Cyclodextrin functionalized magnetic iron oxide nanocrystals: a host-carrier for magnetic separation of non-polar molecules and arsenic from aqueous media

A single-step magnetic separation procedure that can remove both organic pollutants and arsenic from contaminated water is clearly a desirable goal. Here we show that water dispersible magnetite nanoparticles prepared by anchoring carboxymethyl-beta-cyclodextrin (CMCD) cavities to the surface of magnetic nanoparticles are suitable host carriers for such a process. Monodisperse, 10 nm, spherical magnetite, Fe3O4, nanocrystals were prepared by the thermal decomposition of FeOOH. Trace amounts of antiferromagnet, FeO, present in the particles provides an exchange bias field that results in a high superparamagnetic blocking temperature and appreciable magnetization values that facilitate easy separation of the nanocrystals from aqueous dispersions on application of modest magnetic fields. We show here that small molecules like naphthalene and naphthol can be removed from aqueous media by forming inclusion complexes with the anchored cavities of the CMCD-Fe3O4 nanocrystals followed by separation of the nanocrystals by application of a magnetic field. The adsorption properties of the iron oxide surface towards As ions are unaffected by the CMCD capping so it too can be simultaneously removed in the separation process. The CMCD-Fe3O4 nanocrystals provide a versatile platform for magnetic separation with potential applications in water remediation.

Quantum capacitance in bilayer graphene nanoribbon

We address a physically based analytical model of quantum capacitance (C-Q) in a bilayer graphene nanoribbon (BGN) under the application of an external longitudinal static bias. We demonstrate that as the gap (Delta) about the Dirac point increases, a phenomenological population inversion of the carriers in the two sets of subbands occurs. This results in a periodic and composite oscillatory behavior in the C-Q with the channel potential, which also decreases with increase in Delta. We also study the quantum size effects on the C-Q, which signatures heavy spatial oscillations due to the occurrence of van Hove singularities in the total density-of-states function of both the sets of subbands. All the mathematical results as derived in this paper converge to the corresponding well-known solution of graphene under certain limiting conditions and this compatibility is an indirect test of our theoretical formalism. (C) 2012 Elsevier By. All rights reserved.

Inclusion of body doping in compact models for fully-depleted common double gate MOSFET adapted to gate-oxide thickness asymmetry

Since it is difficult to find the analytical solution of the governing Poisson equation for double gate MOSFETs with the body doping term included, the majority of the compact models are developed for undoped-body devices for which the analytical solution is available. Proposed is a simple technique to included a body doping term in such surface potential based common double gate MOSFET models also by taking into account any differences between the gate oxide thickness. The proposed technique is validated against TCAD simulation and found to be accurate as long as the channel is fully depleted.

Thermoelectricity in graphene: Effects of a gap and magnetic fields

We calculate the thermopower of monolayer graphene in various circumstances. We consider acoustic phonon scattering which might be the operative scattering mechanism in freestanding films and predict that the thermopower will be linear in any induced gap in the system. Further, the thermopower peaks at the same value of chemical potential (tunable by gate voltage) independent of the gap. We show that in the semiclassical approximation, the thermopower in a magnetic field saturates at high field to a value which can be calculated exactly and is independent of the details of the scattering. This effect might be observable experimentally. We also note that a Yukawa scattering potential can be used to fit experimental data for the thermopower for reasonable values of the screening length parameter.

Threshold voltage modeling under size quantization for ultra-thin silicon double-gate metal-oxide-semiconductor field-effect transistor

We report on the threshold voltage modeling of ultra-thin (1 nm-5 nm) silicon body double-gate (DG) MOSFETs using self-consistent Poisson-Schrodinger solver (SCHRED). We define the threshold voltage (V th) of symmetric DG MOSFETs as the gate voltage at which the center potential (Φ c) saturates to Φ c (s a t), and analyze the effects of oxide thickness (t ox) and substrate doping (N A) variations on V th. The validity of this definition is demonstrated by comparing the results with the charge transition (from weak to strong inversion) based model using SCHRED simulations. In addition, it is also shown that the proposed V t h definition, electrically corresponds to a condition where the inversion layer capacitance (C i n v) is equal to the oxide capacitance (C o x) across a wide-range of substrate doping densities. A capacitance based analytical model based on the criteria C i n v C o x is proposed to compute Φ c (s a t), while accounting for band-gap widening. This is validated through comparisons with the Poisson-Schrodinger solution. Further, we show that at the threshold voltage condition, the electron distribution (n(x)) along the depth (x) of the silicon film makes a transition from a strong single peak at the center of the silicon film to the onset of a symmetric double-peak away from the center of the silicon film. © 2012 American Institute of Physics.

Zinc Oxide Modified Au Electrode as Sensor for an Efficient Detection of Hydrazine

ZnO nanoparticles (ZnO NPs) prepared by microwave heating technique are used to modify a gold electrode (ZnO/Au) for the hydrazine detection study. The synthesized product is well characterized by various techniques. Detailed electrochemical investigation of the oxidation of hydrazine on the ZnO/Au electrode in 0.02 M phosphate buffer solution (PBS) of pH 7.4 was carried out. A very low detection limit of 66 nM (S/N=4) and a wide linearity in current for a concentration range from 66.0X10-3 to 415 mu M was achieved by amperometry. The electrode was found to be stable for over a month when preserved in PBS.

