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In this work, the first use of electrospun nanofibrous materials as highly responsive fluorescence quenching-based optical silver sensors is reported. Poly(methyl methacrylate) and ethyl cellulose were used as polymeric support materials. Silver sensing materials were fabricated by electrospinning technique. A fiber-optic bundle was used for measurements. Sensors were based on the change in the fluorescence signal intensity of methoxy azomethine ionophore (M-AZM). The preliminary results of Stern-Volmer analysis show that the sensitivities of electrospun nanofibrous membranes to detect silver ions are 10-100-fold higher than those of the thin film based sensors. The extraordinary sensitivities can be attributed to the high surface area of the nanofibrous membrane structures. It was found that the stability of the sensing agent in the employed matrix materials was excellent and when stored in the ambient air of the laboratory there was no significant drift in signal intensity after 5 months. Our stability tests are still in progress. (C) 2010 Elsevier B.V. All rights reserved.

Owing to their strong photon emission, low excitonic binding energies, and nearly-ideal band offset values for water splitting reactions, direct gap quasi-2D gallium chalcogenides are potential candidates for applications in energy harvesting, optoelectronics, and photonics. Unlike other 2D materials systems, chemical functionalization of gallium chalcogenides is still at its seminal stages. Here, we propose vapor phase pyridine intercalation technique to manipulate optical properties of gallium chalcogenides. After functionalization, the excitonic dynamics of quasi-2D GaSe change significantly as evidenced by an increase in integrated PL intensity and emergence of a new emission feature that is below the band edge. Based on our DFT calculations, we attribute these to formation of bound exciton complexes at the trap sites introduced by chemical reaction between pyridine and GaSe. On the contrary, pyridine functionalization does not impact the optical properties of GaTe, instead treats GaTe surface to prevent oxidization of tellurium atoms. Overall, results suggest novel ways to control properties of gallium chalcogenides on demand and unleash their full potential for a range of applications in photonics and optoelectronics.

Creating materials with ultimate control over their physical properties is vital for a wide range of applications. From a traditional materials design perspective, this task often requires precise control over the atomic composition and structure. However, owing to their mechanical properties, low-dimensional layered materials can actually withstand a significant amount of strain and thus sustain elastic deformations before fracture. This, in return, presents a unique technique for tuning their physical properties by strain engineering. Here, we find that local strain induced on ReSe2, a new member of the transition metal dichalcogenides family, greatly changes its magnetic, optical, and electrical properties. Local strain induced by generation of wrinkle (1) modulates the optical gap as evidenced by red-shifted photoluminescence peak, (2) enhances light emission, (3) induces magnetism, and (4) modulates the electrical properties. The results not only allow us to create materials with vastly different properties at the nanoscale, but also enable a wide range of applications based on 2D materials, including strain sensors, stretchable electrodes, flexible field-effect transistors, artificial-muscle actuators, solar cells, and other spintronic, electromechanical, piezoelectric, photonic devices.

Monolayers of group VI transition metal dichalcogenides possess direct gaps in the visible spectrum with the exception of MoTe2, where its gap is suitably located in the infrared region but its stability is of particular interest, as tellurium compounds are acutely sensitive to oxygen exposure. Here, our environmental (time-dependent) measurements reveal two distinct effects on MoTe2 monolayers: For weakly luminescent monolayers, photoluminescence signal and optical contrast disappear, as if they are decomposed, but yet remain intact as evidenced by AFM and Raman measurements. In contrast, strongly luminescent monolayers retain their optical contrast for a prolonged amount of time, while their PL peak blue-shifts and PL intensity saturates to slightly lower values. Our X-ray photoelectron spectroscopy measurements and DFT calculations suggest that the presence of defects and functionalization of these defect sites with O-2 molecules strongly dictate their material properties and aging response by changing the excitonic dynamics due to deep or shallow states that are created within the optical band gap. Presented results not only shed light on environmental effects on fundamental material properties and excitonic dynamics of MoTe2 monolayers but also highlight striking material transformation for metastable 20 systems such as WTe2, silicone, and phosphorene.

