The photo-physical aspects of non-covalently linked assemblies of a series of fullerenes, namely, C60, C70, tert-butyl-(1,2-methanofullerene)-61-carboxylate (1) and [6,6]-phenyl C70 butyric acid methyl ester (2) with a designed zinc phthalocyanine (ZnPc), viz., zinc-1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (3) in toluene medium are studied employing absorption spectrophotometric, steady state and time resolved fluorescence spectroscopic measurements. Of central interest in these investigations is the preferential binding of various fullerenes with ZnPc in toluene. The ground state interaction between fullerenes and 3 is first evidenced from UV-Vis measurements. Steady state fluorescence experiment reveals efficient quenching of the excited singlet state of 3 in presence of both underivatized and derivatized fullerenes. K values for the complexes of C60, C70, 1 and 2 with 3 are determined to be 6500, 22,230, 47,800 and 54,770 dm3 mol(-1), respectively. The magnitude of K suggests that 3 preferentially binds C70 and derivatized C70 in comparison to C60 and 1. Time resolved emission measurements establish that C(70)-3 and 2-3 complexes are stabilized much more in comparison to C(60)-3 and 1-3 systems in terms of charge separation process. Semi empirical calculations employing third parametric method substantiate the strong binding of C70 and its derivative with 3 in terms of heat of formation values of the respective complexes, and at the same time, determine the orientation of bound guest (here fullerenes) with the molecular plane of 3. 相似文献
The reactions of N-(aryl)pyridine-2-aldimines (L-R; R = OCH3, CH3, H, Cl and NO2), derived from pyridine-2-aldehyde and para-substituted anilines, with CuI in methanol under ambient conditions afford a series of brown complexes of the type [{Cu(L-R)I}2]. The structure of the [{Cu(L-OCH3)I}2] complex has been determined by X-ray crystallography. In these dimeric complexes the two copper centers are linked through an iodo-bridge, and the L-R ligands are coordinated to the metal center through the pyridine-nitrogen and imine-nitrogen. All the complexes show characteristic 1H NMR signals and intense MLCT transitions in the visible region. These complexes also show an emission near 465 nm, whilst they are excited at 340 nm, with relatively poor quantum yields (φ ∼0.002 at 298 K). Cyclic voltammetry on all the complexes shows two successive Cu(I)-Cu(II) oxidations on the positive side of SCE, and a reduction of the coordinated imine ligand on the negative side. These copper(I) complexes are found to efficiently catalyze Suzuki type C-C coupling reactions. 相似文献
The thiocarbohydrazone Schiff-base ligand with a nitrogen and sulphur donor was synthesized through condensation of pyridine-2-carbaldehyde and thiocarbohydrazide. Schiff-base ligands have the ability to conjugate with metal salts. A series of metal complexes with a general formula [MCl2(H2L)]·nH2O (MNi, Co, Cu and Zn) were synthesized by forming complexes of the N1,N5-bis[pyridine-2-methylene]-thiocarbohydrazone (H2L) Schiff-base ligand. These metal complexes and ligand were characterized by using ultraviolet-visible (UV-Vis), Fourier Transform Infrared (FT-IR), 1H and 13C NMR spectroscopy and mass spectroscopy, physicochemical characterization, CHNS and conductivity. The biological activity of the synthesized ligand was investigated by using Escherichia coli DNA as target. The DNA interaction of the synthesized ligand and complexes on E. coli plasmid DNA was investigated in the aqueous medium by UV-Vis spectroscopy and the binding constant (Kb) was calculated. The DNA binding studies showed that the metal complexes had an improved interaction due to trans-geometrical isomers of the complexes than ligand isomers in cis-positions. 相似文献
The present paper deals with the synthesis and characterization of Schiff base complexes of pyrazinamide an antitubercular drug. Metals selected for complexation are copper, silver, gold, zinc, mercury, iron and cobalt. The complexes have been suitably synthesized and isolated in pure powdered form. Analytical data agrees with the compositions M(L), M′(L)2 and M″(L)2·2H2O, respectively where M = Ag, M′ = Cu, Au, Zn and Hg and M″ = Fe and Co, ligand metal ratios were also confirmed by monovariation method and Job’s method of continuous variation. Molar conductance values suggest the non ionic nature of the complexes. The tentative structure assigned to the complexes on the basis of stoichiometry and analytical data were further supported by spectral studies viz; IR, NMR, magnetic susceptibility and electronic spectra. A preliminary attempt has also been made to compare the potencies of metal complexes with parent drug. The Cu and Ag complexes are giving encouraging results. Particle size studies further suggest that the drug molecule undergoes reduction in size on complexation. 相似文献
CO2 and steam/CO2 electroreduction to CO and methane in solid oxide electrolytic cells (SOEC) has gained major attention in the past few years. This work evaluates, for the very first time, the performance of two different ZnO–Ag cathodes: one where ZnO nanopowder was mixed with Ag powder for preparing the cathode ink (ZnOmix–Ag cathode) and the other one where Ag cathode was infiltrated with a zinc nitrate solution (ZnOinf –Ag cathode). ZnOmix–Ag cathode had a better distribution of ZnO particles throughout the cathode, resulting in almost double CO generation while electrolysing both dry CO2 and H2/CO2 (4:1 v/v). A maximum overall CO2 conversion of 48% (in H2/CO2) at 1.7 V and 700 °C clearly indicated that as low as 5 wt% zinc loading is capable of CO2 electroreduction. It was further revealed that for ZnOinf –Ag cathode, most of CO generation took place through RWGS reaction, but for ZnOmix–Ag cathode, it was the synergistic effect of both RWGS reaction and CO2 electrolysis. Although ZnOinf –Ag cathode produced trace amount of methane at higher voltages, with ZnOmix–Ag cathode, there was absolutely no methane. This seems to be due to strong electronic interaction between Zn and Ag that might have suppressed the catalytic activity of the cathode towards methanation.
