Spectrophotometric studies of molecular complex formation between water-soluble cobalt(II) Schiff base complex and nucleotides in mixed solvent systems

The formation constants for 1:1 molecular complex formation between water-soluble cobalt(II) tetradentate Schiff base complex, disodium[{bis(4-methoxy-5-sulfo-salicylaldehyde)-4,5-dimethyl-o-phenylenediiminato}cobalt(II)], Na2[Co(SO3-4-meosal-4,5-dmophen)], and nucleotides, adenosine-5'-triphosphate (ATP) and cytidine-5'-triphosphate (CTP), in mixed solvent systems of ethanol and water with different volume fractions of ethanol and water have been determined spectrophotometrically at constant ionic strength (I = 0.2 mol dm(-3) NaClO4) and temperature 278 K. Trends in the values of formation constants according to the volume fractions of ethanol and water in ethanol and water mixed solvent systems, suggest that the trend of molecular complex formation increases with increasing the volume fraction of ethanol in mixed solvent systems.     

Interaction of copper(II) complex of compartmental Schiff base ligand N,N'-bis(3-hydroxysalicylidene)ethylenediamine with bovine serum albumin

Circular dichroism (CD) spectroscopy, cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to investigate the interaction between copper(II) complex of compartmental Schiff base ligand (L), N,N'-bis(3-hydroxysalicylidene)ethylenediamine, and bovine serum albumin (BSA) in 0.1 mol dm(-3) phosphate buffer solution adjusted to physiological pH 7.0 containing 20% (w/w) dimethylsulfoxide at room temperature. CD spectra show that the interaction of the copper(II) complex with BSA leads to changes in the alpha-helical content of BSA and therefore changes in secondary structure of the protein with the slight red shift (2 nm) in CD spectra. From the voltammetric data, i.e. changes in limiting current with addition of BSA, the binding constant (K) of the interaction of copper(II) complex with BSA was found to be 1.96 x 10(4)dm(3)mol(-1). From the shifts in potential with the addition of BSA, the equilibrium constant ratio (K(2)/K(1)) for the binding of the oxidized Cu(II)L (K(1)) and reduced Cu(I)L (K(2)) species to BSA was found to be 3.77, which shows that the reduced form Cu(I)L is bound more strongly to BSA than the oxidized form Cu(II)L.     

Synthesis of Mn3O4 nanoparticles by thermal decomposition of a [bis(salicylidiminato)manganese(II)] complex

The present investigation reports on the novel synthesis of Mn₃O₄ nanoparticles using thermal decomposition and their physicochemical characterization. The Mn₃O₄ nanoparticle powder has been prepared using [bis(salicylidiminato)manganese(II)] as a precursor. The effect of oleyl amine and triphenylphosphine on the particle morphology has been investigated. Transmission electron microscopy (TEM) analysis demonstrated Mn₃O₄ nanoparticles with an average diameter of about 25 nm. The structural study by X-ray diffraction (XRD) indicates that these nanoparticles have a pure tetragonal phase. The phase pure samples were characterized using X-ray photoelectron spectroscopy (XPS) for both Mn 2p and Mn 3s levels. The values of binding energies are consistent with related values reported in the literature.     

Exceptional times and invariance for dynamical random walks

Consider a sequence of i.i.d. random variables. Associate to each X _i (0) an independent mean-one Poisson clock. Every time a clock rings replace that X-variable by an independent copy and restart the clock. In this way, we obtain i.i.d. stationary processes {X _i (t)} _{t ≥0} (i=1,2,···) whose invariant distribution is the law ν of X ₁(0). Benjamini et al. (2003) introduced the dynamical walk S _n (t)=X ₁(t)+···+X _n (t), and proved among other things that the LIL holds for n↦S _n (t) for all t. In other words, the LIL is dynamically stable. Subsequently (2004b), we showed that in the case that the X _i (0)'s are standard normal, the classical integral test is not dynamically stable. Presently, we study the set of times t when n↦S _n (t) exceeds a given envelope infinitely often. Our analysis is made possible thanks to a connection to the Kolmogorov ɛ-entropy. When used in conjunction with the invariance principle of this paper, this connection has other interesting by-products some of which we relate. We prove also that the infinite-dimensional process converges weakly in to the Ornstein–Uhlenbeck process in For this we assume only that the increments have mean zero and variance one. In addition, we extend a result of Benjamini et al. (2003) by proving that if the X _i (0)'s are lattice, mean-zero variance-one, and possess (2+ɛ) finite absolute moments for some ɛ>0, then the recurrence of the origin is dynamically stable. To prove this we derive a gambler's ruin estimate that is valid for all lattice random walks that have mean zero and finite variance. We believe the latter may be of independent interest. The research of D. Kh. is partially supported by a grant from the NSF.     

