A novel PVDF-TiO2@g-C3N4 composite electrospun fiber for efficient photocatalytic degradation of tetracycline under visible light irradiation.

A novel composite electrospun fiber with high photocatalytic efficiency, good stability, strong hydrophobicity, good pollution resistance, and easy separation and recovery was synthesized. The TiO2@g-C3N4 (TCN) with special core-shell structure (5-10 nm shell) facilitated the separation of photogenerated electron-holes and had high photocatalytic performance. The poly (vinylidene fluoride) (PVDF) electrospun fiber immobilized with TCN was successfully fabricated (PVDF-TCN) with uniform distribution and size of nanofibers by using electrospinning, which was used for degrading tetracycline under visible-light irradiation (> 400 nm). A special rougher surface of electrospun fiber obtained by washing of sacrificial PVP increased the specific surface area, which became more conducive to the adhesion of the catalyst. The water contact angle and FTIR results demonstrated that the electrospun fiber became extremely hydrophilic after adding TCN catalyst, which could effectively mitigate the fiber pollution. The PVDF-TCN-0.2g electrospun fiber exhibited excellent photocatalytic performance and the degradation efficiency of tetracycline was up to 97% in 300 min under visible-light irradiation. The mechanism of PVDF-TCN electrospun fiber degradation of tetracycline in the photocatalytic process was also proposed. In addition, the PVDF-TCN-0.2g exhibited a stable activity after 4 cycles experiments since the degradation efficiency remained about 90%. Therefore, we believed this study provided a new strategy in catalyst immobilization and wastewater treatment.

One-Dimensional Nanostructures of Polypyrrole for Shielding of Electromagnetic Interference in the Microwave Region.

Polypyrrole one-dimensional nanostructures (nanotubes, nanobelts and nanofibers) were prepared using three various dyes (Methyl Orange, Methylene Blue and Eriochrome Black T). Their high electrical conductivity (from 17.1 to 60.9 S cm-1), good thermal stability (in the range from 25 to 150 °C) and resistivity against ageing (half-time of electrical conductivity around 80 days and better) were used in preparation of lightweight and flexible composites with silicone for electromagnetic interference shielding in the C-band region (5.85-8.2 GHz). The nanostructures' morphology and chemical structure were characterized by scanning electron microscopy, Brunauer-Emmett-Teller specific surface measurement and attenuated total reflection Fourier-transform infrared spectroscopy. DC electrical conductivity was measured using the Van der Pauw method. Complex permittivity and AC electrical conductivity of respective silicone composites were calculated from the measured scattering parameters. The relationships between structure, electrical properties and shielding efficiency were studied. It was found that 2 mm-thick silicone composites of polypyrrole nanotubes and nanobelts shield almost 80% of incident radiation in the C-band at very low loading of conductive filler in the silicone (5% w/w). Resulting lightweight and flexible polypyrrole composites exhibit promising properties for shielding of electromagnetic interference in sensitive biological and electronic systems.

Sensitive Discrimination of Nerve Agent and Sulfur Mustard Simulants Using Fluorescent Coassembled Nanofibers with Förster Resonance Energy Transfer-Enhanced Photostability and Emission.

In this work, highly sensitive discrimination of nerve agent and sulfur mustard simulants is achieved by using photostable and fluorescent coassembled nanofibers from molecules 1 and 2. We demonstrate that the introduction of 2 as a Förster resonance energy transfer (FRET) acceptor not only enhances the photostability and emission efficiency compared to individual 1 nanofibers but also induces different binding interactions between analytes and 1-2 coassembled nanofibers and thereby distinct fluorescence quenching behaviors used for the discrimination of nerve agent and sulfur mustard simulants. Our findings represent an important advance toward sensitive detection and discrimination of chemical warfare agents (CWAs).

Strong, Ductile, and Waterproof Cellulose Nanofibril Composite Films with Colloidal Lignin Particles.

Brittleness has hindered commercialization of cellulose nanofibril (CNF) films. The use of synthetic polymers and plasticizers is a known detour that impairs biodegradability and carbon footprint of the product. Herein, we utilize a variety of softwood Kraft lignin morphologies to obtain strong and ductile CNF nanocomposite films. An optimum 10 wt % content of colloidal lignin particles (CLPs) produced films with nearly double the toughness compared to a CNF film without lignin. CLPs rendered the films waterproof, provided antioxidant activity and UV-shielding with better visible light transmittance than obtained with irregular lignin aggregates. We conclude based on electron microscopy, dynamic water sorption analysis, and tp-DSC that homogeneously distributed CLPs act as ball bearing lubricating and stress transferring agents in the CNF matrix. Overall, our results open new avenues for the utilization of lignin nanoparticles in biopolymer composites equipped with versatile functionalities for applications in food packaging, water purification, and biomedicine.

