Fac-mer equilibria of coordinated iminodiacetate (IDA2?) in ternary CuII(ida)(H?1B)? complex formation (B = imidazole, benzimidazole) in aqueous solution

pH potentiometric and spectrophotometric investigations on the complex formation equilibria of Cu^II with iminodiacetate (ida²⁻) and heterocyclic N-bases, viz. imidazole and benzimidazole (B), in aqueous solution in binary and ternary systems using different molar ratios of the reactants indicated the formation of complexes of the types, Cu(ida), Cu(ida)(OH)⁻, (ida)Cu(OH)Cu(ida)⁻, Cu(B)²⁺, Cu(H^-1B)⁺, Cu(ida)(H₋₁B)⁻, (ida)Cu(B)Cu(ida) and (ida)Cu(H₋₁B)Cu(ida)⁻. Formation constants of the complexes at 25 ±1° at a fixed ionic strength,I = 0.1 mol dm⁻³ (NaNO₃) in aqueous solution were evaluated and the complex formation equilibria were elucidated with the aid of speciation curves. Departure of the experimental values of the reproportionation constants(ΔlogK _cu) of ternary Cu(ida)(H₋₁B)⁻ complexes from the statistically expected values, despite their formation in appreciable amounts at equilibrium, were assigned tofac(f)-mer(m) equilibria of the ida²⁻ ligand coordinated to Cu^II, as the N-heterocyclic donors, (H₋₁B)⁻, coordinatetrans- to the N-(ida²⁻) atom in the binary Cu(ida) _f complex to form the ternary Cu(ida) _m (H₋₁B)⁻ complexes     

Dual-reagent catalysis within Ir-Sn domain: highly selective alkylation of arenes and heteroarenes with aromatic aldehydes

Reactions of arenes and heteroarenes with aromatic aldehydes proceeded smoothly in the presence of a catalytic combination of [Ir(COD)Cl]2-SnCl4 to afford the corresponding triarylmethane derivatives (TRAMs) in high yields. This 100% TRAM selective transformation is clean and eliminates the use of acid systems.     

Predicting the redox properties of uranyl complexes using electronic structure calculations

A plethora of chemical reactions is redox driven processes. The conversion of toxic and highly soluble U(VI) complexes to nontoxic and insoluble U(IV) form are carried out through proton coupled electron transfer by iron containing cytochromes and mineral surfaces such as machinawite. This redox process takes place through the formation of U(V) species which is unstable and immediately undergo the disproportionation reaction. Thus, theoretical methods are extremely useful to understand the reduction process of U(VI) to U(V) species. We here have carried out the structures and reduction properties of several U(VI) to U(V) complexes using a variety of electronic structure methods. Due to the lack of experimental ionization energies for uranyl (UO₂(V)‐UO₂(VI)) couple, we have benchmarked the current and popularly used density functionals and cost effective ab initio methods against the experimental electron detachment energies of [UO₂F₄]^1‐/2‐ and [UO₂Cl₄]^1‐/2‐. We find that electron detachment energy of U(VI) predicted by RI‐MP2 level on the BP86 geometries correlate nicely with the experimental and CCSD(T) data. Based on our benchmark studies, we have predicted the structures and electron detachment energies of U(V) to U(VI) species for a series of uranium complexes at the RI‐MP2//BP86 level which are experimentally inaccessible till date. We find that the redox active molecular orbital is ligand centered for the oxidation of U(VI) species, where it is metal centered (primarily f‐orbital) for the oxidation of U(V) species. Finally, we have also calculated the detachment energies of a known uranyl [UO₂]¹⁺ complex whose X‐ray crystal structures of both oxidation states are available. The large bulky nature of the ligand stabilizing the uncommon U(V) species which cannot be routinely studied by present day CCSD(T) methods as the system size are more than 20–30 atoms. The success of our efficient computational strategy can be experimentally verified in the near future for the complex as the structures are stable in gas phase which can undergo oxidation.     

Ion solvation in biologically active magnesium salt with lactose–water mixed solvent system at different temperatures: a thermo-acoustics study

This paper presents the ion-solvations in biologically important metal ion like magnesium in lactose–water mixed solvent systems at different temperatures. The investigation involves the measurement of ultrasonic velocity, density and viscosity of different concentration of magnesium sulphate in various proportions of lactose–water mixed solvents at temperature 303.15, 308.15, 313.15 K and at atmospheric pressure. Different thermo-acoustic parameters have been calculated from the measured values and have been discussed in the light of ion–solvent interactions.     

