Novel reduction (Zn-AcOH) of DDHQ esters - A new route to tropone synthesis

Zn/acetic acid reaction of DDHQ esters 1 a-d gave the saturated acids 3 a-d and the hydrocarbons 7 a-d. The intermediacy of the aldehydes 10 and 11 in the formation of the products has been established. Oxidation of hydrocarbons 7a and 7b gave the corresponding tropones (5a and 5b).

Crystal growth and defects characterization of zinc tris (thiourea) sulfate: a novel metalorganic nonlinear optical crystal

Single crystals of the metalorganic nonlinear optical material zinc tris (thiourea) sulfate (ZTS) were grown from aqueous solution. The morphology of the crystals was indexed. The grown crystals were characterized by recording the powder X-ray diffraction pattern and by identifying the diffracting planes. Spectrophotometric studies on ZTS reveal that it has good transparency for the Nd: YAG laser fundamental wavelength. Differential thermal analysis of ZTS indicates that the material does not sublime before melting but decomposes immediately after melting. The defect content of the crystals was estimated using etching and X-ray topography. The mechanical hardness anisotropy was evaluated in the (100) plane, which indicates the presence of soft directions.

Stabilisation of unusual simultaneous binding of four cytosine nucleobases to copper(II) by a novel network of bifurcated hydrogen bonding

The crystal structure of tetrakis(cytosine)copper(II) perchlorate dihydrate has been determined. All the hydrogen atoms were obtained from Fourier-difference synthesis. The geometry around. copper is a bicapped octahedron (4 + 2 + 2*). The adjacent cytosine rings are oriented head-to-tail with respect to each other and are roughly at right angles to the co-ordination plane. The exocyclic oxo groups form an interligand, intracomplex hydrogen-bonding network above and below the co-ordination plane with the exocyclic amino groups of alternate cytosine bases. The EPR and electronic spectra are consistent with the retention of the solid-state structure in solution. The steric effect of the C(2)=O group of cytosine is offset by the presence of the intracomplex hydrogen-bonding network. The trend in Ei values of Cu-II-Cu-I couples for 1.4 complexes of cytosine, cytodine, pyridine, 2-methylpyridine and N-methylimidazole suggests that both steric effects and pi-delocalization in imidazole and pyridine ligands and the steric effect of C(2)=O in pyrimidine ligands are important in stabilising Cu-I relative to Cu-II.

Synthetic Studies Towards Prismanes - Rearrangements In Some Pentacyclic Precursors And X-Ray Crystal-Structure Of A Novel Heptacyclic Ether

In order to gain access to the heptacyclic tetraone 3, efforts were directed towards the utilisation of the major 'unwanted' [4 + 2]-adduct 11 of tetrachlorodimethoxycyclopentadiene and norbornenobenzoquinone. Epoxides derived from the diol and dimethoxy derivatives of the adduct 11 undergo facile Wagner-Meerwein rearrangement resulting in the required endo, syn, endo stereochemistry as well as methano-bridge functionalisation to deliver 18 and 24, respectively. However, intramolecular ether formation, occurring via the capture of carbocation intermediate with the transannularly poised oxygen functionality, is a more facile process. Attempts to cleave the ether linkage resulted in the formation of a novel transannularly cyclised twisted bowl shape heptacyclic compound 30 and its structure has been established through X-ray crystallography.

A novel zinc bis(thiosemicarbazone) complex for live cell imaging

Fluorescent zinc complexes have recently attracted a lot of interest owing to their vast applications in cellular imaging. We report the synthesis as well as physical, chemical and biological studies of a novel zinc glyoxalbis(4-methyl-4-phenyl-3-thiosemicarbazone), Zn (GTSC)](3), complex. As compared with the well-studied zinc biacetylbis(4-methyl-3-thiosemicarbazone), Zn(ATSM), complex, which was used as a reference, Zn(GTSC)](3) had 2.5-fold higher fluorescence. When cellular fluorescence was measured using flow cytometry, we observed that Zn(GTSC)](3) had 3.4-fold to 12-fold higher fluorescence than Zn(ATSM) in various cell lines (n = 9) of different tissue origin. Confocal fluorescence microscopy results showed that Zn(GTSC)](3) appeared to have a nuclear localization within 30 mm of addition to MCF7 cells. Moreover, Zn(GTSC)](3) showed minimal cytotoxicity compared with Zn(ATSM), suggesting that Zn(GTSC)](3) may be less deleterious to cells when used as an imaging agent. Our data suggest that the novel Zn(GTSC)](3) complex can potentially serve as a biocompatible fluorescent imaging agent for live cells.

Organic Additive-Mediated Synthesis of Novel Cobalt(II) Hydroxides

Electrochemical precipitation of cobalt(II) hydroxide from nitrate solutions containing organic molecules, such as glucose, fructose, lactose, glycerol, and citric acid, yields a new modification of cobalt (II) hydroxide (a = 3.09 +/- 0.03 Angstrom, c = 23.34 +/- 0.36 Angstrom) that is isostructural with cu-nickel hydroxide; precipitation in the absence of organic additives gives the stable, brucite-like, beta-CO (OH)(2). (C) 1995 Academic Press, Inc.

