Synthesis and characterization of spherical and rod like nanocrystalline Nd2O3 phosphors

Spherical and rod like nanocrystalline Nd2O3 phosphors have been prepared by solution combustion and hydrothermal methods respectively The Powder X-ray diffraction (PXRD) results confirm that hexagonal A-type Nd2O3 has been obtained with calcination at 900 C for 3 h and the lattice parameters have been evaluated by Rietveld refinement Surface morphology of Nd2O3 phosphors show the formation of nanorods in hydrothermal synthesis whereas spherical particles in combustion method TEM results also confirm the same Raman studies show major peaks which are assigned to F-g and combination of A(g) + E-g modes The PL spectrum shows a series of emission bands at similar to 326-373 nm (UV) 421-485 nm (blue) 529-542 nm (green) and 622 nm (red) The UV blue green and red emission in the PL spectrum indicates that Nd2O3 nanocrystals are promising for high performance materials and white light emitting diodes (LEDs) (C) 2010 Elsevier B V All rights reserved

Dye sensitized visible light degradation of phenolic compounds

The present research work reports the eosin Y (EY) and fluorescein (FL) sensitized visible light degradation of phenol, 4-chlorophenol (CP), 2,4-dichlorophenol (DCP) and 2,4,6-trichlorophenol (TCP) using combustion synthesized nano-TiO2 (CS TiO2). The rate of degradation of the phenolic compounds was higher in the presence of EY/CS TiO2 compared to FL/CS TiO2 system. A detailed mechanism of sensitized degradation was proposed and a mechanistic model for the rate of degradation of the phenolic compound was derived using the pyramidal network reduction technique. It was found that at low initial dye concentrations, the rate of degradation of the phenolic compound is first order in the concentration of the dye, while at high initial dye concentrations, the rate is first order in the concentration of the phenolic compound. The order of degradation of the different phenolic compounds follows: CP > TCP > DCP > phenol. The different phenolic and dye intermediates that were formed during the degradation were identified by liquid chromatography-mass spectrometry (LC-MS) and the most probable pathway of degradation is proposed. (C) 2010 Elsevier B.V. All rights reserved.

Localization of light in coherently amplifying random media

We derive and analyze the statistics of reflection coefficient of light backscattered coherently from an amplifying and disordered optical medium modeled by a spatially random refractive index having a uniform imaginary part in one dimension. We find enhancement of reflected intensity owing to a synergy between wave confinement by Anderson localization and coherent amplification by the active medium. This is not the same as that due to enhanced optical path lengths expected from photon diffusion in the random active medium. Our study is relevant to the physical realizability of a mirrorless laser by photon confinement due to Anderson localization.

Terpyridine Oxovanadium(IV) Complexes of Phenanthroline Bases for Cellular Imaging and Photocytotoxicity in HeLa Cells

Oxovanadium(IV) complexes VO(N-N-N)(N-N)](NO3)(2) (1-4) of (4'-phenyl)-2,2': 6',2 `'-terpyridine (ph-tpy in 1 and 2) or (4'-pyrenyl)-2,2':6',2 `'-terpyridine (py-tpy in 3 and 4) having N-N as 1,10-phenanthroline (phen in 1 and 3) or dipyrido3,2-a:2',3'-c]phenazine (dppz in 2 and 4) are prepared and characterized. The crystal structure of 1 has VO2+ group in VN5O coordination geometry. The terpyridine ligand coordinates in a meridional binding mode. The phen ligand displays a chelating mode of binding with an N-donor site trans to the vanadyl oxo group. The complexes show a d-d band in the range of 710-770 nm in aqueous DMF (4:1 v/v). The complexes exhibit an irreversible V-IV/V-III redox response near -1.0 V vs. SCE in aqueous DMF/0.1 M KCl. The complexes bind to CT DNA giving K-b values within 3.5 x 10(5) to 1.2 x 10(6) M-1. The complexes show poor chemical nuclease activity in dark. Complexes 2-4 show photonuclease activity in UV-A light of 365 nm forming O-1(2) and (OH)-O-center dot. Complex 4 shows DNA photocleavage activity at near-IR light of 785 nm forming (OH)-O-center dot radicals. Complexes 2 and 4 show significant photocytotoxicity in HeLa cancer cells. Uptake of the complexes in HeLa cells, studied by fluorescence imaging, show predominantly cytosolic localization inside the cells.