Synthesis,characterization, crystal structure and oxygen-evolution activity of a manganese(II) complex with 2,4,6-tris (2-pyridyl)-1,3,5-triazine

The title complex [Mn(tptz)(CH₃COO)(OH₂)₂]NO₃ was synthesized through the reaction of tptz (2,4,6-tris(2-pyridyl)-1,3,5-triazine), nitric acid and manganese(II) acetate. The molecular structure was characterized by X-ray diffraction, elemental analysis, electrochemistry, EPR, IR, fluorescence and UV–Vis spectroscopy and its oxygen evolving activity has been studied. X-ray structure analysis shows that each Mn(II) ion is seven coordinated by a bidentate acetate, three nitrogen atoms of tptz and two oxygen atoms from two water ligands, which are coordinated in axial positions. The complex acts as an oxygen evolving complex with oxone (2KHSO₅·KHSO₄·K₂SO₄) as primary oxidant in aqueous solution with a turnover number of 1 (mol of O₂/mol of the complex). Kinetic studies revealed a first-order dependence on the complex and oxidant. The EPR spectrum shows that the mononuclear complex oxidize to a Mn^III,IV₂ di-μ-oxo by oxone.     

Heterogeneous water oxidation by bidentate Schiff base manganese complexes in the presence of cerium(IV) ammonium nitrate

Oxygen evolution was observed upon mixing solid manganese(III) bidentate Schiff base complexes with aqueous solutions of cerium(IV) ammonium nitrate. However, oxygen evolution was not observed upon mixing solutions of the complexes (in acetonitrile) with Ce(IV). Electron-withdrawing substituents on the Schiff base ligands (NO₂, Br) enhanced the reactivity of the manganese complexes toward oxygen evolution. Oxygen evolution was also affected by R groups on the ligands, in the order Me > Et ≫ Bz. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Simple Hydrothermal Synthesis of Nickel Hydroxide Flower-Like Nanostructures

α-Ni(OH)₂ flower-like nanostructures were successfully synthesized through one-step hydrothermal method with nickel acetate tetrahydrate, ethylene-1,2-diamine (en), hexamethylenetetramine (HMT) and cetyltrimethylammonium bromide (CTAB) as morphology-directing agents. Optimum conditions to obtain high yield and pure phase α-Ni(OH)₂ were identified by varying experimental parameters such as: en, HMT and CTAB concentration and reaction temperature. The products were characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared and thermogravimetric analysis. These results indicated that the α-nickel hydroxide contains water molecules and anions. The hierarchical NiO nanostructures were obtained by the as-synthesized α-Ni(OH)₂ nanostructures annealed at 300 °C for 4 h.     

Thermal decomposition of [bis(salicylaldehydato)cadmium(II)] to CdS nanocrystals

The present investigation reports, the novel synthesis of nanocrystals CdS using thermal decomposition of [bis(salicylaldehydato)cadmium(II)], as a new precursor, and elemental sulfur in oleylamine. The as-synthesized CdS crystals have diameters about 10 nm. The products were characterized by X-ray diffraction (XRD) transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), ultraviolet–visible (UV–Vis) spectroscopy and Fourier transformed infrared (FT-IR) spectra. The results of this paper show that the shape and size of cadmium sulfide nanocrystals can be controlled systematically by adjusting certain reaction parameters, such as the reactant concentration, the reaction temperature and the reaction time. Cadmium sulfide nanoparticles and nanorods with different lengths have been successfully prepared.     

Synthesis of cobalt nanoparticles from [bis(2-hydroxyacetophenato)cobalt(II)] by thermal decomposition

[Bis(2-hydroxyacetophenato)cobalt(II)] was used as a new precursor to prepare cobalt (Co) and tricobalt tetraoxide (Co₃O₄) nanoparticles of 15–25 nm in average diameter by thermal decomposition. The different combinations of triphenylphosphine, and oleylamine were added as surfactants to control the particle size. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and Fourier transform infrared (FT-IR) spectroscopy. Time-dependent FT-IR studies indicate that oxidation of the as-synthesized cobalt nanoparticles in air is slow. The valence change of cobalt from the nanoparticle sample is not observed after it is kept in hexane under air for 30 days. The magnetic property was studied with vibrating sample magnetometer (VSM). The hysteresis loops of the obtained samples reveal the soft magnet behaviors the enhanced coercivity (H_c) and decreased saturation magnetization (M_s) in contrast to their respective bulk materials.