Electrospun Polymer Fibers Research Articles

Investigating the Impact of Geometric and Surface Factors on the Aerosol Capture Efficiency of Electrospun Polymeric Fibers

Investigating the Impact of Geometric and Surface Factors on the Aerosol Capture Efficiency of Electrospun Polymeric Fibers

Quantification of Airborne Concentrations of Nanoscale Dusts by Particle Gravimetry Using Ionic‐Liquid Modified Polymeric Electrospun Fibers

Quantification of Airborne Concentrations of Nanoscale Dusts by Particle Gravimetry Using Ionic‐Liquid Modified Polymeric Electrospun Fibers

Quantification of Airborne Concentrations of Nanoscale Dusts by Particle Gravimetry Using Ionic‐Liquid Modified Polymeric Electrospun Fibers

AbstractIn this work, functional polymeric filters are prepared by electrospinning using four different non‐ionic polymers or their blends together with deliberately selected additives, and then tested for quantification of the nano‐sized powders. Particle gravimetry is used for the quantitative determination of the dusts. Validation studies are carried out using the ICP‐OES technique. The polymeric fibers prepared with different contents consist of PS/PMMA, PVDF/EC/PMMA, chitosan, chitosan/PMMA and PMMA/PVDF, respectively. The ionic liquids of tetra‐n‐butylammonium tetrafluoroborate, 1‐ethyl‐3‐methylimidazolium hexafluorophosphate and hexadecyltrimethylammonium bromide are used as additives for the preparation of the functional polymeric fibers. The prepared nanoscale dusts and electrospun fibers are characterized by SEM, XRD, XPS, and size distribution analysis techniques, respectively. Among them, the CTAB‐modified chitosan fibers exhibit the highest dust retention efficiency. This study introduces a new approach to the quantification of nano‐sized powders. In addition, it is concluded that the proposed method can be used in pre‐concentration before testing, cleaning powders from the working environment and quantitative analysis of nanoscale powders. The presented materials can also be used to improve indoor air quality and potential worker exposure in workplaces.

Advanced Electrospinning Technology Applied to Polymer-Based Sensors in Energy and Environmental Applications.

Due to its designable nanostructure and simple and inexpensive preparation process, electrospun nanofibers have important applications in energy collection, wearable sports health detection, environmental pollutant detection, pollutant filtration and degradation, and other fields. In recent years, a series of polymer-based fiber materials have been prepared using this method, and detailed research and discussion have been conducted on the material structure and performance factors. This article summarizes the effects of preparation parameters, environmental factors, a combination of other methods, and surface modification of electrospinning on the properties of composite nanofibers. Meanwhile, the effects of different collection devices and electrospinning preparation parameters on material properties were compared. Subsequently, it summarized the material structure design and specific applications in wearable device power supply, energy collection, environmental pollutant sensing, air quality detection, air pollution particle filtration, and environmental pollutant degradation. We aim to review the latest developments in electrospinning applications to inspire new energy collection, detection, and pollutant treatment equipment, and achieve the commercial promotion of polymer fibers in the fields of energy and environment. Finally, we have identified some unresolved issues in the detection and treatment of environmental issues with electrospun polymer fibers and proposed some suggestions and new ideas for these issues.

Monitoring of multiple fabrication parameters of electrospun polymer fibers using mueller matrix analysis

Electrospun polymer fiber mats feature versatile applications in tissue engineering, drug delivery, water treatment and chemical processes. The orientation of fibers within these mats is a crucial factor that significantly influences their properties and performance. However, the analysis of fiber samples using scanning electron microscopy (SEM) has limitations such as time consumption, fixed assembly, and restricted field of vision. Therefore, a fast and reliable method for qualitative measurements of fiber orientation is required. Mueller matrix polarimetry, a well-established method for measuring orientation of chemical and biological species, was employed in this case. We investigated the effect of four important parameters of the electrospinning process, namely collector speed, applied voltage, needle-to-collector distance, and solution concentration, on fiber orientation using Mueller matrix polarimetry thus extending the range of parameters analyzed. Measurements were performed using two extreme values and a central optimized value for each fabrication parameter. Changes in matrix values were observed for each fabrication parameter, and their correlation with fiber orientation was analyzed based on the Lu-Chipman decomposition. The results were compared with SEM images, which served as the ground truth, and showed overall good agreement. In the future, the analysis of electrospun polymer fibers can be done by using Mueller matrix polarimetry as alternative to current technology and fabrication parameters, including solution concentration for the first time in this context and the production can quickly be adjusted based on the outcome of the measurements.

