• Volume 119, Issue 3

May 2007,   pages  219-274

• Engineering macrocyclic figure-eight motif

The design and synthesis of figure-eight macrocycles are very scarce owing to the intricacies and lack of predictability from first principles. This review emphasizes on discrete macrocyclic systems both synthetic and natural with a defined figure eight knotted topology. In almost all the helical macrocycles, the helical arrangement is held by intramolecular hydrogen bonding or as a backbone requirement, but in all cases, a planar graph can be drawn and so these compounds are trivial from the topological stand point. Nature presents great deal of complexity in terms of structures in macromolecules like DNA and proteins and also displays intriguing topology in simple natural products. Patellamide, tawicyclamides, nosiheptide and thiostrepton are natural products with figure eight topology which shows interesting biological activity. Expanded porphyrins, Cu(II) complexes of thiomacrocycles, cyclic peptides and oligoesters are synthetic macrocycles showing intriguing topology. Analysis of structure and folding behaviour will enable chemists to design molecules with intriguing topology.

• Luminescence quenching of Ru(phen)$^{2+}_3$ by some polymer-cobalt(III) complexes - Effect of micelles and DNA

Studies on the luminescence quenching of Ru(phen)$^{2+}_3$ (phen = 1,10-phenanthroline) by the polymer-cobalt(III) complex ions, cis-[Co(phen)2(BPEI)Cl]2+ and cis-[Co(bpy)2(BPEI)Cl]2+ (bpy = 2,2'-bipyridine, BPEI = branched polyethyleneimine) in DNA as well as in various micellar media by steadystate emission spectroscopic technique have been reported. The quenching rate constants were arrived through Stern-Volmer equation. The results have been analysed based on hydrophobic as well as electrostatic binding between polymer-cobalt(III) complexes and DNA/micelles.

• Combustion synthesis and characterization of porous perovskite catalysts

Porous perovskite-type complex oxides LaCoO3 and La0.95Sr0.05Ni0.05Co0.95O3 were produced by combustion method. The properties of these porous materials such as crystal structures, particle sizes, surface patterns, pore size, surface area and pore volume were characterized by X-ray diffraction( XRD), scanning electron microscopy(SEM) and BET measurements. The results indicated that all porous materials are of the perovskite-type complex oxides. Doping Sr2+ ions on site A and doping Ni2+ ions on site B entered the crystal lattices of LaCoO3 in the place of La3+ and Co3+, respectively, and the maximum peak of XRD patterns of doping sample was weaken and broaden. Morphological microscopy demonstrated agglomerates involved mostly thin smooth flakes and layers perforated by a large number of pores and its lamella decreased with the introduction of Sr2+ and Ni2+. Hysteresis loop in the N2 adsorption-desorption isotherm of samples indicated its porous structures and the doping effect on its pore size, surface area and pore volume were improved. The porous catalysts have been tested for methane catalytic combustion and the results showed that these catalysts possessed high catalytic activity.

• Synthesis, spectroscopy and supramolecular structures of two magnesium 4-nitrobenzoate complexes

The aqueous reaction of [Mg(H2O)6]Cl2 with the in situ generated sodium salt of 4-nitrobenzoic acid (4-nbaH) and N-methylimidazole (N-MeIm) results in the formation of the dinuclear complex [Mg(H2O)(N-MeIm)2(4-nba)2]2 1 (4-nba = 4-nitro benzoate), while the direct reaction of [Mg(H2O)6]Cl2 with sodium 4-nba leads to the formation of the mononuclear complex, [Mg(H2O)6](4-nba)2.2H2O 2. In the centrosymmetric dimer 1, each Mg atom is coordinated to an aquo ligand, two monodentate N-MeIm ligands and a monodentate 4-nba ligand. The second 4-nba ligand functions as a bridging bidentate ligand, linking the metal centers and completes the hexacoordination around each Mg(II). The dimeric molecules of 1 are linked into a one-dimensional chain along 𝑏 with the aid of intra- as well as intermolecular H-bonding interactions between the coordinated water and the free oxygen atom of the monodentate 4-nba ligand. In the mononuclear complex [Mg(H2O)6](4-nba)2.2H2O 2, the Mg(II) is located on an inversion center and its structure consists of an octahedral [Mg(H2O)6]2+ dication, a free uncoordinated 4-nba anion and a lattice water molecule. One of the H atoms attached of the lattice water is disordered over two positions. The hexaaquomagnesium(II) dication, the 4-nba anion and the lattice water molecule are linked by intra- and intermolecular H-bonding interactions resulting in the formation of alternating layers of [Mg(H2O)6]2+ dications and 4-nba anions in the crystallographic $bc$ plane. The lattice water molecules are situated between the cations, while the 4-nba anions are arranged antiparallel to each other along 𝑏.

• Isomerization of 𝛽-carotene by titanium tetrachloride catalyst

Isomerization of all-trans-𝛽-carotene occurs during shaking with 0.5% of titanium tetrachloride catalyst in methylene chloride at room temperature. In the present study we compared two types of columns C18 and C30 and various solvent systems for the separation of 𝛽-carotene and its cis isomers by high performance liquid chromatography (HPLC). Results showed that 𝛽-carotene isomers were resolved by employing a C30 column with a mobile phase of methanol (100%) (A) and methylene chloride (100%) (B) under a gradient elution condition. A total of eleven cis isomers and one all-trans-𝛽-carotene isomer were resolved within 50 min at a flow rate of 1 ml/min and detection wave-length of 470 nm.

• New amidines from intramolecular cyclization in triflic acid of nitroketene aminals with a tethered phenyl ring

Nitroketene aminals with a tethered phenyl group underwent an intramolecular cyclization in trifluoromethanesulfonic acid to afford the corresponding N-(3-ethyl-hydrohydroxyiminobenzocycloalkenylidene) methylamine trifluoromethanesulfonate. The yields were fair to good excepted for the starting compound 1-[N-ethyl-N-(2-phenylethyl)amino]-1-methylamino-2-nitroethene.

• Electrooxidation of carbo/thiocarbohydrazide and their hydrazone derivatives at a glassy carbon electrode

Electrochemical oxidation of thio/carbohydrazide and their hydrazone derivatives Benzaldehyde thiocarbohydrazone [BTCH] diacetylene thiocarbohydrazone [DATCH] have been studied in Britton Robinson buffer in aqueous and nonaqueous media at a glassy carbon electrode. The effects of pH, sweep rate, concentration, temperature and surfactants have been studied. The complex bis (carbo/thiocabohydrazide) Zn(II) chloride was also subjected to voltammetric analysis in order to understand the reactivity both in free and metal bound states. The reaction conditions were optimized for the determination of above compounds in micrograms quantities by differential pulse voltammetry, analytical utility of this investigation is also highlighted.

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