Comparison of structural and luminescence properties of Dy2O3 nanopowders synthesized by co-precipitation and green combustion routes

Dysprosium oxide (Dy2O3) nanopowders were prepared by co-precipitation (CP) and eco-friendly green combustion (GC) routes. SEM micrographs prepared by CP route show smooth rods with various lengths and diameters while, GC route show porous, agglomerated particles. The results were further confirmed by TEM. Thermoluminescence (TL) responses of the nanopowder prepared by both the routes were studied using gamma-rays. A well resolved glow peak at 353 degrees C along with less intense peak at 183 degrees C was observed in GC route while, in CP a single glow peak at 364 degrees C was observed. The kinetic parameters were estimated using Chen's glow peak route. Photoluminescence (PL) of Dy2O3 shows peaks at 481, 577,666 and 756 nm which were attributed to Dy3+ transitions of F-4(9/2)-H-6(15/2), H-6(11/2), H-6(11/2) and H-6(9/2), respectively. Color co-ordinate values were located in the white region as a result the product may be useful for the fabrication of WLED'S. (C) 2014 Elsevier Ltd. All rights reserved.

Inferring biochemical routes from biochemical networks

Metabolism is a defining feature of life, and its study is important to understand how a cell works, alterations that lead to disease and for applications in drug discovery. From a systems perspective, metabolism can be represented as a network that captures all the metabolites as nodes and the inter-conversions among pairs of them as edges. Such an abstraction enables the networks to be studied by applying graph theory, particularly, to infer the flow of chemical information in the networks by identifying relevant metabolic pathways. In this study, different weighting schemes are used to illustrate that appropriately weighted networks can capture the quantitative cellular dynamics quite accurately. Thus, the networks now combine the elegance and simplicity of representation of the system and ease of analysing metabolic graphs. Metabolic routes or paths determined by this therefore are likely to be more biologically meaningful. The usefulness of the approach is demonstrated with two examples, first for understanding bacterial stress response and second for studying metabolic alterations that occurs in cancer cells.

USEFUL EXTENSIONS OF THE HENRY REACTION: EXPEDITIOUS ROUTES TO NITROALKANES AND NITROALKENES IN AQUEOUS MEDIA

The products of the Henry nitroaldol reaction from nitromethane and several aldehydes were reduced to the corresponding nitroalkanes with (n-Bu)(3)SnH in water under microwave irradiation (80 degrees C/10 min), or dehydrated to the corresponding nitroalkenes with K2CO3 in water (generally 0-5 degrees C/20 min). Both ``one-pot'' reactions occur in excellent yields across a range of aliphatic and aromatic (including heteroaromatic) substrates. It seems likely that the deoxygenation of the nitroaldols occurs via coordination of an oxygen atom of the nitro group with a tin atom, which facilitates hydride delivery in the transition state. The elimination of water from the nitroaldols in mild base is likely driven by the stability of the conjugated nitroalkene products. The elimination required workup with 2N HCl, which likely displaces a nitroalkane-nitroalkene equilibrium towards the latter. These extensions of the Henry reaction lead to products not easily obtained otherwise.

Understanding Self-Segregation of Immiscible Peripheral Segments in Pseudodendritic Hyperbranched Polydithioacetals: Formation of Improved Janus Structures

Peripherally heterofunctionalized hyperbranched polymers (HBPs) undergo immiscibility-driven self-segregation of the outer segments to form Janus molecular entities (Macromolecules 2012, 45, 2348). In HBPs prepared via AB2 type self-condensation, single-step peripheral heterofunctionalization would lead to random distribution of the two types of terminal units, namely, homofunctionalized (homo-T) and heterofunctionalized (hetero-T) termini. Here, we examine the role of such hetero-T units on the self-segregation of heterofunctionalized pseudodendritic hyperbranched polydithioacetals. Three different heterofunctionalized HB dithioacetals bearing roughly 50 mol % each of docsyl (C-22) and MPEG-350 chains at the periphery were prepared: one of them carried a statistical distribution of homo-T and hetero-T units, and the other carried only two types of homo-T (-TR1R1 and -TR2R2) termini, whereas the third carried largely hetero-T (-TR1R2) termini. Careful examination of DSC and SAXS data reveals that the self-segregation is most effective in HBPs devoid of hetero-T units; interestingly, however, it also showed that randomly heterofunctionalized HBPs self-segregated nearly as effectively.