Palladium-Coated Submicron Electrospun Polymeric Fibers with Immobilized Uricase for Uric Acid Determination in Body Fluids

Palladium-Coated Submicron Electrospun Polymeric Fibers with Immobilized Uricase for Uric Acid Determination in Body Fluids

Unveiling the Dual-Enhancing Mechanisms of Kinetically Controlled Silver Nanoparticles on Piezoelectric PVDF Nanofibers for Optimized SERS Performance.

Noble metal nanoparticle (NMP)-based composite substrates have garnered significant attention as a highly promising technique for surface-enhanced Raman scattering (SERS) in diverse scientific disciplines because their remarkable ability to amplify and functionalize Raman signals has positioned them as valuable tools for molecular detection. However, optimizing the size and distribution of NMPs has not received sufficient emphasis because of challenges associated with the precise control of deposition and the modulation of reducing rates during growth. In this research, we achieved the optimized size and spatial patterns of AgNWs on electrospun poly(vinylidene fluoride) (PVDF) nanofibers by utilizing a polydopamine (PDA) layer as a mild and controllable reduction mediator, by which the size and density of the AgNWs could be relatively precisely manipulated, achieving a dense distribution of effective "hot spots". On the other hand, harnessing the inherent piezoelectric properties of the electrospun PVDF nanofibers further boosted the LSPR effect during the SERS test, forming a flexible dual-enhancing composite SERS substrate with excellent sensitivity. In addition to addressing structural aspects, exploiting synergistic systems capable of transferring external energy or forces to enhance the SERS performances presents a compelling avenue to broaden the practical applications of SERS. The dual-enhanced substrate achieved an exceptional enhancement factor (EF) of 1.05 × 108 and a low detection limit (LOD) of 10-10 M during the SERS test. This study focuses on integrating NMPs with electrospun piezoelectric polymer nanofibers to develop a dual-enhancing SERS substrate with excellent sensitivity and practicality. The findings provide valuable insights into controllably depositing NMPs on electrospun polymer fibers and hold significant implications for the development of highly sensitive and practical SERS substrates across various applications.

Modified Carbon Nanotubes Favor Fibroblast Growth by Tuning the Cell Membrane Potential.

As is known, carbon nanotubes favor cell growth in vitro, although the underlying mechanisms are not yet fully elucidated. In this study, we explore the hypothesis that electrostatic fields generated at the interface between nonexcitable cells and appropriate scaffold might favor cell growth by tuning their membrane potential. We focused on primary human fibroblasts grown on electrospun polymer fibers (poly(lactic acid)─PLA) with embedded multiwall carbon nanotubes (MWCNTs). The MWCNTs were functionalized with either the p-methoxyphenyl (PhOME) or the p-acetylphenyl (PhCOMe) moiety, both of which allowed uniform dispersion in a solvent, good mixing with PLA and the consequent smooth and homogeneous electrospinning process. The inclusion of the electrically conductive MWCNTs in the insulating PLA matrix resulted in differences in the surface potential of the fibers. Both PLA and PLA/MWCNT fiber samples were found to be biocompatible. The main features of fibroblasts cultured on different substrates were characterized by scanning electron microscopy, immunocytochemistry, Rt-qPCR, and electrophysiology revealing that fibroblasts grown on PLA/MWCNT reached a healthier state as compared to pure PLA. In particular, we observed physiological spreading, attachment, and Vmem of fibroblasts on PLA/MWCNT. Interestingly, the electrical functionalization of the scaffold resulted in a more suitable extracellular environment for the correct biofunctionality of these nonexcitable cells. Finally, numerical simulations were also performed in order to understand the mechanism behind the different cell behavior when grown either on PLA or PLA/MWCNT samples. The results show a clear effect on the cell membrane potential, depending on the underlying substrate.

