Electrochemical, phosphate hydrolysis, DNA binding and DNA cleavage properties of new polyaza macrobicyclic dinickel(II) complexes

A new class of macrobicyclic dinickel(II) complexes Ni2L1,2 B](ClO4)(4) (1-6), where L-1,L-2 are polyaza macrobicyclic binucleating ligands, and B is a N,N-donor heterocyclic base (viz. 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen)) are synthesized and characterized. The redox, catalytic, DNA binding and DNA cleavage properties were studied. They exhibit two irreversible waves in the cathodic region around E-pc = -0.95 V and E-pa = -0.85 V vs. Ag/Ag+ in CH3CN-0.1 M TBAP, respectively. The first order rate constants for the hydrolysis of 4-nitrophenylphosphate to 4-nitrophenolate by the dinickel(II) complexes 1-6 are in the range from 3.36 x 10(-5) to 10.83 x 10(-5) Ms-1. The complexes 3 and 6 show good binding propensity to calf thymus DNA giving binding constant values (K-b) in the range from 3.08 x 10(5) to 5.37 x 10(5) M-1. The binding site sizes and viscosity data suggest the DNA intercalative and/or groove binding nature of the complexes. The complexes display significant hydrolytic cleavage of supercoiled pBR322DNA at pH 7.2 and 37 degrees C. The hydrolytic cleavage of DNA by the complexes is supported by the evidence from free radical quenching and T4 ligase ligation. The pseudo Michaelis-Menten kinetic parameters k(cat) = 5.44 x 10(-2) h(-1) and K-M = 6.23 x 10(-3) M for complex 3 were obtained. Complex 3 also shows an enormous enhancement of the cleavage rate, of 1.5 x 10(6), in comparison to the uncatalysed hydrolysis rate (k = 3.6 x 10(-8) h(-1)) of ds-DNA.

Gibbs Energy of Formation of Ca3Ti8Al12O37 and Phase Relations and Chemical Potentials in the System Al2O3-TiO2-CaO

The quaternary oxide in the system Al2O3-CaO-TiO2 is found to have the composition Ca3Ti8Al12O37 rather than CaTi3Al8O19 as reported in the literature. The standard Gibbs energy of formation of Ca3Ti8Al12O37 from component binary oxides is measured in the temperature range from 900 to 1250 K using a solid-state electrochemical cell incorporating single crystal CaF2 as the solid electrolyte. The results can be represented by the equation: delta G(f(0x))(0) (+/- 70)/J mol(-1) = -248474 - 15.706(T/K). Combining this information with thermodynamic data on calcium aluminates and titanates available in the literature, subsolidus phase relations in the pseudo-ternary system Al2O3-CaO-TiO2 are computed and presented as isothermal sections. The evolution of phase relations with temperature is highlighted. Chemical potential diagrams are computed at 1200 K, showing the stability domains of the various phases in the chemical potential-composition space. In each chemical potential diagram, chemical potential of one component is plotted against the cationic fraction of the other two components. The diagrams are valid at relatively high oxygen potentials where Ti is present in its four-valent state in all the oxide phases.

Nucleation-Growth Mode of Cubic-Tetragonal Transition with Coexistence of Phases over a Wide Temperature Interval in the High Temperature Ferroelectric Systems PbTiO3-BiMeO3:Me = Sc , and Zn1/2Ti1/2

Temperature dependent X-ray powder diffraction and dielectric studies have been carried out on tetragonal compositions of (1-x) PbTiO 3(x) BiMeO 3; Me similar to Sc and Zn 1/2 Ti 1/2. The cubic and the tetragonal phases coexist over more than 100 degrees C for 0.70 PbTiO 30.3 Bi ( Zn 1/2 Ti 1/2) O 3 and 0.66 PbTiO 30.34 BiScO 3. The wide temperature range of phase coexistence is shown to be an intrinsic feature of the system, and is attributed to the increase in the degree of the covalent character of the ( Pb +Bi ) O bond with increasing concentration of Bi at the Pb -site. The d-values of the {111} planes of the coexisting phases are nearly identical, suggesting this plane to be the invariant plane for the martensitic type cubic-tetragonal transformation occurring in these systems.