We report, for the first time, a detailed crystallographic study of the supramolecular arrangement for a set of zinc(II) Schiff base complexes containing the ligand 2,6-bis((E)-((2-(dimethylamino)ethyl)imino)methyl)-4-R-phenol], where R=methyl/tert-butyl/chloro. The supramolecular study acts as a pre-screening tool for selecting the compartmental ligand R of the Schiff base for effective binding with a targeted protein, bovine serum albumin (BSA). The most stable hexagonal arrangement of the complex [Zn − Me] (R=Me) stabilises the ligand with the highest FMO energy gap (ΔE=4.22 eV) and lowest number of conformations during binding with BSA. In contrast, formation of unstable 3D columnar vertebra for [Zn − Cl] (R=Cl) tend to activate the system with lowest FMO gap (3.75 eV) with highest spontaneity factor in molecular docking. Molecular docking analyses reported in terms of 2D LigPlot+ identified site A, a cleft of domains IB, IIIA and IIIB, as the most probable protein binding site of BSA. Arg144, Glu424, Ser428, Ile455 and Lys114 form the most probable interactions irrespective of the type of compartmental ligands R of the Schiff base whereas Arg185, Glu519, His145, Ile522 act as the differentiating residues with ΔG=−7.3 kcal mol−1. 相似文献
Aesthetic and utilitarian properties of traditional ceramic wares as well as engineering properties of modern advanced ceramics are attained by maintaining an optimum temperature-time-atmosphere relationship, called firing schedule, in the kiln. The contribution of modern thermal analysis (TA) techniques such as TG/DTG, TG/EGA, TG/MS, DTA, DSC, TDA, etc. in 1) optimizing production steps by raw material quality control, by studying binder burn out, product densification, 2) in simulating appropriate preheating, firing and cooling schedules as well as 3) in developing shorter firing cycles has been extensively reported in recent literature. The paper will first discuss theoretical curves and energy required for ceramic firing and present from the literature selected examples of applications of thermal analysis in ceramic technology. 相似文献
In recent decades it has become increasingly clear that induction of autophagy plays an important role in the development of treatment resistance and dormancy in many cancer types. Unfortunately, chloroquine (CQ) and hydroxychloroquine (HCQ), two autophagy inhibitors in clinical trials, suffer from poor pharmacokinetics and high toxicity at therapeutic dosages. This has prompted intense interest in the development of targeted autophagy inhibitors to re-sensitize disease to treatment with minimal impact on normal tissue. We utilized Scanning Unnatural Protease Resistant (SUPR) mRNA display to develop macrocyclic peptides targeting the autophagy protein LC3. The resulting peptides bound LC3A and LC3B—two essential components of the autophagosome maturation machinery—with mid-nanomolar affinities and disrupted protein–protein interactions (PPIs) between LC3 and its binding partners in vitro. The most promising LC3-binding SUPR peptide accessed the cytosol at low micromolar concentrations as measured by chloroalkane penetration assay (CAPA) and inhibited starvation-mediated GFP-LC3 puncta formation in a concentration-dependent manner. LC3-binding SUPR peptides re-sensitized platinum-resistant ovarian cancer cells to cisplatin treatment and triggered accumulation of the adapter protein p62 suggesting decreased autophagic flux through successful disruption of LC3 PPIs in cell culture. In mouse models of metastatic ovarian cancer, treatment with LC3-binding SUPR peptides and carboplatin resulted in almost complete inhibition of tumor growth after four weeks of treatment. These results indicate that SUPR peptide mRNA display can be used to develop cell-penetrating macrocyclic peptides that target and disrupt the autophagic machinery in vitro and in vivo.SUPR peptide mRNA display was used to evolve a cell-permeable, macrocyclic peptide for autophagy inhibition.相似文献