Synergistic effect of heterointerface engineering and oxygen vacancy in electro-spun polymer fibres derived carbon-supported 1D hierarchical WO3/SnO2 nanostructures for high-performance supercapacitor devices

Graphical illustration depicting WO3/SnO2@C as a flexible supercapacitor device for power applications.

Reductive quenching of photosensitizer [Ru(bpy)3]2+ reveals the inhomogeneous distribution of sites in PAN polymer nanofibers for light-driven redox catalysis.

Integration of molecular photocatalysts into redox-inert polymers constitutes a path towards photocatalytically active, lightweight materials. In particular, electrospun polymer fibers hold potential due to their favorable surface-to-volume ratio and their straightforward fabrication. This study focuses on the polyacrylonitrile (PAN) fibers, into which the prototype photosensitizer (PS) ruthenium tris(bipyridine) [Ru(bpy)3]2+, has been embedded by electrospinning. Studying the interaction between the optically excited [Ru(bpy)3]2+ with a non-redox inert solvent within the nanofibers, we resolve a distribution of microenvironments, which differ by the extent to which the photosensitizer is exposed to the solvent. This results in a non-exponential decay of the complex's emission and pronounced differences in the transient absorption signals.

Atomic Layer Depostion within Polymers Templates for Spatially Controlled Growth and Doped Materials

Today’s nanofabrication techniques require multistep and costly processes in order to fabricate complex, multi-materials nanostructures. Performing atomic layer deposition (ALD) within polymeric templates can offer a simple solution for nanostructure fabrication. In this process, named sequential infiltration synthesis (SIS), high partial pressures and long exposures times lead to inorganic materials growth within polymers. Sequential polymer removal results in polymer-templated inorganic nanostructure. While SIS shows great potential in fabricating large variety of structures, it is currently limited to a single material growth process.In our research, we utilized SIS properties to achieve two different objectives: selective spatial growth and homogenous growth for doped materials. We demonstrated, for the first time, multi-material SIS process with control over the spatial location of each material and fabricate heterostructure nanorods and nanowires. Doping materials were fabricated using simultaneously growth of two precursors.We studied SIS within self-assembled block copolymer (BCP) films and electrospun polymer fibers and developed multi-material SIS, where two metal oxides are grown together in a single process, with precise control over their location within the polymer template. We used cylinder forming poly (styrene-block-methyl methacrylate) (PS-b-PMMA) films and electrospun PMMA as the polymeric template and DEZ (diethyl zinc), TMA (trimethyl aluminum) as the organometallic precursors. We achieved control over the growth location of each metal oxide by tuning the organometallic precursors diffusion time, forming heterostructures after polymer removal. A short exposure of the first precursor resulted in a limited growth only at the outer part of the polymer, while a long exposure of the second precursor enabled it to reach the full depth of the polymer besides the section which was already occupied by the first precursor. An exposure to water completed the cycle. We demonstrated this process on BCP films to achieve AlOx-ZnO nanorods arrays (Figure 1A-B) and on polymer fibers to achieve AlOx-ZnO fibers (Figure 1C-D). We performed structural characterization using scanning and transmission electron microscopy (SEM and TEM, respectively) to characterize the nanowires and nanorods as well as three-dimensional characterization scanning TEM (STEM) tomography and energy-dispersive X-ray spectroscopy (EDS) STEM tomography in order to probe the structure and the chemical composition in 3D. To fabricate doped materials, we applied SIS process with TMA and DEZ in the same exposure within homopolymer film. We preformed SEM-EDS to quantify each element and evaluate the doping percentage. This research opens new pathways for multi-materials nano scale structure fabrication through ALD-based growth within polymers.Figure 1 caption: AlOx-ZnO nanorods array: cross-sectional views using A) EsB detector and B) secondary electron in-lens detector. AlOx-ZnO fibers C) EDS map D) HAADF image [1] R. Azoulay et al., Small, 15, 1904657 (2019).[2] R. Azoulay et al., ACS Appl. Nano Mater., 5, 7228 (2022). Figure 1

