Kinetics and mechanism of formation and dissociation of copper(II) and nickel(II) complexes of the Schiff base bis(acetylacetone)ethylenediimine in aqueous-organic solvent media

Summary In NH₄NO₃+NH₄OH buffered 10% (v/v) dioxan-water media (pH 7.0–8.5), thePseudo-first-order rate constant for the formation of the title complexes M(baen),i.e. ML, conforms to the equation 1/k_obs=1/k+1/(kK_o.s · T_L), where T_L stands for the total ligand concentration in the solution, K_o.s is the equilibrium constant for the formation of an intermediate outer sphere complex and k is the rate constant for the formation of the complex ML from the intermediate. Under the experimental conditions the free ligand (pK_a>14) exists virtually exclusively in the undissociated form (baenH₂ or LH₂) which is present mostly as a keto-amine in the internally hydrogen-bonded state. Although the observed formation-rate ratio k^Cu/k^Ni is of the order of 10⁵, as expected for systems having normal behaviour, the individual rate constants are very low (at 25°C, k^Cu=50 s^–1 and k^Ni=4.7×10^–4s^–1) due to the highly negative S values (–84.2±3.3 JK^–1M^–1 for CuL and –105.8±4.1 JK^–1M^–1 for NiL); the much slower rate of formation of the nickel(II) complex is due to higher H value (41.2±1.0 kJM^–1 for CuL and 78.2±1.2 kJM^–1 for NiL) and more negative S value compared to that of CuL. The K_o.s values are much higher than expected for simple outer-sphere association between [M(H₂O)₆] and LH₂ and may be due to hydrogen bonding interaction.In acid media ([H⁺], 0.01–0.04 M) these complexes M(baen) dissociate very rapidly into the [M(H₂O)₆]²⁺ species and baenH₂, followed by a much slower hydrolytic cleavage of the ligand into its components,viz. acetylacetone and ethylenediamine (protonated). For the dissociation of the complexes k_obs=k₁[H⁺]+k₂[H⁺]². The reactions have been studied in 10% (v/v) dioxan-water media and also ethanolwater media of varying ethanol content (10–25% v/v) and the results are in conformity with a solvent-assisted dissociativeinterchange mechanism involving the protonated complexes.     

Studies on the kinetics and mechanism of dissociation of copper(II) and nickel(II) complexes of the macrocyclic ligand 1, 5, 9, 13-tetraaza-2, 4, 4, 10, 12, 12-hexamethyl-cyclohexadecane-1, 9-diene in perchloric acid media

Summary Acid catalysed dissociation of the copper(II) and nickel(II) complexes (ML²⁺ of the quadridentate macrocyclic ligand 1, 5, 9, 13-tetraaza-2, 4, 4, 10, 12, 12-hexamethyl-cyclohexadecane-1, 9-diene (L) has been studied spectrophotometrically. Both complexes dissociate quite slowly with the observed pseudo-first order rate constants (k_obs) showing acid dependence; for the nickel(II) complex (k_obs)=k_O+k_H[H⁺], the k_o path is however absent with the copper(II) complex. At 60°C (I=0.1M) the k_H values areca 10^–4 M^–1 s^–1 for both complexes; k _H ^Cu /k _H ^Ni =ca. 3.9, comparable to some other square-planar complexes of these metal ions. The rate difference is primarily due to H values [copper(II) complex, 29.4±0.5 kJ mol^–1; nickel(II) complex, 35.6±1.5 kJ mol^–1] with highly negative S values [for copper(II), –215.5 ±6.1 JK^–1 mol^–1 and for nickel(II), –208.1 ±5.6 JK^–1 mol^–1] which are much higher than the entropy of solvation of Ni²⁺ (ca. –160 JK^–1 mol^–1) and Cu²⁺ (ca. –99 JK^–1 mol^–1) ions; significant solvation of the released metal ions and the ligand is indicated.     

Kinetics of substitution of aquo ligands fromcis-diaquo-bis-(biguanide) cobalt(III) and chromium(III) ions by aspartic acid in ethanol—water mixtures

The kinetics of substitution of aqua ligands fromcis-diaqua-bis(biguanide)cobalt(III) and chromium(III) ions by aspartic acid in EtOH–H₂O media have been studied spectrophotometrically in the 30 to 45°C range. We propose the following rate law for the anation

Honeycomb nets with interpenetrating frameworks involving iminodiacetato-copper(II) blocks and bipyridine spacers: syntheses, characterization, and magnetic studies

