Multinuclear (Sn/Pd) complexes with disodium 2,2′-(dithiocarboxyazanediyl)diacetate hydrate; Synthesis,characterization and biological activities

Bimetallic chlorodi-/triorganotin(IV) derivatives of general formulas R₂(H₂O)SnLCSSSn(Cl)R₂ (R=Me: 1; Ph: 2) and R₃Sn(Na)LCSSSnR₃·H₂O (R=Bu: 3; Ph: 4) were prepared by reaction of iminodiacetic acid disodium salt hydrate (Na₂LH) with CS₂ and R₂SnCl₂/R₃SnCl in methanol. The reaction between Na₂LH, CS₂, and PdCl₂ produced [Na₂LCSS]₂Pd·2H₂O (5) which was treated with R₃SnCl to synthesize the heterobimetallic derivatives [R₃Sn(Na)LCSS]₂Pd·2H₂O (R=Me: 6; Ph: 7). The complexes were characterized by microanalysis, spectroscopic, and thermogravimetric analyses. Elemental analysis data, mass fragmentation, and thermal degradation patterns supported the molecular composition of the complexes. FT-IR data indicated monodentate binding of carboxylate while a chelating coordination mode of the dithiocarboxylate was verified in the solid state. A five-coordinate tin(IV) was demonstrated in the solid state. In solution, a tetrahedral/trigonal bipyramidal configuration around Sn(IV) and a square planar geometry of Pd(II) was indicated by multinuclear NMR (¹H and ¹³C) and UV-visible studies. The Pd(II) derivatives showed interaction with salmon sperm-DNA and caused an inhibition of alkaline phosphatase (ALPs). The antibacterial/antifungal potential of the coordination products varied with the nature of incorporated metal and a substitution pattern at tin(IV); the palladium metallation decreased the antimicrobial activities. The triorganotin(IV) products exhibited more powerful action against bacteria/fungi as compared to their diorganotin(IV) counterparts. The complexes displayed sufficiently lower hemolytic effects in vitro as compared to triton X-100 and slightly higher than PBS.     

Direct simulation of compressible turbulence in a shear flow

The purpose of this study is to investigate compressibility effects on the turbulence in homogeneous shear flow. We find that the growth of the turbulent kinetic energy decreases with increasing Mach number—a phenomenon which is similar to the reduction of turbulent velocity intensities observed in experiments on supersonic free shear layers. An examination of the turbulent energy budget shows that both the compressible dissipation and the pressure-dilatation contribute to the decrease in the growth of kinetic energy. The pressure-dilatation is predominantly negative in homogeneous shear flow, in contrast to its predominantly positive behavior in isotropic turbulence. The different signs of the pressure-dilatation are explained by theoretical consideration of the equations for the pressure variance and density variance. We previously obtained the following results for isotropic turbulence: first, the normalized compressible dissipation is of O(M _t ² ), and, second, there is approximate equipartition between the kinetic and potential energies associated with the fluctuating compressible mode. Both these results have now been substantiated in the case of homogeneous shear. The dilatation field is significantly more skewed and intermittent than the vorticity field. Strong compressions seem to be more likely than strong expansions.Dedicated to Professor J.L. Lumley on the occasion of his 60th birthday.This research was supported by the National Aeronautics and Space Administration under NASA Contract No. NAS1-18605 while the authors were in residence at the Institute for Computer Applications in Science and Engineering (ICASE), NASA Langley Research Center, Hampton, VA 23665, U.S.A.     

