Anitha Senthamizhan

Highly Fluorescent Pyrene-Functional Polystyrene Copolymer Nanofibers for Enhanced Sensing Performance of TNT.

A pyrene-functional polystyrene copolymer was prepared via 1,3-dipolar cycloaddition reaction (Sharpless-type click recation) between azide-functional styrene copolymer and 1-ethynylpyrene. Subsequently, nanofibers of pyrene-functional polystyrene copolymer were obtained by using electrospinning technique. The nanofibers thus obtained, found to preserve their parent fluorescence nature, confirmed the avoidance of aggregation during fiber formation. The trace detection of trinitrotoluene (TNT) in water with a detection limit of 5 nM was demonstrated, which is much lower than the maximum allowable limit set by the U.S. Environmental Protection Agency. Interestingly, the sensing performance was found to be selective toward TNT in water, even in the presence of higher concentrations of toxic metal pollutants such as Cd(2+), Co(2+), Cu(2+), and Hg(2+). The enhanced sensing performance was found to be due to the enlarged contact area and intrinsic nanoporous fiber morphology. Effortlessly, the visual colorimetric sensing performance can be seen by naked eye with a color change in a response time of few seconds. Furthermore, vapor-phase detection of TNT was studied, and the results are discussed herein. In terms of practical application, electrospun nanofibrous web of pyrene-functional polystyrene copolymer has various salient features including flexibility, reproducibility, and ease of use, and visual outputs increase their value and add to their advantage.

Flexible and highly stable electrospun nanofibrous membrane incorporating gold nanoclusters as an efficient probe for visual colorimetric detection of Hg(II)

Here, we describe the visual colorimetric detection of Hg2+ based on a flexible fluorescent electrospun nanofibrous membrane (NFM). It is an efficient approach, in which we have effectively integrated fluorescent gold nanoclusters (AuNC) into electrospun polyvinyl alcohol nanofibers. Interestingly, the resulting composite nanofibers (AuNC*NFM) are shown to retain the fluorescence properties of AuNC and exhibit red fluorescence under UV light, being cogent criteria for the production of a visual colorimetric sensor. Furthermore, capabilities with regard to the stability of the AuNC*NFM have been under observation for a period of six months, with conditions matching those of typical atmosphere, and the resulting outcome has thrown light on their long-term storability and usability. It is clear, from the fact that the nanofibrous membrane preserves the fluorescence ability up to a temperature of 100 °C, that temperature does not have an effect on the sensing performance in real-time application. The water-insoluble AuNC*NFM have been successfully tailored by cross-linking with glutaraldehyde vapor. Further, the contact mode approach has been taken into consideration for the visual fluorescent response to Hg2+, and the observed change of color indicates the utility of the composite nanofibers for onsite detection of Hg2+ with a detection limit of 1 ppb. The selectivity of the AuNC*NFM hybrid system has been analyzed by its response to other common toxic metal interferences (Pb2+, Mn2+, Cu2+, Ni2+, Zn2+, Cd2+) in water. Several unique features of the hybrid system have been determined, including high stability, self-standing ability, naked-eye detection, selectivity, reproducibility and easy handling – setting a new trend in membrane-based sensor systems.

Glucose sensors based on electrospun nanofibers: a review

The worldwide increase in the number of people suffering from diabetes has been the driving force for the development of glucose sensors. The recent past has devised various approaches to formulate glucose sensors using various nanostructure materials. This review presents a combined survey of these various approaches, with emphasis on the current progress in the use of electrospun nanofibers and their composites. Outstanding characteristics of electrospun nanofibers, including high surface area, porosity, flexibility, cost effectiveness, and portable nature, make them a good choice for sensor applications. Particularly, their nature of possessing a high surface area makes them the right fit for large immobilization sites, resulting in increased interaction with analytes. Thus, these electrospun nanofiber-based glucose sensors present a number of advantages, including increased life time, which is greatly needed for practical applications. Taking all these facts into consideration, we have highlighted the latest significant developments in the field of glucose sensors across diverse approaches.

Real-time selective visual monitoring of Hg(2+) detection at ppt level: An approach to lighting electrospun nanofibers using gold nanoclusters.

In this work, fluorescent gold nanocluster (AuNC) decorated polycaprolactone (PCL) nanofibers (AuNC*PCL-NF) for real time visual monitoring of Hg2+ detection at ppt level in water is demonstrated. The resultant AuNC*PCL-NF exhibiting remarkable stability more than four months at ambient environment and facilitates increased accessibility to active sites resulting in improved sensing performance with rapid response time. The fluorescence changes of AuNC*PCL-NF and their corresponding time dependent spectra, upon introduction of Hg2+, led to the visual identification of the sensor performance. It is observed that the effective removal of excess ligand (bovine serum albumin (BSA) greatly enhances the surface exposure of AuNC and therefore their selective sensing performance is achieved over competent metal ions such as Cu2+, Ni2+, Mn2+, Zn2+, Cd2+, and Pb2+ present in the water. An exceptional interaction is observed between AuNC and Hg2+, wherein the absence of excess interrupting ligand makes AuNC more selective towards Hg2+. The underlying mechanism is found to be due to the formation of Au-Hg amalgam, which was further investigated with XPS, TEM and elemental mapping studies. In short, our findings may lead to develop very efficient fluorescent-based nanofibrous mercury sensor, keeping in view of its stability, simplicity, reproducibility, and low cost.

