Distance dependence of fluorescence resonance energy transfer

Deviations from the usual R (-6) dependence of the rate of fluorescence resonance energy transfer (FRET) on the distance between the donor and the acceptor have been a common scenario in the recent times. In this paper, we present a critical analysis of the distance dependence of FRET, and try to illustrate the non R (-6) type behaviour of the rate for the case of transfer from a localized electronic excitation on the donor, a dye molecule to three different energy acceptors with delocalized electronic excitations namely, graphene,two-dimensional semiconducting sheet and the case of such a semiconducting sheet rolled to obtain a nanotube. We use simple analytic models to understand the distance dependence in each case.

Graphene-like two-dimensional ionic boron with double dirac cones at ambient condition

Recently, partially ionic boron (γ-B28) has been predicted and observed in pure boron, in bulk phase and controlled by pressure [Nature, 457 (2009) 863]. By using ab initio evolutionary structure search, we report the prediction of ionic boron at a reduced dimension and ambient pressure, namely, the two-dimensional (2D) ionic boron. This 2D boron structure consists of graphene-like plane and B2 atom pairs, with the P6/mmm space group and 6 atoms in the unit cell, and has lower energy than the previously reported α-sheet structure and its analogues. Its dynamical and thermal stability are confirmed by the phonon-spectrum and ab initio molecular dynamics simulation. In addition, this phase exhibits double Dirac cones with massless Dirac fermions due to the significant charge transfer between the graphene-like plane and B2 pair that enhances the energetic stability of the P6/mmm boron. A Fermi velocity (vf) as high as 2.3 x 106 m/s, which is even higher than that of graphene (0.82 x 106 m/s), is predicted for the P6/mmm boron. The present work is the first report of the 2D ionic boron at atmospheric pressure. The unique electronic structure renders the 2D ionic boron a promising 2D material for applications in nanoelectronics.

Irradiation effects in graphene and related materials

Nanomaterials with a hexagonally ordered atomic structure, e.g., graphene, carbon and boron nitride nanotubes, and white graphene (a monolayer of hexagonal boron nitride) possess many impressive properties. For example, the mechanical stiffness and strength of these materials are unprecedented. Also, the extraordinary electronic properties of graphene and carbon nanotubes suggest that these materials may serve as building blocks of next generation electronics. However, the properties of pristine materials are not always what is needed in applications, but careful manipulation of their atomic structure, e.g., via particle irradiation can be used to tailor the properties. On the other hand, inadvertently introduced defects can deteriorate the useful properties of these materials in radiation hostile environments, such as outer space. In this thesis, defect production via energetic particle bombardment in the aforementioned materials is investigated. The effects of ion irradiation on multi-walled carbon and boron nitride nanotubes are studied experimentally by first conducting controlled irradiation treatments of the samples using an ion accelerator and subsequently characterizing the induced changes by transmission electron microscopy and Raman spectroscopy. The usefulness of the characterization methods is critically evaluated and a damage grading scale is proposed, based on transmission electron microscopy images. Theoretical predictions are made on defect production in graphene and white graphene under particle bombardment. A stochastic model based on first-principles molecular dynamics simulations is used together with electron irradiation experiments for understanding the formation of peculiar triangular defect structures in white graphene. An extensive set of classical molecular dynamics simulations is conducted, in order to study defect production under ion irradiation in graphene and white graphene. In the experimental studies the response of carbon and boron nitride multi-walled nanotubes to irradiation with a wide range of ion types, energies and fluences is explored. The stabilities of these structures under ion irradiation are investigated, as well as the issue of how the mechanism of energy transfer affects the irradiation-induced damage. An irradiation fluence of 5.5x10^15 ions/cm^2 with 40 keV Ar+ ions is established to be sufficient to amorphize a multi-walled nanotube. In the case of 350 keV He+ ion irradiation, where most of the energy transfer happens through inelastic collisions between the ion and the target electrons, an irradiation fluence of 1.4x10^17 ions/cm^2 heavily damages carbon nanotubes, whereas a larger irradiation fluence of 1.2x10^18 ions/cm^2 leaves a boron nitride nanotube in much better condition, indicating that carbon nanotubes might be more susceptible to damage via electronic excitations than their boron nitride counterparts. An elevated temperature was discovered to considerably reduce the accumulated damage created by energetic ions in both carbon and boron nitride nanotubes, attributed to enhanced defect mobility and efficient recombination at high temperatures. Additionally, cobalt nanorods encapsulated inside multi-walled carbon nanotubes were observed to transform into spherical nanoparticles after ion irradiation at an elevated temperature, which can be explained by the inverse Ostwald ripening effect. The simulation studies on ion irradiation of the hexagonal monolayers yielded quantitative estimates on types and abundances of defects produced within a large range of irradiation parameters. He, Ne, Ar, Kr, Xe, and Ga ions were considered in the simulations with kinetic energies ranging from 35 eV to 10 MeV, and the role of the angle of incidence of the ions was studied in detail. A stochastic model was developed for utilizing the large amount of data produced by the molecular dynamics simulations. It was discovered that a high degree of selectivity over the types and abundances of defects can be achieved by carefully selecting the irradiation parameters, which can be of great use when precise pattering of graphene or white graphene using focused ion beams is planned.

