Designing an Effective and Scalable UV-Protective Cooling Textile with Nanoporous Fibers.

Although radiative cooling concepts guarantee reduction of air conditioning energy consumption by maximizing the scattering of solar radiation and dissipation of thermal radiation of a human body or building, large-scale implementation is challenging due to the need of radical adaptation in manufacturing processes, materials, and design. Here, we introduce an extremely thin layer of nanoporous microfibers without any additional materials or post-treatments. The optical and thermal effectiveness of porous fibers are presented to report a nondisruptive method of preventing the transmission of energy-intensive radiation such as ultraviolet radiation (UV) through textiles. Results show ∼1.4 °C cooling by adding 1 g/m2 (GSM) of porous fibers on a 160 GSM cotton t-shirt, and 91% of UV was prevented with 7.5 GSM of a porous fiber mat. This minimalistic additive approach would widen the scope of optical and radiative cooling research and accelerate both functional and sustainable materials research to be more accessible.

Bioanalytical approaches for the detection, characterization, and risk assessment of micro/nanoplastics in agriculture and food systems.

This review discusses the most recent literature (mostly since 2019) on the presence and impact of microplastics (MPs, particle size of 1 µm to 5 mm) and nanoplastics (NPs, particle size of 1 to 1000 nm) throughout the agricultural and food supply chain, focusing on the methods and technologies for the detection and characterization of these materials at key entry points. Methods for the detection of M/NPs include electron and atomic force microscopy, vibrational spectroscopy (FTIR and Raman), hyperspectral (bright field and dark field) and fluorescence imaging, and pyrolysis-gas chromatography coupled to mass spectrometry. Microfluidic biosensors and risk assessment assays of MP/NP for in vitro, in vivo, and in silico models have also been used. Advantages and limitations of each method or approach in specific application scenarios are discussed to highlight the scientific and technological obstacles to be overcome in future research. Although progress in recent years has increased our understanding of the mechanisms and the extent to which MP/NP affects health and the environment, many challenges remain largely due to the lack of standardized and reliable detection and characterization methods. Most of the methods available today are low-throughput, which limits their practical application to food and agricultural samples. Development of rapid and high-throughput field-deployable methods for onsite screening of MP/NPs is therefore a high priority. Based on the current literature, we conclude that detecting the presence and understanding the impact of MP/NP throughout the agricultural and food supply chain require the development of novel deployable analytical methods and sensors, the combination of high-precision lab analysis with rapid onsite screening, and a data hub(s) that hosts and curates data for future analysis.

Structure and Properties of Polyamide Fabrics with Insect-Repellent Functionality by Electrospinning and Oxygen Plasma-Treated Surface Coating.

The need for light-weight and high-strength insect-repellant fabrics is of critical importance to the cessation of viral diseases. The goal of the study is to investigate the structure and properties of insect-repellent polyamide fabrics for use in protective garments to guard against mosquitos. Permethrin was applied to the polyamide fabrics through incorporation into the nylon 6 polymer solution during electrospinning and dip coating onto the control untreated and oxygen plasma-treated polyamide fabrics: electropun nylon 6 nanofiber nonwovens, commercially available nylon 6 warp knit tricot, and nylon 66 double weft, knit interlock fabrics. The incorporation of permethrin into the polymer solution before the formation of fibers demonstrated the most efficient way to apply permethrin to the fiber/fabric systems. The plasma treatment significantly increased the amount of permethrin on the surface of the fabrics. All permethrin-containing polyamide fabrics showed excellent fastness of the insecticide to light. The electrospun nylon 6 nonwovens demonstrated the best fastness to washing among the plasma-treated electrospun nylon 6, nylon 66 double weft knit, and nylon 6 warp-knit tricot. All permethrin-treated fabrics were repellent and caused higher percentage of mosquito escape compared to the control untreated fabrics.

Electrospun Nanofibers for Chemical Separation.