Depalladation of Neutral Monoalkyne- and Dialkyne-Inserted Palladacycles and Alkyne Insertion/Depalladation Reactions of Cationic Palladacycles Derived from N,N `,N `'-Triarylguanidines as Facile Routes for Guanidine-Containing Heterocycles/Carbocycles: Synthetic, Structural, and Mechanistic Aspects

Depalladation of the monoalkyne-inserted cyclopalldated guanidines (kappa 2(C,N)Pd(2,6-Me2C5H3N)Br] (I and II) in PhCl under reflux conditions and that of the dialkyne-inserted cyclopalladated guanidine kappa(2)(C,N):eta(2)(C=C)PdBr] (III) in pyridine under reflux conditions afforded a guanidine-containing indole (1), imidaziondole (2), and benzazepine (3) in 80%, 67%, and 76%, yields, respectively. trans-L2PdBr2] species (L = 2,6-Me2C5H3N, C5H5N) were also isolated in the aforementioned reactions in 35%, 42%, and 40% yields. Further , the reaction of the cyclopalladated guanidine kappa(2)(C,N)Pd(mu-Br)](2) (IV) with AgBF4 in a CH2Cl2/MeCN mixture afforded the cationic pincer type cyclopalladated guanidine kappa(3)(C,N,O)Pd(MeCN)]BF4] (4) in 85% yield and this palladacycle upon crystallization in MeCN and the reaction of kappa(2)(C,N)Pd(mu-Br)](2) (V) with AgBf(4) in a CH2Cl2/MeCN mixture afforded the cationic palladacycles {kappa(2)(C,N)Pd(MeCN)(2)]BF4](5 and 6) in 89% and 91% yields, respectively. The separate reactions of 4 with 2 equiv of methyl phenylpropiolate (MPP) or diphenylacetylene (DPA) and the reaction of 5 with 2 equiv of MPP in PhCl at 110 degrees C afforded the guanidine-containing quinazolinium tetrafluoroborate 7 in 25-32% yields. The reaction of 6 with 2 equiv of DPA under otherwise identical conditions afforded the unsymmetrically substituted guanidinium tetrafluoroborate 8, containing a highly substituted naphthalene unit, in 82% yield. Compounds 1-8 were characterized by analytical and spectroscopic techniques, and all compounds except 4 were characterized by single-crystal X-ray diffraction. The Molecular structure of 2 and 3 are nove, as the framework in the former arises due to the formation of two C-N bonds upon depalladation while the butadienyl unit in the latter revealed cis,cis stereochemistry, a-feature unprecedented in alkyne insertion chemistry. Plausible pathways for the formation of heterocycles/carbocycles are proposed. the influence of substitutents on the aryl rings fo the cyclopalladated guanidine moiety and those on alkynes upon the nature of the products in addressed. Heterocycles 1 and 7 revealed the presence of two rotamers in about a 1.00:0.43 ratio in CDCl3 and in about a 1.00:0.14 ratio in CD3OD, respectively, as detected by H-1 NMR spectroscopy while in CD3CN and DMSO-d(6) (1) and CD3CN and CDCl3 (7), these heterocycles revealed the presence of a single rotamer. These spectral features are attributed to the restricted C-N single-bond rotation of the CN3 unit of the guanidine moiety, which possibly arises from steric constraint due to the formation of a N-H center dot center dot center dot Cl hydrogen bond with CDCl3 (1) and N-H center dot center dot center dot O and O-D center dot center dot center dot O hydrogen bonds with CD3OD (7).