(Invited) Monopolar and Bipolar Membranes Based on Nanofiber Electrospinning

Cation-exchange, anion-exchange, and bipolar membranes play crucial roles in a variety of electrochemical processes and devices, including chloralkali cells, electrodialysis separations for water purification, proton-exchange membrane and hydroxide-exchange membrane (alkaline) fuel cells, redox flow batteries, and processes for direct air capture of CO2. The incorporation of polymeric nanofibers into such membranes provides an attractive and tunable method of creating materials with new nano-morphologies and highly desirable properties.The impregnation of an ionomer solution into a pre-formed nonwoven porous mat of electrospun polymer fibers is a well-known method of making reinforced proton-exchange membranes. The use of simultaneous dual-fiber electrospinning or the electrospinning of polymer blends can be used to intermix/incorporate/co-locate dissimilar and incompatible polymers on the nanoscale. Although less studied in the literature, these methods offer many interesting possibilities for new membrane structures with targeted and unique transport and mechanical properties.In this review talk, the use of dual fiber and blended polymer fiber electrospinning for membrane fabrication will be presented for the following: (1) Nanofiber reinforced cation (proton) exchange membranes, (2) Electrospun NafionTM/PVDF dual fiber and single-fiber membranes for H2/Br2 redox flow batteries, (3) Composite anion exchange membranes, and (4) Bipolar membranes with a 3D nanofiber junction. Materials and methods for membrane fabrication will be described and the properties of the membranes will be discussed.

Multi-level structured polylactic acid electrospun fiber membrane based on green solvents for high-performance air filtration

Particle matter (PM) pollution seriously threatens public health as it can combine with viruses and heavy metals to enter the human body and cause various diseases. Electrospun polymer fiber membranes, especially biodegradable materials such as polylactic acid, have great potential in PM filtration. However, most polylactic acid fiber membranes are imbalanced between filtration efficiency and resistance. Porous and bead-like fibers offer higher filtration efficiency and are expected to address these challenges with their larger specific surface area. Nonetheless, this structure may compromise the mechanical strength of the fiber membrane, thereby affecting the stability of gas purification and separation. Additionally, the significant volatilization of solvents during solution electrospinning can result in environmental concerns. Here, we prepared a double-layer filter with beads and cracks using a green mixed solvent of N, N-dimethylacetamide and dimethyl carbonate. The difference in the volatilization rate of mixed solvents increases the roughness of the membrane surface and enhances the adsorption of PMs. The structural difference between the two layers of membranes enables graded filtration of particles, further reducing pressure drop. Moreover, the entanglement at the interfaces enhances the mechanical properties of the bilayer membrane. It is worth mentioning that the design of the double-layer membrane improves the overall hydrophobicity and has practical application potential.

Water-Mediated Conversion of BaTiO3 Nanoparticles into BaCO3 Nanorods in Electrospun Polymer Fibers: Implications for Carbon Capture Applications.

Under ambient conditions and in aqueous environments, transformations of nanoparticle-based ferroelectric components can raise important stability issues that are relevant for applications as multilayer capacitors, flexible piezoelectrics, or biomedical devices. We show that X-ray amorphous BaTiO3 nanoparticles that were grown by flame spray pyrolysis and which can be incorporated into electrospun polymer fibers undergo incongruent Ba2+ dissolution in the presence of water. At pH > 5 and in contact with air, corresponding Ba solutes spontaneously convert into crystalline BaCO3 needles to produce characteristic nano- and microstructures. We compared the reactivity of amorphous BaTiO3 nanoparticle powders with those of nanocrystals after annealing-induced crystallization. The stability of aqueous nanoparticle-polymer formulations, which are typically part of nanoparticle encapsulation in polymers and electrospinning, was included in this analysis. Nanoparticle size, crystallinity, surface area, the presence of carbonaceous surface contaminants, and the effect of surface passivation with polymers are addressed to underline the critical role of condensed water during the synthesis, storage, and processing of BaTiO3 nanoparticle-based composites.