The separation and purification of specific chemicals from a mixture have become necessities for many environments, including agriculture, food science, and pharmaceutical and biomedical industries. Electrospun nanofiber membranes are promising materials for the separation of various species such as particles, biomolecules, dyes, and metals from liquids because of the combined properties of a large specific surface, light weight, high porosity, good connectivity, and tunable wettability. This paper reviews the recent progress in the design and fabrication of electrospun nanofibers for chemical separation. Different capture mechanisms including electrostatic, affinity, covalent bonding, chelation, and magnetic adsorption are explained and their distinct characteristics are highlighted. Finally, the challenges and future aspects of nanofibers for membrane applications are discussed.

Effective Suppression of the Polysulfide Shuttle Effect in Lithium-Sulfur Batteries by Implementing rGO-PEDOT:PSS-Coated Separators via Air-Controlled Electrospray.

Lithium-sulfur (Li-S) batteries have been earning significant attention because of their high energy density and cost efficiency. Albeit these outstanding qualities, the polysulfide shuttling effect and low electrical conductivity of the sulfur active material in this battery chemistry results in poor cycling performance. In an attempt to overcome these problems, a hybrid structure of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) and reduced graphene oxide was developed and coated on the surface of a conventional separator using air-controlled electrospray. Implementing these coated separators in Li-S batteries led to lower polarization and stymied the polysulfide shuttling effect through the combining effects of electrostatic, physical, and chemical interactions. Our results reveal that the capacity and rate capacity are drastically improved via coating the separator, leading to more than twice the capacity of over 800 mA h g-1 after 100 cycles at 0.5 C rate, when it is compared to those with the pristine separator. Overall, this hybrid coating material shows great promise in enhancing the current Li-S battery technology.

Direct characterization of cotton fabrics treated with di-epoxide by nuclear magnetic resonance.

A non-acid-based, di-functional epoxide, neopentyl glycol diglycidyl ether (NPGDGE), was used to modify cotton fabrics. Direct characterization of the modified cotton was conducted by Nuclear Magnetic Resonance (NMR) without grinding the fabric into a fine powder. NaOH and MgBr2 were compared in catalyzing the reaction between the epoxide groups of NPGDGE and the hydroxyl groups of cellulose. Possible reaction routes were discussed. Scanning electron microscopy (SEM) images showed that while the MgBr2-catalyzed reaction resulted in self-polymerization of NPGDGE, the NaOH-catalyzed reaction did not. Fourier transform infrared spectroscopy (FTIR) showed that at high NaOH concentration cellulose restructures from allomorph I to II. NMR studies verified the incorporation of NPGDGE into cotton fabrics with a clear NMR signal, and confirmed that at higher NaOH concentration the efficiency of grafting of NPGDGE was increased. This demonstrates that use of solid state NMR directly on woven fabric samples can simultaneously characterize chemical modification and crystalline polymorph of cotton. No loss of tensile strength was observed for cotton fabrics modified with NPGDGE.

Increasing Stability of Biotin Functionalized Electrospun Fibers for Biosensor Applications.

This paper describes the effects of both solvent and copolymer block lengths on the stability of electrospun poly(lactic acid)/poly(lactic acid)-b-poly(ethylene glycol) (PLA/PLA-b-PEG) and PLA/PLA-b-PEG-Biotin fibers in water. By tailoring the block length of copolymers PLA-b-PEG, water stability of electrospun fibers is improved over fibers reported previously. The solvent used also influenced the stability and hydrophilicity of resulting fibers. Fibers formed using 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) have greater water stability, but less PEG at the surface of fibers than fibers spun from dimethylformamide (DMF). Attaching biotin to the end of PLA(3600)-b-PEG(2000) and spinning from DMF resulted, initially, in 7.6% of the total biotin incorporated into the fiber, assuming every PEG terminal had one biotin attached (1.1 mg of biotin per gram of fiber) available at the fibers' surface. In addition, PLA/PLA(3600)-b-PEG(2000)-Biotin spun from DMF hindered biotin migration to the aqueous phase, leaving 2% of the incorporated biotin remaining at the surface of fibers after 7 days of water exposure. The water wicking ability of DMF spun fibers also increased significantly with the biotin attachment to the PEG terminal. While HFIP spun fibers lost little biotin from fibers, there was no detectable surface available biotin, indicating biotin was at the interior. With biotin and PEG at the interior of the fibers spun from HFIP, the water wicking remained the same for PLA/PLA(3600)-b-PEG(2000) spun samples and decreased for PLA/PLA(5700)-b-PEG(1000). The dissimilarities observed in water wicking for HFIP spun samples are primarily the result of differences in fiber morphology.

