First row divalent transition metal complexes of aryl-appended tris((pyridyl)methyl)amine ligands: syntheses, structures, electrochemistry, and hydroxamate binding properties

Divalent manganese, cobalt, nickel, and zinc complexes of 6-Ph(2)TPA (N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine; [(6-Ph(2)TPA)Mn(CH(3)OH)(3)](ClO(4))(2) (1), [(6-Ph(2)TPA)Co(CH(3)CN)](ClO(4))(2) (2), [(6-Ph(2)TPA)Ni(CH(3)CN)(CH(3)OH)](ClO(4))(2) (3), [(6-Ph(2)TPA)Zn(CH(3)CN)](ClO(4))(2) (4)) and 6-(Me(2)Ph)(2)TPA (N,N-bis((6-(3,5-dimethyl)phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine; [(6-(Me(2)Ph)(2)TPA)Ni(CH(3)CN)(2)](ClO(4))(2) (5) and [(6-(Me(2)Ph)(2)TPA)Zn(CH(3)CN)](ClO(4))(2) (6)) have been prepared and characterized. X-ray crystallographic characterization of 1A.CH(3)()OH and 1B.2CH(3)()OH (differing solvates of 1), 2.2CH(3)()CN, 3.CH(3)()OH, 4.2CH(3)()CN, and 6.2.5CH(3)()CN revealed mononuclear cations with one to three coordinated solvent molecules. In 1A.CH(3)()OH and 1B.2CH(3)()OH, one phenyl-substituted pyridyl arm is not coordinated and forms a secondary hydrogen-bonding interaction with a manganese bound methanol molecule. In 2.2CH(3)()CN, 3.CH(3)()OH, 4.2CH(3)()CN, and 6.2.5CH(3)()CN, all pyridyl donors of the 6-Ph(2)TPA and 6-(Me(2)Ph)(2)TPA ligands are coordinated to the divalent metal center. In the cobalt, nickel, and zinc derivatives, CH/pi interactions are found between a bound acetonitrile molecule and the aryl appendages of the 6-Ph(2)TPA and 6-(Me(2)Ph)(2)TPA ligands. (1)H NMR spectra of 4 and 6 in CD(3)NO(2) solution indicate the presence of CH/pi interactions, as an upfield-shifted methyl resonance for a bound acetonitrile molecule is present. Examination of the cyclic voltammetry of 1-3 and 5 revealed no oxidative (M(II)/M(III)) couples. Admixture of equimolar amounts of 6-Ph(2)TPA, M(ClO(4))(2).6H(2)O, and Me(4)NOH.5H(2)O, followed by the addition of an equimolar amount of acetohydroxamic acid, yielded the acetohydroxamate complexes [((6-Ph(2)TPA)Mn)(2)(micro-ONHC(O)CH(3))(2)](ClO(4))(2) (8), [(6-Ph(2)TPA)Co(ONHC(O)CH(3))](ClO(4))(2) (9), [(6-Ph(2)TPA)Ni(ONHC(O)CH(3))](ClO(4))(2) (10), and [(6-Ph(2)TPA)Zn(ONHC(O)CH(3))](ClO(4))(2) (11), all of which were characterized by X-ray crystallography. The Mn(II) complex 8.0.75CH(3)()CN.0.75Et(2)()O exhibits a dinuclear structure with bridging hydroxamate ligands, whereas the Co(II), Ni(II), and Zn(II) derivatives all exhibit mononuclear six-coordinate structures with a chelating hydroxamate ligand.     

Sorptive potential of sunflower stem for Cr(III) ions from aqueous solutions and its kinetic and thermodynamic profile

The sorptive potential of sunflower stem (180-300 μm) for Cr(III) ions has been investigated in detail. The maximum sorption (≥85%) of Cr(III) ions (70.2 μM) has been accomplished using 30 mg of high density sunflower stem in 10 min from 0.001 M nitric and 0.0001 M hydrochloric acid solutions. The accumulation of Cr(III) ions on the sorbent follows Dubinin-Radushkevich (D-R), Freundlich and Langmuir isotherms. The isotherm yields D-R saturation capacity X_m = 1.60 ± 0.23 mmol g⁻¹, β = −0.00654 ± 0.00017 kJ² mol⁻², mean free energy E = 8.74 ± 0.12 kJ mol⁻¹, Freundlich sorption capacity K_F = 0.24 ± 0.11 mol g⁻¹, 1/n = 0.90 ± 0.04 and of Langmuir constant K_L = 6800 ± 600 dm³ mol⁻¹ and C_m = 120 ± 18 μmol g⁻¹. The variation of sorption with temperature (283-323 K) gives ΔH = −23.3 ± 0.8 kJ mol⁻¹, ΔS = −64.0 ± 2.7 J mol⁻¹ K⁻¹ and ΔG_298k = −4.04 ± 0.09 kJ mol⁻¹. The negative enthalpy and free energy envisage exothermic and spontaneous nature of sorption, respectively. Bisulphate, Fe(III), molybdate, citrate, Fe(II), Y(III) suppress the sorption significantly. The selectivity studies indicate that Cr(III), Eu(III) and Tb(III) ions can be separated from Tc(VII) and I(I). Sunflower stem can be used for the preconcentration and removal of Cr(III) ions from aqueous medium. This cheaper and novel sorbent has potential applications in analytical and environmental chemistry, in water decontamination, industrial waste treatment and in pollution abatement. A possible mechanism of biosorption of Cr(III) ions onto the sunflower stem has been proposed.     