Synthesis dependent characteristics of Sr1-xMnxTiO3 (x=0.03, 0.05, 0.07 and 0.09)

Sr1-xMnxTiO3 (where x=0.03, 0.05, 0.07 and 0.09) was synthesized via different routes that include solid-state, oxalate precipitation and freeze drying. In oxalate precipitation technique, compositions corresponding to 3 and 5 mol% doping of Mn were monophasic whereas the higher compositions revealed the presence of the secondary phases such as MnO, Mn3O4 etc., as confirmed by high resolution X-ray diffraction (XRD) studies. The decomposition behavior of the precursors prepared using oxalate precipitation method corresponding to the above mentioned compositions was studied. Nanopowders of compositions pertaining to 5 to 9 mol% of Mn doping were obtained using freeze-drying technique. The average crystallite size of these nanopowders was found to be in the 35 to 65 nm range. The microstructural studies carried out on the sintered ceramics, fabricated using powders synthesized by different routes established the fine grained nature ( < 1 mu m) of the one obtained by freeze drying method. Raman scattering studies were carried out in order to complement the observations made from XRD regarding the phase purity. The dielectric properties of the ceramics obtained by different synthesis routes were studied in the 80-300 K temperature range at 100 kHz and the effect of grain size has been discussed. (C) 2012 Elsevier Inc. All rights reserved.

Phase relationships and magnetic properties of TbxDy1-xFe1.95 alloys

The effect of Tb/Dy ratio on the structural and magnetic properties of (Tb,Dy)Fe-2 class of alloys has been investigated using nine alloys of TbxDy1-xFe1.95 (x = 0-1) covering the entire range. Our results indicate that the three phases viz. (Tb,Dy)Fe-2 (major phase), (Tb,Dy)Fe-3 and(Tb,Dy)-solid solution (minor phases) coexist in all the alloys. The volume fraction of pro-peritectic (Tb,Dy)Fe-3 phase however, has a minimum at x = 0.4 and a maximum at x = 0.6 compositions. The volume fraction of this phase decreases upon heat treatment at 850 degrees C and 1000 degrees C. A Widmanstatten type precipitate of (Tb,Dy)Fe-3 was observed for Dy-rich compositions (0 <= x <= 0.5). The microstructural investigations indicate that the ternary phase equilibria of Tb-Dy-Fe are sensitive to Tb/Dy ratio including the expansion of (Tb,Dy)Fe-2 phase field which is in contrast to the pseudo-binary assumption that is followed in available literature to date. The lattice parameter, Curie temperature and coercivity are found to increase with Tb addition. Split of (440) peak of (Tb,Dy)Fe-2 observed in x >= 0.3 alloys indicate, a spin reorientation transition from 100] to 111] occurs with Tb addition. (C) 2012 Elsevier B. V. All rights reserved.

Role of Specific Cations and Water Entropy on the Stability of Branched DNA Motif Structures

DNA three-way junctions (TWJs) are important intermediates in various cellular processes and are the simplest of a family of branched nucleic acids being considered as scaffolds for biomolecular nanotechnology. Branched nucleic acids are stabilized by divalent cations such as Mg2+, presumably due to condensation and neutralization of the negatively charged DNA backbone. However, electrostatic screening effects point to more complex solvation dynamics and a large role of interfacial waters in thermodynamic stability. Here, we report extensive computer simulations in explicit water and salt on a model TWJ and use free energy calculations to quantify the role of ionic character and strength on stability. We find that enthalpic stabilization of the first and second hydration shells by Mg2+ accounts for 1/3 and all of the free energy gain in 50% and pure MgCl2 solutions, respectively. The more distorted DNA molecule is actually destabilized in pure MgCl2 compared to pure NaCl. Notably, the first shell, interfacial waters have very low translational and rotational entropy (i.e., mobility) compared to the bulk, an entropic loss that is overcompensated by increased enthalpy from additional electrostatic interactions with Mg2+. In contrast, the second hydration shell has anomalously high entropy as it is trapped between an immobile and bulklike layer. The nonmonotonic entropic signature and long-range perturbations of the hydration shells to Mg2+ may have implications in the molecular recognition of these motifs. For example, we find that low salt stabilizes the parallel configuration of the three-way junction, whereas at normal salt we find antiparallel configurations deduced from the NMR. We use the 2PT analysis to follow the thermodynamics of this transition and find that the free energy barrier is dominated by entropic effects that result from the decreased surface area of the antiparallel form which has a smaller number of low entropy waters in the first monolayer.