Passive Mixing Capabilities of Micro- and Nanofibres When Used in Microfluidic Systems.

Nanofibres are increasingly being used in the field of bioanalytics due to their large surface-area-to-volume ratios and easy-to-functionalize surfaces. To date, nanofibres have been studied as effective filters, concentrators, and immobilization matrices within microfluidic devices. In addition, they are frequently used as optical and electrochemical transduction materials. In this work, we demonstrate that electrospun nanofibre mats cause appreciable passive mixing and therefore provide dual functionality when incorporated within microfluidic systems. Specifically, electrospun nanofibre mats were integrated into Y-shaped poly(methyl methacrylate) microchannels and the degree of mixing was quantified using fluorescence microscopy and ImageJ analysis. The degree of mixing afforded in relationship to fibre diameter, mat height, and mat length was studied. We observed that the most mixing was caused by small diameter PVA nanofibres (450-550 nm in diameter), producing up to 71% mixing at the microchannel outlet, compared to up to 51% with polystyrene microfibres (0.8-2.7 µm in diameter) and 29% mixing in control channels containing no fibres. The mixing afforded by the PVA nanofibres is caused by significant inhomogeneity in pore size and distribution leading to percolation. As expected, within all the studies, fluid mixing increased with fibre mat height, which corresponds to the vertical space of the microchannel occupied by the fibre mats. Doubling the height of the fibre mat led to an average increase in mixing of 14% for the PVA nanofibres and 8% for the PS microfibres. Overall, mixing was independent of the length of the fibre mat used (3-10 mm), suggesting that most mixing occurs as fluid enters and exits the fibre mat. The mixing effects observed within the fibre mats were comparable to or better than many passive mixers reported in literature. Since the nanofibre mats can be further functionalized to couple analyte concentration, immobilization, and detection with enhanced fluid mixing, they are a promising nanomaterial providing dual-functionality within lab-on-a-chip devices.

Increasing Mechanical Properties of 2-D-Structured Electrospun Nylon 6 Non-Woven Fiber Mats.

Tensile strength, Young's modulus, and toughness of electrospun nylon 6 non-woven fiber mats were improved by increasing individual nanofiber strength and fiber-fiber load sharing. Single-walled carbon nanotubes (CNTs) were used as reinforcement to increase the strength of the electrospun nylon 6 nanofibers. Young's modulus, tensile strength, and toughness of the nylon 6 non-woven fiber mats electrospun from 20 wt % solutions increased 51%, 87%, and 136%, respectively, after incorporating 1 wt % CNTs into the nylon 6 nanofibers. Three methods were investigated to enhance fiber-fiber load sharing: increasing friction between fibers, thermal bonding, and solvent bonding. The addition of beaded nylon 6 nanofibers into the non-woven fiber mats to increase fiber-fiber friction resulted in a statistically significantly increase in Young's modulus over comparable smooth non-woven fiber mats. After annealing, tensile strength, elongation, and toughness of the nylon 6 non-woven fiber mats electrospun from 20 wt % + 10 wt % solutions increased 26%, 28%, and 68% compared to those from 20 wt % solutions. Solvent bonding with formic acid vapor at room temperature for 30 min caused increases of 56%, 67%, and 39% in the Young's modulus, tensile strength, and toughness of non-woven fiber mats, respectively. The increases attributed to increased individual nanofiber strength and solvent bonding synergistically resulted in the improvement of Young's modulus of the electrospun nylon 6 non-woven fiber mats.

Surface Functional Poly(lactic Acid) Electrospun Nanofibers for Biosensor Applications.

