L. S. Panchakarla

Differential nano-bio interactions and toxicity effects of pristine versus functionalized graphene

We report the effect of carboxyl functionalization of graphene in pacifying its strong hydrophobic interaction with cells and associated toxic effects. Pristine graphene was found to accumulate on the cell membrane causing high oxidative stress leading to apoptosis, whereas carboxyl functionalized hydrophilic graphene was internalized by the cells without causing any toxicity.

Infrared Photodetectors Based on Reduced Graphene Oxide and Graphene Nanoribbons

The use of reduced graphene oxide (RGO) and graphene nanoribbons (GNRs) as infrared photodetectors is explored, based on recent results dealing with solar cells, light-emitting devices, photodetectors, and ultrafast lasers. IR detection is demonstrated by both RGO and GNRs in terms of the time-resolved photocurrent and photoresponse. The responsivity of the detectors and their functioning are presented.

Hemocompatibility and Macrophage Response of Pristine and Functionalized Graphene

Graphene and its derivatives are being proposed for several important biomedical applications including drug delivery, gene delivery, contrast imaging, and anticancer therapy. Most of these applications demand intravenous injection of graphene and hence evaluation of its hemocompatibility is an essential prerequisite. Herein, both pristine and functionalized graphene are extensively characterized for their interactions with murine macrophage RAW 264.7 cells and human primary blood components. Detailed analyses of the potential uptake by macrophages, effects on its metabolic activity, membrane integrity, induction of reactive oxygen stress, hemolysis, platelet activation, platelet aggregation, coagulation cascade, cytokine induction, immune cell activation, and immune cell suppression are performed using optimized protocols for nanotoxicity evaluation. Electron microscopy, confocal Raman spectral mapping, and confocal fluorescence imaging studies show active interaction of both the graphene systems with macrophage cells, and the reactive oxygen species mediated toxicity effects of hydrophobic pristine samples are significantly reduced by surface functionalization. In the case of hemocompatibility, both types of graphene show excellent compatibility with red blood cells, platelets, and plasma coagulation pathways, and minimal alteration in the cytokine expression by human peripheral blood mononuclear cells. Further, both samples do not cause any premature immune cell activation or suppression up to a relatively high concentration of 75 μg mL(-1) after 72 h of incubation under in vitro conditions. This study clearly suggests that the observed toxicity effects of pristine graphene towards macrophage cells can be easily averted by surface functionalization and both the systems show excellent hemocompatibility.

Nitrogen- and Boron-Doped Double-Walled Carbon Nanotubes

Double-walled carbon nanotubes (DWNTs) doped with nitrogen and boron have been prepared by the decomposition of a CH(4) + Ar mixture along with pyridine (or NH(3)) and diborane, respectively, over a Mo(0.1)Fe(0.9)Mg(13)O catalyst, prepared by the combustion route. The doped DWNTs bave been characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy, electron energy loss spectroscopy, and Raman spectroscopy. The dopant concentration is around 1 atom % for both boron and nitrogen. The radial breathing modes in the Raman spectra have been employed along with TEM to obtain the inner and outer diameters of the DWNTs. The diameter ranges for the undoped, N-doped (pyridine), N-doped (NH(3)), and B-doped DWNTs are 0.73-2.20, 0.74-2.30, 0.73-2.32, and 0.74-2.36 nm, respectively, the boron-doped DWNTs giving rise to a high proportion of the large diameter DWNTs. Besides affecting the G-band in the Raman spectra, N- and B-doping affect the proportion of semiconducting nanotubes.

NO2 AND HUMIDITY SENSING CHARACTERISTICS OF FEW-LAYER GRAPHENES

Sensing characteristics of few-layer graphenes for NO2 and humidity have been investigated with graphene samples prepared by the thermal exfoliation of graphitic oxide, conversion of nanodiamond (DG) and arc-discharge of graphite in hydrogen (HG). The sensitivity for NO2 is found to be highest with DG. Nitrogen-doped HG (n-type) shows increased sensitivity for NO2 compared with pure HG. The highest sensitivity for humidity is observed with HG. Sensing characteristics of graphene have been examined for different aliphatic alcohols and the sensitivity is found to vary with the chain length and branching.

Remarkably low turn-on field emission in undoped, nitrogen-doped, and boron-doped graphene

Field emission studies have been carried out on undoped as well as N- and B-doped graphene samples prepared by arc-discharge method in a hydrogen atmosphere. These graphene samples exhibit very low turn-on fields. N-doped graphene shows the lowest turn-on field of 0.6 V/μm, corresponding to emission current density of 10 μA/cm2. These characteristics are superior to the other types of nanomaterials reported in the literature. Furthermore, emission currents are stable over the period of more than 3 h for the graphene samples. The observed emission behavior has been explained on the basis of nanometric features of graphene and resonance tunneling phenomenon.