Variation of Snowline and Mass Balance of Glaciers of Warwan and Bhut Basins of Western Himalaya Using Remote Sensing Technique

Glaciers are natural reservoirs of fresh water in frozen state and sensitive indicators of climate change. Among all the mountainous glaciated regions, glaciers of Himalayas form one of the largest concentrations of ice outside the Polar Regions. Almost all the major rivers of northern India originate from these glaciers and sustain perennial flow. Therefore, in view of the importance and role of the glaciers in sustaining the life on the Earth, monitoring the health of glaciers is necessary. Glacier's health is monitored in two ways (i) by mapping the change in extent of glaciers (ii) by finding variation in the annual mass balance. This paper has been discussed the later approach for monitoring the health of glaciers of Warwan and Bhut basins. Mass balance of glaciers of these two basins was determined based on the extraction of snow line at the end of ablation season. A series of satellite images of AWiFS sensor were analysed for extraction of snowline on the glaciers for the period of 2005, 2006 and 2007. The snow line at the end of ablation season is used to compute accumulation area ratio (AAR = Accumulation area/Glacier area) for each glacier of basins. An approach based on relationship of AAR to specific mass balance (computed in field) for glaciers of Basapa basin was employed in the present study. Mean of specific mass balance of individual glacier for the year 2005, 2006 and 2007 of Warwan basin was found to be -ve 0.19 m, -ve 0.27 m and -ve 0.2 m respectively. It is 0.05 m, -ve 0.11 m and -ve 0.19 m for Bhut basin. The analysis suggests a loss of 4.3 and 0.83 kmA(3) of glacier in the monitoring period of 3 years for Warwan and Bhut basins respectively. The overall results suggest that the glaciers of Warwan basin and Bhut basins have suffered more loss of ice than gain in the monitoring period of 3 years.

Nuclear targeting terpyridine iron(II) complexes for cellular imaging and remarkable photocytotoxicity

Iron(II) complexes Fe(L)(2)](2+) as perchlorate (1-3) and chloride (1a-3a) salts, where L is 4'-phenyl-2,2':6',2 `'-terpyridine (phtpy in 1, 1a), 4'-(9-anthracenyl)-2,2':6',2 `'-terpyridine (antpy in 2, 2a) and 4'-(1-pyrenyl)-2,2':6',2 `'-terpyridine (pytpy in 3, 3a), were prepared and their photocytotoxicity studied. The diamagnetic complexes 1-3 having an FeN6 core showed an Fe(III)-Fe(II) redox couple near 1.0 V vs. saturated calomel electrode in MeCN-0.1 M tetrabutylammonium perchlorate. Complexes 2 and 3, in addition, displayed a quasi-reversible ligand-based redox process near 0.0 V. The redox and spectral properties are rationalized from the theoretical studies. The complexes bind to DNA in a partial intercalative mode. The pytpy complex efficiently photo-cleaves DNA in green light via superoxide and hydroxyl radical formation. The antpy and pytpy complexes exhibited a remarkable photocytotoxic effect in HeLa cancer cells (IC50, similar to 9 mu M) in visible light (400-700 nm), while remaining essentially nontoxic in dark (IC50, similar to 90 mu M). Formation of reactive oxygen species (ROS) inside the HeLa cells was evidenced from the fluorescence enhancement of dichlorofluorescein upon treatment with the pytpy complex followed by photo-exposure. The antpy and pytpy complexes were used for cellular imaging. Confocal imaging and dual staining study using propidium iodide (PI) showed nuclear localization of the complexes. (c) 2012 Elsevier Inc. All rights reserved.