In this work, biotin surface functionalized hydrophilic non-water-soluble biocompatible poly(lactic acid) (PLA) nanofibers are created for their potential use as biosensors. Varying concentrations of biotin (up to 18 weight total percent (wt %)) were incorporated into PLA fibers together with poly(lactic acid)-block-poly(ethylene glycol) (PLA-b-PEG) block polymers. While biotin provided surface functionalization, PLA-b-PEG provided hydrophilicity to the final fibers. Morphology and surface-available biotin of the final fibers were studied by Field Emission Scanning Electron Microscopy (FESEM) and competitive colorimetric assays. The incorporation of PLA-b-PEG block copolymers not only decreased fiber diameters but also dramatically increased the amount of biotin available at the fiber surface able to bind avidin. Finally, fiber water stability tests revealed that both biotin and PLA-b-PEG, migrated to the aqueous phase after relatively extended periods of water exposure. The functional hydrophilic nanofiber created in this work shows a potential application as a biosensor for point-of-care diagnostics.

Functionalized electrospun poly(vinyl alcohol) nanofibers for on-chip concentration of E. coli cells.

Positively and negatively charged electrospun poly(vinyl alcohol) (PVA) nanofibers were incorporated into poly(methyl methacrylate) (PMMA) microchannels in order to facilitate on-chip concentration of Escherichia coli K12 cells. The effects of fiber distribution and fiber mat height on analyte retention were investigated. The 3D morphology of the mats was optimized to prevent size-related retention of the E. coli cells while also providing a large enough surface area for analyte concentration. Positively charged nanofibers produced an 87% retention and over 80-fold concentration of the bacterial cells by mere electrostatic interaction, while negatively charged nanofibers reduced nonspecific analyte retention when compared to an empty microfluidic channel. In order to take advantage of this reduction in nonspecific retention, these negatively charged nanofibers were then modified with anti-E. coli antibodies. These proof-of-principle experiments showed that antibody-functionalized negatively charged nanofiber mats were capable of the specific capture of 72% of the E. coli cells while also significantly reducing nonspecific analyte retention within the channel as expected. The ease of fabrication and immense surface area of the functionalized electrospun nanofibers make them a promising alternative for on-chip concentration of analytes. The pore size and fiber mat morphology, as well as surface functionality of the fibers, can be tailored to allow for specific capture and concentration of a wide range of analytes.

Detection of diisocyanates in nesting material associated with mortality in pigeon chicks.

Diisocyanates, commonly used in the production of polyurethane foams, paints, elastomers, varnishes, and coatings, are considered among the most hazardous inhalation toxicants. The present report describes 2 unusual cases of mortality in pigeon chicks associated with nesting material contaminated by diisocyanates. Case 1 was submitted by a racing pigeon breeder who had lost all the hatchlings (n = 125) following replacement of the nesting material with a different lot. All adult birds appeared healthy, and hatchability was not significantly affected, but hatchlings became lethargic and dyspneic after a day of hatch. At necropsy, dark wet lungs were found in the hatchlings. Case 2 was submitted by a show-roller pigeon breeder. In this case, the owner reported lower hatchability, and all hatchlings (approximately 100) died within 2 days of hatching with clinical signs similar to the first case. Necropsy did not reveal any significant findings. For both cases, nesting materials were screened for toxic compounds using gas chromatography-mass spectrometry. Toluene-2,4-diisocyanate (approximately 190-290 ppm) and 4,4'-methylene diphenyl diisocyanate (unquantified) were detected in the nesting pads. While there is very limited information on toxicosis in birds, there are reports of inhalant exposure of diisocyanates causing pulmonary edema and death in various mammalian species. Although cause-effect relationship of mortality and the nesting material was not established in the present cases, the presence of toxic compounds in the nesting materials is a cause for concern. Further investigation is needed to determine the prevalence and toxicity of diisocyanates-contaminated nesting material in avian species.

Preparation and characterization of amphiphilic triblock terpolymer-based nanofibers as antifouling biomaterials.