Interaction of Inorganic Nanoparticles with Graphene

The changes in the electronic and magnetic properties of graphene induced by interaction with semiconducting oxide nanoparticles such as ZnO and TiO2 and with magnetic nanoparticles such as Fe3O4, CoFe2O4, and Ni are investigated by using Raman spectroscopy, magnetic measurements, and first-principles calculations. Significant electronic and magnetic interactions between the nanoparticles and graphene are found. The findings suggest that changes in magnetization as well as the Raman shifts are directly linked to charge transfer between the deposited nanoparticles and graphene. The study thus demonstrates significant effects in tailoring the electronic structure of graphene for applications in futuristic electronic devices.

The interaction of halogen molecules with SWNTs and graphene

The interaction of halogen molecules of varying electron affinity, such as iodine monochloride (ICl), bromine (Br(2)), iodine monobromide (IBr) and iodine (I(2)) with single-walled carbon nanotubes (SWNTs) and graphene has been investigated in detail. Halogen doping of the two nanocarbons has been examined using Raman spectroscopy in conjunction with electronic absorption spectroscopy and extensive theoretical calculations. The halogen molecules, being electron withdrawing in nature, induce distinct changes in the electronic states of both the SWNTs and graphene, which manifests with a change in the spectroscopic signatures. Stiffening of the Raman G-bands of the nanocarbons upon treatment with the different halogen molecules and the emergence of new bands in the electronic absorption spectra, both point to the fact that the halogen molecules are involved in molecular charge-transfer with the nanocarbons. The experimental findings have been explained through density functional theory (DFT) calculations, which suggest that the extent of charge-transfer depends on the electron affinities of the different halogens, which determines the overall spectroscopic properties. The magnitude of the molecular charge-transfer between the halogens and the nanocarbons generally varies in the order ICl > Br(2) > IBr > I(2), which is consistent with the expected order of electron affinities.

Electrochemical Detection of Bisphenol A Using Graphene-Modified Glassy Carbon Electrode

Graphene's nano-dimensional nature and excellent electron transfer properties underlie its electrocatalytic behavior towards certain substances. In this light, we have used graphene in the electrochemical detection of bisphenol A. Graphene sheets were produced via soft chemistry route involving graphite oxidation and chemical reduction. X-ray diffraction, Fourier transform infra-red (FT-IR) and Raman spectroscopy were used for the characterization of the as-synthesized graphene. Graphene exhibited amorphous structure in comparison with pristine graphite from XRD spectra. FTIR showed that graphene exhibits OH and COOH groups due to incomplete reduction. Raman spectroscopy revealed that multi-layered graphene was produced due to low intensity of the 2D-peak. Glassy carbon electrode was modified with graphene by a simple drop and dry method. Cyclic voltammetry was used to study the electrochemical properties of the prepared graphene-modified glassy carbon electrode using potassium ferricyanide as a redox probe. The prepared graphene- modified glassy carbon electrode exhibited more facile electron kinetics and enhanced current of about 75% when compared to the unmodified glassy carbon electrode. The modified electrode was used for the detection of bisphenol A. Under the optimum conditions, the oxidation peak current of bisphenol A varied linearly with concentration over a wide range of 5 x 10(-8) mol L-1 to 1 x 10(-6) mol L-1 and the detection limit of this method was as low as 4.689 x 10(-8) M. This method was also employed to determine bisphenol A in a real sample

Hydrothermal synthesis of a monoclinic VO2 nanotube-graphene hybrid for use as cathode material in lithium ion batteries