Electrospun Polymeric Fibers Decorated with Silk Microcapsules via Encapsulation and Surface Immobilization for Drug Delivery.

Hollow polymer microcapsules as drug carriers have the advantages of drug protection, storage, and controlled release. Microcapsules combined with tissue engineering scaffolds such as electrospun microfibers can enhance long-term local drug retention. However, the combination methods of microcapsules and fibers still need to be further explored. Here, we developed different technical approaches to functionalize electrospun polycaprolactone (PCL) microfibers with silk fibroin (SF) microcapsules through encapsulation and surface immobilization, including direct blending and emulsion electrospinning for encapsulation, as well as covalent and cleavable disulfide-linkage for surface immobilization. The results of "blending" approach showed that silk microcapsules with different sizes could be uniformly encapsulated inside electrospun fibers without aggregation. To further reduce the use of organic solvents, the microcapsules in the aqueous phase can be uniformly distributed in the PCL organic phase and successfully electrospun into fibers using surfactant span-80. For surface immobilization, silk microcapsules were efficiently covalent binding to the surface of electrospun PCL fibers via click chemistry and exhibited noncytotoxic. Based on this method, with the incorporation of a disulfide bond, the linkages between microcapsule and fiber could be cleaved under reducing conditions. These microcapsule-electrospun fiber combination methods provide sufficient options for different drug delivery requirements. This article is protected by copyright. All rights reserved.

Vapor phase-grown TiO2 and ZnO nanoparticles inside electrospun polymer fibers and their calcination-induced organization

The spatial organization of metal oxide nanoparticles represents an important factor in the chemical utilization of resulting structures. For the production of networks that are composed of metal oxide nanoparticle chains, we dispersed vapor phase-grown TiO2 and ZnO nanoparticles homogeneously in an aqueous polyvinyl alcohol solution. After electrospinning, we analyzed the sizes and diameters of the compositionally homogeneous electrospun fibers and discussed the size distribution and morphology of the nanoparticles inside. Calcination-induced polymer removal gives rise to self-supported nanoparticle-based nanofibers. Particle coarsening by a factor of ~ 2 for TiO2 and ~ 3 for ZnO nanoparticles is observed.Graphical abstract

A Polymorph of Dipeptide Halide Glycyl-L-Alanine Hydroiodide Monohydrate: Crystal Structure, Optical Second Harmonic Generation, Piezoelectricity and Pyroelectricity.

A polymorph of glycyl-L-alanine HI.H2O is synthesized from chiral cyclo-glycyl-L-alanine dipeptide. The dipeptide is known to show molecular flexibility in different environments, which leads to polymorphism. The crystal structure of the glycyl-L-alanine HI.H2O polymorph is determined at room temperature and indicates that the space group is polar (P21), with two molecules per unit cell and unit cell parameters a = 7.747 Å, b = 6.435 Å, c = 10.941 Å, α = 90°, β = 107.53(3)°, γ = 90° and V = 520.1(7) Å3. Crystallization in the polar point group 2, with one polar axis parallel to the b axis, allows pyroelectricity and optical second harmonic generation. Thermal melting of the glycyl-L-alanine HI.H2O polymorph starts at 533 K, close to the melting temperature reported for cyclo-glycyl-L-alanine (531 K) and 32 K lower than that reported for linear glycyl-L-alanine dipeptide (563 K), suggesting that although the dipeptide, when crystallized in the polymorphic form, is not anymore in its cyclic form, it keeps a memory of its initial closed chain and therefore shows a thermal memory effect. Here, we report a pyroelectric coefficient as high as 45 µC/m2K occurring at 345 K, one order of magnitude smaller than that of semi-organic ferroelectric triglycine sulphate (TGS) crystal. Moreover, the glycyl-L-alanine HI.H2O polymorph displays a nonlinear optical effective coefficient of 0.14 pm/V, around 14 times smaller than the value from a phase-matched inorganic barium borate (BBO) single crystal. The new polymorph displays an effective piezoelectric coefficient equal to deff=280 pCN-1, when embedded into electrospun polymer fibers, indicating its suitability as an active system for energy harvesting.

