The Role of α, γ, and Metastable Polymorphs on Electrospun Polyamide 6/Functionalized Graphene Oxide.

The present paper describes the addition of nitroxide-functionalized graphene oxide (GOFT) into polyamide 6 (PA6) micro- and nanofibers, which are obtained through electrospinning. Scanning electron microscopy micrographs demonstrate the presence of fibers. Tensile testing presents an unexpected and non-obvious behavior, in which the Young's modulus, tensile strength, and elongation simultaneously and remarkably increase compared to the pristine polymer nanofibers. GOFT induces the hydrogen bonding between the NH group from PA6 with the functional groups, thus promoting higher crystallinity of the polymer matrix. Nonetheless, deconvoluted curves by differential scanning calorimetry reveal the presence of two quasi-steady polymorphs (ß and Î´ phases) contributing to 46% of the total crystallinity. This evidence suggests that their presence and high ratios are responsible for the unexpected and simultaneous enhancement of tensile properties.

EELS Analysis of Nylon 6 Nanofibers Reinforced with Nitroxide-Functionalized Graphene Oxide.

A detailed analysis by transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) of nitroxide-functionalized graphene oxide layers (GOFT) dispersed in Nylon 6 nanofibers is reported herein. The functionalization and exfoliation process of graphite oxide to GOFT was confirmed by TEM using electron diffraction patterns (EDP), wherein 1 to 4 graphene layers of GOFT were observed. The distribution and alignment of GOFT layers within a sample of Nylon 6 nanofiber reveals that GOFT platelets are mainly within the fiber, but some were partially protruding from it. Furthermore, Nylon 6 nanofibers exhibit an average diameter of 225 nm with several microns in length. GOFT platelets embedded into the fiber, the pristine fiber, and amorphous carbon were analyzed by EELS where each spectra [corresponding to the carbon edge (C-K)] exhibited changes in the fine structure, allowing a clear distinction between: i) GOFT single-layers, ii) Nylon-6 nanofibers, and iii) the carbon substrate. EELS analysis is presented here for the first time as a powerful tool to identify functionalized graphene single-layers (< 4 layers of GOFT) into a Nylon 6 nanofiber composite.

Imaging, Spectroscopic, Mechanical and Biocompatibility Studies of Electrospun Tecoflex® EG 80A Nanofibers and Composites Thereof Containing Multiwalled Carbon Nanotubes.

The present study discusses the design, development and characterization of electrospun Tecoflex® EG 80A class of polyurethane nanofibers and the incorporation of multiwalled carbon nanotubes (MWCNTs) to these materials. Scanning electron microscopy results confirmed the presence of polymer nanofibers, which showed a decrease in fiber diameter at 0.5% wt. and 1% wt. MWCNTs loadings, while transmission electron microscopy showed evidence of the MWCNTs embedded within the polymer matrix. The fourier transform infrared spectroscopy and Raman spectroscopy were used to elucidate the polymer-MWCNTs intermolecular interactions, indicating that the C-N and N-H bonds in polyurethanes are responsible for the interactions with MWCNTs. Furthermore, tensile testing indicated an increase in the Young's modulus of the nanofibers as the MWCNTs concentration was increased. Finally, NIH 3T3 fibroblasts were seeded on the obtained nanofibers, demonstrating cell biocompatibility and proliferation. Therefore, the results indicate the successful formation of polyurethane nanofibers with enhanced mechanical properties, and demonstrate their biocompatibility, suggesting their potential application in biomedical areas.

Nitroxide-Functionalized Graphene Oxide from Graphite Oxide.

A facile method for preparing functionalized graphene oxide single layers with nitroxide groups is reported herein. Highly oxidized graphite oxide (GO=90.6%) was obtained, slightly modifying an improved Hummer's method. Oxoammonium salts (OS) were investigated to introduce nitroxide groups to GO, resulting in a one-step functionalization and exfoliation. The mechanisms of functionalization/exfoliation are proposed, where the oxidation of aromatic alcohols to ketone groups, and the formation of alkoxyamine species are suggested. Two kinds of functionalized graphene oxide layers (GOFT1 and GOFT2) were obtained by controlling the amount of OS added. GOFT1 and GOFT2 exhibited a high interlayer spacing (d0001 = 1.12nm), which was determined by X-ray diffraction. The presence of new chemical bonds C-N (~9.5 %) and O-O (~4.3 %) from nitroxide attached onto graphene layers were observed by X-ray photoelectron spectroscopy. Single-layers of GOFT1 were observed by HRTEM, exhibiting amorphous and crystalline zones at a 50:50 ratio; in contrast, layers of GOFT2 exhibited a fully amorphous surface. Fingerprint of GOFT1 single layers was obtained by electron diffraction at several tilts. Finally, the potential use of these materials within Nylon 6 matrices was investigated, where an unusual simultaneous increase in tensile stress, tensile strain and Young's modulus was observed.

