Studies on binuclear hydroxo/carboxylato-bridged manganese(III) complexes and a mononuclear manganese(III) complex involving salen type ligands

Synthesis of six hydroxo-bridged binuclear manganese(III) complexes of formulae [MnL-X-MnL](ClO₄) [X = OH (1–6)] along with a mononuclear manganese(III) complex (7) [Mn(L)(L′)(MeOH)₂] [HL′ = 2-(2-hydroxy-phen-yl)benzimidazole] and two carboxylate-bridged binuclear manganese(III) complexes (8) and (9) are described. The complexes have been characterized by the combination of i.r., u.v.-vis spectroscopy, magnetic moments and by their redox properties. The electronic spectra of all the complexes exhibit almost identical features consisting of two d–d bands at ca. 550 and 600 nm, one MLCT band at ca.400 nm, together with two π–π^* intra-ligand transitions at ca. 250 nm and ca.300 nm. Room temperature magnetic data range from μ = 2.7–3.0 BM indicates some super-exchange between the binuclear metal centers via bridging hydroxo/carboxylato groups. The X-ray crystal structure of the binuclear complex (5) revealed that it has a symmetric Mn^IIIN₂O₂ core bridged by a hydroxyl group. The X-ray analysis of the mononuclear complex (7) showed that the manganese-center possesses a distorted octahedral geometry. Electrochemical properties of hydroxo-bridged manganese(III) complexes (1–6) show identical features consisting of an irreversible and a quasi-reversible reduction corresponding to the Mn₂^III → Mn^IIMn^III → Mn^IIMn^II couples in the voltammogram. It was found that electron withdrawing substituents on the ligand result in easier reduction. Complex (7) displays an irreversible reduction at 0.08 V and a reversible oxidation at 0.45V assignable to the Mn^III → Mn^II reduction and Mn^III → Mn^IV oxidation, respectively. The carboxylate-bridged compound (8) exhibits two irreversible oxidations at 0.4 and 0.6 V, probably due to Mn₂^III → Mn^IIIMn^IV → Mn^IVMn^IV oxidations and shows a quasi-reversible reductive wave at −0.85 V, tentatively assigned to Mn₂^III → Mn^IIMn^III reduction.     

A single amino acid Gly-tag enables metal-free protein purification

Analytically pure proteins are indispensable for diverse applications, including therapeutics. Here, we report a methodology where a single amino acid, glycine, enables metal-free protein purification. This robust platform is enabled by a Gly-tag resin for site-specific capture, enrichment, and release through chemically triggered C–C bond dissociation by resonance-assisted electron density polarization.

Gly-tag resin precisely captures and releases a protein with one glycine at the N-terminus. The user-friendly protocol delivers analytically pure protein free of metal contaminants.     

Reaction of 3,6-diphenyl-1,2,4,5-tetrazine with cis,cis-1,5-cyclooctadiene : An attempt at preparing some dihydropyridazine derivatives

The reaction of 3,6-diphenyl-1,2,4,5-tetrazine 1 with cis,cis-cycloocta-1,5-diene 7 has been studied with a view to preparing some interesting dihydropyridazine derivatives. Refluxing a mixture of 1 with excess of 7 in benzene solution for 8hr resulted in the formation of a mixture of products consisting of 1,4-diphenyl-10a-hydroperoxy-4a, 5,6,9,10,10a-hexahydrocycloocta[d]pyridazine (8, 27%) and 2,4a,5,6,8,10a,11,12-octahydro-1,4,7,10-tetraphenyldipyridazo[4,5-a:4',5'-e]cyclooctene ( However, when the reaction of 1 with 7 was carried out in refluxing benzene for nearly 40 hr, the products formed were a 14% yield of 8, a 17% yield of 9 and a 37% yield of 1,4-diphenyl-5,6,9,10-tetrahydrocycloocta[d]pyridazine (10). Neat heating of 1 with 7 around 150° for 10 hr, on the other hand, gave a 20% yield of 9, as the only isolable product. Thermolysis of 8 around 155° gave a mixture of products consisting of 2-oxocyclooct-5-enyl phenyl ketone N-benzoylhydrazone (15,30%) and 1H-3-phenyl-4,5,8,9-tetrahydrocycloocta[d]pyrazole (16, 22%). Nickel peroxide-oxidation of the adduct 9 gave a 67% yield of 1,4,7,10-tetraphenyldipyridazo[4,5-a:4',5'-e]cyclooctene (27). Acetylation of 9, on the other hand, gave a 70% yield of 2,3,8,9-tetraacetyl-2,3,5,6,8,9,11,12-octahydro-1,4,7,10-tetraphenyldipyridazo[4,5-a:4',5'-e]cyclooctene(28).     

