Speciation and Multinuclear NMR Spectroscopic Studies of Di- and Trimethyltin(IV) Moieties with MESNA in Aqueous Medium

The interaction of Me₂Sn(IV)²⁺ and Me₃Sn(IV)⁺ with a prodrug, sodium 2-mercaptoethane sulfonate (HSCH₂CH₂SO₃Na, MESNA) abbreviated as (HL), has been studied potentiometrically in aqueous solution (I = 0.1 mol·L^?1 KNO₃, 298 K). The concentration distribution of various species formed in the solution was studied with changes in pH (~3–11). A strong coordination of MESNA with metal through the S atom of thiol group has been found. In the Me₂Sn(IV)–HL system, the species [Me₂Sn(L)]⁺ (53.1–75.6%) is predominant at acidic pH (3.73 ± 0.02) and the species [Me₂Sn(L)₂OH]^? (29.4–38.5%) is predominant at basic pH (10.32 ± 0.08). In contrast, for the Me₃Sn(IV)⁺ system, [Me₃SnL] (37.0–57.4%) is the major species at pH 7.65 ± 0.03 and [Me₃Sn(OH)] (49.9–67.2%) and [Me₃Sn(L)(OH)]^? (30.2–46.5%) are the major species at pH 11.05 ± 0.01. However, at physiological pH (7.01 ± 0.32), in both (1:1) and (1:2) Me₂Sn(IV)–HL systems, the species [Me₂Sn(L)(OH)] (67.2–89.9%) is predominant, whereas for Me₃Sn(IV)–HL (1:1) and (1:2) systems, [Me₃Sn(OH)] (53.5%) and [Me₃SnL] (56.8%) are the respective predominant species. In order to characterize the possible geometry of the proposed complex species, multinuclear (¹H, ¹³C and ¹¹⁹Sn) NMR studies were carried out at different pHs. No polymeric species were detected in the experimental pH range.     

Functional analysis of repositioned anilide derivatives as anticancer compounds

Off the different types cancers 40% of the population have been observed to be affected by leukemia. Contemporary therapeutics is focusing on generation of new synthetic analogues that can exert maximum positive physiological effect with minimum dosage and negligible deleterious side effects. New generation pharmacists are focusing on such promising effects of Imatinib (a potential anti-cancer drug molecule), Dasatinib, Pelitinib and Nilotinib. The present research study focuses on novel synthesized anilides derivative against BCR-ABL kinase as potential anti-leukemic agent. Validation of the compounds by molecular docking with specific BCR-ABL kinase confirmed their activity. Toxicity prediction of these compounds helped to identify sustainability as therapeutic molecules. The IC₅₀ values were calculated (211 ug, 175 ug, 272ug for compounds A, B, C resp.) and the mode of cell death was gauged by DNA laddering assay. The cells were observed to be induced for programmed cell death. By validating and in-vivo testing of three synthesized compounds, the compound B was observed to be more stable thermodynamically with a potentially vital active site and appears to be a promising anti-leukemic factor. The present research thus lays a preliminary platform in world of pharmaceutics, where these new analogues appear to be efficient, target specific and less toxic molecules.     

Stannoxane capping derived from chiral tridentate NNO donor ligand for nickel and copper macrocycles: Comparative binding studies of stannoxane moiety and its modulated copper complex with CTDNA

Novel stannoxane type dinuclear tin complex C₁₆H₁₃N₄O₂Sn₂Cl₇ (1) and its modulated macrocyclic complexes [C₂₄H₃₆N₁₀O₃Sn₂CuCl₇] ClO₄ (2) and [C₂₄H₃₄N₁₀O₂Sn₂NiCl₇] ClO₄ (3) were synthesized and characterized by elemental analysis and various spectroscopic techniques (IR, ¹H, ¹³C, ¹¹⁹Sn NMR, ESI-MS, EPR and UV-Vis). ¹¹⁹Sn NMR shows the presence of two tin metal centers in different environment. The proposed pseudo-octahedral geometry of copper in complex 2 and square pyramidal geometry of nickel in complex 3 were established by the analysis of spectroscopic data. Absorption and fluorescence spectral studies and viscosity measurements have been carried out to assess the comparative binding of dinuclear stannoxane complex 1 and its modulated copper complex 2 with calf thymus DNA. The intrinsic binding constants K_b of the complex 1 and 2 were determined as 4.4 × 10⁴ M⁻¹ and 7.5 × 10⁴ M⁻¹, respectively. Cyclic voltammetric studies have also been employed to ascertain the binding of complex 2 with CTDNA. The results suggest that the complex 2 binds to CTDNA twice in the order of magnitude compared to complex 1. Interaction studies of complex 2 with guanosine 5′-monophosphate further confirm the binding via N₇ position of guanine and phosphate moiety.     