“Nanotraps” in porous electrospun fibers for effective removal of lead(II) in water

Here, we have put in conscientious effort to demonstrate the careful design of binding sites in fibers and their stability for enhanced adsorption of metal ions, which has proven to be a challenging task until now. Dithiothreitol capped gold nanoclusters (AuNCs) are successfully encapsulated into a cavity in the form of pores in electrospun porous cellulose acetate fibers (pCAFs) and their assembly creates a “nanotrap” for effective capture of Pb2+. The enhanced immobilization capacity of AuNCs into the interiors of the fibers and their non-aggregated nature offer enhanced adsorption sites, thus reaching maximum extraction capacity up to 1587 mg g−1 for Pb2+. The remarkable finding from this approach has shown that the diffusion of Pb2+ into the interiors of the AuNC encapsulated porous cellulose acetate fiber (pCAF/AuNC) is in line with the penetration depth of AuNCs. The effectiveness of the pCAF/AuNC has been compared with that of the AuNC decorated non-porous cellulose acetate fibers (nCAF/AuNC). The findings have shown a remarkable improvement in the adsorption efficiency by increasing the availability and stability of adsorption sites in the pCAF/AuNC. We strongly believe that the proposed approach might provide a new insight into developing nanotraps to eliminate the usual limitations including denaturation of adsorbents on supported matrices.

Immobilization of gold nanoclusters inside porous electrospun fibers for selective detection of Cu(II): A strategic approach to shielding pristine performance.

Here, a distinct demonstration of highly sensitive and selective detection of copper (Cu2+) in a vastly porous cellulose acetate fibers (pCAF) has been carried out using dithiothreitol capped gold nanocluster (DTT.AuNC) as fluorescent probe. A careful optimization of all potential factors affecting the performance of the probe for effective detection of Cu2+ were studied and the resultant sensor strip exhibiting unique features including high stability, retained parent fluorescence nature and reproducibility. The visual colorimetric detection of Cu2+ in water, presenting the selective sensing performance towards Cu2+ ions over Zn2+, Cd2+ and Hg2+ under UV light in naked eye, contrast to other metal ions that didn’t significantly produce such a change. The comparative sensing performance of DTT.AuNC@pCAF, keeping the nonporous CA fiber (DTT.AuNC@nCAF) as a support matrix has been demonstrated. The resulting weak response of DTT.AuNC@nCAF denotes the lack of ligand protection leading to the poor coordination ability with Cu2+. The determined detection limit (50 ppb) is far lower than the maximum level of Cu2+ in drinking water (1.3 ppm) set by U.S. Environmental Protection Agency (EPA). An interesting find from this study has been the specific oxidation nature between Cu2+ and DTT.AuNC, offering solid evidence for selective sensors.

Nanograined surface shell wall controlled ZnO–ZnS core–shell nanofibers and their shell wall thickness dependent visible photocatalytic properties

The core–shell form of ZnO–ZnS based heterostructural nanofibers (NF) has received increased attention for use as a photocatalyst owing to its potential for outstanding performance under visible irradiation. One viable strategy to realize the efficient separation of photoinduced charge carriers in order to improve catalytic efficiency is to design core–shell nanostructures. But the shell wall thickness plays a vital role in effective carrier separation and lowering the recombination rate. A one dimensional (1D) form of shell wall controlled ZnO–ZnS core–shell nanofibers has been successfully prepared via electrospinning followed by a sulfidation process. The ZnS shell wall thickness can be adjusted from 5 to 50 nm with a variation in the sulfidation reaction time between 30 min and 540 min. The results indicate that the surfaces of the ZnO nanofibers were converted to a ZnS shell layer via the sulfidation process, inducing visible absorption behavior. Photoluminescence (PL) spectral analysis indicated that the introduction of a ZnS shell layer improved electron and hole separation efficiency. A strong correlation between effective charge separation and the shell wall thickness aids the catalytic behavior of the nanofiber network and improves its visible responsive nature. The comparative degradation efficiency toward methylene blue (MB) has been studied and the results showed that the ZnO–ZnS nanofibers with a shell wall thickness of ∼20 nm have 9 times higher efficiency than pristine ZnO nanofibers, which was attributed to effective charge separation and the visible response of the heterostructural nanofibers. In addition, they have been shown to have a strong effect on the degradation of Rhodamine B (Rh B) and 4-nitrophenol (4-NP), with promising reusable catalytic efficiency. The shell layer upgraded the nanofiber by acting as a protective layer, thus avoiding the photo-corrosion of ZnO during the catalytic process. A credible mechanism for the charge transfer process and a mechanism for photocatalysis supported by trapping experiments in the ZnO–ZnS heterostructural system for the degradation of an aqueous solution of MB are also explicated. Trapping experiments indicate that h+ and ˙OH are the main active species in the ZnO–ZnS heterostructural catalyst, which do not effectively contribute in a bare ZnO catalytic system. Our work also highlights the stability and recyclability of the core–shell nanostructure photocatalyst and supports its potential for environmental applications. We thus anticipate that our results show broad potential in the photocatalysis domain for the design of a visible light functional and reusable core–shell nanostructured photocatalyst.

