Synthesis and characterization of carbon-covered alumina (CCA) supported TiO2 nanocatalysts with enhanced visible light photodegradation of Rhodamine B

The anatase phase of titania (TiO2) nano-photocatalysts was prepared using a modified sol gel process and thereafter embedded on carbon-covered alumina supports. The carbon-covered alumina (CCA) supports were prepared via the adsorption of toluene 2,4-diisocyanate (TDI) on the surface of the alumina. TDI was used as the carbon source for the first time for the carbon-covered alumina support system. The adsorption of TDI on alumina is irreversible; hence, the resulting organic moiety can undergo pyrolysis at high temperatures resulting in the formation of a carbon coating on the surface of the alumina. The TiO2 catalysts were impregnated on the CCA supports. X-ray diffraction analysis indicated that the carbon deposited on the alumina was not crystalline and also showed the successful impregnation of TiO2 on the CCA supports. In the Raman spectra, it could be deduced that the carbon was rather a conjugated olefinic or polycyclic hydrocarbons which can be considered as molecular units of a graphitic plane. The Raman analysis of the catalysed CCAs showed the presence of both the anatase titania and D and G band associated with the carbon of the CCAs. The scanning electron microscope micrographs indicated that the alumina was coated by a carbon layer and the energy dispersive X-ray spectra showed the presence of Al, O and C in the CCA samples, with the addition of Ti for the catalyst impregnated supports. The Brunauer Emmet and Teller surface area analysis showed that the incorporating of carbon on the alumina surface resulted in an increase in surface area, while the impregnation with TiO2 resulted in a further increase in surface area. However, a decrease in the pore volume and diameter was observed. The photocatalytic activity of the nanocatalysts was studied for the degradation of Rhodamine B dye. The CCA-TiO2 nanocatalysts were found to be more photocatalytically active under both visible and UV light irradiation compared to the free TIO2 nanocatalysts.

Swift heavy ion induced structural, iono and photoluminescence properties of beta-CaSiO3:Dy3+ nanophosphor

CaSiO3:Dy3+ (1-5 mol%) nanophosphors have been prepared by a low temperature solution combustion method. The structural and luminescence (ionoluminescence; IL and photoluminescence; PL) studies have been carried out for pristine and ion irradiated samples. The XRD patterns of pristine sample show a prominent peak at (320) for the monoclinic structure of beta-CaSiO3. Upon ion irradiation, the intensity of the prominent peak is decreased at the fluence of 7.81 x 10(12) ions cm(-2) and at higher fluence of 15.62 x 10(12) ions cm(-2), the prominent peak completely vanishes. The decrease in peak intensity might be due to the stress induced point defects. On-line IL and in situ PL studies have been carried out on pelletized samples bombarded with 100 MeV Si7+ ions with fluences in the range (7.81-15.62) x 10(12) ions cm(-2). The characteristic emission peaks at 481,574, 664 and 754 nm recorded in both IL and PL are attributed to the luminescence centers activated by Dy3+ ions. It is found that IL and PL emissions intensity decreases with increase in Si7+ ion fluence. The decrease in intensity can be due to the destruction of Si-O-Si and O-Si-O type species present on the surface of the sample. FTIR studies also confirm the Si-O-Si and O-Si-O type species observed to be sensitive for swift heavy ion (SHI) irradiated samples. (C) 2012 Elsevier B.V. All rights reserved.

Physics-Based Band Gap Model for Relaxed and Strained 100] Silicon Nanowires

In this paper, we propose a physics-based simplified analytical model of the energy band gap and electron effective mass in a relaxed and strained rectangular 100] silicon nanowires (SiNWs). Our proposed formulation is based on the effective mass approximation for the nondegenerate two-band model and 4 x 4 Luttinger Hamiltonian for energy dispersion relation of conduction band electrons and the valence band heavy and light holes, respectively. Using this, we demonstrate the effect of the uniaxial strain applied along 100]-direction and a biaxial strain, which is assumed to be decomposed from a hydrostatic deformation along 001] followed by a uniaxial one along the 100]-direction, respectively, on both the band gap and the transport and subband electron effective masses in SiNW. Our analytical model is in good agreement with the extracted data using the extended-Huckel-method-based numerical simulations over a wide range of device dimensions and applied strain.