Effect of Temperature on Cd2+ Sorption by Mixed Oxides of Iron and Silicon

The current study focuses on the synthesis and sorption properties of two mixed oxides of iron and silicon prepared by physical mixing (M₁) and sequential precipitation methods (M₂). Both the mixed oxides were synthesized from equimolar ratios of Fe(OH)₃ and SiO₂ and characterized for surface area, EDX, XRD and PZC. The surface area, micropore volume and average pore width of the oxide M₁ were higher as compared to the oxide M₂. However, potentiometric titrations revealed that mixed oxide synthesized by this method had a very high capacity towards Cd²⁺ ions as compared to the mixed oxide M₁. Sorption of Cd²⁺ ions at pH 5 on mixed oxide, M₂ was found to increase with temperature in the range 288 to 318 K. Langmuir equation was found applicable to the sorption data with R²>0.99. Entropy (ΔS^?), enthalpy (ΔH^?) and free energy changes (ΔG^?) were calculated which revealed the process to be endothermic and spontaneous in nature.     

Adsorption Studies of Radionuclides and Toxic Metal Ions on a Modified Mesoporous Lanthanum(III) Silicate

A new adsorbent, modified mesoporous lanthanum(III) silicate, has been prepared with various molar ratios of Si/La (10, 20, 40, 80) and cethyltrimethylammonium bromide (CTAB) as structure directing agent. XRD, nitrogen sorption, SEM, IR, thermogravimetry and sorption of radionuclides and toxic metal ions have been studied. The results show that adsorption amount of some element such as Pb(II) and Th(IV) has been increased significantly by incorporation of lanthanum ions in the framework of adsorbent. Separation of Co(II)‐Th(IV), Co(II)‐U(VI) and Mo(VI)‐U(VI) has been developed on columns of this adsorbent.     

Oral feeding of pomegranate fruit extract inhibits early biomarkers of UVB radiation-induced carcinogenesis in SKH-1 hairless mouse epidermis

Pomegranate from the plant Punica granatum L. possesses strong antioxidant and anti-inflammatory properties. Recently, we have demonstrated that treatment of normal human epidermal keratinocytes with pomegranate fruit extract (PFE) inhibited UVB-mediated activation of nuclear factor kappa B (NF-κB) and mitogen activated protein kinases pathways. Here, we evaluated the effect of PFE on early biomarkers of photocarcinogenesis employing SKH-1 hairless mice. PFE was provided in drinking water (0.2%, wt/vol) to SKH-1 hairless mice for 14 days before a single UVB (180 mJ cm⁻²) irradiation. We found that oral feeding of PFE inhibited UVB-induced: (1) skin edema; (2) hyperplasia; (3) infiltration of leukocytes; (4) lipid peroxidation; (5) hydrogen peroxide generation; (6) ornithine decarboxylase (ODC) activity; and (7) ODC, cyclooxygenase-2 and proliferating cell nuclear antigen protein expression. Oral feeding of PFE enhanced repair of UVB-mediated formation of cyclobutane pyrimidine dimers (CPDs) and 8-oxo-7,8-dihydro-2′-deoxyguanosine (8-oxodG). Importantly, PFE treatment further enhanced UVB-mediated increase in tumor suppressor p53 and cyclin kinase inhibitor p21. Furthermore, oral feeding of PFE inhibited UVB-mediated: (1) nuclear translocation of NF-κB; (2) activation of IKKα; and (3) phosphorylation and degradation of IκBα. Taken together, we provide evidence that oral feeding of PFE to mice affords substantial protection from the adverse effects of UVB radiation via modulation in early biomarkers of photocarcinogenesis and provide suggestion for its photochemopreventive potential.     

Modification of tricine–SDS–PAGE for online and offline analysis of phosphoproteins by ICP-MS

This study describes a modification to tricine sodium dodecyl sulphate polyacrylamide gel electrophoresis to make it more effective for the separation of low molecular mass proteins and for coupling with inductively coupled plasma mass spectrometry (ICP-MS). The modified method employs low-percentage polyacrylamide gels (7–10%) (w/v) and low reagent concentrations that provide efficient separations, good quantitation and low matrix levels that are compatible with ICP-MS. Using phosphopeptides as a model system, and offline analysis, we obtained recoveries of 73% (w/v) in a 9% gel compared with 55% in a conventional 16% gel. Online coupling was achieved by modification of a standard commercially available gel electroelution apparatus and casting of the gel into a 7.3-cm-long tube. Online separation of a digest of β-casein was demonstrated with recovery of the mono- and tetraphosphopeptides, which were identified by comparison with peptide standards. A mass balance study with the standards yielded recoveries of 95% for tetraphosphopeptides and 48% for monophosphopeptides. The factors affecting the separations and recoveries are discussed in detail. The detection limits for 10-μL samples of the mono- and tetraphosphopeptides were 0.7 μM (7 pmol) and 0.2 μM (2 pmol) respectively.     

