Auto-ignition based synthesis of Y2O3 for photo- and thermo-luminescent applications

We present a simple route for synthesis of Y2O3 for both photoluminescent (PL) and thermoluminescent (TL) applications. We show that by simply switching the fuel from ethylene di-amine tetracetic acid (EDTA) to its disodium derivative (Na-2-EDTA), we obtain a better photoluminescent material. On the other hand, use of EDTA aids in formation of Y2O3 which is a better thermoluminescent material. In both cases pure cubic nano-Y2O3 is obtained. For both the material systems, structural characterization, photoluminescence, thermoluminescence, and absorbance spectra are reported and analyzed. Use of EDTA results in nano Y2O3 with crystallite size similar to 10 nm. Crystallinity improves, and crystallite size is larger (similar to 30 nm) when Na-2-EDTA is used. TL response of Y2O3 nanophosphors prepared by both fuels is examined using UV radiation. Samples prepared with EDTA show well resolved glow curve at 140 degrees C, while samples prepared with Na-2-EDTA shows a glow curve at 155 degrees C. Effect of UV exposure time on TL characteristics is investigated. The TL kinetic parameters are also calculated using glow curve shape method. Results indicate that the TL behavior of both the samples follow a second order kinetic model. (C) 2013 Elsevier B.V. All rights reserved.

Plant latex mediated green synthesis of ZnAl2O4:Dy3+ (1-9 mol%) nanophosphor for white light generation

ZnAl2O4:Dy3+ (1-9 mol%) nanophosphors were synthesized by a simple, cost effective and environmental friendly route using Euphorbia tirucalli plant latex. The structural properties and morphological features of the phosphors were well studied by PXRD, FTIR, SEM and TEM measurements. The luminescent properties of ZnAl2O4:Dy3+ (1-9 mol%) nanophosphors were investigated from the excitation and emission spectra. The phosphor performance was evaluated by color co-ordinates. The values were well located in the near white region as a result it was highly useful for the fabrication of green component in WLEDs. The average particle size was found to be similar to 9-18 nm and same was confirmed by TEM and Scherrer's method. The highest photoluminescence (PL) and thermoluminescence (TL) intensity was obtained to be similar to 7 mol% Dy3+ concentration. A single TL glow peak was recorded at 172 degrees C at a warming rate of 2.5 degrees Cs (1). The intensity at 172 degrees C peak increases linearly up to 1 kGy and after that it diminishes. PL intensity was studied with different plant latex concentration (2-8 ml) and highest PL intensity was recorded for similar to 8 ml. The optimized phosphor showed good reusability, low fading and wide range of linearity with gamma-dose hence the phosphor was quite useful in radiation dosimetry. (C) 2013 Elsevier B.V. All rights reserved.

De novo synthesis of 1-deoxythiosugars

A short and efficient chemical synthesis of biologically potent and novel 1-deoxythiosugars is accomplished. Introduction of sulfur mediated by benzyltriethylammonium tetrathiomolybdate, as a sulfur transfer reagent through nucleophilic double displacement of tosylate in alpha,omega-di-O-tosyl aldonolactones in an intramolecular fashion is the key feature. The subsequent reduction of thiosugar lactones with borohydride exchange resin (BER) offers a number of deoxythiosugars in good overall yield. (C) 2013 Elsevier Ltd. All rights reserved.

A catalytic michael/horner-wadsworth-emmons cascade reaction for enantioselective synthesis of thiochromenes

A catalytic enantioselective sulfa-Michael/Horner-Wadsworth-Emmons reaction cascade has been developed, taking advantage of phosphonate as an electrophilic activator and a traceless binding site. Using a chiral bifunctional urea derivative as the catalyst, a variety of aryl and heteroaryl substituted thiochromenes was obtained in excellent yield with a high level of enantioselectivity.

Pd-Catalyzed Cross-Coupling Reactions of Hydrazones: Regioselective Synthesis of Highly Branched Dienes

The regioselective formation of highly branched dienes is a challenging task. Design and exploration of alternative working models to achieve such a regioselectivity to accomplish highly branched dienes is considered to be a historical advancement of Heck reaction to construct branched dienes. On the basis of the utility of carbene transfer reactions, in the reaction of hydrazones with Pd(II) under oxidative conditions, we envisioned obtaining a Pd-bis-carbene complex with alpha-hydrogens, which can lead to branched dienes. Herein, we report a novel Pd-catalyzed selective coupling reaction of hydrazones in the presence of t-BuOLi and benzoquinone to form the corresponding branched dienes. The utility of the Pd catalyst for the cross-coupling reactions for synthesizing branched conjugated dienes is rare. The reaction is very versatile and compatible with a variety of functional groups and is useful in synthesizing heterocyclic molecules. We anticipate that this Pd-catalyzed cross-coupling reaction will open new avenues for synthesizing useful compounds.

