This review addresses recent progress made in the use of nanofibers for analyte detection and sample preparation within analytical devices. The unique characteristics of nanofibers make them ideal for incorporation within sensors designed to allow for sensitive detection of clinical, environmental, and food safety analytes. In particular, the extremely large surface area provided by nanofiber mats and arrays drastically increases the availability of immobilization sites within biosensors. Additionally, nanofibers can be made from a variety of biocompatible materials and can be functionalized through the incorporation of nanoscale materials within spinning dopes or polymerization solutions. Finally, methods of nanofiber formation are largely well understood, allowing for controlled synthesis of nanofiber mats with specific sizes, shapes, pore sizes, and tensile strengths. In this paper, we present a survey of the different materials that are currently being used to produce nanofibers for use within sensing devices. In addition, we compare the limits of detection and linear ranges of nanofiber-based sensors and conventional sensors to determine if detection is improved by the inclusion of nanoscale materials.
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.
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.
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.
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