The hydrothermal reaction of a mixture of a colloidal dispersion of graphite oxide and ammonium vanadate yielded a hybrid made of graphene and a nanotubular metastable monoclinic polymorph of VO2, known as VO2(B). The formation of VO2(B) nanotubes is accompanied by the reduction of graphite oxide. Initially the partially scrolled graphite oxide layers act as templates for the crystallization of VO2(B) in the tubular morphology. This is followed by the reduction of graphite oxide to graphene resulting in a hybrid in which VO2(B) nanotubes are dispersed in graphene. Electron microscopic studies of the hybrid reveal that the VO2(B) nanotubes are wrapped by and trapped between graphene sheets. The hybrid shows potential to be a high capacity cathode material for lithium ion batteries. It exhibits a high capacity (similar to 450 mAh/g) and cycling stability. The high capacity of the hybrid is attributed to the interaction between the graphene sheets and the VO2(B) tubes which improves the charge-transfer. The graphene matrix prevents the aggregation of the VO2(B) nanotubes leading to high cycling stability. (C) 2012 Elsevier Ltd. All rights reserved.

A Raman study of the interaction of electron-donor and -acceptor molecules with chemically doped graphene

Effect of interaction of tetracyanoethylene (TCNE) and tetrathia fulvalene (TTF) with boron- and nitrogen-doped graphene has been investigated by Raman spectroscopy. The G- and 2D bands of boron- and nitrogen-doped graphenes in the Raman spectra show significantly different changes on interaction with electron-donor and -acceptor molecules. Thus, tetracyanoethylene (TCNE) and tetrathiafulvalene (TTF) have different effects on the Raman spectra of boron- and nitrogen-doped graphenes. The changes in the Raman spectra brought about by electron-donor and -acceptor molecules can be understood in general terms on the basis of molecular charge transfer. (c) 2012 Elsevier B.V. All rights reserved.

Graphene based E. coli sensor on flexible acetate sheet

A low cost, reagent free, Escherichia coli sensor is demonstrated with graphene, on transparent flexible acetate substrate. Graphene is grown on 100 mu m thick Cu foil, using CVD process and subsequently transferred on to a flexible acetate substrate. Gold electrodes are deposited on graphene to form a two terminal, interdigitated capacitor structure. Impedance spectroscopy (10 Hz to 100 kHz) is performed to characterize the change in impedance, as a function of E. coli concentration on graphene surface. The residual methyl groups on graphene, resulting from the transfer process, act as binding sites for E. coli. It has been observed that the resistance of graphene decreases with increasing E. coli concentration. This is due to the increased hole doping induced by negatively charged E. coli. A sensitivity of 60% is achieved for an E. coli concentration of 4.5 x 10(7) cfu/ml. An equivalent RC model is proposed to explain the sensing mechanism. (C) 2013 Elsevier B.V. All rights reserved.

Molecular Dynamics Study of Phonon Screening in Graphene

Phonon interaction with electrons or phonons or with structural defects result in a phonon mode conversion. The mode conversion is governed by the frequency wave-vector dispersion relation. The control over phonon mode or the screening of phonon in graphene is studied using the propagation of amplitude modulated phonon wave-packet. Control over phonon properties like frequency and velocity opens up several wave guiding, energy transport and thermo-electric applications of graphene. One way to achieve this control is with the introduction of nano-structured scattering in the phonon path. Atomistic model of thermal energy transport is developed which is applicable to devices consisting of source, channel and drain parts. Longitudinal acoustic phonon mode is excited from one end of the device. Molecular dynamics based time integration is adopted for the propagation of excited phonon to the other end of the device. The amount of energy transfer is estimated from the relative change of kinetic energy. Increase in the phonon frequency decreases the kinetic energy transmission linearly in the frequency band of interest. Further reduction in transmission is observed with the tuning of channel height of the device by increasing the boundary scattering. Phonon mode selective transmission control have potential application in thermal insulation or thermo-electric application or photo-thermal amplification.

Synthesis of benzimidazole-grafted graphene oxide/multi-walled carbon nanotubes composite for supercapacitance application

We are reporting the fabrication, characterizations and supercapacitance performance of benzimidazole-grafted graphene oxide/multi-walled carbon nanotubes (BI-GO/MWCNTs) composite. The synthesis of BI-GO materials involves cyclization reaction of carboxylic groups on GO among the hydroxyl and amino groups on o-phenylenediamine. The BI-GO/MWCNTs composite has been fabricated via in situ reduction of BI-GO using hydrazine in presence of MWCNTs. Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Raman spectroscopy, X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) have been used to characterize its surface and elemental composition. The uniform dispersion of MWCNTs with BI-GO helps to improve the charge transfer reaction during electrochemical process. The specific capacitance of BI-GO/MWCNTs composite is 275 and 460 F/g at 200 and 5 mV/s scan rate in 1 mol/L aqueous solution of H2SO4. This BI-GO/MWCNTs composite has shown 224 F/g capacitance after 1300 cycles at 200 mV/s scan rate, which represents its good electrochemical stability. (C) 2014 Elsevier B.V. All rights reserved.

