Phase equilibria and crystal chemical relations in copper-nickel-selenium system

Phase equilibria in the copper-nickel-selenium system has been investigated using x-ray diffraction and scanning electron microscopy. Ternary isotherms at 703 and 573 K show interesting differences. In the Cu-Se system, Cu₃Se₂, CuSe, and CuSe₂ phases decompose at higher temperatures. Only two phases viz., Cu_2-xSe and Cu₂Se are stable at 703 K. Solid solubility of nickel in these stable phases is ≈2 at %. Tetragonal Ni₃Se₂ phase has a solid solubility of about 8 at % copper in the ternary system. At 573 K, NiSe phase dissolves ≈5 at % copper. Rapid quenching of alloys on the Cu₂Se-Ni₃Se₂ quasi-binary section resulted no change in crystal structure. Phase relations and crystal chemistry of the system has been discussed in detail.     

Products active on arthropod—5 : Insect juvenile hormone mimics: sesquiterpene acids having jh activity from the wood of cedrus deodara loud

Juvenile hormone activity of the wood of Cedrus deodara is due to Δ¹⁰-dehydroepitodomatuic acid (6) and two new related compounds characterised as Δ⁷-dehydrotodomatuic acid (8) and 7-hydroxytodomatuic acid (13). Besides these, minor amounts of limonene-8-carboxylic acid, geronic acid, and 4-acetylcyclohex-l-ene-l-carboxylic acid were isolated.     

Resolution of optical systems involving smoothened blanks in white light

Different smoothened blanks have been studied in partially coherent white light illumination to assess the possible maximum resolutions that can be obtained. The object can be placed either in contact with the diffuser or can be imaged onto the diffuser. Lower resolution is obtained in the latter case, which could be good enough for many practical requirements.     

Ring closure of diethyl 2-methoxy-2-[N-(5-amino-1-benzylimidazolyl-4-carbonyl)amino]malonate: Product structures and pathways of product formation

Ring closure of the title compound (1) with sodium methoxide in methanol yielded three products, one 56-fused and two 57-fused heterocyclic systems: 9-benzyl-2-methoxycarbonylhypoxanthine (2), 3-benzyl-4,5,7,8-tetrahydro-6-methoxy-6-methoxycarbonyl-6H-imidazo[4,5-e][1,4]-diazepine-5,8-dione (3), and 3-benzyl-4,5,7,8-tetrahydro-6-methoxy-6H-imidazo[4,5-e][1,4]-diazepine-5,8-dione (4). Structures and pathways of formation of all three products have been described. Structures of2 and3 were confirmed by single-crystal X-ray diffraction analyses.     

Chlorine substitution promotes phenyl radical loss from C8‐phenoxy‐2′‐deoxyguanosine adducts: implications for biomarker identification from chlorophenol exposure

Chlorophenols are persistent organic pollutants, which undergo peroxidase‐mediated oxidation to afford phenolic radical intermediates that react at the C8‐site of 2′‐deoxyguanosine (dG) to generate oxygen‐linked C8‐dG adducts. Such adducts are expected to contribute to chlorophenol toxicity and serve as effective dose biomarkers for chlorophenol exposure. Electrospray ionization mass spectrometry (ESI‐MS) was employed to study collision induced dissociation (CID) for a family of such phenolic O‐linked C8‐dG adducts. Fragmentation of the deprotonated nucleosides demonstrates that an unexpected homolytic cleavage of the ether linkage to release phenyl radicals and a nucleoside distonic ion with m/z 281 competes effectively with commonly observed breakage of the glycosidic bond to release the deprotonated nucleobase. Increased chlorination of the phenyl ring enhances phenyl radical loss. Density functional theory calculations demonstrate that Cl‐substitution decreases phenyl radical stability but promotes homolytic breakage of the C8–phenyl bond in the C8‐dG adduct. The calculations suggest that phenyl radical loss is driven by destabilizing steric (electrostatic repulsion) interactions between the ether oxygen atom and ortho‐chlorines on the phenyl ring. The distonic ion at m/z 281 represents a unique dissociation product for deprotonated O‐linked C8‐dG adducts and may prove useful for selective detection of relevant biomarkers for chlorophenol exposure by tandem mass spectrometry using selective reaction monitoring. Copyright © 2015 John Wiley & Sons, Ltd.     