La- and Mn-doped cobalt spinel oxygen evolution catalyst for proton exchange membrane electrolysis.

Discovery of earth-abundant electrocatalysts to replace iridium for the oxygen evolution reaction (OER) in a proton exchange membrane water electrolyzer (PEMWE) represents a critical step in reducing the cost for green hydrogen production. We report a nanofibrous cobalt spinel catalyst codoped with lanthanum (La) and manganese (Mn) prepared from a zeolitic imidazolate framework embedded in electrospun polymer fiber. The catalyst demonstrated a low overpotential of 353 millivolts at 10 milliamperes per square centimeter and a low degradation for OER over 360 hours in acidic electrolyte. A PEMWE containing this catalyst at the anode demonstrated a current density of 2000 milliamperes per square centimeter at 2.47 volts (Nafion 115 membrane) or 4000 milliamperes per square centimeter at 3.00 volts (Nafion 212 membrane) and low degradation in an accelerated stress test.

Tailored functional group vitalization on mesoporous carbon nanofibers for ultrafast electrochemical capacitors

Electric double layer capacitors (EDLCs) are attracting attention as rational energy storage platforms owing to their rapid and reversible charge adsorption/desorption at the electrode interface. Despite these advantages, EDLCs still face challenges in improving their ultrafast-rate capability for realizing its tailored applicability. In this study, tailored functional group vitalization was introduced on carbon nanofibers (CNFs) using chemical interactions between poly(methyl methacrylate-co-methacrylic acid), thiourea, and phosphorus red during thermal activation of electrospun polymer fibers. The tailored functional group vitalization effects include a simultaneous introduction of sulfur and phosphorus co-incorporated heterostructures from surface to interior of the CNFs (SPD-PCNF). In the surface region, sulfur and phosphorus containing functional groups are developed, which promotes electrolyte wettability and fast ionic diffusion kinetics at the CNFs/electrolyte interface. In the interior region, sulfur (2.4 at%) and phosphorus (2.0 at%) atoms are co-doped inside the carbon lattice, which improves electrical conductivity. In both the surface and interior region, accelerated specific mesopore area (1318.9 m2/g) and proportion are developed throughout the CNFs, which accommodates increased amounts and favorable ionic transport routes for charge adsorption/desorption. With these synergistic effects on charge transfer kinetics, SPD-PCNF electrode exhibited ultrafast-rate capability (112.8 F/g at 20 A/g and 14.0 Wh/kg at 36,000 W/kg).

Evaluation of strategies to incorporate silver nanoparticles into electrospun microfibers for the preparation of wound dressings and their antimicrobial activity

ABSTRACT Currently, wound dressing technology is of significant interest in order to avoid undesired effects when burns or skin wounds are treated, especially their risk for microbial contamination and subsequent infection. Silver nanoparticles (AgNPs) have claimed importance as antimicrobial agents. For these reasons, a comparative study of different methods to synthesize electrospun polymeric fibers loaded with AgNPs (Ag+/PCLPVP) such as direct blending, ultraviolet irradiation, thermal treatment, and silver mirror reaction methods were done. The morphology and size of the fibers were investigated using the SEM, where the loading of the AgNPs in the fibers was measured with EDS analysis. FTIR, Raman spectroscopy, XRD, and TGA analysis were applied to measure the physicochemical properties of the fibers. DLS study allowed us to measure the size and surface charge of the obtained materials. The antimicrobial efficiency was carried out against Staphylococcus aureus and Escherichia coli bacteria for 24 h. Cytotoxicity was evaluated with the MTT assay using HFF1 cells. The results showed that the method with the best antimicrobial effect in both bacteria is the UV irradiation conducted before the electrospinning process. The UV radiation method also promotes good distribution efficiency, the physicochemical properties obtained were desirable for wound dressings, and the particle size within nanoparticle interval (~17 nm). Therefore, the most promising method for the preparation of Ag+/PCLPVPbased wound dressings was UV irradiation.