On the Mechanism of Phase Transfer Catalysis in Brust-Schiffrin Synthesis of Metal Nanoparticles

The two-phase Brust-Schiffrin method (BSM) is used to synthesize highly stable nanoparticles of noble metals. A phase transfer catalyst (PTC) is used to bring in aqueous phase soluble precursors into the organic phase to enable particle synthesis there. Two different mechanisms for phase transfer are advanced in the literature. The first mechanism considers PTC to bring in an aqueous phase soluble precursor by complexing with it. The second mechanism considers the ionic species to be contained in inverse micelles of PTC, with a water core inside. A comprehensive experimental study involving measurement of interfacial tension, viscosity, water content by Karl-Fischer titration, static light scattering, H-1 NMR, and small-angle X-ray scattering is reported in this work to establish that the phase transfer catalyst tetraoctylammonium bromide transfers ions by complexing with them, instead of encapsulating them in inverse micelles. The findings have implications for particle synthesis in two-phase methods such as BSM and their modification to produce more monodispersed particles.

Regioselective Synthesis of 4-Substituted Indoles via C-H Activation: A Ruthenium Catalyzed Novel Directing Group Strategy

A highly regioselective functionalization of indole at the C-4 position by employing an aldehyde functional group as a directing group, and Ru as a catalyst, under mild reaction conditions (open flask) has been uncovered. This strategy to synthesize 4-substituted indoles is important, as this class of privileged molecules serves as a precursor for ergot alkaloids and related heterocyclic compounds.

Hydrothermal synthesis of Gd2O3:Eu3+ nanophosphors: Effect of surfactant on structural and luminescence properties

Various morphologies of Eu3+ activated gadolinium oxide have been prepared by hydrothermal method using hexadecylamine (HDA) as surfactant at different experimental conditions. The powder X-ray diffraction studies reveal as-formed product is hexagonal Gd(OH)(3):Eu3+ phase and subsequent heat treatment at 350 and 600 degrees C transforms to monoclinic GdOOH:Eu3+ and cubic Gd2O3:Eu3+ phases respectively. SEM pictures of without surfactant show irregular shaped rods along with flakes. However, in the presence of HDA surfactant, the particles are converted into rods of various sizes. The temperature dependent morphological evolution of Gd2O3:Eu3+ without and with HDA surfactant is studied. TEM micrographs of Gd(OH)(3):Eu3+ sample with HDA confirms smooth nanorods with various diameters in the range 20-100 nm. FTIR studies reveal that HDA surfactant plays an important role in conversion of cubic to hexagonal phases. Among these three phases, cubic phase Gd2O3:Eu3+ (lambda(ex) = 254 nm) show red emission at 612 nm corresponding to D-5(0)-> F-7(2) and is more efficient host than the monoclinic counterpart. The band gap for hexagonal Gd(OH)(3):Eu3+ is more when compared to monoclinic GdOOH:Eu3+ and cubic Gd2O3:Eu3+. (C) 2013 Elsevier B. V. All rights reserved.

The exploration of Kemp's triacid (KTA) as the core for the synthesis of 3-fold symmetric 2(3)-cyclophane, 2(2)-cyclophane and novel linker directed designs

For the first time, two units of KTA have been linked to three units of cyst-di-OMe. The reaction is noteworthy since it involves the formation of six amide bonds leading to a three-fold symmetric 23-cyclophane (3) harboring a cluster of three S-S bridges. The major product is a di-imide (4), arising from the interaction of a cystine NH with a neighbouring activated ester. A third reaction of tethering KTA with a single cyst-di-OMe unit afforded the flexible compound 6 and, with benzidine, the novel linker directed 7 with orthogonally disposed anchor modules.