Preparation and characterization chemistry of nano-crystalline Ni-Cu-Zn ferrite

In submitted research; nanocrystalline powders having elements Ni0.5Cu0.25Zn0.25Fe2 xInxO4 with varied amounts of indium ( x = 0.0, 0.1, 0.2, 0.3 and 0.4) were grown-up by modified citrate to nitrate alchemy. The realism of single phase cubic spinel creation of the synthesized ferrite samples was studied by the DTA-TGA, XRD, SEM, EDX, FT-IR, VSM and dielectric measurements. SEM was applied to inspect the morphological variations and EDX was used to determine the compositional mass ratios. The studies on the dielectric constant (epsilon'), dielectric loss (epsilon `'), loss tangent (tan delta), ac conductivity (sigma(ac)), resistive and reactive parts of the impedance analysis (Z' and Z `') at room temperature were also carried out. The saturation magnetizations (Ms) were determined using the vibrating sample magnetometer (VSM). Ms. decreased with the increase In3+ doping content, as Fe3+ of 5(mu B) ions are replaced by In3+ of 5 mu(B) ions. (C) 2012 Elsevier B. V. All rights reserved.

Thermally reversing window in Ge15Te85-xInx glasses: Nanoindentation and micro-Raman studies

Nanoindentation studies on Ge15Te85-xInx glasses indicate that the hardness and elastic modulus of these glasses increase with indium concentration. While a pronounced plateau is seen in the elastic modulus in the composition range 3 <= x <= 7, the hardness exhibits a change in slope at compositions x = 3 and x = 7. Also, the density exhibits a broad maximum in this composition range. The observed changes in the mechanical properties and density are clearly associated with the thermally reversing window in Ge15Te85-xInx glasses in the composition range 3 <= x <= 7. In addition, a local minimum is seen in density and hardness around x = 9, the chemical threshold of the system. Further, micro-Raman studies reveal that as-quenched Ge15Te85-xInx samples exhibit two prominent peaks, at 123 cm(-1) and 155 cm(-1). In thermally annealed samples, the peaks at 120 cm(-1) and 140 cm(-1), which are due to crystalline Te, emerge as the strongest peaks. The Raman spectra of polished samples are similar to those of annealed samples, with strong peaks at 123 cm(-1) and 141 cm(-1). The spectra of lightly polished samples outside the thermally reversing window resemble those of thermally annealed samples; however, the spectra of glasses with compositions in the thermally reversing window resemble those of as-quenched samples. This observation confirms the earlier idea that compositions in the thermally reversing window are non-aging and are more stable. (C) 2012 Elsevier B.V. All rights reserved.

Air oxygenation chemistry of 4-TBC catalyzed by chloro bridged dinuclear copper(II) complexes of pyrazole based tridentate ligands: synthesis, structure, magnetic and computational studies

Four dinuclear bis(mu-Cl) bridged copper(II) complexes, Cu-2(mu-Cl)(2)(L-X)(2)](ClO4)(2) (L-X = N,N-bis(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine with X = H(1), OMe(2), Me(3) and Cl(4)), have been synthesized and characterized by the single crystal X-ray diffraction method. In these complexes, each copper(II) center is penta-coordinated with square-pyramidal geometry. In addition to the tridentate L-X ligand, a chloride ion occupies the last position of the square plane. This chloride ion is also bonded to the neighboring Cu(II) site in its axial position forming an SP-I dinuclear Cu(II) unit that exhibits small intramolecular ferromagnetic interactions and supported by DFT calculations. The complexes 1-3 exhibit methylmonooxygenase (pMMO) behaviour and oxidise 4-tert-butylcatechol (4-TBCH2) with molecular oxygen in MeOH or MeCN to 4-tert-butyl-benzoquinone (4-TBQ), 5-methoxy-4-tert-butyl-benzoquinone (5-MeO-4-TBQ) as the major products along with 6,6'-Bu-t-biphenyl-3,4,3',4'-tetraol and others as minor products. These are further confirmed by ESI- and FAB-mass analyses. A tentative catalytic cycle has been framed based on the mass spectral analysis of the products and DFT calculations on individual intermediates that are energetically feasible.