Photoluminescence, white light emitting properties and related aspects of ZnO nanoparticles admixed with graphene and GaN

ZnO nanoparticles exhibit a broad band centred around 530 nm in the photoluminescence (PL) spectrum due to the presence of oxygen vacancies. Composites of ZnO nanoparticles with graphenes show marked changes in the PL spectrum with broad bands covering the entire visible region, making them candidates for solid state lighting, while graphene prepared by arc discharge of graphite in a hydrogen atmosphere (HG) containing 2-3 layers as well as boron-doped (BHG) and nitrogen-doped (NHG) samples of HG give white light when admixed with ZnO nanoparticles; excellent results are obtained with the addition of just 7 wt% of BHG to the ZnO nanoparticles. Mixtures of ZnO and GaN nanoparticles also exhibit white light emission. The quantum yields of these ZnO nanoparticle based white light sources are in the 4-6% range. Photoconductivity characteristics of ZnO nanoparticles are affected by the addition of even a small amount of graphene (<0.5 wt%).

P-Type Nitrogen-Doped ZnO Nanostructures with Controlled Shape and Doping Level by Facile Microwave Synthesis

We report herein the development of a facile microwave irradiation (MWI) method for the synthesis of high-quality N-doped ZnO nanostructures with controlled morphology and doping level. We present two different approaches for the MWI-assisted synthesis of N-doped ZnO nanostructures. In the first approach, N-doping of Zn-poor ZnO prepared using zinc peroxide (ZnO2) as a precursor is carried out under MWI in the presence of urea as a nitrogen source and oleylamine (OAm) as a capping agent for the shape control of the resulting N-doped ZnO nanostructures. Our approach utilizes the MWI process for the decomposition of ZnO2, where the rapid transfer of energy directly to ZnO2 can cause an instantaneous internal temperature rise and, thus, the activation energy for the ZnO2 decomposition is essentially decreased as compared to the decomposition under conductive heating. In the second synthesis method, a one-step synthesis of N-doped ZnO nanostructures is achieved by the rapid decomposition of zinc acetate in a mixture of urea and OAm under MWI. We demonstrate, for the first time, that MWI decomposition of zinc acetate in a mixture of OAm and urea results in the formation of N-doped nanostructures with controlled shape and N-doping level. We report a direct correlation between the intensity of the Raman scattering bands in N-doped ZnO and the concentration of urea used in the synthesis. Electrochemical measurements demonstrate the successful synthesis of stable p-type N-doped ZnO nanostructures using the one-step MWI synthesis and, therefore, allow us to investigate, for the first time, the relationship between the doping level and morphology of the ZnO nanostructures. The results provide strong evidence for the control of the electrical behavior and the nanostructured shapes of ZnO nanoparticles using the facile MWI synthesis method developed in this work.

Nanotubes from Misfit Layered Compounds: A New Family of Materials with Low Dimensionality

Nanotubes that are formed from layered materials have emerged to be exciting one-dimensional materials in the last two decades due to their remarkable structures and properties. Misfit layered compounds (MLC) can be produced from alternating assemblies of two different molecular slabs with different periodicities with the general formula [(MX)1+x]m[TX2]n (or more simply MS-TS2), where M is Sn, Pb, Bi, Sb, rare earths, T is Sn, Nb, Ta, Ti, V, Cr, and so on, and X is S, Se. The presence of misfit stresses between adjacent layers in MLC provides a driving force for curling of the layers that acts in addition to the elimination of dangling bonds. The combination of these two independent forces leads to the synthesis of misfit layered nanotubes, which are newcomers to the broad field of one-dimensional nanostructures and nanotubes. The synthesis, characterization, and microscopic details of misfit layered nanotubes are discussed, and directions for future research are presented.

Electron energy loss spectroscopy of ZnO nanocrystals with different oxygen vacancy concentrations

ZnO nanocrystals with different oxygen vacancy concentrations were characterized by high-resolution electron energy loss spectroscopy (HREELS). ZnO nanocrystals show a decrease in green emission with increasing annealing temperature in an oxygen environment and which significantly quenches in a sample annealed at 400 °C. O K and Zn L3 pre-edge absorption structures of ZnO nanocrystals were studied by HREELS as a function of annealing temperature. Absorption edge peak broadening and variation in pre-edge absorption edge structure of Zn L3 were observed in experimental electron energy loss spectroscopy spectra with different oxygen defect concentrations. All electron density functional theory (DFT) based (WIEN2k) calculation of electronic density of states and electron energy loss near edge structure were carried out with different oxygen vacancy concentrations and compared with experimental observations. Appearance of additional peaks in pre-edge electron energy loss structure with increasing oxygen vacanc...