Influence of anion on the quadratic nonlinearity and depolarization ratios of scattered second harmonic light from cation-pi complexes

We have investigated quadratic nonlinearity (beta(HRS)) and linear and circular depolarization ratios (D and D', respectively) of a series of 1:1 complexes of tropyliumtetrafluoroborate as a cation and methyl-substituted benzenes as pi-donors by making polarization resolved hyper-Rayleigh scattering measurements in solution. The measured D and D' values are much lower than the values expected from a typical sandwich or a T-shaped geometry of a complex. In the cation-pi complexes studied here, the D value varies from 1.36 to 1.46 and D' from 1.62 to 1.72 depending on the number of methyl substitutions on the benzene ring. In order to probe it further, beta, D and D' were computed using the Zerner intermediate neglect of differential overlap-correction vector self-consistent reaction field technique including single and double configuration interactions in the absence and presence of BF4- anion. In the absence of the anion, the calculated value of D varies from 4.20 to 4.60 and that of D' from 2.45 to 2.72 which disagree with experimental values. However, by arranging three cation-pi BF4- complexes in a trigonal symmetry, the computed values are brought to agreement with experiments. When such an arrangement was not considered, the calculated beta values were lower than the experimental values by more than a factor of two. This unprecedented influence of the otherwise ``unimportant'' anion in solution on the beta value and depolarization ratios of these cation-pi complexes is highlighted and emphasized in this paper. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4716020]

Flux tube model signals for baryon correlations in heavy ion collisions

The flux tube model offers a pictorial description of what happens during the deconfinement phase transition in QCD. The three-point vertices of a flux tube network lead to formation of baryons upon hadronization. Therefore, correlations in the baryon number distribution at the last scattering surface are related to the preceding pattern of the flux tube vertices in the quark-gluon plasma, and provide a signature of the nearby deconfinement phase transition. I discuss the nature of the expected signal, and how to extract it from the experimental data for heavy ion collisions at RHIC and LHC.

Layer-by-Layer Self-Assembled Metal-Ion- (Ag-, Co-, Ni-, and Pd-) Doped TiO2 Nanoparticles: Synthesis, Characterisation, and Visible Light Degradation of Rhodamine B

Metal-ion- (Ag, Co, Ni and Pd) doped titania nanocatalysts were successfully deposited on glass slides by layer-by-layer (LbL) self-assembly technique using a poly(styrene sulfonate sodium salt) (PSS) and poly(allylamine hydrochloride) (PAH) polyelectrolyte system. Solid diffuse reflectance (SDR) studies showed a linear increase in absorbance at 416 nm with increase in the number of m-TiO2 thin films. The LbL assembled thin films were tested for their photocatalytic activity through the degradation of Rhodamine B under visible-light illumination. From the scanning electron microscope (SEM), the thin films had a porous morphology and the atomic force microscope (AFM) studies showed ``rough'' surfaces. The porous and rough surface morphology resulted in high surface areas hence the high photocatalytic degradation (up to 97% over a 6.5 h irradiation period) using visible-light observed. Increasing the number of multilayers deposited on the glass slides resulted in increased film thickness and an increased rate of photodegradation due to increase in the availability of more nanocatalysts (more sites for photodegradation). The LbL assembled thin films had strong adhesion properties which made them highly stable thus displaying the same efficiencies after five (5) reusability cycles.

Large mass splittings for fourth generation fermions allowed by LHC Higgs boson exclusion

In the context of the standard model with a fourth generation, we explore the allowed mass spectra in the fourth-generation quark and lepton sectors as functions of the Higgs mass. Using the constraints from unitarity and oblique parameters, we show that a heavy Higgs allows large mass splittings in these sectors, opening up new decay channels involving W emission. Assuming that the hints for a light Higgs do not yet constitute an evidence, we work in a scenario where a heavy Higgs is viable. A Higgs heavier than similar to 800 GeV would in fact necessitate either a heavy quark decay channel t' -> b'W/b' -> t'W or a heavy lepton decay channel tau' -> nu'W as long as the mixing between the third and fourth generations is small. This mixing tends to suppress the mass splittings and hence the W-emission channels. The possibility of the W-emission channel could substantially change the search strategies of fourth-generation fermions at the LHC and impact the currently reported mass limits.

Selective colorimetric detection of nanomolar Cr (VI) in aqueous solutions using unmodified silver nanoparticles

In this study we present a colorimetric detection method for Cr (VI) in aqueous solution based on as synthesized silver nanoparticles (Ag NPs) without surface functionalization. The method principle involves reduction of Cr (VI) to Cr (III) by excess reductant present in as synthesized Ag NP dispersion, and subsequent aggregation of Ag NPs by Cr (III) leading to red-shift of the surface plasmon resonance (SPR) peak. The UV-vis absorption spectra. Zeta potentials, dynamic light scattering measurements, and scanning electron microscopy (SEM) confirmed the aggregation of the Ag NPs. Under the optimized conditions, a good linear relationship (correlation coefficient r=0.981) was obtained between the ratio of the absorbance at 550 nm to that at 390 nm (A(550/390)) and the concentration of Cr (VI) over the range of 10(-3)-10(-9) M 50 mg/L to 50 ng/L]. The reported probe has a limit of detection down to 1 nM, which, to the best of our knowledge, is the lowest ever reported for the colorimetric detection of Cr (VI). Furthermore, a remarkable feature of this method is that it involves a simple technique exhibiting high selectivity to Cr (VI) over other tested heavy metal ions. (C) 2012 Elsevier BM. All rights reserved.

