Yield stress, thixotropy and shear banding in a dilute aqueous suspension of few layer graphene oxide platelets

We demonstrate a rigidity percolation transition and the onset of yield stress in a dilute aqueous dispersion of graphene oxide platelets (aspect ratio similar to 5000) above a critical volume fraction of 3.75 x 10(-4) with a percolation exponent of 2.4 +/- 0.1. The viscoelastic moduli of the gel at rest measured as a function of time indicate the absence of structural evolution of the 3D percolated network of disks. However a shear-induced aging giving rise to a compact jammed state and shear rejuvenation indicating a homogenous flow is observed when a steady shear stress (sigma) is imposed in creep experiments. We construct a shear diagram (sigma vs. volume fraction phi) and the critical stress above which shear rejuvenation occurs is identified as the yield stress sigma(y) of the gel. The minimum steady state shear rate (gamma) over dot(m) obtained from creep experiments agrees well with the end of the plateau region in a controlled shear rate flow curve, indicating a shear localization below (gamma) over dot(m). A steady state shear banding in the plateau region of the flow curve observed in particle velocimetry measurements in a Couette geometry confirms that the dilute suspensions of GO platelets form a thixotropic yield stress fluid.

Metal doped nanosized titania used for the photocatalytic degradation of rhodamine B dye under visible-light

Metal-doped anatase nanosized titania photocatalysts were successfully synthesized using a sal gel process. Different amounts of the dopants (0.2, 0.4, 0.6, 0.8 and 1.0%) of the metals (Ag, Ni, Co and Pd) were utilized. The UV-Vis spectra (solid state diffuse reflectance spectra) of the doped nanoparticles exhibited a red shift in the absorption edge as a result of metal doping. The metal-doped nanoparticles were investigated for their photocatalytic activity under visible-light irradiation using Rhodamine B (Rh B) as a control pollutant. The results obtained indicate that the metal-doped titania had the highest activity at 0.4% metal loading. The kinetic models revealed that the photodegradation of Rh B followed a pseudo first order reaction. From ion chromatography (IC) analysis the degradation by-products Rhodamine B fragments were found to be acetate, chloride, nitrite, carbonate and nitrate ions.

Nitrogen deposition: how important is it for global terrestrial carbon uptake?

Global carbon budget studies indicate that the terrestrial ecosystems have remained a large sink for carbon despite widespread deforestation activities. CO2 fertilization, N deposition and re-growth of mid-latitude forests are believed to be key drivers for land carbon uptake. In this study, we assess the importance of N deposition by performing idealized near-equilibrium simulations using the Community Land Model 4.0 (CLM4). In our equilibrium simulations, only 12-17% of the deposited nitrogen is assimilated into the ecosystem and the corresponding carbon uptake can be inferred from a C : N ratio of 20 : 1. We calculate the sensitivity of the terrestrial biosphere for CO2 fertilization, climate warming and N deposition as changes in total ecosystem carbon for unit changes in global mean atmospheric CO2 concentration, global mean temperature and Tera grams of nitrogen deposition per year, respectively. Based on these sensitivities, it is estimated that about 242 PgC could have been taken up by land due to the CO2 fertilization effect and an additional 175 PgC taken up as a result of the increased N deposition since the pre-industrial period. Because of climate warming, the terrestrial ecosystem could have lost about 152 PgC during the same period. Therefore, since pre-industrial times terrestrial carbon losses due to warming may have been more or less compensated by effects of increased N deposition, whereas the effect of CO2 fertilization is approximately indicative of the current increase in terrestrial carbon stock. Our simulations also suggest that the sensitivity of carbon storage to increased N deposition decreases beyond current levels, indicating that climate warming effects on carbon storage may overwhelm N deposition effects in the future.

Iron(III) benzhydroxamates of dipicolylamines for photocytotoxicity in red light and cellular imaging

Benzhydroxamate (BHA) iron(III) complexes Fe(BHA)(L)ClICI (I, 2)], where L is (phenyl)dipicolylamine (phdpa in I) and (pyrenyl)dipicolylamine (pydpa in 2), were prepared and their photocytotoxicity in visible (400-700 nm) and red (600-720 nm) light was studied. Complex 1 was structurally characterized by X-ray crystallography. The complexes have high-spin iron(III) centers. Complex 2, with a pyrenyl fluorophore, was used for cellular imaging, showing both mitochondrial and nuclear localization in the fluorescence microscopic study. The complex exhibited photocytotoxicity in red light in HeLa cancer cells, giving IC50 value of 24.4(+/- 0.4) pM, but remained essentially non-toxic in the dark. The involvement of reactive oxygen species and an apoptotic nature of cell death were observed from the cellular studies. (C) 2014 Elsevier Ltd. All rights reserved.

Solution Processed Cu2CoSnS4 Thin Films for Photovoltaic Applications

Earth abundant alternative chalcopyrite Cu2CoSnS4 (CCTS) thin films were deposited by a facile sol-gel process onto larger substrates. Temperature dependence of the process control of deposition and desired phase formations was studied in detail. Films were analyzed for complete transformation from amorphous to polycrystalline, with textured structures for stannite phase, as reflected from the X-ray diffraction and with nearly stoichiometric compositions of Cu:Co:Sn:S = 2:0:1:0:1:0:4:0 from EDAX analysis. Morphological investigations revealed that the CCTS films with larger grains, on the order of its thickness, were synthesized at higher temperature of 500 degrees C. The optimal band gap for application in photovoltaics was estimated to be 1.4 eV. Devices with SLG/CCTS/Al geometry were fabricated for real time demonstration of photoconductivity under A.M 1.5 G solar and 1064 rim infrared laser illuminations. A photodetector showed one order current amplification from similar to 1.9 X 10(-6) A in the dark to 2.2 x 10(-5) A and 9.8 X 10(-6) A under A.M 1.5 G illumination and 50 mW cm(-2) IR laser, respectively. Detector sensitivity, responsivity, external quantum efficiency, and gain were estimated as 4.2, 0.12 A/W, 14.74% and 14.77%, respectively, at 50 mW cm(-2) laser illuminations. An ON and OFF ratio of 2.5 proved that CCTS can be considered as a potential absorber in low cost photovoltaics applications.