Impact of sterilization by electron beam, gamma radiation and X-rays on electrospun poly-(ε-caprolactone) fiber mats.

Biodegradable polymers such as polycaprolactone (PCL) are increasingly used for electrospinning substrates for tissue engineering. These materials offer great advantages such as biocompatibility and good mechanical properties. However, in order to be approved for human implantation they have to be sterilized. The impact of commonly used irradiation sterilization methods on electrospun PCL fiber mats was investigated systematically. Electron beam (ß-irradiation), gamma and X-ray irradiation with two different doses (25 and 33 kGy) were investigated. To determine the impact on the fiber mats, mechanical, chemical, thermal properties and crystallinity were investigated. Irradiation resulted in a significant decrease in molecular weight. At the same time, crystallinity of fiber mats increased significantly. However, the mechanical properties did not change significantly upon irradiation, mostly likely because effects of a lower molecular weight were balanced with the higher degree of crystallinity. The irradiation effects were dose dependent, a higher irradiation dose led to stronger changes. Gamma irradiation seemed to be the least suited method, while electron beams (ß irradiation) had a lower impact. Therefore, ß irradiation is recommended as sterilization method for electrospun PCL fiber mats.

Supramolecular nanofiber of pyrene-lactose conjugates and its two-photon fluorescence imaging.

A lactose modified pyrene derivative (Py-Lac) was synthesized, with which novel twisted supramolecular nanofibers in diameter about 20 nm were constructed by self-assembly. The nanofibers showed solid-state fluorescence between 400 nm and 650 nm with the maximum emission at 495 nm. Furthermore, its recognition reaction with PNA lectin was investigated by fluorescence spectra and turbidity assays. It is interesting found that the supramolecular assembly as multivalent glycocluster exhibited unique and selectively binding interactions with PNA lectin with the binding constant of 5.74 × 106 M-1. Moreover, compound Py-Lac showed two-photon fluorescence imaging with Hep G2 cells.

Optically Monitoring Mineralization and Demineralization on Photoluminescent Bioactive Nanofibers.

Bone regeneration and scaffold degradation do not usually follow the same rate, representing a daunting challenge in bone repair. Toward this end, we propose to use an external field such as light (in particular, a tissue-penetrating near-infrared light) to precisely monitor the degradation of the mineralized scaffold (demineralization) and the formation of apatite mineral (mineralization). Herein, CaTiO3:Yb(3+),Er(3+)@bioactive glass (CaTiO3:Yb(3+),Er(3+)@BG) nanofibers with upconversion (UC) photoluminescence (PL) were synthesized. Such nanofibers are biocompatible and can emit green and red light under 980 nm excitation. The UC PL intensity is quenched during the bone-like apatite formation on the surface of the nanofibers in simulated body fluid; more mineral formation on the nanofibers induces more rapid optical quenching of the UC PL. Furthermore, the quenched UC PL can recover back to its original magnitude when the apatite on the nanofibers is degraded. Our work suggests that it is possible to optically monitor the apatite mineralization and demineralization on the surface of nanofibers used in bone repair.

Crystal Structure and Photocatalytic Activity of Al-Doped TiO2 Nanofibers for Methylene Blue Dye Degradation.

Al-TiO2 nanofibers were prepared using a sol-gel derived electrospinning by varying the Al/Ti molar ratio from 0 to 0.73 to investigate the effect of Al doping on the crystal structure and the photocatalytic activity of Al-TiO2 for methylene blue (MB) degradation. XRD results indicated that as the Al/Ti molar ratio rose, crystal structure of Al-TiO2 was changed from anatase/rutile (undoped), anatase (0.07-0.18), to amorphous phase (0.38-0.73), which was confirmed by XPS and Raman analysis. The degradation kinetic constant increased from 7.3 x 10(-4) min(-1) to 4.5 x 10(-3) min(-1) with the increase of Al/Ti molar ratios from 0 to 0.38, but decreased to 3.4 x 10(-3) min(-1) when the Al/Ti molar ratio reached 0.73. The Al-TiO2 catalyst doped with 0.38 Al/Ti molar ratio demonstrated the best MB degradation. Experimental results indicated that the Al doping in Al-TiO2 was mainly attributed to the crystal structure of TiO2 and the photocatalytic degradation of MB.