Higgs boson in the MSSM in light of the LHC

We investigate the expectations for the light Higgs signal in the minimal supersymmetric standard model in different search channels at the LHC. After taking into account dark matter and flavor constraints in the minimal supersymmetric standard model with 11 free parameters as well as LHC results on the Higgs sector, we show that the light Higgs signal in the gamma channel is expected to be at most at the level of the standard model Higgs, while the h -> b (b) over bar from W fusion and/or the h -> tau(tau) over bar can be enhanced. For the main discovery mode, we show that a strong suppression of the signal occurs in two different cases: low M-A or large invisible width. The former is however strongly constrained by the recent LHC results. A more modest suppression is associated with the effect of light supersymmetric particles. Looking for such modification of the Higgs properties and searching directly for supersymmetric partners and pseudoscalar Higgs offer two complementary probes of supersymmetry at the LHC.

Remarkable photocytotoxicity of curcumin in HeLa cells in visible light and arresting its degradation on oxovanadium(IV) complex formation

Curcumin (Hcur) as a cellular imaging and PDT agent shows remarkable photocytotoxicity in HeLa cells in visible light of 400-700 nm giving IC50 = 8.2 +/- 0.2 mu M and its degradation is arrested on formation of photocytotoxic dipyridophenazine (dppz) complex VO(cur)(dppz)Cl] (IC50 = 3.3 +/- 0.4 mu M), while both are less toxic in the dark.

Estimation of heavy rainfall during cyclonic storms from microwave observations using nonlinear approach over Indian Ocean

In this study, an effort has been made to study heavy rainfall events during cyclonic storms over Indian Ocean. This estimate is based on microwave observations from tropical rainfall measuring mission (TRMM) Microwave Imager (TMI). Regional scattering index (SI) developed for Indian region based on measurements at 19-, 21- and 85-GHz brightness temperature and polarization corrected temperature (PCT) at 85 GHz have been utilized in this study. These PCT and SI are collocated against Precipitation Radar (PR) onboard TRMM to establish a relationship between rainfall rate, PCT and SI. The retrieval technique using both linear and nonlinear regressions has been developed utilizing SI, PCT and the combination of SI and PCT. The results have been compared with the observations from PR. It was found that a nonlinear algorithm using combination of SI and PCT is more accurate than linear algorithm or nonlinear algorithm using either SI or PCT. Statistical comparison with PR exhibits the correlation coefficients (CC) of 0.68, 0.66 and 0.70, and root mean square error (RMSE) of 1.78, 1.96 and 1.68 mm/h from the observations of SI, PCT and combination of SI and PCT respectively using linear regressions. When nonlinear regression is used, the CC of 0.73, 0.71, 0.79 and RMSE of 1.64, 1.95, 1.54 mm/h are observed from the observations of SI, PCT and combination of SI and PCT, respectively. The error statistics for high rain events (above 10 mm/h) shows the CC of 0.58, 0.59, 0.60 and RMSE of 5.07, 5.47, 5.03 mm/h from the observations of SI, PCT and combination of SI and PCT, respectively, using linear regression, and on the other hand, use of nonlinear regression yields the CC of 0.66, 0.64, 0.71 and RMSE of 4.68, 5.78 and 4.02 mm/h from the observations of SI, PCT and combined SI and PCT, respectively.

Light Induced Optical Properties Change in Sb20S40Se40 Thin Films

Thin films of Sb20S40Se40 of thickness 800 nm were prepared by thermal evaporation method. The as-prepared and illuminated thin films were studied by X-ray diffraction, Fourier Transform Infrared Spectroscopy and X-ray Photoelectron Spectroscopy and Raman spectroscopy. The optical band gap was reduced due to photo induced effects along with the increase in disorder. These optical properties changes are due to the change of homopolar bond densities. The core level peak shifting in XPS and Raman spectra supports the optical changes happening in the film due to light exposure.