Antifouling surfaces are critical for the good performance of functional materials in various applications including water filtration, medical implants, and biosensors. In this study, we synthesized amphiphilic triblock terpolymers (tri-BCPs, coded as KB) and fabricated amphiphilic nanofibers by electrospinning of solutions prepared by mixing the KB with poly(lactic acid) (PLA) polymer. The resulting fibers with amphiphilic polymer groups exhibited superior antifouling performance to the fibers without such groups. The adsorption of bovine serum albumin (BSA) on the amphiphilic fibers was about 10-fold less than that on the control surfaces from PLA and PET fibers. With the increase of the KB content in the amphiphilic fibers, the resistance to adsorption of BSA was increased. BSA was released more easily from the surface of the amphiphilic fibers than from the surface of hydrophobic PLA or PET fibers. We have also investigated the structural conformation of KB in fibers before and after annealing by contact angle measurements, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and coarse-grained molecular dynamics (CGMD) simulation to probe the effect of amphiphilic chain conformation on antifouling. The results reveal that the amphiphilic KB was evenly distributed within as-spun hybrid fibers, while migrated toward the core from the fiber surface during thermal treatment, leading to the reduction in antifouling. This suggests that the antifouling effect of the amphiphilic fibers is greatly influenced by the arrangement of amphiphilic groups in the fibers.

Functionalized electrospun nanofibers as bioseparators in microfluidic systems.

Functionalized electrospun nanofibers were integrated into microfluidic channels to serve as on-chip bioseparators. Specifically, poly(vinyl alcohol) (PVA) nanofiber mats were shown to successfully serve as bioseparators for negatively charged nanoparticles. Nanofibers were electrospun onto gold microelectrodes, which were incorporated into poly(methyl methacrylate) (PMMA) microfluidic devices using UV-assisted thermal bonding. PVA nanofibers functionalized with poly(hexadimethrine bromide) (polybrene) were positively charged and successfully filtered negatively charged liposomes out of a buffer solution, while negatively charged nanofibers functionalized with Poly(methyl vinyl ether-alt-maleic anhydride) (POLY(MVE/MA)) were shown to repel the liposomes. The effect of fiber mat thickness was studied using confocal fluorescence microscopy, determining a quite broad optimal range of thicknesses for specific liposome retention, which simplifies fiber mat production with respect to retention reliability. Finally, it was demonstrated that liposomes bound to positively charged nanofibers could be selectively released using a 4-(2-Hydroxyethyl)piperazine-1-ethanesulfonic acid (HEPES)-sucrose-saline (HSS) solution of pH 9, which dramatically changes the nanofiber zeta potential and renders the positively charged nanofibers negatively charged. This is the first demonstration of functional electrospun nanofibers used to enable sample preparation procedures of isolation and concentration in lab-on-a-chip devices. This has far reaching impact on the ability to integrate functional surfaces and materials into microfluidic devices and to significantly expand their ability toward simple lab-on-a-chip devices.

Characterizing zeta potential of functional nanofibers in a microfluidic device.

The measurement of surface charge on nanofibers was achieved by characterizing zeta potential of the nanofibers via a newly developed device for streaming current measurement. Low flow rates were sufficient to generate detectable streaming currents in the absence of an externally applied voltage without damaging nanofiber samples. Zeta potential was calculated by using the Helmholtz-Smoluchowski equation and the measured streaming currents. Two acrylic plates were machined and assembled to form a microfluidic channel that is 150 µm high, 2.0mm wide, and 30 mm long. Two electrodes for the measurement of streaming currents were housed in the top plate. Two nanofibers of pure polyacrylonitrile (PAN) fibers and charged (TiO(2) incorporated) PAN fibers were prepared and characterized in the device. Monobasic sodium phosphate and dibasic sodium phosphate were used to prepare four different pH buffer solutions ranging from pH 5 to pH 8 in order to characterize the zeta potentials. The pure PAN nanofibers had negatively-charged surfaces regardless of pH. However, the zeta potentials of PAN/TiO(2) nanofibers changed from positive to negative at pH 6.5. The zeta potential measurements made on the nanofibers in this new microfluidic device matched with those of the powdered raw materials using a commercial Zetasizer.