Dual Role of Acetate as a Nucleophile and as an Internal Base in Cycloplatination Reaction of sym-N,N `,N `'-Triarylguanidines

Reaction of cis-Cl2Pt(S(O)Me-2)(2)] with 1 equiv of sym-N,N',N `'-triarylguanidines, ArN=C(NHAr)(2) (sym = symmetrical; Ar = 2-MeC6H4 (LH22-tolyl), 2-(MeO)C6H4 (LH22-anisyl), 4-MeC6H4 (LH24-tolyl), 2,5-Me2C6H3 (LH22,5-xylyl), and 2,6-Me2C6H3 (LH22,6-xylyl)) in toluene under reflux condition for 3 h afforded cis- or trans-Cl2Pt(S(O)Me-2)(ArN=C(NHAr)(2))] (Ar = 2-MeC6H4 (1), 2-(MeO)C6H4 (2), 4-MeC6H4 (3), 2,5-h Me2C6H3 (4), and 2,6-Me2C6H3 (5), respectively) in 83-96% yield. Reaction of cis-Cl2Pt(S(O)Me-2)(2)] with 1 equiv of LH22-tolyl and LH24-tolyl in the presence of 1 equiv of NaOAc in methanol under reflux condition for 3 h afforded acetate-substituted products, cis-(AcO)ClPt(S(O)Me-2)(ArN=C(NHAr)(2))] (Ar = 2-MeC6H4 (6) and 4-MeC6H4 (7)) in 83% and 84% yields, respectively. Reaction of cis-Cl2Pt(S(O)Me-2)(2)] with 1 equiv of LH22-anisyl and LH22-tolyl in the presence of 1 equiv of NaOAc in methanol under reflux condition for 3 and 12 h afforded six-membered C,N] platinacycles, Pt{kappa(2)(C,N)-C6H3R-3(NHC(NHAr)(=NAr))-2}Cl(S(O)Me-2)] (Ar = 2-RC6H4; R = OMe (8) and Me (9)), in 92% and 79% yields, respectively. The new complexes have been characterized by analytical and spectroscopic techniques, and further the molecular structures of 1, 2, 4, 5, 6, and 8 have been determined by single-crystal X-ray diffraction. The platinum atom in 1, 4, and 5 exhibited the trans configuration, while that in 2, 6, and 8 exhibited the cis configuration. Complex 6 is shown to be the precursor for 9, and the former is suggested to transform to the latter possibly via an intramolecular C-H activation followed by elimination of AcOH. The solution behavior of new complexes has been studied by multinuclear NMR (H-1, Pt-195, and C-13) spectroscopy. The new complexes exist exclusively as a single isomer (trans (1 and 5) and cis (6 and 7)), a mixture of cis and trans isomers with the former isomer being predominant in the case of 2 and the latter isomer being predominant in the case of 3. Complex 5 in the trans form revealed the presence of one isomer at 0.007 mM concentration and two isomers in about 1.00:0.12 ratio at 0.154 mM concentration as revealed by H-1 NMR spectroscopy, and this has been ascribed to the restricted Pt-S bond rotation at higher concentration. Platinacycle 8 exists as one isomer, while 9 exists as a mixture of seven isomers in solution. The influence of steric factor, pi-acceptor property of the guanidine, subtle solid-state packing forces upon the configuration of the platinum atom, and the number of isomers in solution have been outlined. Factors that accelerate or slow down the cycloplatination reaction, the role of NaOAc, and a plausible mechanism of this reaction have been discussed.