Synthesis of O,O Ethane Bridged Bis-copper(II) Macrocycles. Selective Enzyme Model for Catecholase Activity

New mononuclear and dinuclear complexes [3-hydroxyethyl-1,3,5,8,11pentaazacyclotridecane]copper(II) (1)/nickel(II) (2) perchlorate and O,O ethane bridged bis-copper(II) (3)/nickel(II) (4) macrocycles have been synthesized and characterized by various spectroscopic techniques, viz. i.r., n.m.r., e.p.r., u.v.–vis. and conductance measurements. Spectral data and conductance measurements reveal that all the complexes are consistent with square-planar geometry and are ionic in nature. The catalytic activity of the dinuclear Cu(II) complex (3) in the presence of pyrocatechol was determined spectrometrically by monitoring the increase of the o-benzoquinone characteristic absorption band at 25,000 cm⁻¹ with respect to time in DMF saturated with molecular oxygen. The kinetic parameters V_max (2.8×10⁻³ M s⁻¹) and K_M (1.4×10⁻³ mm) have been determined by Michaelis–Menten method. Electrochemistry of the dinuclear Cu(II) complex has been studied in the presence of molecular oxygen with pyrocatechol and without pyrocatechol at a scan rate of 0.1 V s⁻¹ by cyclic voltammetry. On addition of pyrocatechol, complex shows a shift in E_pc, E_pa and E_1/2 values indicating the oxidation of substrate (pyrocatechol).     

New diorganotin(IV) derivatives of 7-hydroxycoumarin (umbelliferone) and their adducts with 1,10-phenanthroline

New diorganotin(IV) derivatives of the general formula R2Sn(Umb)2 (where R = n-Bu, n-Oct and Ph; Umb = umbelliferone anion) have been synthesized either by the reaction of R2SnO with umbelliferone under azeotropic removal of water or by the reaction of R2SnCl2 with sodium salt of umbelliferone. Further, the adducts of the general formula R2Sn(Umb)2.phen (where R = n-Bu and n-Oct; phen = 1,10-phenanthroline) have also been synthesized by the interaction of R2Sn(Umb)2 with 1,10-phenanthroline. The bonding and coordination behavior in these derivatives are discussed on the basis of IR and 119Sn M?ssbauer spectroscopic studies in solid state. Their coordination behavior in solution is discussed by the multinuclear (1H, 13C and 119Sn) NMR spectral studies. The M?ssbauer and IR studies indicate that umbelliferone acts as a monoanionic bidentate ligand in R2Sn(Umb)2 coordinating through O(7) and O(1). A distorted octahedral geometry around tin has been proposed for R2Sn(Umb)2 as well as for R2Sn(Umb)2.phen in solid state. The newly synthesized derivatives have been tested for their anti-inflammatory and cardiovascular activities. The average LD50 value >1000 mg kg(-1) of these compounds indicates their safety margin.     

Multi-objective Energy Aware Scheduling of Deadline Constrained Workflows in Clouds using Hybrid Approach

Cloud computing is undoubtedly one of the most significant advances in the domain of information technology. It facilitates elastic and on-demand provisioning of high performance computing capabilities employing pay-per-use model that has snowballed its adoption by scientists and engineers over the past few years. They often exploit workflows to represent their massive applications. Workflow scheduling in cloud has been devoted considerable investigation by researchers owing to its NP-complete nature of problem. Most of the previous studies targeted optimization of schedule length and execution cost within given deadlines/budget restrictions, or both. However, enormous energy consumption in the cloud data centers is not only negatively impacting the environment but also resulting in increased operational costs and thus cannot be ignored. Efficient scheduling strategies can significantly lessen the energy usage while complying with the user’s Quality of Service limitations. This research study proposes a Hybrid Approach for Energy aware scheduling of Deadline constrained workflows (HAED) using Intelligent Water Drops algorithm and Genetic Algorithm, which provides non-dominated solutions to the user. In particular, it focuses on multiple objectives i.e. reduction of schedule length, execution cost and energy usage within deadlines specified by the user. Its performance has been assessed on four scientific workflows from diverse domains using hypervolume and set coverage. The results achieved with the simulations demonstrate that the solutions produced by HAED are of better quality in terms of accuracy and diversity than non-dominated sorting genetic algorithm and hybrid particle swarm optimization.

     

Determining Honesty of Accuser Nodes in Key Revocation Procedure for MANETs

Mobile Networks and Applications - Management of encryption keys is an essential task for establishing secure communication in a mobile ad hoc network (MANET). Any key management scheme must be...     

Rotational dynamics of propylene inside Na-Y zeolite cages

We report here the quasielastic neutron scattering (QENS) studies on the dynamics of propylene inside Na-Y zeolite using triple axis spectrometer (TAS) at Dhruva reactor, Trombay. Molecular dynamics (MD) simulations performed on the system had shown that the rotational motion involves energy larger than that involved in the translational motion. Therefore, rotational motion was not observed in our earlier QENS studies on propylene adsorbed Na-Y zeolite using a higher resolution spectrometer at Dhruva. Analysis of the TAS spectra revealed that the quasielastic broadening observed in propylene-loaded zeolite spectra is due to the rotational motion of the propylene molecules. This is consistent with our simulation result. Further, the rotational motion is found to be isotropic. The rotational diffusion coefficient has been obtained.      

Characterization and pH stability of insoluble products of the reaction between cyanide and ferrous sulphate

X-ray diffraction (XRD), infrared (IR) spectroscopy and⁵⁷Fe Mössbauer effect spectroscopy were used to characterize and monitor the pH stability of cyanide and ferrous sulphate reaction mixtures. Limited information was obtained from the XRD and IR measurements because of the amorphous nature of the samples. The Mössbauer studies show that considerable changes occur when there is an increase in pH at which the sample is prepared. Prussian-blue type compounds and iron oxide in the form of small particles crystallize out at low and high pH values, while additional complexes are formed at intermediate pH values of 6 to 9.⁵⁷Fe Mössbauer effect spectroscopy is thus a powerful technique for monitoring the environmental stability of cyanide waste streams that result when modern methods of extractive metallurgy of gold are employed on mineral ores.