Solvation dynamics, energy distribution and trapping of a light solute ion

In the theoretical treatments of the dynamics of solvation of a newly created ion in a dipolar solvent, the self-motion of the solute is usually ignored. Recently, it has been shown that for a light ion the translational motion of the ion can significantly enhance its own rate of solvation. Therefore, solvation itself may not be the rate determining step in the equilibration. Instead, the rate determining step is the search of the low energy configuration which serves to localize the light ion. In this article a microscopic calculation of the probability distribution of the interaction energy of the nascent charge with the dipolar solvent molecules is presented in order to address this problem of solute trapping. It is found that to a good approximation, this distribution is Gaussian and the second moment of this distribution is exactly equal to the half of its own solvation energy. It is shown that this is in excellent agreement with the simulation results that are available for the model Brownian dipolar lattice and for liquid acetonitrile. If the distortion of the solvent by the ion is negligible then the same relation gives the energy distribution for the solvated ion, with the average centered at the final equilibrium solvation energy. These results are expected to be useful in understanding various chemical processes in dipolar liquids. Another interesting outcome of the present study is a simple dynamic argument that supports Onsager's ''inverse snow-ball'' conjecture of solvation of a light ion. A simple derivation of the semi-phenomenological relation between the solvation time correlation function and the single particle orientation, reported recently by Maroncelli et al. (J. Phys. Chem. 97 (1993) 13), is also presented.

Microwave assisted synthesis and UV-Vis spectroscopic studies of silver nanoparticles synthesized using vanillin as a reducing agent

The present investigation explores the adaptability of a microwave assisted route to obtain silver nanoparticles by the reduction of AgNO3 with vanillin, an environmentally benign material. Anionic surfactants such as AOT and SDS were used separately for encapsulating AgNPs and their role was compared. The UV-Visible absorption spectra present a broad SPR band consisting of two peaks suggesting the formation of silver nanoparticle with bimodal size distribution. The TEM image shows particles with spherical and hexagonal morphologies which confirms the results of UV-Vis studies. The anisotropy in the particle morphology can be attributed to the surface oxidation which in turn produces Ag@Ag2O core-shell nanostructures. Thus an intriguing feature of this system is that the obtained colloid is a mixture of AgNPs with and without Ag2O layers. Studies on the influence of pH on the stability of the synthesized nanoparticles revealed that the presence of excess Ag2O layers has a profound influence on it. Ag2O layers can be removed from AgNPs' surface by changing the solution pH to the acidic regime. The present study attests the enhanced ability of AOT in stabilizing the AgNPs in aqueous media. (C) 2011 Elsevier B.V. All rights reserved.

Characterization of the DNA-binding domain of beta protein, a component of phage lambda Red-pathway by UV catalyzed cross-linking

beta protein, a key component of Red-pathway of phage lambda is necessary for its growth and general genetic recombination in recombination-deficient mutants of Escherichia coli. To facilitate studies on structure-function relationships, we overexpressed beta protein and purified it to homogeneity. A chemical cross-linking reagent, glutaraldehyde, was used to stabilize the physical association of beta protein in solution. A 67-kDa band, corresponding to homodimer, was identified after separation by SDS-polyacrylamide gel electrophoresis. Stoichiometric measurements indicated a site-size of 1 monomer of beta protein/5 nucleotide residues. Electrophoretic gel mobility shift assays suggested that beta protein formed stable nucleoprotein complexes with 36-mer, but not with 27- or 17-mer DNA. Interestingly, the interaction of beta protein with DNA and the stability of nucleoprotein complexes was dependent on the presence of MgCl2, and the binding was abolished by 250 mM NaCl. The K-d of beta protein binding to 36-mer DNA was on the order of 1.8 x 10(-6) M. Photochemical cross-linking of native beta protein or its fragments, generated by chymotrypsin, to 36-mer DNA was performed to identify its DNA-binding domain. Characterization of the cross-linked peptide disclosed that amino acids required for DNA-binding specificity resided within a 20-kDa peptide at the N-terminal end. These findings provide a basis for further understanding oi the structure and function of beta protein.

DNA cleavage by intercalatable cobalt-bispicolylamine complexes activated by visible light

Two intercalatable Co-II-complexes of anthryl or anthraquinone attached bispicolylamine derivatives cleave plasmid pTZ19R DNA spontaneously upon exposure to visible light under ambient conditions.