Reproducible preparation of a stable polypyrrole-coated-silver nanoparticles decorated polypyrrole-coated-polycaprolactone-nanofiber-based cloth electrode for electrochemical sensor application.

A piece of conductive cloth has been successfully constructed from polypyrrole-coated silver nanoparticle (Ag@PPy) composites decorated on electrospun polycaprolactone (PCL) nanofibers that formed the core-shell structure of Ag@PPy/PCL@PPy via a photo-induced one-step redox reaction. The photochemical reaction method both accelerated the rate of formation of silver nanoparticles (Ag NPs) and enhanced the dispersion of Ag NPs at the surface of PCL@PPy film. The resulting Ag@PPy/PCL@PPy-based cloth was flexible enough to be cut and pasted onto a glass carbon electrode for the preparation of a biosensor. The resulting biosensor showed good electrochemical activity toward the reduction of H2O2 with low detection limit down to 1 µM (S/N = 3) and wide linear detection ranging from 0.01 mM to 3.5 mM (R(2) = 0.990). This sensor has been applied to detect the trace H2O2 residual in milk. The cloth electrode has been proved to exhibit long-term stability, high selectivity, and excellent reproducibility.

Preparation of cocrystal nanofibres of cobalt octaethylporphyrin and tetracyanoquinodimethane with good photoresponse.

Cocrystal nanofibres of cobalt octaethylporphyrin and tetracyanoquinodimethane were prepared by a facile solution method and fully characterized by SEM, AFM, XRD, Raman, EDX, and UV-vis-NIR. The as-prepared cocrystal nanofibres had smooth surfaces and uniform dimension. When incorporated into prototype devices, they exhibited good photoresponse at ambient conditions. Additionally, the phototransistor characteristics with a maximum I(on)/I(off) ratio of -460 was demonstrated. The facile synthesis and good photoresponse may boost the potential applications of cocrystal-based nanostructures in future miniaturized devices.

Enhanced conversion efficiency in dye-sensitized solar cells based on bilayered nano-composite photoanode film consisting of TiO2 nanoparticles and nanofibers.

Novel TiO2 nanoparticles/nanofibers (NPs/NFs) bilayered nano-composite photoanode film for dye-sensitized solar cells (DSSCs) was fabricated through the combination of spin-coating and electrospinning. The NPs and NFs layers have complementary roles. The underlaid spin-coated NPs layer provides the photoanode film with higher specific surface area for dye adsorption and improved adhesion to conductive glass substrate. The overlaid electrospun NFs layer endows the photoanode film with better dye-loading and light-harvesting capabilities due to its porous meshwork structure. And the NFs layer also offers larger pore volume, which can facilitate the electrolyte diffusion and the activity regeneration of dye sensitizers. As a result, the electron transport is accelerated while the charge recombination is suppressed. Ascribing to the synergic effect of the NPs and NFs layers, the TiO2 NPs/NFs-based DSSCs achieve a conversion efficiency of 4.46%, which is nearly 14% higher than that of the pure TiO2 NPs-based ones.

Low frequency magnetic force augments hepatic differentiation of mesenchymal stem cells on a biomagnetic nanofibrous scaffold.

Liver tissue engineering using polymeric nanofibrous scaffold and stem cells holds great promises for treating end-stage liver failures. The aim of this study was to evaluate hepatic trans-differentiation potential of human mesenchymal stem cells (hMSCs) on a biomagnetic electrospun nanofibrous scaffold fabricated from a blend of poly-L-lactide (PLLA), collagen and fibrin-rich blood clot, under the influence of a low frequency magnetic field. The scaffold was characterized for surface properties, biochemical and biomechanical parameters and bio-magnetic behaviour. Cell proliferation assay revealed that the scaffold was suitable for hMSCs adhesion and proliferation. Hepatic trans-differentiation potential of hMSCs was augmented on nanofibrous scaffold in magnetic field exposure group compared to control groups, as evident by strong expression of hepatocyte specific markers, albumin release, urea synthesis and presence of an inducible cytochrome P450 system. Our results conclude that biomagnetic scaffold of PLLA/collagen/blood clot augments hepatic trans-differentiation of hMSCs under magnetic field influence.