Effect of doping concentration on the structural and optical properties of pure and tin doped zinc oxide thin films by nebulizer spray pyrolysis (NSP) technique

Pure and tin doped zinc oxide (Sn:ZnO) thin films were prepared for the first time by NSP technique using aqueous solutions of zinc acetate dehydrate, tin (IV) chloride fendahydrate and methanol. X-ray diffraction patterns confirm that the films are polycrystalline in nature exhibiting hexagonal wurtzite type, with (0 0 2) as preferred orientation. The structural parameters such as lattice constant ('a' and `c'), crystallite size, dislocation density, micro strain, stress and texture coefficient were calculated from X-ray diffraction studies. Surface morphology was found to be modified with increasing Sn doping concentration. The ZnO films have high transmittance 85% in the visible region, and the transmittance is found to be decreased with the increase of Sn doping concentration. The corresponding optical band gap decreases from 3.25 to 3.08 eV. Room temperature photoluminescence reveals the sharp emission of strong UV peak at 400 nm (3.10 eV) and a strong sharp green luminescence at 528 nm (2.34 eV) in the Sn doped ZnO films. The electrical resistivity is found to be 10(6) Omega-cm at higher temperature and 10(5) Omega-cm at lower temperature. (C) 2012 Elsevier Ltd. All rights reserved.

Synthesis of zinc oxide porous structures by anodization with water as an electrolyte

We report a simple, reliable and one-step method of synthesizing ZnO porous structures at room temperature by anodization of zinc (Zn) sheet with water as an electrolyte and graphite as a counter electrode. We observed that the de-ionized (DI) water used in the experiment is slightly acidic (pH=5.8), which is due to the dissolution of carbon dioxide from the atmosphere forming carbonic acid. Porous ZnO is characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy and photoluminescence (PL) studies. The current-transient measurement is carried out using a Gamry Instruments Reference 3000 and the thickness of the deposited films is measured using a Dektak surface profilometer. The PL, Raman and X-ray photoelectron spectroscopy are used to confirm the presence of ZnO phase. We have demonstrated that the hybrid structures of ZnO and poly (3,4-ethylenedioxythiophene):poly (styrene sulfonate) (PEDOT:PSS) exhibit good rectifying characteristics. The evaluated barrier height and the ideality factor are 0.45 eV and 3.6, respectively.

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.

High field carrier transport in graphene: Insights from fast current transient

In this work, we observe gate tunable negative differential conductance (NDC) and current saturation in single layer and bilayer graphene transistor at high source-drain field, which arise due to the interplay among (1) self-heating, (2) hot carrier injection, and (3) drain induced minority carrier injection. The magnitude of the NDC is found to be reduced for a bilayer, in agreement with its weaker carrier-optical phonon coupling and less efficient hot carrier injection. The contributions of different mechanisms to the observed results are decoupled through fast transient measurements with nanosecond resolution. The findings provide insights into high field transport in graphene. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4754103]

Unraveling siRNA unzipping kinetics with graphene

Using all atom molecular dynamics simulations, we report spontaneous unzipping and strong binding of small interfering RNA (siRNA) on graphene. Our dispersion corrected density functional theory based calculations suggest that nucleosides of RNA have stronger attractive interactions with graphene as compared to DNA residues. These stronger interactions force the double stranded siRNA to spontaneously unzip and bind to the graphene surface. Unzipping always nucleates at one end of the siRNA and propagates to the other end after few base-pairs get unzipped. While both the ends get unzipped, the middle part remains in double stranded form because of torsional constraint. Unzipping probability distributions fitted to single exponential function give unzipping time (tau) of the order of few nanoseconds which decrease exponentially with temperature. From the temperature variation of unzipping time we estimate the energy barrier to unzipping. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4742189]

Methane and carbon dioxide adsorption on edge-functionalized graphene: a comparative DFT study

With a view towards optimizing gas storage and separation in crystalline and disordered nanoporous carbon-based materials, we use ab initio density functional theory calculations to explore the effect of chemical functionalization on gas binding to exposed edges within model carbon nanostructures. We test the geometry, energetics, and charge distribution of in-plane and out-of-plane binding of CO2 and CH4 to model zigzag graphene nanoribbons edge-functionalized with COOH, OH, NH2, H2PO3, NO2, and CH3. Although different choices for the exchange-correlation functional lead to a spread of values for the binding energy, trends across the functional groups are largely preserved for each choice, as are the final orientations of the adsorbed gas molecules. We find binding of CO2 to exceed that of CH4 by roughly a factor of two. However, the two gases follow very similar trends with changes in the attached functional group, despite different molecular symmetries. Our results indicate that the presence of NH2, H2PO3, NO2, and COOH functional groups can significantly enhance gas binding, making the edges potentially viable binding sites in materials with high concentrations of edge carbons. To first order, in-plane binding strength correlates with the larger permanent and induced dipole moments on these groups. Implications for tailoring carbon structures for increased gas uptake and improved CO2/CH4 selectivity are discussed. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4736568]