Photocytotoxicity and DNA photocleavage activity of La(III) and Gd(III) complexes of phenanthroline bases

Lanthanide(II) complexes La(B)(acac)(3)] (1-3) and Gd(B)(acac)(3)] (4-6), where B is a N,N-donor phenanthroline base, viz., 1,10-phenanthroline (phen in 1, 4), dipyrido3,2-d:2',3'-f]quinoxaline (dpq in 2, 5) and dipyrido3,2-a:2',3'-c]phenazine (dppz in 3, 6), have been prepared and characterized. The Gd(111) complexes 4 6 are structurally characterized by single crystal X-ray crystallography. The complexes display GdO6N2 coordination with the ligands showing bidentate chelating mode of bonding. The complexes are non-electrolytic in aqueous DMF and exhibit ligand-centered absorption bands in the UV region. The dppz complexes show a band at 380 nm in DMF. The La(111) complexes are diamagnetic. The Gd(III) complexes are paramagnetic with magnetic moment that corresponds to seven unpaired electrons. The Complexes are avid binders to calf thymus DNA giving K-b values in the range of 4.7 x 10(4) 6.1 x 10(5) M-1 with a relative binding order: 3, 6 (dppz) > 2, 5 (dpq) > 1, 4 (phen). The binding data suggest DNA surface and/or groove binding nature of the complexes. The dpq and dppz complexes efficiently cleave SC DNA to its nicked circular form in UV-A light of 365 nm via formation of both singlet oxygen (O-1(2)) and hydroxyl radical (HO center dot) species. The dppz complexes 3 and 6 exhibit significant PDT effect in He La cervical cancer cells giving respective IC50 value of 460(+/- 50) and 530(+/- 30) nM in UV-A light of 365 rim, and are essentially non-toxic in dark with an IC50 value of >100 mu M. The dppz ligand alone is cytotoxic in dark and UV-A light. A significant decrease in the dark toxicity of the dppz base is observed on binding to the Ln(III) ion while retaining its photocytotoxicity.

Impact of metal binding on the antitumor activity and cellular imaging of a metal chelator cationic imidazopyridine derivative

A new water soluble cationic imidazopyridine species, viz. (1E)-1-((pyridin-2-yl)methyleneamino)-3-(3(pyridin-2-yl) imidazo1,5-a]pyridin-2(3H)-yl)propan-2-ol (1), as a metal chelator is prepared as its PF6 salt and characterized. Compound 1 shows fluorescence at 438 nm on excitation at 342 nm in Tris-HCl buffer giving a fluorescence quantum yield (phi) of 0.105 and a life-time of 5.4 ns. Compound 1, as an avid DNA minor groove binder, shows pUC19 DNA cleavage activity in UV-A light of 365 nm forming singlet oxygen species in a type-II pathway. The photonuclease potential of 1 gets enhanced in the presence of Fe2+, Cu2+ or Zn2+. Compound 1 itself displays anticancer activity in HeLa, HepG2 and Jurkat cells with an enhancement on addition of the metal ions. Photodynamic effect of 1 at 365 nm also gets enhanced in the presence of Fe2+ and Zn2+. Fluorescence-based cell cycle analysis shows a significant dead cell population in the sub-G1 phase of the cell cycle suggesting apoptosis via ROS generation. A significant change in the nuclear morphology is observed from Hoechst 33258 and an acridine orange/ethidium bromide (AO/EB) dual nuclear staining suggesting apoptosis in cells when treated with 1 alone or in the presence of the metal ions. Apoptosis is found to be caspase-dependent. Fluorescence imaging to monitor the distribution of 1 in cells shows that 1 in the presence of metal ions accumulates predominantly in the cytoplasm. Enhanced uptake of 1 into the cells within 12 h is observed in the presence of Fe2+ and Zn2+.

A polynomial bound on the number of light cycles in an undirected graph

Let G be an undirected graph with a positive real weight on each edge. It is shown that the number of minimum-weight cycles of G is bounded above by a polynomial in the number of edges of G. A similar bound holds if we wish to count the number of cycles with weight at most a constant multiple of the minimum weight of a cycle of G.

Raman evidence for the superconducting gap and spin-phonon coupling in the superconductor Ca( Fe0.95Co0.05)(2)As-2

Inelastic light scattering studies on a single crystal of electron-doped Ca(Fe0.95Co0.05)(2)As-2 superconductor, covering the tetragonal-to-orthorhombic structural transition as well as the magnetic transition at T-SM similar to 140 K and the superconducting transition temperature T-c similar to 23 K, reveal evidence for superconductivity-induced phonon renormalization. In particular, the phonon mode near 260 cm(-1) shows hardening below T-c, signaling its coupling with the superconducting gap. All three Raman active phonon modes show anomalous temperature dependence between room temperature and T-c, i.e. the phonon frequency decreases with lowering temperature. Further, the frequency of one of the modes shows a sudden change in temperature dependence at TSM. Using first-principles density functional theory based calculations, we show that the low temperature phase (T-c < T < T-SM) exhibits short-ranged stripe antiferromagnetic ordering, and estimate the spin-phonon couplings that are responsible for these phonon anomalies.