Si isotope variability in Proterozoic cherts

We report Si-isotopic compositions of 75 sedimentologically and petrographically characterized chert samples with ages ranging from similar to 2600 to 750 Ma using multi-collector inductively coupled plasma mass spectrometry. delta Si-30 values of the cherts analyzed in this study show a similar to 7 parts per thousand range, from -4.29 to +2.85. This variability can be explained in part by (1) simple mixing of silica derived from continental (higher delta Si-30) and hydrothermal (lower delta Si-30) sources, (2) multiple mechanisms of silica precipitation and (3) Rayleigh-type fractionations within pore waters of individual basins. We observe similar to 3 parts per thousand variation in peritidal cherts from a single Neoproterozoic sedimentary basin (Spitsbergen). This variation can be explained by Rayleigh-type fractionation during precipitation from silica-saturated porewaters. In some samples, post-dissolution and reprecipitation of silica could have added to this effect. Our data also indicate that peritidal cherts are enriched in the heavier isotopes of Si whereas basinal cherts associated with banded iron formations (BIF) show lower delta Si-30. This difference could partly be due to Si being derived from hydrothermal sources in BIFs. We postulate that the difference in delta Si-30 between non-BIF and BIF cherts is consistent with the contrasting genesis of these deposits. Low delta Si-30 in BIF is consistent with laboratory experiments showing that silica adsorbed onto Fe-hydroxide particles preferentially incorporates lighter Si isotopes. Despite large intrabasinal variation and environmental differences, the data show a clear pattern of secular variation. Low delta Si-30 in Archean cherts is consistent with a dominantly hydrothermal source of silica to the oceans at that time. The monotonically increasing delta Si-30 from 3.8 to 1.5 Ga appears to reflect a general increase in continental versus hydrothermal sources of Si in seawater, as well as the preferential removal of lighter Si isotopes during silica precipitation in iron-associated cherts from silica-saturated seawater. The highest delta Si-30 values are observed in 1.5 Ga peritidal cherts; in part, these enriched values could reflect increasing sequestration of light silica during soil-forming processes, thus, delivering relatively heavy dissolved silica to the oceans from continental sources. The causes behind the reversal in trend towards lower delta Si-30 in cherts younger than 1.5 Ga old are less clear. Cherts deposited 1800-1900 Ma are especially low delta Si-30, a possible indication of transiently strong hydrothermal input at this time. (C) 2012 Elsevier Ltd. All rights reserved.

Visible light photocatalytic inactivation of Escherichia coli with combustion synthesized TiO2

The photocatalytic inactivation of Escherichia coil was studied with combustion synthesized TiO2 photocatalysts in the presence of visible light. A series of 400W lamps irradiating in the visible region of the solar spectrum was used. The effect of various parameters, such as catalyst loading, light intensity, presence of inorganic ions, addition of hydrogen peroxide and pH, on the photocatalytic inactivation of E. coil was investigated. Photolysis alone had a small effect on inactivation while the dark experiment resulted in no inactivation and Ag/TiO2 showed the maximum inactivation. At a catalyst loading of 0.25 g/L, all the combustion synthesized catalysts showed better inactivation of E. coil compared to commercial Degussa P-25 (DP-25) TiO2 catalyst. An improved inactivation was observed with increasing lamp intensity and addition of H2O2. A negative effect on inactivation was observed by addition of inorganic ions such as HCO3-, SO42-, Cl-, NO3-, Na+, K+ and Ca2+. The photocatalytic inactivation of E. coli remained unaltered at different pH of the solution. The inactivation of E. coli was modeled with power law kinetics and was observed to follow first order kinetics. (C) 2012 Elsevier B.V. All rights reserved.

Photocytotoxic Oxidovanadium(IV) Complexes of Polypyridyl Ligands Showing DNA-Cleavage Activity in Near-IR Light

Oxidovanadium(IV) complexes VO(pyphen)(L)]Cl2 (1, 2) and VO(pydppz)(L)]Cl2 (3, 4), where L is 1,10-phenanthroline (phen in 1 and 3) and dipyrido3,2-a:2',3'-c]phenazine (dppz in 2 and 4) are prepared and characterized. The crystal structure of VO(pyphen)(phen)](ClO4)2 (1a) shows a six-coordinate VN5O geometry with a VO2+ moiety in which the polypyridyl ligand binds in a meridional fashion and the phen ligand displays a chelating binding mode with an N-donor site trans to the oxidovanadyl group. The complexes show a dd band within 720-750 nm in DMF. The one-electron paramagnetic complexes are 1:2 electrolytes in DMF. The complexes exhibit an irreversible VIV/VIII redox response near -0.85 V vs. SCE in DMF/0.1 M TBAP. The complexes bind to calf thymus (ct) DNA giving Kb values within 7.5 x 104 to 1.1 x 106 M1. The complexes show poor chemical nuclease activity in the dark and exhibit significant DNA-photocleaving activity in near-IR light of 705 and 785 nm forming .OH radicals. Complexes 2-4 show remarkable photocytotoxicity in HeLa cancer cells. FACS analysis of the HeLa cells treated with complex 4 shows cell death as highlighted by the sub G1 peak. Propidium iodide staining data indicate apoptosis as the primary mode of cell death.