon nanotubes in confined polyacrylonitrile environments: electrospun composite nanofiber sheets.

Highly oriented, large area continuous composite nanofiber sheets made from surface-oxidized multiwalled carbon nanotubes (MWNTs) and polyacrylonitrile (PAN) were successfully developed using electrospinning. The preferred orientation of surface-oxidized MWNTs along the fiber axis was determined with transmission electron microscopy and electron diffraction. The surface morphology and height profile of the composite nanofibers were also investigated using an atomic force microscope in tapping mode. For the first time, it was observed that the orientation of the carbon nanotubes within the nanofibers was much higher than that of the PAN polymer crystal matrix as detected by two-dimensional wide-angle X-ray diffraction experiments. This suggests that not only surface tension and jet elongation but also the slow relaxation of the carbon nanotubes in the nanofibers are determining factors in the orientation of carbon nanotubes. The extensive fine absorption structure detected via UV/vis spectroscopy indicated that charge-transfer complexes formed between the surface-oxidized nanotubes and negatively charged (-CN[triple bond]N:) functional groups in PAN during electrospinning, leading to a strong interfacial bonding between the nanotubes and surrounding polymer chains. As a result of the highly anisotropic orientation and the formation of complexes, the composite nanofiber sheets possessed enhanced electrical conductivity, mechanical properties, thermal deformation temperature, thermal stability, and dimensional stability. The electrical conductivity of the PAN/MWNT composite nanofibers containing 20 wt % nanotubes was enhanced to approximately 1 S/cm. The tensile modulus values of the compressed composite nanofiber sheets were improved significantly to 10.9 and 14.5 GPa along the fiber winding direction at the MWNT loading of 10 and 20 wt %, respectively. The thermal deformation temperature increased with increased MWNT loading. The thermal expansion coefficient of the composite nanofiber sheets was also reduced by more than an order of magnitude to 13 x 10(-6)/ degrees C along the axis of aligned nanofibers containing 20 wt % MWNTs.

Enzyme-carrying polymeric nanofibers prepared via electrospinning for use as unique biocatalysts.

Improvement of catalytic efficiency of immobilized enzymes via materials engineering was demonstrated through the preparation of bioactive nanofibers. Bioactive polystyrene (PS) nanofibers with a typical diameter of 120 nm were prepared and examined for catalytic efficiency for biotransformations. The nanofibers were produced by electrospinning functionalized PS, followed by the chemical attachment of a model enzyme, alpha-chymotrypsin. The observed enzyme loading as determined by active site titration was up to 1.4% (wt/wt), corresponding to over 27.4% monolayer coverage of the external surface of nanofibers. The apparent hydrolytic activity of the nanofibrous enzyme in aqueous solutions was over 65% of that of the native enzyme, indicating a high catalytic efficiency as compared to other forms of immobilized enzymes. Furthermore, nanofibrous alpha-chymotrypsin exhibited a much-improved nonaqueous activity that was over 3 orders of magnitude higher than that of its native counterpart suspended in organic solvents including hexane and isooctane. It appeared that the covalent binding also improved the enzyme's stability against structural denaturation, such that the half-life of the nanofibrous enzyme in methanol was 18-fold longer than that of the native enzyme.