Thermal Studies on Some Ionic Chelates of Hafnium(IV)

Ionic chelate complexes of kojic acid(I) and hafnium(IV) of the type [(η⁵-C₅H₅)₂HfL]⁺[MCl₃]^– (II)[HL=kojic acid; M=Zn(II), Cd(II), Hg(II), Cu(II)] have been synthesised and characterised by spectral studies (IR, UV, ¹H NMR and ¹³CNMR). Thermogravimetric (TG) and differential thermal analytical (DTA) studies have been carried out for these complexes and from the TG curves, the order and apparent activation energy for the thermal decomposition reactions have been elucidated. The various thermal studies have been correlated with some structural aspects of the complexes concerned. From DTA curves, the heat of reaction has been calculated. This revised version was published online in July 2006 with corrections to the Cover Date.     

Chalcogen-doped zinc oxide nanoparticles for photocatalytic degradation of Rhodamine B under the irradiation of ultraviolet light

In the present work, the chalcogen (Se²⁺)-doped ZnO nanoparticles (SeZO-NPs) were synthesized using sol-gel precipitation method and tested for photocatalytic degradation of Rhodamine B (RhB). X-ray diffraction pattern of SeZO-NPs showed the hexagonal wurtzite crystal structure regardless of Se concentration. The band edge and defect-level emissions of SeZO-NPs were determined by using the photoluminescence spectra with the excitation source of 370 nm. The bandgap, E_g, of SeZO-NPs was measured from diffused reflectance spectroscopy, which increased from 3.22 to 3.26 eV as Se concentration increased from 0 to 10 wt.%. The highest specific surface area and lowest pore size of 5-SeZO-NPs were observed to be 36.42 m²/g and 13.48 nm, respectively. The photocatalytic degradation of SeZO-NPs was measured under the illumination of ultraviolet (UV) light. The double donor (Se) played an important role toward photodegradation of RhB via reducing the recombination of charge carriers. The highest photocatalytic degradation (98.23%) and mineralization were achieved for the sample 5-SeZO (Se: 5 wt.%). The improved photocatalytic performance of 5-SeZO was attributed to the optimum Se dopant concentration for the production of more reactive oxygen species because of effective separation of charge carriers in UV light.     

Advanced green analytical chemistry for environmental pesticide detection

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Numerical analysis of a mathematical model for propagation of an electrical pulse in a neuron

This article is devoted to the study of a mathematical model arising in the mathematical modeling of pulse propagation in nerve fibers. A widely accepted model of nerve conduction is based on nonlinear parabolic partial differential equations. When considered as part of a particular initial boundary value problem the equation models the electrical activity in a neuron. A small perturbation parameter ε is introduced to the highest order derivative term. The parameter if decreased, speeds up the fast variables of the model equations whereas it does not affect the slow variables. In order to formally reduce the problem to a discussion of the moment of fronts and backs we take the limit ε → 0. This limit is singular and is therefore the solution tends to a slowly moving solution of the limiting equation. This leads to the boundary layers located in the neighborhoods of the boundary of the domain where the solution has very steep gradient. Most of the classical methods are incapable of providing helpful information about this limiting solution. To this effort a parameter robust numerical method is constructed on a piecewise uniform fitted mesh. The method consists of standard upwind finite difference operator. A rigorous analysis is carried out to obtain priori estimates on the solution of the problem and its derivatives. A parameter uniform error estimate for the numerical scheme so constructed is established in the maximum norm. It is then proven that the numerical method is unconditionally stable and provides a solution that converges to the solution of the differential equation. A set of numerical experiment is carried out in support of the predicted theory, which validates computationally the theoretical results. © 2008 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 2008     

Sol–gel derived 12BaO·7Al<Subscript>2</Subscript>O<Subscript>3</Subscript> thin films using metal alkoxides

The 12BaO·7Al₂O₃ (B12A7) thin films have been prepared via sol–gel process. Optical and electrical properties of B12A7 films have been investigated. The films were coated on soda lime float glass by the dip coating process, and annealed in air and hydrogen (H₂) at 450 °C for 2 h. The UV absorption edge was red shifted for films annealed in H₂ atmosphere. The B12A7 films had high transparency about 90% in wide visible range with maximum of 95% at 575 nm wavelength. The sheet resistance of the 300 nm films corresponding to 90.57 and 0.974 kΩ per square has been observed for air and H₂ annealed, respectively.     

An efficient synthesis of naphtha[1,2-e]oxazinone and 14-substituted-14H-dibenzo[a,j]xanthene derivatives promoted by zinc oxide nanoparticle under thermal and solvent-free conditions

A general synthetic route to the synthesis of 1,2-dihydro-1-arylnaphtho[1,2-e][1,3]oxazine-3-one and 14-substituted-14H-dibenzo[a,j]xanthenes derivatives has been developed using ZnO-NPs under thermal and solvent-free conditions. The union of 2-naphthol, aldehyde, urea enabling the synthesis of naphtho[1,2-e][1,3]oxazinone and 2-naphthol, aldehyde gave dibenzo[a,j]xanthenes in excellent yields. This method provides several advantages like simple work-up, environmentally benign, and shorter reaction times along with high yields.     