Actively manipulation of operation states in passively pulsed fiber lasers by using graphene saturable absorber on microfiber.

We experimentally demonstrate an operation switchable Erbium-doped fiber laser by employing graphene saturable absorber (GSA) on microfiber. With the introducing of a polydimethylsiloxane layer, a graphene can be considered as a parallel plate on microfiber and induces different propagation losses to TE and TM modes. By the use of such polarization sensitive GSA on microfiber, Erbium doped fiber laser with switchable operation states such as continuous wave, stable Q-switching, Q-switched mode-locking, and continuous-wave mode-locking, can be achieved by simply tuning the polarization states in the laser cavity. Our results show that covering graphene on microfibers could be a promising method for fabricating all fiber SA, and may have high potential in wide applications.

A low-loss photonic silica nanofiber for higher-order modes.

Optical nanofibers confine light to subwavelength scales, and are of interest for the design, integration, and interconnection of nanophotonic devices. Here we demonstrate high transmission (> 97%) of the first family of excited modes through a 350 nm radius fiber, by appropriate choice of the fiber and precise control of the taper geometry. We can design the nanofibers so that these modes propagate with most of their energy outside the waist region. We also present an optical setup for selectively launching these modes with less than 1% fundamental mode contamination. Our experimental results are in good agreement with simulations of the propagation. Multimode optical nanofibers expand the photonic toolbox, and may aid in the realization of a fully integrated nanoscale device for communication science, laser science or other sensing applications.

Formation of ß-lactoglobulin nanofibrils by microwave heating gives a peptide composition different from conventional heating.

A novel procedure involving microwave heating (MH) at 80 °C can be used to induce self-assembly of ß-lactoglobulin (ß-lg) into amyloid-like nanofibrils at low pH. We examined the self-assembly induced by MH, and evaluated structural and compositional differences between MH fibrils and those formed by conventional heating (CH). MH significantly accelerated the self-assembly of ß-lg, resulting in fully developed fibrils in ≤2 h. However, longer MH caused irreversible disintegration of fibrils. An increase in the fibril yield was observed during the storage of the 2 h MH sample, which gave a yield similar to that of 16 h CH sample. Fourier transform infrared (FTIR) and circular dichroism (CD) spectra suggested that the fibrils formed by the two methods do not show significant differences in their secondary structure components. However, they exhibited differences in surface hydrophobicity, and mass spectrometry showed that the MH fibrils contained larger peptides than CH fibrils, including intact ß-lg monomers, providing evidence for a different composition between the MH and CH fibrils, in spite of no observed differences in their morphology. We suggest MH initially accelerates the self-assembly of ß-lg due to its nonthermal effects on unfolding, nucleation, and subsequent stacking of ß-sheets, rather than promoting partial hydrolysis. Thus, MH fibrils are composed of larger peptides, and the observed higher surface hydrophobicity for the MH fibrils was attributed to the parts of the larger peptides extending out of the core structure of the fibrils.

Self-Assembled Peptide Nanofibers with Voltage-Regulated Inverse Photoconductance.

Inverse photoconductance is an uncommon phenomenon observed in selective low-dimensional materials, in which the electrical conductivity of the materials decreases under light illumination. The unique material property holds great promise for biomedical applications in photodetectors, photoelectric logic gates, and low-power nonvolatile memory, which remains a daunting challenge. Especially, tunable photoconductivity for biocompatible materials is highly desired for interfacing with biological systems but is less explored in organic materials. Here, we report nanofibers self-assembled with cyclo-tyrosine-tyrosine (cyclo-YY) having voltage-regulated inverse photoconductance and photoconductance. The peptide nanofibers can be switched back and forth by a bias voltage for imitating biological sensing in artificial vision and memory devices. A peptide optoelectronic resistive random access memory (PORRAM) device has also been fabricated using the nanofibers that can be electrically switched between long-term and short-term memory. The underlying mechanism of the reversible photoconductance is discussed in this paper. Due to the inherent biocompatibility of peptide materials, the reversible photoconductive nanofibers may have broad applications in sensing and storage for biotic and abiotic interfaces.

Light-driven dissipative self-assembly of a peptide hydrogel.