Polyurethane and cellulose acetate micro-nanofibers containing rosemary essential oil, and decorated with silver nanoparticles for wound healing application.

In this study, polyurethane (PU) and cellulose acetate (CA) electrospun fibers encapsulating rosemary essential oil (REO) and adsorbed silver (Ag) nanoparticles (NPs) were fabricated. The biologically inspired materials were analyzed for physicochemical characteristics using scanning electron microscopy, X-ray diffractometer, Fourier transform infrared, thermal gravimetric analysis, X-ray photoelectron spectroscopy, water contact angle, and water uptake studies. Results confirmed the presence of CA and Ag NPs on the PU micro-nanofibers increased the hydrophilicity from 107.1 ± 0.36o to 26.35 ± 1.06o. The water absorption potential increased from 0.07 ± 0.04 for pristine PU fibers to 12.43 ± 0.49 % for fibers with 7 wt% of CA, REO, and Ag NPs. The diffractometer confirmed the 2θ of 38.01°, 44.13o, and 64.33o, corresponding to the diffraction planes of Ag on the fibers. The X-ray photoelectron spectroscopy confirmed microfibers interfacial chemical interaction and surface changes due to CA, REO, and Ag presence. The inhibition tests on Staphylococcus aureus and Escherichia coli indicated that composites are antibacterial in activity. Moreover, synergistic interactions of REO and Ag NPs resulted in superior antibacterial activity. The cell viability and attachment assay showed improved hydrophilicity of the fibers, which resulted in better attachment of cells to the micro-nanofibers, similar to the natural extracellular matrix in the human body.

Graphite Intercalation Compounds Derived by Green Chemistry as Oxygen Reduction Reaction Catalysts.

Precious group metal (PGM) catalysts such as Pt supported on carbon supports are expensive catalysts utilized for the oxygen reduction reaction (ORR) due to their unmatched catalytic activity and durability. As an alternative, PGM-free ORR electrocatalysts that offer respectable catalytic activity are being pursued. Most of the notable PGM-free catalysts are obtained either from a bottom-up approach synthesis utilizing nitrogen-rich polymers as building blocks, or from a top down approach, where nitrogen and metal moieties are incorporated to carbonaceous matrixes. The systematic understanding of the origin of catalytic activity for either case is speculative and currently employed synthesis techniques typically generate large amounts of hazardous waste such as acids, oxidizing agents, and solvents. Herein, for the first time, we investigate the catalytic activity of graphite-based materials obtained via intercalation strategies that minimally perturb the graphitic backbone. Our outlined approaches demonstrate initial efforts to not only elucidate the role of each element but also significantly reduce the use of hazardous chemicals, which remains a pressing challenge. Graphite intercalation compounds (GIC) were obtained using fewer steps and solvent-free processes. X-ray diffraction and Raman results confirm the successful intercalation of FeCl3 between graphite layers. Electrochemical data shows that the ORR performance of FeCl3-intercalated GIC displays slight improvement where the onset potential reaches 0.77 V vs RHE in alkaline environments. However, expansion of the graphite and solvent-free incorporation of iron and nitrogen moieties resulted in a significant increase in ORR activity with onset potential to 0.89 V vs RHE, a maximum half-wave of 0.72 V vs RHE, and a limiting current of about 2.5 mA cm-2. We anticipate that the use of near solvent-free processes that result in a high yield of catalysts along with the fundamental insight into the origin of electrochemical activity will tremendously impact the methodologies for developing next-generation ORR catalysts.

Imaging, spectroscopy, mechanical, alignment and biocompatibility studies of electrospun medical grade polyurethane (Carbothane™ 3575A) nanofibers and composite nanofibers containing multiwalled carbon nanotubes.

In the present study, we discuss the electrospinning of medical grade polyurethane (Carbothane™ 3575A) nanofibers containing multi-walled-carbon-nanotubes (MWCNTs). A simple method that does not depend on additional foreign chemicals has been employed to disperse MWCNTs through high intensity sonication. Typically, a polymer solution consisting of polymer/MWCNTs has been electrospun to form nanofibers. Physiochemical aspects of prepared nanofibers were evaluated by SEM, TEM, FT-IR and Raman spectroscopy, confirming nanofibers containing MWCNTs. The biocompatibility and cell attachment of the produced nanofiber mats were investigated while culturing them in the presence of NIH 3T3 fibroblasts. The results from these tests indicated non-toxic behavior of the prepared nanofiber mats and had a significant attachment of cells towards nanofibers. The incorporation of MWCNTs into polymeric nanofibers led to an improvement in tensile stress from 11.40 ± 0.9 to 51.25 ± 5.5 MPa. Furthermore, complete alignment of the nanofibers resulted in an enhancement on tensile stress to 72.78 ± 5.5 MPa. Displaying these attributes of high mechanical properties and non-toxic nature of nanofibers are recommended for an ideal candidate for future tendon and ligament grafts.

Biodegradable electrospun nanofibers coated with platelet-rich plasma for cell adhesion and proliferation.

