Palladium(II) and platinum(II) complexes of Schiff bases derived from 2,6-diacetylpyridine and S-methyldithiocarbazate and the X-ray crystal structure of the [Pd(mdapsme)Cl] complex

Condensation of 2,6-diacetylpyridine (dap) with S-methyldithiocarbazate (smdtc) in a 1:2 molar ratio yields a bicondensed pentadentate Schiff base (H₂dapsme) which reacts with K₂MCl₄ (M = Pd^II, Pt^II) giving stable complexes of empirical formula, [M(dapsme)] · 0.5Me₂CO. These complexes have been characterized by a variety of physico-chemical techniques. Condensation of dap with smdtc in a 1:1 molar ratio also yields the bicondensed Schiff base (H₂dapsme) as the major product, but a mono-condensed one-armed Schiff base (Hmdapsme) is also obtained as a minor product. The latter reacts with K₂PdCl₄ in an EtOH–H₂O mixture yielding a crystalline complex of empirical formula, [Pd(mdapsme)Cl], the crystal structure of which has been determined by X-ray diffraction. The complex has a distorted square-planar structure in which the ligand is coordinated to the palladium(II) ion as a uninegatively charged tridentate chelating agent via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom; the oxygen atom of the acetyl group does not participate in coordination.     

Interaction of glucose oxidase with alkyl-substituted sepharose 4B

Glucose oxidase (GOD) is often used in immobilized forms for determination of glucose. To examine the possibility of its adsorption by hydrophobic interactions, palmityl-substituted Sepharose 4B (Sepharoselipid) was employed as an adsorptive matrix. Various conditions were used in tests to improve the limited immobilization of the enzyme observed under normal (native) conditions, including use of high concentrations of denaturing agents. Of the denaturants used, only the cationic detergent dodecyl trimethyl ammonium bromide was effective in denaturing the protein and exposing its hydrophobic sites for interaction with alkyl residues on the support. This, followed by the process of renaturation, provided catalytically active immobilized preparations. The apoenzyme, prepared by treatment of the holoenzyme with acidified (NH4)2SO4 or thermal denaturation, was totally immobilized on the support. Furthermore, it was shown that either flavin adenine dinucleotide (FAD) or the alkyl residues, not both, may interact with the nucleotide site at any given time. Results are discussed in terms of high rigidity of GOD molecule and limited exposure of hydrophobic sites in its native structure. The observations are in accord with suggestions in the literature that the FAD pocket is a very narrow channel of hydrophobic properties, adapted to accept its natural coenzyme.     

New nickel(II), copper(II), platinum(II) and palladium(II) complexes of a multidentate sulfur–nitrogen chelating agent

A new, potentially polydentate sulfur–nitrogen chelating agent, 2,6–bis(N-methyl-S-methyldithiocarbazato)pyridine (L) has been synthesized and characterized. With nickel(II) salts, the ligand yields complexes of empirical formula NiLX2·nH2O (X=Cl−, NCS− or NO3−; n=0 or 1) in which it behaves as a quadridentate NSSN chelating agent, coordinating to the nickel(II) ion via the two amino nitrogen atoms and the two sulfur atoms. Magnetic and spectral evidence support a distorted octahedral structure for these complexes. The ligand reacts with copper(II), platinum(II) and palladium(II) salts to yield homo-binuclear complexes of general formula [M2LX4]·nSol (M=CuII, PtII or PdII; X=Cl− or Br−; n=0.5, 1 or 2; Sol=H2O, MeOH or MeCOMe), in which each of the metal ions is in a square-planar environment. These complexes have been characterized by a variety of physicochemical techniques. This revised version was published online in June 2006 with corrections to the Cover Date.     

Computational explorations to gain insight into the structural features of TNF-α receptor I inhibitors

TNF-α is a crucial cytokine in the process of inflammatory diseases. The adverse effect of TNF-α is mostly mediated by interaction of TNF-α with TNF-α receptor type I (TNFR1); therefore, discovery of molecules which can bind to TNFR1 preventing TNF-α-receptor complex formation would be of great interest. In the current study, using GRID/GOLPE program, a 3D-QSAR study was conducted on a series of synthetic TNFR1 binders, which resulted in a 3D-QSAR model with appropriate power of predictivity in internal (r²?=?0.94 and q²_LOO?=?0.74) and external (r²?=?0.66 and SDEP?=?0.42) validations. The structural features of TNFR1 inhibitors essential for exerting activity were explored by analyzing the contour maps of the 3D-QSAR model showing that steric interactions and hydrogen bonds are responsible for exerting TNFR1 inhibitory activity. To propose potential chemical entities for TNFR1 inhibition, PubChem database was searched and the selected compounds were virtually tested for anti-TNFR1 activity using the generated model, resulting in two potential anti-TNFR1 compounds. Finally, the possible interactions of the compounds with TNFR1 were investigated using docking studies. The findings in the current work can pave the way for designing more potent anti-TNFR1 inhibitors.     