Light energy provides an attractive fuel source for energy dissipating systems because of the lack of waste production, wavelength tunability and the potential for spatial and temporal resolution. In this work, we describe a peptide-spiropyran conjugate that assembled into a transient nanofiber hydrogel in the presence of visible light, and dissociated when the light source was removed.

Photocatalytic exoskeleton: Chitin nanofiber for retrievable and sustainable TiO2 carriers for the decomposition of various pollutants.

Loading a photocatalytic TiO2 to organic carriers has been desired for volumetric TiO2 incorporation, facile retrieval, and sustainable utilization. Traditionally, suspended TiO2 nanoparticles or its thin film on two-dimensional substrate are popularly fabricated for pollutants decomposition without carriers; due to poor thermomechanical properties of the organic carriers. Herein, a combination of the chitin nanofiber carrier and atomic layer deposition proves relevance for formation of anatase TiO2 thin layer so that photocatalytic decomposition in three-dimensional surface. Moreover, chitin nanofiber is capable of holding the TiO2 nanoparticles for multiple cycles of photocatalysis. Those types of TiO2 show characteristic degradation performance for gaseous (acetaldehyde) and aqueous pollutants (4-chlorophenol and rhodamine B). After catalytic reaction, chitin/TiO2 is retrievable owing to carrier's robustness even in water without TiO2 aggregation and loss. This work suggests that chitin-based photocatalyst is applicable to numerous pollutants through chitin's relatively high chemical resistance and stably wedged TiO2 during photocatalytic reaction.

Swift heavy ion irradiation induced enhancement in the antioxidant activity and biocompatibility of polyaniline nanofibers.

Polyaniline (PAni) nanofibers doped with HCl and CSA have been irradiated with 90 MeV O(7+) ions with fluence of 3 x 10(10), 3 x 10(11) and 1 x 10(12) ions cm(-2). TEM micrographs show a decrease in the fiber diameter with increasing irradiation fluence, which has been explained on the basis of the Coulomb explosion model. XRD analysis reveals a decrease in the crystalline domain length and an increase in the strain. The increase in d-spacing for the (100) reflection with increasing irradiation fluence is ascribed to the increase in the tilt angle of the polymer chain, which is also evident from micro-Raman spectra. UV-vis spectra of the PAni nanofibers exhibit blue-shift in the absorption bands attributed to pi-pi* band transitions indicating a reduction in particle size after SHI irradiation; as also observed in TEM micrographs. Micro-Raman spectra also reveal a transition from the benzenoid to quinoid structures in the PAni chain as the fluence is increased. Although the quinoid unit has no hydrogen for DPPH scavenging, the antioxidant activity of PAni nanofibers is found to increase with increasing fluence. This has been attributed to the availability of more reaction sites as a result of fragmentation of the PAni nanofibers which compensates for the benzenoid to quinoid transition after irradiation. The biocompatibility of the PAni nanofibers is also found to increase with increasing irradiation fluence, indicating the possibility of employing swift heavy ion irradiation as an effective technique in order to modify conducting polymer nanostructures for biomedical applications.

Visible-light driven degradation of tetracycline hydrochloride and 2,4-dichlorophenol by film-like N-carbon@N-ZnO catalyst with three-dimensional interconnected nanofibrous structure.

The emergence of more and more persistent organic molecules as contaminants in water simulates research towards the development of more advanced technologies, among which photocatalysis is a feasible choice. However, it is still challenging to design a photocatalyst that fulfills all the requirements for industrial application, i.e., active under visible-light irradiation, shape with handy convenience, highly uniform distribution of active sites, substrate with excellent electronic properties, etc. In this study, we report an attempt to solve these issues at once by designing a film-like photocatalyst with uniform distribution of nitrogen-doped ZnO nanoparticles along nitrogen-doped carbon ultrafine nanofibers with three-dimensional interconnected structure. Under visible-light irradiation, the product exhibited remarkable reactivity for the degradation of two model pollutants tetracycline hydrochloride and 2,4-dichlorophenol within 100 min. The cyclic experiments demonstrated only a slight loss (ca. 5 %) of reactivity after five consecutive photocatalytic reactions. We also investigated the detailed relationship between the structural features and the superior properties of this product, as well as the degradation mechanisms. The convenient shape of the product with excellent performances for the treatment of real polluted water increases its suitability for larger scale application. Our work provides a rational design of photocatalysts for environmental remediation.