Biodegradable electrospun poly(ε-caprolactone) (PCL) scaffolds were coated with platelet-rich plasma (PRP) to improve cell adhesion and proliferation. PRP was obtained from human buffy coat, and tested on human adipose-derived mesenchymal stem cells (MSCs) to confirm cell proliferation and cytocompatibility. Then, PRP was adsorbed on the PCL scaffolds via lyophilization, which resulted in a uniform sponge-like coating of 2.85 (S.D. 0.14) mg/mg. The scaffolds were evaluated regarding mechanical properties (Young's modulus, tensile stress and tensile strain), sustained release of total protein and growth factors (PDGF-BB, TGF-ß1 and VEGF), and hemocompatibility. MSC seeded on the PRP-PCL nanofibers showed an increased adhesion and proliferation compared to pristine PCL fibers. Moreover, the adsorbed PRP enabled angiogenesis features observed as neovascularization in a chicken chorioallantoic membrane (CAM) model. Overall, these results suggest that PRP-PCL scaffolds hold promise for tissue regeneration applications.

Titanium Dioxide Nanofibers and Microparticles Containing Nickel Nanoparticles.

The present study reports on the introduction of various nanocatalysts containing nickel (Ni) nanoparticles (NPs) embedded within TiO2 nanofibers and TiO2 microparticles. Typically, a sol-gel consisting of titanium isopropoxide and Ni NPs was prepared to produce TiO2 nanofibers by the electrospinning process. Similarly, TiO2 microparticles containing Ni were prepared using a sol-gel syntheses process. The resultant structures were studied by SEM analyses, which confirmed well-obtained nanofibers and microparticles. Further, the XRD results demonstrated the crystalline feature of both TiO2 and Ni in the obtained composites. Internal morphology of prepared nanofibers and microparticles containing Ni NPs was characterized by TEM, which demonstrated characteristic structures with good dispersion of Ni NPs. In addition, the prepared structures were studied as a model for hydrogen production applications. The catalytic activity of the prepared materials was studied by in situ hydrolysis of NaBH4, which indicated that the nanofibers containing Ni NPs can lead to produce higher amounts of hydrogen when compared to other microparticles, also reported in this paper. Overall, these results confirm the potential use of these materials in hydrogen production systems.

Fabrication of Poly(vinylidene fluoride) (PVDF) Nanofibers Containing Nickel Nanoparticles as Future Energy Server Materials.

In the present study, we introduce Poly(vinylidene fluoride) (PVDF) nanofibers containing nickel (Ni) nanoparticles (NPs) as a result of an electrospinning. Typically, a colloidal solution consisting of PVDF/Ni NPs was prepared to produce nanofibers embedded with solid NPs by electrospinning process. The resultant nanostructures were studied by SEM analyses, which confirmed well oriented nanofibers and good dispersion of Ni NPs over them. The XRD results demonstrated well crystalline feature of PVDF and Ni in the obtained nanostructures. Physiochemical aspects of prepared nano-structures were characterized for TEM which confirmed nanofibers were well-oriented and had good dispersion of Ni NPs. Furthermore, the prepared nano-structures were studied for hydrogen production applications. Due to high surface to volume ratio of nanofibers form than the thin film ones, there was tremendous increase in the rate of hydrogen production. Overall, results satisfactorily confirmed the use of these materials in hydrogen production.

Fabrication of Mineralized Collagen from Bovine Waste Materials by Hydrothermal Method as Promised Biomaterials.

In the present study, we aimed to produce mineralized-collagen by hydrothermal process. A simple method not depending on additional foreign chemicals has been employed to isolate the mineralized-collagen fibers from bovine waste. The process of extraction involves the use of hydrothermal method from available bovine bones. The structural and morphological properties of the collagen fibers were characterized by using scanning electron microscopy and transmission electron microscopy. These results indicated well received collagen fibers, having a diameter less than 1 µm and with established mineral content in the individual fibers. The X-ray diffraction showed the crystalline feature of the obtained nano-compounds. The thermo gravimetric analysis was used to differentiate between the collagen and mineral parts of obtained product. Overall, the results generously indicated production of well received collagen fibers from bovine bones.

Microscopic and Spectroscopic Studies of Thermally Enhanced Electrospun PMMA Micro- and Nanofibers.

Carbon nanofibers (CNFs) have been incorporated into poly(methyl methacrylate) (PMMA) through electrospinning. The resulting micro- and nanofibers have been characterized by Scanning Electron Microscopy (SEM), which confirmed fiber formation and demonstrated a core-sheath structure of the PMMA fibers. Thermogravimetric Analysis (TGA) was used to obtain the thermal properties of the materials, indicating an enhancement in the thermal properties of the composite fibers. In addition, Fourier Transform Infrared Spectroscopy (FTIR) was utilized to investigate the interactions of PMMA micro- and nanofibers with CNFs, demonstrating the preferred sites of intermolecular interactions between the polymer matrix and the filler.