ChemInform Abstract: Slicing the Perovskite Structure into Layers: Synthesis of Novel Three- Dimensional and Layered Perovskite Oxides, ALaSrNb2M(II)O9 (A: Na, Cs)

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SrB4O7:Bi2VO5.5 - A novel nanocomposite

Glass composites of strontium tetraborate, SrB4O7 (SBO) with bismuth vanadate, Bi2VO5.5 (BiV) of the composition (1-x) SBO-x BN (0 less than or equal to x less than or equal to 0.75), have been synthesized. X-ray powder diffraction and electron microscopy indicate as-quenched composites to be amorphous and the annealed samples showed the presence of nanometer sized particles of BN dispersed in the glassy matrix of SBO. The dielectric constant of these composites increases with increase in the volume fraction of BiV, at 300 K. The measured dielectric constant of the composite very nearly obeys the Maxwell's relationship. Optical transmission studies confirm a steady shirt in the optical absorption edge towards longer wavelengths with increase in x

Structural and Dielectric-Properties Of A Novel BI2O3-(1-X)WO3-XCUO Solid-Solution

A novel solid solution in the system Bi-W-Cu-O has been synthesized and its structural and dielectric properties studied. The solid solution Bi2O3-(1-x)WO3-xCuO exists up to x = 0.7; the solid solutions up to x = 0.65 are orthorhombic but stabilize in tetragonal structure in a narrow range around x = 0.7. The solid solutions are non-centrosymmetric and exhibit ferroelectric behaviour similar to their parent phase Bi2WO6. The Curie point of the solid solution is found to decrease with increase in x.

Novel Metastable Structures of WO3, MoO3 and W1-xMoxO3 Obtained by the Deintercalation of Layered Amine Adducts

Deintercalation of amines from the layered amine adducts of WO3, MoO3 and W1-xMoxO3 has been employed as a soft chemical route to produce unusual metastable structures of the oxides. After the adducts of WO3, MoO3 and W1-xMoxO3 (x = 0.25, 0.5, 0.75) with amines such as triethylamine (TEA), pyridine, n-butylamine and n-octylamine had been characterized, deintercalation was carried out thermally as well as by acid leaching. Thermal deintercalation yielded novel metastable structures of WO3 and MoO3 that were significantly different from the stable forms, which contain distorted metal-oxygen octahedra. Thus, ReO3-type cubic WO3 was obtained by the thermal deintercalation of WO3 . 0.5 TEA. Acid leaching of the amines gave metastable phases of WO3, MoO3 and W1-xMoxO3, which were different from those obtained thermally. All the metastable phases transformed to the corresponding stable forms at higher temperatures.

Novel materials synthesis by mechanical alloying/milling

An account is given of the research that has been carried out on mechanical alloying/milling (MA/MM) during the past 25 years. Mechanical alloying, a high energy ball milling process, has established itself as a viable solid state processing route for the synthesis of a variety of equilibrium and non-equilibrium phases and phase mixtures. The process was initially invented for the production of oxide dispersion strengthened (ODS) Ni-base superalloys and later extended to other ODS alloys. The success of MA in producing ODS alloys with better high temperature capabilities in comparison with other processing routes is highlighted. Mechanical alloying has also been successfully used for extending terminal solid solubilities in many commercially important metallic systems. Many high melting intermetallics that are difficult to prepare by conventional processing techniques could be easily synthesised with homogeneous structure and composition by MA. It has also, over the years, proved itself to be superior to rapid solidification processing as a non-equilibrium processing tool. The considerable literature on the synthesis of amorphous, quasicrystalline, and nanocrystalline materials by MA is critically reviewed. The possibility of achieving solid solubility in liquid immiscible systems has made MA a unique process. Reactive milling has opened new avenues for the solid state metallothermic reduction and for the synthesis of nanocrystalline intermetallics and intermetallic matrix composites. Despite numerous efforts, understanding of the process of MA, being far from equilibrium, is far from complete, leaving large scope for further research in this exciting field.

A novel structural derivative of natural alkaloid ellipticine, MDPSQ, induces necrosis in leukemic cells

DNA intercalating molecules are promising chemotherapeutic agents. In the present study, a novel DNA intercalating compound of pyrimido4',5':4,5]selenolo(2,3-b)quinoline series having 8-methyl-4-(3 diethylaminopropylamino) side chain is studied for its chemotherapeutic properties. Our results showed that 8-methyl-4-(3 diethylaminopropylamino) pyrimido 4',5':4,5] selenolo(2,3-b)quinoline (MDPSQ) induces cytotoxicity in a time- and concentration-dependent manner on leukemic cell lines. Both cell cycle analysis and tritiated thymidine assays revealed that MDPSQ affects DNA replication. Treatment with MDPSQ resulted in both elevated levels of DNA strand breaks and repair proteins, further indicating its cytotoxic effects. Besides, Annexin V/PI staining revealed that MDPSQ induces cell death by triggering necrosis rather than apoptosis.