Ring opening of activated cyclopropanes with NIS/NaN3: synthesis of C-1 linked pseudodisaccharides

NIS/NaN3 mediated ring opening of various donor-acceptor cyclopropanes has been investigated. The study shows the necessity of the donor oxygen lone pair in such ring opening reactions. This methodology has been utilized in the synthesis of C-1 linked pseudodisaccharides through the use of click chemistry. (C) 2013 Elsevier Ltd. All rights reserved.

Controlled synthesis of TiO2 nanoparticles and nanospheres using a microwave assisted approach for their application in dye-sensitized solar cells

Rapid and facile synthesis of similar to 7 nm and similar to 100-400 nm nano-structures of anatase titania is achieved by exploiting the chemical nature of solvents through a microwave based approach. After using these nanostructures as a photoanode in dye-sensitized solar cells, a modest yet appreciable efficiency of 6.5% was achieved under the illumination of AM 1.5 G one sun (100 mW cm(-2)).

Polymer Template Assisted Synthesis of Porous Li1.2Mn0.53Ni0.13Co0.13O2 as a High Capacity and High Rate Capability Positive Electrode Material

A porous layered composite of Li2MnO3 and LiMn1/3Co1/3Ni1/3O2 (composition: Li1.2Mn0.53Ni0.13Co0.13O2) is prepared by reverse microemulsion method employing a soft polymer template and studied as a positive electrode material. The precursor is heated at several temperatures between 500 and 900 degrees C. The product samples possess mesoporosity with broadly distributed pores of about 30 nm diameters. There is a decrease in pore volume as well as in surface area by increasing the temperature of preparation. Nevertheless, the electrochemical activity of the composite increases with an increase in temperature. The discharge capacity values of the samples prepared at 800 and 900 degrees C are about 250 mAh g(-1) at a specific current of 40 mA g(-1) with an excellent cycling stability. A value of 225 mAh g(-1) is obtained at the end of 30 charge-discharge cycles. Both these composite samples possess high rate capability, but the 800 degrees C sample is marginally superior to the 900 degrees C sample. A discharge capacity of 100 mAh g(-1) is obtained at a specific current of 1000 mA g(-1). The high rate capability is attributed to porous nature of the composite samples. (C) 2013 The Electrochemical Society. All rights reserved.

Total Synthesis of (+)-Seimatopolide A

Total synthesis of 10-membered lactone (+)-seimatopolide A is presented from furfural. Key reactions in the present strategy include the effective use of furan as a E-but-2-ene-1,4-dione surrogate, Nagao acetate aldol reaction, and Shiina lactonization.

Low temperature synthesis of pure cubic ZrO2 nanopowder: Structural and luminescence studies

Pure cubic zirconia (ZrO2) nanopowder is prepared for the first time by simple low temperature solution combustion method without calcination. The product is characterized by Powder X-ray Diffraction (PXRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Fourier Transform Infra Red spectroscopy (FTIR) and Ultraviolet-Visible spectroscopy (UV-Vis). The PXRD showed the formation of pure stable cubic ZrO2 nanopowders with average crystallite size ranging from 6 to 12 nm. The lattice parameters were calculated from Rietveld refinement method. SEM micrograph shows fluffy, mesoporous, agglomerated particles with large number of voids. TEM micrograph shows honey comb like arrangement of particles with particle size similar to 10 nm. The PL emission spectrum excited at 210 nm and 240 nm consists of intense bands centered at similar to 365 and similar to 390 nm. Both the samples show shoulder peak at 420 nm, along with four weak emission bands at similar to 484, similar to 528, similar to 614 and similar to 726 nm. TL studies were carried out pre-irradiating samples with gamma-rays ranging from 1 to 5 KGy at room temperature. A well resolved glow peak at 377 degrees C is recorded which can be ascribed to deep traps. With increase in gamma radiation there is linear increase in TL intensity which shows the possible use of ZrO2 as dosimetric material. (C) 2013 Elsevier B.V. All rights reserved.

A room temperature, templated synthesis of lanthanide trifluoride nanoparticles and their unusual self-assembly

A new methodology has been developed for synthesizing lanthanide trifluoride (LnF(3)) nanoparticles using a simple diffusion technique. The approach uses a lanthanide based hydrogel matrix to control the kinetics of the reaction, which also acts as a stabilizing platform, thus enabling the room temperature, in situ synthesis of finely sized (3-5 nm), monodisperse nanoparticles that were found to form in an ordered pattern on the gel fibers.