Mixed-ligand nickel(II) thiosemicarbazone complexes: Synthesis, characterization and biological evaluation

The syntheses and characterization of some new mixed-ligand nickel(II) complexes {Ni(L-1)(PPh3)] (1), Ni(L-1)(Py)] (2), Ni(L-2)(PPh3)]center dot DMSO (3), Ni(L-2)(Imz)] (4), Ni(L-3)(4-pic)] (5) and RNi(L-3))(2)(mu-4,4'-byp)]center dot 2DMSO (6)1 of three selected thiosemicarbazones the 4-(p-X-phenyl)thiosemicarbazones of salicylaldehyde) (H2L1-3) (A, Scheme 1) are described in the present study, differing in the inductive effect of the substituent X (X = F, Br and OCH3), in order to observe its influence, if any, on the redox potentials and biological activity of the complexes. All the synthesized ligands and the metal complexes were successfully characterized by elemental analysis, IR, UV-Vis, NMR spectroscopy and cyclic voltammetry. The molecular structures of four mononuclear (1-3 and 5) and one dinuclear (6) Ni(II) complex have been determined by X-ray crystallography. The complexes have been screened for their antibacterial activity against Escherichia coli and Bacillus. The minimum inhibitory concentrations of these complexes and their antibacterial activities indicate that compound 4 is the potential lead molecule for drug designing. (C) 2012 Elsevier Ltd. All rights reserved.

Planar triazinium cations from vanadyl-mediated ring cyclizations: the thiazole species for efficient nuclear staining and photocytotoxicity

Planar triazinium cationic species from vanadyl-assisted cyclization of 1-(2-thiazolylazo)-2-naphthol (H-TAN, 1), 1-(2-pyridylazo)-2-naphthol (H-PAN, 2), 2-(2'-thiazolylazo)-p-cresol (H-TAC, 3) and 6-(2'-thiazolylazo)- resorcinol (H-TAR, 5) were prepared and characterized. A dioxovanadium(V) species VO2(TAR)] (4) was also isolated. Compounds 1, 2 and 4 were structurally characterized. Both 1 and 2 have planar structures. Complex 4 has (VO3N2)-O-V coordination geometry. The cyclised triazinium compound forms a radical species within -0.06 to -0.29 V vs. SCE in DMF-0.1 M tetrabutylammonium perchlorate with a second response due to formation of an anionic species. A confocal microscopic study showed higher nuclear uptake for 1 having a fused thiazole moiety than 2 with a fused pyridine ring. The compounds showed a partial intercalative mode of binding to calf thymus DNA. Compound 1 showed plasmid DNA photo-cleavage activity under argon and photocytotoxicity in HeLa and MCF-7 cells with IC50 values of 15.1 and 3.4 mu M respectively in visible light of 400-700 nm, while being essentially non-toxic in the dark with IC50 values of 90.4 and 21.9 mu M. ATDDFT study was done to rationalize the experimental data.

Breakdown of the Stokes-Einstein relation in two, three, and four dimensions

The breakdown of the Stokes-Einstein (SE) relation between diffusivity and viscosity at low temperatures is considered to be one of the hallmarks of glassy dynamics in liquids. Theoretical analyses relate this breakdown with the presence of heterogeneous dynamics, and by extension, with the fragility of glass formers. We perform an investigation of the breakdown of the SE relation in 2, 3, and 4 dimensions in order to understand these interrelations. Results from simulations of model glass formers show that the degree of the breakdown of the SE relation decreases with increasing spatial dimensionality. The breakdown itself can be rationalized via the difference between the activation free energies for diffusivity and viscosity (or relaxation times) in the Adam-Gibbs relation in three and four dimensions. The behavior in two dimensions also can be understood in terms of a generalized Adam-Gibbs relation that is observed in previous work. We calculate various measures of heterogeneity of dynamics and find that the degree of the SE breakdown and measures of heterogeneity of dynamics are generally well correlated but with some exceptions. The two-dimensional systems we study show deviations from the pattern of behavior of the three-and four-dimensional systems both at high and low temperatures. The fragility of the studied liquids is found to increase with spatial dimensionality, contrary to the expectation based on the association of fragility with heterogeneous dynamics.