Inhibitory effect of safranal and crocin,two principle compounds of <Emphasis Type="Italic">Crocus sativus</Emphasis>, on fibrillation of lysozyme

A key feature in more than twenty amyloid-related diseases is the aggregation of intra-and/or extracellular misfolded proteins as amyloid fibrils. Therefore, preventing or reversing amyloid aggregation by using of small molecules is considered as useful approaches to the treatment of these diseases. We have evaluated the ability of safranal and crocin, to inhibit amyloid self-assembly of hen egg white lysozyme (HEWL), as an in vitro model system. Structural properties of HEWL in the presence of these compounds were investigated individually using thioflavin T, anilinonaphthalene-8-sulfonic acid fluorescence assays, far-UV circular dichroism and scanning electron microscopy as well as docking method. Our results showed that incubation of HEWL with either crocin or safranal at various concentrations leads a significant inhibition in the rate of amyloid formation. Docking analysis revealed crocin and safranal interact with the central hydrophobic region of lysozyme through van der Waals interaction. Hydroxyl group in crocin through hydrogen bonds connected to the several hydrophilic amino acids of lysozyme, while in safranal there are just one aldehyde group that through hydrogen bonds connected to aspartic acid in lysozyme. It can be concluded that both hydrophobic and hydrophilic groups contribute to lower lysozyme fibril accumulation.     

Cobalt determination with FI-FAAS after on-line sorbent preconcentration using 1-nitroso-2-naphthol

The suitability of 1-nitroso-2-naphthol (NN) as a complexing agent for on-line preconcentration of cobalt using C(18) microcolumn with FI-FAAS system has been tested. Various parameters affecting the complex formation and its elution were optimized. Reagent solution (2.5x10(-3) mol l(-1)) and aqueous sample solution acidified with 0.1% (v/v) nitric acid were on-line mixed in a reaction coil set at 65+/-1 degrees C and flowed through the microcolumn for 30 s. The pH of the mixed solution was adjusted to 3 approximately 4 by adding HNO(3) (1 mol l(-1)) or NaOH (1 mol l(-1)) in the reagent solution. The adsorbed complexes in the microcolumn were eluted with ethanol (acidified to 1% nitric acid) in 10 s into the nebulizer of FAAS. A good precision (1.6% for 100 mug l(-1) Co(II), n=10), high enrichment factor 17.2, with detection limit (3sigma) 3.2 mug l(-1), and sample throughput (90 h(-1)) were obtained. The method was applied on the certified reference materials (CRMs) i.e. NBS-362 and NBS-364 (special low alloy steel), for the determination of cobalt and the results were in good agreement with the certified values.     

Synthesis,Characterization and Photocatalytic Activity of Mg‐Impregnated ZnO–SnO2 Coupled Nanoparticles

ZnO–SnO₂ nanoparticles were prepared by coprecipitation method; then Mg, with different molar ratios and calcination temperatures, was loaded on the coupled nanoparticles by impregnation method. The synthesized nanoparticles were characterized by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X‐ray spectroscopy (EDX), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), and Brunauer–Emmett–Teller (BET) techniques. Based on XRD results, the ZnO–SnO₂ and Mg/ZnO–SnO₂ nanoparticles were made of ZnO and SnO₂ nanocrystallites. According to DRS spectra, the band gap energy value of 3.13 and 3.18 eV were obtained for ZnO–SnO₂ and Mg/ZnO–SnO₂ nanoparticles, respectively. BET analysis revealed a Type III isotherm with a microporous structure and surface area of 32.051 and 49.065 m² g^?1 for ZnO–SnO₂ and Mg/ZnO–SnO₂, respectively. Also, the spherical shape of nanocrystallites was deduced from TEM and FESEM images. The photocatalytic performance of pure ZnO–SnO₂ and Mg/ZnO–SnO₂ was analyzed in the photocatalytic removal of methyl orange (MO). The results indicated that Mg/ZnO–SnO₂ exhibited superior photocatalytic activity to bare ZnO–SnO₂ photocatalyst due to high surface area, increased MO adsorption and larger band gap energy. Maximum photocatalytic activity of Mg/ZnO–SnO₂ nanoparticles was obtained with 0.8 mol% Mg and calcination temperature of 350°C.     

When is a right orderable group locally indicable?

If a group has an ascending series of subgroups such that for each ordinal , and has no non-abelian free subsemigroup, then is right orderable if and only if it is locally indicable. In particular if is a radical-by-periodic group, then it is right orderable if and only if it is locally indicable.

     

Enrichment of Zinc and Iron Micronutrients in Lentil (Lens culinaris Medik.) through Biofortification

Biofortification of pulse crops with Zn and Fe is a viable approach to combat their widespread deficiencies in humans. Lentil (Lens culinaris Medik.) is a widely consumed edible crop possessing a high level of Zn and Fe micronutrients. Thus, the present study was conducted to examine the influence of foliar application of Zn and Fe on productivity, concentration, uptake and the economics of lentil cultivation (LL 931). For this, different treatment combinations of ZnSO₄·7H₂O (0.5%) and FeSO₄·7H₂O (0.5%), along with the recommended dose of fertilizer (RDF), were applied to the lentil. The results of study reported that the combined foliar application of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at pre-flowering (S1) and pod formation (S2) stages was most effective in enhancing grain and straw yield, Zn and Fe concentration, and uptake. However, the outcome of this treatment was statistically on par with the results obtained under the treatment ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage. A single spray of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage enhanced the grain and straw yield up to 39.6% and 51.8%, respectively. Similarly, Zn and Fe concentrations showed enhancement in grain (10.9% and 20.4%, respectively) and straw (27.5% and 27.6% respectively) of the lentil. The increase in Zn and Fe uptake by grain was 54.8% and 68.0%, respectively, whereas uptake by straw was 93.6% and 93.7%, respectively. Also the benefit:cost was the highest (1.96) with application of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage. Conclusively, the combined use of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage can contribute significantly towards yield, Zn and Fe concentration, as well as uptake and the economic returns of lentil to remediate the Zn and Fe deficiency.