Tailoring the interface of an immiscible polymer blend by a mutually miscible homopolymer grafted onto graphene oxide: outstanding mechanical properties

A unique strategy was adopted here to improve the compatibility between the components of an immiscible polymer blend and strengthen the interface. PMMA, a mutually miscible polymer to both PVDF and ABS, improved the compatibility between the phases by localizing at the blends interface. This was supported by the core-shell formation with PMMA as the shell and ABS as the core as observed from the SEM micrographs. This phenomenon was strongly contingent on the concentration of PMMA in the blends. This strategy was further extended to localize graphene oxide (GO) sheets at the blends interface by chemically coupling it to PMMA (PMMA-g-GO). A dramatic increment of ca. 84% in the Young's modulus and ca. 124% in the yield strength was observed in the presence of PMMA-g-GO with respect to the neat blends. A simultaneous increment in both the strength and the modulus was observed in the presence of PMMA-g-GO whereas, only addition of GO resulted in a moderate improvement in the yield strength. This study reveals that a mutually miscible polymer can render compatibility between the immiscible pair and can improve the stress transfer at the interface.

Graphene based multifunctional flame sensor

Recently, graphene has attracted much attention due to its unique electrical and thermal properties along with its high surface area, and hence presents an ideal sensing material. We report a novel configuration of a graphene based flame sensor by exploiting the response of few layer graphene to a flame along two different directions, where flame detection results from a difference in heat transfer mechanisms. A complete sensor module was developed with a signal conditioning circuit that compensates for any drift in the baseline of the sensor, along with a flame detection algorithm implemented in a microcontroller to detect the flame. A pre-defined threshold for either of the sensors is tunable, which can be varied based on the nature of the flame, hence presenting a system that can be used for detection of any kind of flame. This finding also presents a scalable method that opens avenues to modify complicated sensing schemes.

Engineering Nanostructures by Decorating Magnetic Nanoparticles onto Graphene Oxide Sheets to Shield Electromagnetic Radiations

In this study, a minimum, reflection loss of 70 a was achieved, for a 6 mm thick shield (at 17.1 GHz frequency) employing a unique approach. This was accomplished by engineering nanostructures through decoration of magnetic nanopartides (nickel, Ni) onto graphene oxide (GO) sheets. Enhanced electromagnetic (EM) shielding was derived by selectively, localizing the nanoscopic particles in a specific phase of polyethylene (PE)/poly(ethylene oxide) (PEO) blends. By introduction of a conducting inclusion (like multiwall carbon nanotubes, MWNTs) together with the engineered nanostructures (nickel-decorated GO, (GO-Ni), the shielding efficiency can be enhanced significantly in contrast to physically mixing the particles in the blends. For instance, the composites showed a shielding efficiency >25 dB for a combination of MWNTS (3 wt %) and Ni nanoparticles (52 wt %) in PE/PEO blends. However, similar shielding effectiveness could be achieved for a combination of MWNTs (3 wt %) and 10 vol % of GO-Ni where in the effective concentration of Ni was only 19 wt %. The GO-Ni sheets facilitated in an efficient charge transfer as manifested from high electrical conductivity in the blends besides enhancing the permeability in the blends. It is envisioned that GO is simultaneously reduced in the process of synthesizing GO-Ni, and this facilitated in efficient charge transfer between the neighboring CNTs. More interestingly, the blends With MWNTs/GO-Ni attenuated the incoming EM radiation mostly by absorption. This study opens new avenues in designing polyolefin-based lightweight shielding materials by engineering nanostructures for numerous applications.

Ultra sensitive NO2 gas detection using the reduced graphene oxide coated etched fiber Bragg gratings

We report a simple and highly sensitive methodology for the room temperature NO2 gas sensing using reduced graphene oxide (RGO) coated clad etched fiber Bragg grating (eFBG). A significant shift (>10 pm) is observed in the reflected Bragg wavelength (lambda(B)) upon exposing RGO coated on the surface of eFBG to the NO2 gas molecules of concentration 0.5 ppm. The shift in Bragg wavelength is due to the change in the refractive index of RGO by charge transfer from the adsorbing NO2 molecules. The range of NO2 concentration is tested from 0.5 ppm to 3 ppm and the estimated time taken for 50% increase in Delta lambda(B) ranges from 20 min (for 0.5 ppm) to 6 min (for 3 ppm). (C) 2015 Elsevier B.V. All rights reserved.