Bone tissue engineering literature conveys investigations regarding biodegradable polymers where bioactive inorganic materials are added either before or after electrospinning process. The goal is to mimic the composition of bone and enhance the biocompatibility of the materials. Yet, most polymeric materials are hydrophobic in nature; therefore, their surfaces are not favorable for human cellular adhesion. In this sense, modifications of the hydrophobic surface of electrospun polymer fibers with hydrophilic and bioactive nanoparticles are beneficial. In this work, dispersion of hydroxyapatite (HAp), which is similar to the mineral component of natural bone, within biodegradable and biocompatible polymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with the aid of a surfactant has been investigated. Non-ionic TWEEN20 and 12-hydroxysteric acid (HSA), cationic dodecyl trimethyl ammonium bromide (DTAB) and anionic sodium deoxycholate and sodium dodecyl sulfate (SDS) surfactants were used for comparison in order to prepare stable and homogenous nanocomposite suspensions of HAp/PHBV for the electrospinning process. Continuous and uniform composite nanofibers were generated successfully within a diameter range of 400-1,000 nm by the mediation of all surfactant types. Results showed that incorporation of HAp and any of the surfactant types strongly activates the precipitation rate of the apatite-like particles and decreases percent crystallinity of the HAp/PHBV mats. Mineralization was greatly enhanced on the fibers produced by using DTAB, HSA, and especially SDS on where also osteoblastic metabolic activity was similarly increased. The produced HAp/PHBV nanofibrous composite scaffolds would be a promising candidate as an osteoconductive bioceramic/polymer composite material for tissue engineering applications.

In this work, the use of electrospun nanofibrous materials as highly responsive fluorescence quenching-based copper sensitive chemosensor is reported. Poly(methyl methacrylate) and ethyl cellulose were used as polymeric support materials. Sensing slides were fabricated by electrospinning technique. Copper sensors based on the change in the fluorescence signal intensity of fluoroionophore; N'-3-(4-(dimethylamino phenly)allylidene)isonicotinohydrazide. The sensor slides exhibited high sensitivities due to the high surface area of the nanofibrous membrane structures. The preliminary results of Stern-Volmer analysis show that the sensitivities of electrospun nanofibrous membranes to detect Cu(II) ions are 6-20-fold higher than those of the continuous thin films. By this way we obtained linear calibration plots for Cu(II) ions in the concentration range of 10(-12)-10(-5) M. The response times of the sensing slides were less than 1 min. Stability of the employed ionophore in the matrix materials was excellent and when stored in the ambient air of the laboratory there was no significant drift in signal intensity after 6 months. Our stability tests are still in progress. (C) 2012 Elsevier B.V. All rights reserved.

Ethyl cellulose (EC) based electrospun nanofibers were exploited for sub-nanomolar level optical chemical sensing of ionic mercury. An azomethine ionophore was used as Hg (I) and Hg (II) sensing material. Ethyl cellulose nanofibers with varying amounts of the ionic liquid; 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF 4 ) were prepared and characterized. The nanofibers were fabricated by electrospinning technique. The offered chemosensor allow determination of mercury ions in a large linear working range between 1.0 × 10 −10 and 1.0 × 10 −4 mol L −1 . Limit of detection was found to be 0.07 nM which makes this technique alternative to cold-vapor atomic absorption spectrometry (CV-AAS), flame emission methods and to inductively coupled plasma-mass spectrometry (ICP-MS). The electrospun nanofibers exhibited excellent sensitivity for Hg (II) with respect to the continuous thin films prepared with same composition. The observed high sensitivity can be attributed to the high surface area of the nanofibrous materials and enhanced diffusibility of the mercury ions to the ionophore.

The first use of electrospun nanofibrous materials as highly responsive fluorescence quenching-based optical CO(2) sensors is reported. Poly(methyl methacrylate) and ethyl cellulose were used as polymeric materials. Sensing slides were fabricated by electrospinning technique. A fiber-optic bundle was used for the gas detection. CO(2) sensors based on the change in the fluorescence signal intensity of ion pair form of 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS). The sensor slides showed high sensitivities due to the high surface area-to-volume ratio of the nanofibrous membrane structures. The preliminary results of Stern-Volmer analysis show that the sensitivities of electrospun nanofibrous membranes to detect CO(2) are 24 to 120 fold higher than those of the thin film based sensors. The response times of the sensing reagents were short and the signal changes were fully reversible. The stability of ion pair form of HPTS in the employed matrix materials was excellent and when stored in the ambient air of the laboratory there was no significant drift in signal intensity after 7 months. Our stability tests are still in progress.