Cyanoacetaldehyde as a building block for prebiotic formation of pyrimidines

The present study uses density functional theory to investigate the possible free radical pathways for cytosine and uracil formation from cyanoacetaldehyde in the presence of urea and ammonia. Our proposed mechanisms are characterized by a smaller number of precursors and relatively lower barriers compared to previously reported reactions with other prebiotic precursors. Thus, the proposed mechanisms are more plausible in environments like prebiotic earth and present-day Titan. Overall, this study suggests a kinetically accessible route to pyrimidine formation and will hopefully contribute toward understanding the relevance of these precursors in prebiotic reactions.     

Recent infrared detector technologies,applications, trends and development of HgCdTe based cooled infrared focal plane arrays and their characterization

Infrared thermal imaging, using cooled and uncooled detectors, is continuously gaining attention because of its wide military and civilian applications. Futuristic requirements of high temperature operation, multispectral imaging, lower cost, higher resolution (using pixels) etc. are driving continuous developments in the field. Although there are good reviews in the literature by Rogalski [1–4], Martyniuk et al. [5] and Rogalski et al. [6] on various types of infrared detectors and technologies, this paper focuses on some of the important recent trends and diverse applications in this field and discusses some important fundamentals of these detectors.     

Viscosities of Binary Liquid Mixtures of 2-Methylpropane Nitrile and Some Aromatic Hydrocarbons at 303.15 K and 308.15 K

Viscosities, ??, of five binary mixtures of 2-methylpropane nitrile with aromatic hydrocarbons, viz. benzene, methylbenzene, 1,4-dimethylbenzene, chlorobenzene and 1,2-dichlorobenzene, have been measured at temperatures 303.15 and 308.15?K. Deviations in viscosities, ????, from the linear mixing rule have been determined for all of the binary mixtures studied at both experimental temperatures. The ???? values are negative for all the five systems at both experimental temperatures. Parameters of the Redlich?CKister and Myers and Scott equations have been fitted to the ???? values and standard deviations, ??(????), have also been evaluated. The correlating performances of several viscosity models have been evaluated. The Hind?CMcLaughlin?CUbbelohde viscosity model gives fairly constant interaction parameters with composition. Results are discussed in terms of unlike molecular interactions between the components of the binary mixtures.     

Reactions of ring-expanded xanthines containing the imidazo[4,5-e][1,4]diazepine ring system

4,5,7,8-Tetrahydro-6H-imidazo[4,5-e][1,4]diazepine-5,8-dione underwent bromination at the 2-position with or without substituents at the 3-, 4- or 7-position, using bromine, N-bromosuccinimide, or acetyl hypobro-mite. The activation of position 6 with an ester functionality, as in 7 , did not alter the site of bromination. The base-catalyzed bromination of the ring-open precursor, diethyl 2-[N-(1-benzyl-5-nitroimidazolyl-4-carbon-yl)amino]malonate ( 5 ), resulted either in introduction of an alkoxy functionality in the above aminomalonate side-chain, yielding 17 when the reaction was quenched with an alcohol, or in degradation of the side-chain, yielding 1-benzyl-5-nitroimidazole-4-carboxamide ( 19 ) when the reaction was quenched with water. Both 17 and 19 are formed by oxidative bromination of 5 via the bromo intermediate 15 . An indirect evidence for the latter was obtained by base-catalyzed methylation of 5 which gave diethyl 2-methyl-2-[N-(1-benzyl-5-nitroimid-azolyl-4-carbonyl)amino]malonate ( 21 ). The base-catalyzed bromination of 5 with N-bromosuccinimide gave rise to two products, the dimer 24a and the monomer 24b that contained the substituted 2,2-diaminomalon-ate side-chain. The structure of 24b was confirmed by single-crystal X-ray diffraction analyses. Reduction of the 5-nitro group of 17 to the corresponding amino derivative 25 , followed by ring-closure with sodium meth-oxide/methanol, yielded three products, a 5:6-fused system 26 and two 5:7 fused systems 27 and 28 . The structures of 26 and 27 were confirmed by single-crystal X-ray diffraction analyses. A tentative reaction pathway for the formation of all three products has been proposed. Hydrolysis of 27 with aqueous hydrochloric acid resulted in ring-opening to form 5-amino-1-benzylimidazole-4-carboxamide ( 40 ). A mechanism for the hydrolysis reaction has been proposed. Catalytic hydrogenation of 5 in acetic acid yielded the aminoimidazo-lone derivative 11 which upon ring-closure with sodium methoxide in methanol produced imidazo[4,5-e][1,4]-diazepine-2,5,8-trione ( 12 ).