Simple gas chromatographic method for the quantification of total cholesterol in fish meats

Six fish species-Cirrhinus mrigala (Morakhi), Labeo rohita (Danbhro), Catla catla (Thalli), Wallago attu (Jarko), Ctenopharyngodon idella (Grass), and Cyprimus carpio (Gulfam)--commonly found in the Pakistani Indus river, were selected for fat and cholesterol evaluation. Fat content was quantified by the Folch method and cholesterol content was determined by a simple GC method. The application of the proposed method to quantify cholesterol content revealed variations among the six breeds evaluated. The breeds studied contained 0.80-1.95% fat, indicating that all investigated fishes were lean; significant variation was found in cholesterol content, and ranged between 72 and 392 mg/100 g. Standard addition analyses showed that the method was accurate, as the recovery of cholesterol varied from 95 to 103%, with a coefficient of variance not more than 5.6%. The results showed that, after the development of suitable calibration, within 11 min, the cholesterol could be accurately determined by GC.     

Ionic studies of sodium alginate isolated from Sargassum terrarium (brown algea) karachi coast with 2,1-electrolyte

Physical and chemical analysis of the polysaccharide isolated from Sargassum Terarrium (brown algae) of Karachi coast showed characteristics of the sodium alginate. Optical rotations and sulphated ash content were found and FTIR spectra showed a sharp and strong absorption band at 1600 cm^?1 representing carboxylate ion which conforms high uronic acid content of the product. The viscosities of aqueous 0.1% sodium alginate solution were measured in the presence of copper II chloride (CuCl₂). The viscosities were found to be increased with the increase in the concentration of electrolyte. Viscosities were also found affected with temperature. ‘A’ and ‘B’ coefficients of Jones–Dole equation were evaluated. The increase in positive values of ‘B’ coefficient with the rise of temperature led to conclusion that given electrolyte in 0.1% aqueous sodium alginate solution behaves as structure maker. Thermodynamic parameters regarding to activated state like energy of activation E_η, change in free energy of activation ΔG_η and change of entropy of activation ΔS_η were also evaluated. Straight-line plots of log η versus 1/T observed with positive slopes show the effect of temperature on the viscosities of solutions. Energy of activation (E_η) was found to be decreased with the rise of temperature. Change in free energy of activation (ΔG_η) was also found to be increased with increase in concentrations of electrolyte and also with rise of temperature. The values of change in entropy of activation (ΔS_η) were also calculated. Negative values of ΔS_η were found to be increased with increase in concentration of electrolyte and also with rise of temperature.     

Influence of substrate temperature on the properties of electron beam evaporated ZnSe films

ZnSe films were deposited on glass substrates keeping the substrate temperatures, at room temperature (RT), 75, 150 and 250 °C. The films have exhibited cubic structure oriented along the (111) direction. Both the crystallinity and the grain size increased with increasing deposition temperature. A very high value of absorption co‐efficient (10⁴ cm^‐1) is observed. The band gap values decrease from a value of 2.94 eV to 2.69 eV with increasing substrate temperature. The average refractive index value is in the range of 2.39 – 2.41 for the films deposited at different substrate temperatures. The conductivity values increases continuously with temperature. Laser Raman spectra showed peaks at 140.8 cm^‐1, 246.7 cm^‐1and 204.5 cm^‐1which are attributable to 2TA LO phonon and TO phonon respectively. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)