Temperature induced hyperchromism exhibited by Hoechst 33258: evidence of drug aggregation from UV-melting method

UV-thermal denaturation is a simple optical method widely employed for determination of DNA stability and interaction with ligands. Thermal denaturation of DNA and DNA-ligand complex is usually monitored at 260 nm. These data are generally presented as a function of the absorption increase of DNA alone with no consideration of the temperature dependent hyperchromism of the free ligand. Since not every ligand has absorption at 260 nm, usually this property of the ligand is ignored. Here, we report the temperature dependent hyperchromicity exhibited by Hoechst 33258 in the presence and absence of DNA. The presence of Hoechst, added to the duplex (monophasic profile, T(m)=75 degrees C) in various ratios generates a new transition at lower temperature displaying biphasic thermal transition profiles. We attributed this new transition (hyperchromic), a mere contribution from Hoechst, which might exist in aggregated forms. The extent of drug aggregation/self-association is concentration dependent. We suggest that prior to UV-melting studies the thermal dependence of the free ligand should be investigated.     

Multiresidue analysis of 83 pesticides and 12 dioxin-like polychlorinated biphenyls in wine by gas chromatography–time-of-flight mass spectrometry

A multiresidue method is described for simultaneous estimation of 83 pesticides and 12 dioxin-like polychlorinated biphenyls (PCBs) in red and white wines. The samples (20 mL wine, acidified with 20 mL 1% HCl) were extracted with 10 mL ethyl acetate (+20 g sodium sulphate) and cleaned by dispersive solid-phase extraction (DSPE) with anhydrous calcium chloride and Florisil successively. The final extract (5 mL) was solvent exchanged to 1 mL of cyclohexane:ethyl acetate (9:1), further cleaned by DSPE with 25 mg primary secondary amine sorbent and analyzed by gas chromatography–time-of-flight mass spectrometry (GC–TOF-MS) within 31 min run time. The limits of quantification of most analytes were ≤10–20 μg/L. Acidification of wine prior to extraction prevented hydrolysis of organophosphorous pesticides as well as dicofol, whereas treatment with CaCl₂ minimized the fatty acid co-extractives significantly. Solvent exchange to cyclohexane:ethyl acetate (9:1) further minimized the co-extractives. Recoveries at 5, 10 and 20 ng/mL were >80% for most analytes except cyprodinil, buprofezin and iprodione. The expanded uncertainties at 10 ng/mL were <20% for most analytes. Intra-laboratory precision in terms of Horwitz ratio of all the analytes was below 0.5, suggesting ruggedness of the method. Effectively, the method detection limit for most analytes was as low as up to 1 ng/mL in both red and white wine, except for cyfluthrin and cypermethrin.     

Synthesis,characterization, and antifungal and antibacterial studies of nickel(II)thiodiamine complexes

Nickel(II) complexes of type [Ni(L)₂Cl₂] and [Ni(L)₂(OCOCH₃)₂], where L = (cyclohexyl-N-thio)-1,2-ethylenediamine (L¹) and (cyclohexyl-N-thio)-1,3-propanediamine (L²) has been synthesized and characterized by elemental analysis, FT-IR, mass, UV-Vis, and ¹H NMR spectroscopic studies. The thiodiamines coordinate as a bidentate N-S ligand. The ratio of the metal: ligand was 1: 2 for all the complexes. The binding sites are the azomethine nitrogen and thioamide sulfur. The complexes are found to be soluble in acetone, dimethylformamide, and dimethylsulfoxide. All the complexes were found amorphous in nature. Molar conductance values in DMSO indicate the nonelectrolyte nature of the complexes. In vitro antifungal and in vitro antibacterial studies were performed against fungal and bacterial strains, Aspergillus fumigatus, Aspergillus flavus, and Aspergillus niger, and Staphylococcus epidermidis, Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa, respectively. Preliminary antimicrobial screening shows the good results against both the fungal and the bacterial strains, which can lead through the investigation of better drug. The article is published in the original.     

In situ formation of magnetic–luminescent, bi-functional, polymer-stabilized cerium sulfide nanoparticles

Polymer-stabilized paramagnetic and fluorescent rare-earth metal sulfide (cerium sulfide, Ce₂S₃) nanoparticles have been synthesized by using an ??in situ polymerization and composite formation?? (IPCF) technique (Mallick et al. in J. Appl. Phys. 106:074303, 2009) at room temperature. Encapsulated cerium sulfide nanoparticles showed photoluminescence when excited with laser irradiation. The composite material exhibited a paramagnetic behavior due to the in situ formation of magnetic Ce³⁺ ionic species at the reaction condition.