Non-isothermal studies of adduct molecules of metallic halides with oxo-compounds in solid state. V

Non-isothermal studies of some adduct molecules of metallic halides with tetrahydropyran as the type MX₂(THP)_y in solid state, were carried out with a Derivatograph, where M  Mn(II), Co(II), Ni(II), Cu(II) or Cd(II), XCl^- or Br^-, THPtetrahydropyran and y0.1–1. These adduct molecules lost tetrahydropyran in single or multiple steps upon heating. Thermally stable intermediate products were isolated and characterised by elemental analysis and IR spectral measurement. The activation energy for each step of decomposition of the adduct was evaluated from the analysis of TG, DTG and DTA curves of the respective derivatogram. The enthalpy change was evaluated from the DTA peak area and the order of reaction was found to be unity, for each step of decomposition. Thermal parameters for the above adducts were compared with the adducts of other oxocompounds like dioxan, tetrahydrofuran, ethylene glycol dimethyl ether and diisopropyl ether.     

Euphorbiasteroid Abrogates EGFR and Wnt/β-Catenin Signaling in Non-Small-Cell Lung Cancer Cells to Impart Anticancer Activity

EGFR and Wnt/β-catenin signaling pathways play a prominent role in tumor progression in various human cancers including non-small-cell lung carcinoma (NSCLC). Transactivation and crosstalk between the EGFR and Wnt/β-catenin pathways may contribute to the aggressiveness of cancers. Targeting these oncogenic pathways with small molecules is an attractive approach to counteract various types of cancers. In this study, we demonstrate the effect of euphorbiasteroid (EPBS) on the EGFR and Wnt/β-catenin pathways in NSCLC cells. EPBS induced preferential cytotoxicity toward A549 (wildtype EGFR-expressing) cells over PC-9 (mutant EGFR-expressing) cells. EPBS suppressed the expression of EGFR, Wnt3a, β-catenin, and FZD-1, and the reduction in β-catenin levels was found to be mediated through the activation of GSK-3β. EPBS reduced the phosphorylation of GSK-3β^S9 with a parallel increase in β-TrCP and phosphorylation of GSK-3β^Y216. Lithium chloride treatment increased the phosphorylation of GSK-3β^S9 and nuclear localization of β-catenin, whereas EPBS reverted these effects. Forced expression or depletion of EGFR in NSCLC cells increased or decreased the levels of Wnt3a, β-catenin, and FZD-1, respectively. Overall, EPBS abrogates EGFR and Wnt/β-catenin pathways to impart its anticancer activity in NSCLC cells.     

Enhanced magnetic anisotropy of nickel nanosheet prepared in Na-4 mica

Nanosheets of nickel with thickness equal to 0.6 nm have been grown within the interlayer spaces of Na-4 mica. The sheets are made up of percolative clusters of nanodisks. Magnetization characteristics indicate a superparamagnetic behavior with a blocking temperature of 428 K. The magnetic anisotropy constant as extracted from the coercivity data has been found to be higher than that of bulk nickel by two orders of magnitude. This is ascribed to a large aspect ratio of the nickel nanophase. The Bloch exponent is also found to be considerably different from that of bulk nickel because of a size effect. The Bloch equation is still found to be valid for the two dimensional structures.