Effect of diffusion on rates and molecular weights in graft polymerization

A theoretical analysis has been made of the graft polymerization process in terms of the quantitative interrelationship between the initiation rate R_i, the k_p/k_t^1/ ratio of the monomer, the equilibrium solubility M of the monomer in the polymer, the polymer film thickness L, and the diffusivity D of the monomer in the polymer. It is shown how the values of these parameters in any grafting system interact to lead to diffusion-controlled graft polymerization. Whether graft polymerization is diffusion-free or diffusion-controlled depends on the values of K_p, d, k_p/k_p^1/2, and L as gathered in the parameter A = [(K_p/k_t^1/2)R_i, D,/^1/2] L/2. When the values of the various terms are such that A is less than 0.1 (i.e., D is large while R_i, k_p, and L are small), the reaction is diffusion-free. When A is greater than 3 (i.e., D is small while R_i, k_p, and L are large), the reaction is diffusion-controlled. The derived equations showing the relationship between kinetic and diffusional parameters are theoretically applicable to all grafting systems, i.e., for all monomer-polymer combinations under all conditions of reaction temperature, radiation intensity and polymer film thickness. The theoretical analysis has been verified for the rate and degree of polymerization for the radiation-induced graft polymerization of styrene to polyethylene.     

Synthesis and extraction properties of new chromogenic azo-calix[4]dibenzothiacrown ethers

Two novel chromogenic cone calix[4]dibenzothiacrown ethers 3 and 4 in which nitrophenylazo groups attached at the phenyl ring of dibenzothiacrown unit were described. The extraction properties of 3 and 4 toward different transition metal ions have been studied using conductometric technique and found to exhibit Cu²⁺ and Hg²⁺ selectivity with very high stability constants range from log K _assoc = 5.19 to log K _assoc = 8.72.     

Phosphodiesterase‐Inhibiting Glycosides from Symplocos racemosa

Phytochemical investigation of Symplocos racemosa resulted in the isolation of two new glycosides, symploracemoside ( 1 ) and symplomoside ( 2 ), which are structurally related to the reported benzoylsalireposide ( 3 ) and salireposide ( 4 ). The structure elucidation of the isolated compounds was based primarily on 1D‐ and 2D‐NMR analysis, including COSY, NOESY, HMQC, and HMBC correlations. These glycosides showed inhibitory activity against snake‐venom phosphodiesterase I.     

Variational bounds on the radius of convergence of the born series

The radius of convergence of the Born series for potential scattering problems is discussed in terms of the eigen-values of the scattering integral equation. Variational procedures yielding upper and lower bounds for these eigen-values are introduced. These bounds axe calculated using various trial functions and compared to the exact values for the square well, exponential repulsive, and Yukawa potentials.     

Convex hull of powers of a complex number,trinomial equations and the Farey sequence

The color of a complex number is defined as the number of vertices of the convex hull of powers of that number. This induces a coloring of the unit disk. The structure of the set of points where the color changes is investigated here. It is observed that there is a connection between this fractal set and some family of trinomial equations. Three algorithms for coloring the unit disk are described, the last one (related to the Farey sequence) arising out of a conjecture. This conjecture is formulated and proved in this presentation.     

Sol-gel approach to in situ creation of high pH-resistant surface-bonded organic-inorganic hybrid zirconia coating for capillary microextraction (in-tube SPME)

A novel zirconia-based hybrid organic-inorganic sol-gel coating was developed for capillary microextraction (CME) (in-tube SPME). High degree of chemical inertness inherent in zirconia makes it very difficult to covalently bind a suitable organic ligand to its surface. In the present work, this problem was addressed from a sol-gel chemistry point of view. Principles of sol-gel chemistry were employed to chemically bind a hydroxy-terminated silicone polymer (polydimethyldiphenylsiloxane, PDMDPS) to a sol-gel zirconia network in the course of its evolution from a highly reactive alkoxide precursor undergoing controlled hydrolytic polycondensation reactions. A fused silica capillary was filled with a properly designed sol solution to allow for the sol-gel reactions to take place within the capillary for a predetermined period of time (typically 15-30 min). In the course of this process, a layer of the evolving hybrid organic-inorganic sol-gel polymer got chemically anchored to the silanol groups on the capillary inner walls via condensation reaction. At the end of this in-capillary residence time, the unbonded part of the sol solution was expelled from the capillary under helium pressure, leaving behind a chemically bonded sol-gel zirconia-PDMDPS coating on the inner walls. Polycyclic aromatic hydrocarbons, ketones, and aldehydes were efficiently extracted and preconcentrated from dilute aqueous samples using sol-gel zirconia-PDMDPS coated capillaries followed by thermal desorption and GC analysis of the extracted solutes. The newly developed sol-gel hybrid zirconia coatings demonstrated excellent pH stability, and retained the extraction characteristics intact even after continuous rinsing with a 0.1 M NaOH solution for 24 h. To our knowledge, this is the first report on the use of a sol-gel zirconia-based hybrid organic-inorganic coating as an extraction medium in solid phase microextraction (SPME).