Grain boundary engineering in electrospun ZnO nanostructures as promising photocatalysts

Electrospun ZnO nanofibers (ZNF) have received increased attention as photocatalysts owing to their potential for incredible performance. However, uncertainty still exists in determining the correlation between grain boundaries (GBs) and photocatalytic activity. Therefore, effective thought has been put into engineering the GBs to convert ZNF into a promising photocatalyst. Herein, the obtained electrospun ZnO structures are composed of nanograins, which are connected to each other in an ordered manner. In-depth studies have revealed that the growth of nanograins severely altered the morphology of ZNF and GB areas at higher annealing temperatures ranging from 500 °C to 1000 °C. Based on the morphological features and their structural evolution, the obtained structures are named as ZnO nanofibers-1 (ZNF-1, 500 °C), ZnO hollow tubes (ZHT, 600 °C), ZnO nanofibers-2 (ZNF-2, 700 °C), ZnO bamboo structured fibers (ZBF, 800 °C), ZnO segmented fibers (ZSF, 900 °C) and ZnO nanoparticles (ZNP, 1000 °C). A strong correlation between the inherent emission features of ZNF and their peak positions have been detected with the GB. The comparative degradation efficiency of methylene blue (MB) has been studied and the results showed that the ZNF-1 with highly stacked nanograins containing rich grain boundaries demonstrated ∼6 times higher efficiency than other structures. In addition, it has been shown to have a strong effect towards the degradation of Rhodamine B (Rh B) and 4-nitro-phenol (4-NP). A critical parameter for improving the photocatalytic activity is found to be the GB mediated defects, which are proposed to be oxygen/zinc vacancies at nanograin fusion interfaces, while supposedly maintaining its fibrous structure, wherein no relationship has been drawn implying the direct domination of morphology, surface area and defect.

Ultrasensitive electrospun fluorescent nanofibrous membrane for rapid visual colorimetric detection of H2O2.

AbstractWe report herein a flexible fluorescent nanofibrous membrane (FNFM) prepared by decorating the gold nanocluster (AuNC) on electrospun polysulfone nanofibrous membrane for rapid visual colorimetric detection of H2O2. The provision of AuNC coupled to NFM has proven to be advantageous for facile and quick visualization of the obtained results, permitting instant, selective, and on-site detection. We strongly suggest that the fast response time is ascribed to the enhanced probabilities of interaction with AuNC located at the surface of NF. It has been observed that the color change from red to blue is dependent on the concentration, which is exclusively selective for hydrogen peroxide. The detection limit has been found to be 500 nM using confocal laser scanning microscope (CLSM), visually recognizable with good accuracy and stability. A systematic comparison was performed between the sensing performance of FNFM and AuNC solution. The underlying sensing mechanism is demonstrated using UV spectra, transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The corresponding disappearance of the characteristic emissions of gold nanoclusters and the emergence of a localized surface plasmon resonance (LSPR) band, stressing this unique characteristic of gold nanoparticles. Hence, it is evident that the conversion of nanoparticles from nanoclusters has taken place in the presence of H2O2. Our work here has paved a new path for the detection of bioanalytes, highlighting the merits of rapid readout, sensitivity, and user-friendliness. Graphical AbstractRapid visual colorimetric detection of H2O2

In vivo safety evaluations of electrospun nanofibers for biomedical applications

In this chapter, we have highlighted an overview on the different types of in vivo studies and clinical trials conducted using electrospun nanofibrous materials, which are intended for various biomedical applications. However, exploitation of electrospun nanofibers in clinical applications has not fulfilled exaggerated promise because of various issues including animal use, reliable correlation between in vitro-in vivo experiments, and high cost. The interaction of nanofiber with biomolecules in animal models may vary in humans and induce different toxic effects. Therefore, investigations of nanofibers on human health are extremely required to fully elucidate them in biomedical applications.