Nonlocal continuum mechanics based ultrasonic flexural wave dispersion characteristics of a monolayer graphene embedded in polymer matrix

Wave propagation in graphene sheet embedded in elastic medium (polymer matrix) has been a topic of great interest in nanomechanics of graphene sheets, where the equivalent continuum models are widely used. In this manuscript, we examined this issue by incorporating the nonlocal theory into the classical plate model. The influence of the nonlocal scale effects has been investigated in detail. The results are qualitatively different from those obtained based on the local/classical plate theory and thus, are important for the development of monolayer graphene-based nanodevices. In the present work, the graphene sheet is modeled as an isotropic plate of one-atom thick. The chemical bonds are assumed to be formed between the graphene sheet and the elastic medium. The polymer matrix is described by a Pasternak foundation model, which accounts for both normal pressure and the transverse shear deformation of the surrounding elastic medium. When the shear effects are neglected, the model reduces to Winkler foundation model. The normal pressure or Winkler elastic foundation parameter is approximated as a series of closely spaced, mutually independent, vertical linear elastic springs where the foundation modulus is assumed equivalent to stiffness of the springs. For this model, the nonlocal governing differential equations of motion are derived from the minimization of the total potential energy of the entire system. An ultrasonic type of flexural wave propagation model is also derived and the results of the wave dispersion analysis are shown for both local and nonlocal elasticity calculations. From this analysis we show that the elastic matrix highly affects the flexural wave mode and it rapidly increases the frequency band gap of flexural mode. The flexural wavenumbers obtained from nonlocal elasticity calculations are higher than the local elasticity calculations. The corresponding wave group speeds are smaller in nonlocal calculation as compared to local elasticity calculation. The effect of y-directional wavenumber (eta(q)) on the spectrum and dispersion relations of the graphene embedded in polymer matrix is also observed. We also show that the cut-off frequencies of flexural wave mode depends not only on the y-direction wavenumber but also on nonlocal scaling parameter (e(0)a). The effect of eta(q) and e(0)a on the cut-off frequency variation is also captured for the cases of with and without elastic matrix effect. For a given nanostructure, nonlocal small scale coefficient can be obtained by matching the results from molecular dynamics (MD) simulations and the nonlocal elasticity calculations. At that value of the nonlocal scale coefficient, the waves will propagate in the nanostructure at that cut-off frequency. In the present paper, different values of e(0)a are used. One can get the exact e(0)a for a given graphene sheet by matching the MD simulation results of graphene with the results presented in this article. (c) 2012 Elsevier Ltd. All rights reserved.

Adsorption on Edge-Functionalized Bilayer Graphene Nanoribbons: Assessing the Role of Functional Groups in Methane Uptake

A combination of ab initio and classical Monte Carlo simulations is used to investigate the effects of functional groups on methane binding. Using Moller-Plesset (MP2) calculations, we obtain the binding energies for benzene functionalized with NH2, OH, CH3, COOH, and H2PO3 and identify the methane binding sites. In all cases, the preferred binding sites are located above the benzene plane in the vicinity of the benzene carbon atom attached to the functional group. Functional groups enhance methane binding relative to benzene (-6.39 kJ/mol), with the largest enhancement observed for H2PO3 (-8.37 kJ/mol) followed by COOH and CH3 (-7.77 kJ/mol). Adsorption isotherms are obtained for edge-functionalized bilayer graphene nanoribbons using grand canonical Monte Carlo simulations with a five-site methane model. Adsorbed excess and heats of adsorption for pressures up to 40 bar and 298 K are obtained with functional group concentrations ranging from 3.125 to 6.25 mol 96 for graphene edges functionalized with OH, NH2, and COOH. The functional groups are found to act as preferred adsorption sites, and in the case of COOH the local methane density in the vicinity of the functional group is found to exceed that of bare graphene. The largest enhancement of 44.5% in the methane excess adsorbed is observed for COOH-functionalized nanoribbons when compared to H terminated ribbons. The corresponding enhancements for OH- and NH2-functionalized ribbons are 10.5% and 3.7%, respectively. The excess adsorption across functional groups reflects the trends observed in the binding energies from MP2 calculations. Our study reveals that specific site functionalization can have a significant effect on the local adsorption characteristics and can be used as a design strategy to tailor materials with enhanced methane storage capacity.

Direct Observation of Valley Hybridization and Universal Symmetry of Graphene with Mesoscopic Conductance Fluctuations

In graphene, the valleys represent spinlike quantities and can act as a physical resource in valley-based electronics to produce novel quantum computation schemes. Here we demonstrate a direct route to tune and read the valley quantum states of disordered graphene by measuring the mesoscopic conductance fluctuations. We show that the conductance fluctuations in graphene at low temperatures are reduced by a factor of 4 when valley triplet states are gapped in the presence of short-range potential scatterers at high carrier densities. We also show that this implies a gate tunable universal symmetry class that outlines a fundamental feature arising from graphene's unique crystal structure.