Three coordination polymers of copper(II), viz. ([Cu(ida)(4,4'-bipyH)]ClO(4))( proportional, variant ) (1), ([Cu(2)(ida)(2)(micro-4,4'-bipy)].2H(2)O)( proportional, variant ) (2), and [Cu(2)(ida)(2)(bpa)]( proportional, variant ) (3) have been synthesized by the process of self-assembly using Cu(ida) [ida = iminodiacetate(2-)] as the building block and 4,4'-bipyridyl and 1,2-bis(4-pyridyl)ethane (bpa) as linkers. Crystals of 1 are orthorhombic, of space group Pna2(1), with a = 13.8956(12) A, b = 16.3362(16) A, c = 7.3340(12), and Z = 4. Both compounds 2 and 3 crystallize in monoclinic space group P2(1)/a with a = 10.1887(8) A (9.6779(10) A for 3), b = 8.0008(11) A (9.1718(10) A), c = 11.6684(9) A (12.9144(12) A), beta = 98.307(11) degrees (102.796(18) degrees ), and Z = 2 (2). Compound 1 has a zigzag chain structure with an extensive hydrogen-bonded network while compounds 2 and 3 are honeycomb (6,3) nets with interpenetrating structures. Variable temperature (2-300 K) magnetic study indicates the presence of weak antiferromagnetic interactions (J = 0.82 +/- 0.01 cm(-)(1)) in 1 and ferromagnetic in 2 (J = -0.45 +/- 0.05 cm(-)(1)) and 3 (J = -0.21 +/- 0.02 cm(-)(1)). The extent of planarity of the bridging "Cu-O-C-O-Cu" moiety, acting as the super-exchange pathway between the neighboring copper centers, probably controls the sign of the magnetic exchange coupling in these compounds.     

Green synthesis and characterization of silver nanoparticles by Allium cepa L. to produce silver nano‐coated fabric and their antimicrobial evaluation

This research work was proposed to study the antimicrobial activity of the silver nanocoated fabric with the purpose of producing good dressing and clothing material. We synthesized simple, ecofriendly, cost‐effective and sustainable silver nanoparticles by using the aqueous extract of Allium cepa L. Here, A. cepa L. acts as a good reducing and capping agent that produced stable silver nanoparticles having particle size of range 36 ± 1 to 98 ± 2 nm, Poly dispersiblity index 0.234 ± 0.61 to 1.023 ± 0.33 and Zeta potential ‐12 ± 1.5 mV to ‐26 ± 1.2 mV. The effect of temperature and extract volume used was considered for optimization of synthetic procedure. The nanocoated fabric was characterized for morphological study, size (using transmission electron microscopy (TEM) and field emission scanning electron microscopy (FE‐SEM) and zeta‐potential (Zeta Potentiometer). The presence of functional groups were observed by using attenuated total reflection‐Fourier transform infrared (ATR‐FTIR) and Raman spectroscopy. The crystallinity and structural property of the synthesized silver nanoparticles were studied in terms of Powder X‐ray diffraction (PXRD). An IC₅₀ value and zone of inhibition was studied which demonstrate that the silver nanocoated fabric have an excellent antibacterial property against Gram‐negative (Escherichia coli) and Gram‐positive (Staphylococcus aureus) bacteria. Further nanocoated fabric material was washed (with function of time 0, 10, 25, and 50 laundry cycles) and still retained their anti‐bacterial activity towards both strain. Initially there was 52 μg/ml of silver nanoparticles on the cotton fabric but after 50 laundry cycle in 500 ml of distilled water the fabric showed 92% efficiency against gram positive and 90% efficacy toward gram negative bacteria. It was found that 4.16 μg/ml nano particles leached in case of S. Aureus and 5.2 μg/mL silver nanoparticles leached in case of E. coli. Nanocoated fabric material synthesized using green synthesis was found to be economical with good resistance to washing.     

Efficient Transition‐Metal‐Free Oxidation of Benzylic and Secondary Alcohols to the Carbonyl Compounds Using an N‐Bromosuccinimide/NH4Cl System

The oxidation of a variety of benzylic and secondary alcohols was achieved in excellent yields using an NBS/NH₄Cl system in aqueous acetonitrile (CH₃CN‐H₂O; 7/3 v/v) at 80°C under very mild conditions.     

The k-essence scalar field in the context of Supernova Ia observations

We study a framework where the hypothesis of a minimum length in space-time is complemented with the notion of reference frame invariance. It turns out natural to interpret the action of the obtained reference frame transformations in the context of doubly special relativity. As a consequence of this formalism we find interesting connections between the minimum length properties and the modified velocity-energy relation for ultra-relativistic particles. For example, we can predict the ratio between the minimum lengths in space and time using the results from OPERA on superluminal neutrinos.     

Antioxidative and anticarcinogenic activities of methylpheophorbide a,isolated from wheat grass (Triticum aestivum Linn.)

Methylphophorbide a (MPa) has been isolated from the ethanol extract of the wheat grass plant. Its antioxidative efficacy is evaluated by hydroxyl radical scavenging activities and reducing capacity which are significantly up regulated in comparison with aqueous extract of the plant. The compound shows iron-binding capacity where the Fe²⁺ binds with MPa by two types of binding patterns with dissociation constants 157.17 and 27.89. It has antioxidative and cytotoxic effects on HeLa and Hep G2 cells. The cancerous cell survivability decreases with increasing concentration of MPa. These findings have provided evidence for the traditional use of the wheat grass plant in the treatment of cancers, oxidative stress and iron overloaded disorders.