Cr(i)Cl as well as Cr+ are stabilised between two cyclic alkyl amino carbenes

Cr(i)Cl is a very unstable species. The present work describes the stabilisation of Cr(i)Cl in the low coordinate environment of cyclic alkyl(amino) carbene ligands and its synthetic application to yield an unprecedented cationic complex with a two coordinate Cr(i). One electron reduction of (cAAC)₂CrCl₂ (1) with equivalent amount of KC₈ results in the formation of (cAAC)₂CrCl (2), with a distorted trigonal planar configuration at the metal centre. SQUID, EPR and theoretical studies reveal a Cr(i) centre with S = 5/2 spin ground state for 2. It represents the first example of a mononuclear Cr complex showing slow relaxation of magnetisation under an applied magnetic field. The chlorine atom in 2 is expected to be prone to further reactions with appropriate reagents. This qualifies 2 as a promising precursor for the preparation of various interesting complexes with Cr(i) in a low coordinate environment. The first example of this metathesis reaction is observed when 2 is treated with Na[B(C₆H₃(CF₃)₂)₄] resulting in [(cAAC)₂Cr]⁺[B(C₆H₃(CF₃)₂)₄]^–, a linear cationic complex with two coordinate Cr(i) and an S = 5/2 spin ground state.     

Kinetics of adsorption of metal ions on inorganic materials: A review

It is necessary to establish the rate law of adsorbate-adsorbent interactions to understand the mechanism by which the solute accumulates on the surface of a solid and gets adsorbed to the surface. A number of theoretical models and equations are available for the purpose and the best fit of the experimental data to any of these models is interpreted as giving the appropriate kinetics for the adsorption process. There is a spate of publications during the last few years on adsorption of various metals and other contaminants on conventional and non-conventional adsorbents, and many have tried to work out the kinetics. This has resulted from the wide interest generated on using adsorption as a practical method for treating contaminated water. In this review, an attempt has been made to discuss the kinetics of adsorption of metal ions on inorganic solids on the basis of published reports. A variety of materials like clays and clay minerals, zeolites, silica gel, soil, activated alumina, inorganic polymer, inorganic oxides, fly ash, etc. have been considered as the adsorbents and cations and anions of As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, and Zn as adsorbate have been covered in this review. The majority of the interactions have been divided into either pseudo first order or second order kinetics on the basis of the best fit obtained by various groups of workers, although second order kinetics has been found to be the most predominant one. The discussion under each category is carried out with respect to each type of metal ion separately. Application of models as given by the Elovich equation, intra-particle diffusion and liquid film diffusion has also been shown by many authors and these have also been reviewed. The time taken for attaining equilibrium in each case has been considered as a significant parameter and is discussed almost in all the cases. The values of the kinetic rate coefficients indicate the speed at which the metal ions adsorb on the materials and these are discussed in all available cases. The review aims to give a comprehensive picture on the studies of kinetics of adsorption during the last few years.     

Dimethyl sulfoxide induced structural transformations and non-monotonic concentration dependence of conformational fluctuation around active site of lysozyme

Experimental studies have observed significant changes in both structure and function of lysozyme (and other proteins) on addition of a small amount of dimethyl sulfoxide (DMSO) in aqueous solution. Our atomistic molecular dynamic simulations of lysozyme in water-DMSO reveal the following sequence of changes on increasing DMSO concentration. (i) At the initial stage (around 5% DMSO concentration) protein's conformational flexibility gets markedly suppressed. From study of radial distribution functions, we attribute this to the preferential solvation of exposed protein hydrophobic residues by the methyl groups of DMSO. (ii) In the next stage (10-15% DMSO concentration range), lysozome partially unfolds accompanied by an increase both in fluctuation and in exposed protein surface area. (iii) Between 15-20% concentration ranges, both conformational fluctuation and solvent accessible protein surface area suddenly decrease again indicating the formation of an intermediate collapse state. These results are in good agreement with near-UV circular dichroism (CD) and fluorescence studies. We explain this apparently surprising behavior in terms of a structural transformation which involves clustering among the methyl groups of DMSO. (iv) Beyond 20% concentration of DMSO, the protein starts its final sojourn towards the unfolding state with further increase in conformational fluctuation and loss in native contacts. Most importantly, analysis of contact map and fluctuation near the active site reveal that both partial unfolding and conformational fluctuations are centered mostly on the hydrophobic core of active site of lysozyme. Our results could offer a general explanation and universal picture of the anomalous behavior of protein structure-function observed in the presence of cosolvents (DMSO, ethanol, tertiary butyl alcohol, dioxane) at their low concentrations.     

Co-existence of multiple attractors in the PWM controlled DC drives

DC shunt and series drives are extensively used in the industry. The occurrence of bifurcation and chaos in dc shunt and permanent magnet drives are well known. It is observed that the behavior of the drives not only depends on the value of system parameters but also on the value of initial conditions. Multiple attractors can exist for same parameter value. Different choice of initial conditions gives different periodic behavior of the system. The drive is intended to operate in a parameter range to give period-1 behavior. We report the existence of sub- harmonic oscillations in the period-1 region of the bifurcation diagram along with co-existing attractor with fractal basin boundaries in PWM controlled dc series drives. The series drive is extensively used in electric traction and other applications. The dc drives are run with dc input voltage. This dc voltage may be derived from a dc source or an ac source with a rectifier. The dc series drive shows different bifurcation behavior when different types of input voltage and switching elements are used. The existence of period-1, period-2 and period-4 orbits are observed with different initial conditions in the desired period-1 region of the bifurcation diagram. The dependence of system’s behavior on initial condition may render the system’s behavior unpredictable. These phenomena may have serious implication in performance.