Zn-doping effect on the energy barrier to magnetization reversal in superparamagnetic nickel ferrite nanoparticles

Measurements of ac-susceptibility and dc-magnetization were carried out on samples of Ni_1-xZn_xFe₂O₄ nanoparticles (x=0, 0.25, 0.5, 0.75) with average diameters 〈D〉≈7 nm. Values of the superparamagnetic blocking temperature T̄_B were obtained from the characteristic temperature behavior of the imaginary susceptibility χ_imag. An Arrhenius-type law, which accurately describes the relationship between the observation time τ_obs and the blocking temperature, was used to determine the effective energy barrier to magnetization reversal U_eff. A Zn-content dependence of the energy barrier is observed, where U_eff changes little for 0≤x≤0.25, it peaks at x=0.5, and decreases back upon further Zn-doping. The large increase of U_eff at x=0.5 is attributed to an enhanced magnetic anisotropy induced by the crossover between two spatial arrangements of spins in the A and B sub-lattices of the ferrimagnetic inverse spinel. PACS 75.50.Bb; 75.50.Gg; 75.30.Et     

Photochemistry and phototoxicity studies of flutamide, a phototoxic anti-cancer drug

The phototoxic anti-cancer drug flutamide is photolabile under UV-B light in either aerobic or anaerobic conditions. Irradiation of a methanol solution of this drug produces several photoproducts, one by photoreduction of the nitro group, one by rupture of the aromatic-NO2 bond of the parent compound, two as a result of the rupture of the CO-NH bond and one derived from the photoreduction product by scission of the aromatic-NH2 bond. Flutamide shows a photohemolytic effect on human erythrocytes and photoinduces lipid peroxidation. Studies on peripheral blood polymorphonuclear cells (neutrophils) demonstrated the phototoxicity of flutamide as well as inhibition of the cytotoxicity respiratory burst by the photoproduct derived from its photoreduction. The results suggest that the inhibition of the respiratory burst observed in phorbol myristate acetate (PMA)-activated cells is mediated by photosensitization and concomitant singlet oxygen production and/or formation of toxic photoproducts.     

Room-temperature synthesis and conductivity of the pyrochlore type Dy2(Ti1−yZry)2O7 (0?y?1) solid solution

Different compositions in a solid solution of general formula Dy₂(Ti_1−yZr_y)₂O₇, showing high oxygen ion conductivity, have been successfully prepared at room temperature via mechanochemical synthesis. Stoichiometric mixtures of the constituent oxides were dry milled together in a planetary ball mill by using zirconia vials and balls. Chemical changes in the powder mixtures as a function of composition and milling time were followed by X-ray diffraction and revealed that, in all cases and after milling for 19 h, the powder mixtures consisted of a single phase. Electrical properties were measured on sintered pellets as a function of frequency, temperature and zirconium content, revealing an increase in conductivity of more than one order of magnitude for y?0.4, which, as observed in the similar Y₂(Ti_1−yZr_y)₂O₇, has been related with the onset of disordering of the anion sublattice. Despite increasing structural disorder with increasing Zr content, conductivity remains almost constant for y>0.6, reaching a maximum value of ∼5×10⁻³ for Dy₂Zr₂O₇ at 900 °C.     

Rhodium-catalyzed hydroformylation of C6 alkenes and alkene mixtures - a comparative study in homogeneous and aqueous-biphasic media using PPh3, TPPTS and TPPMS ligands

The complexes RhH(CO)L₃, where L = PPh₃, P(m-C₆H₄SO₃Na)₃ (TPPTS), and (C₆H₅)₂P(m-C₆H₄SO₃Na) (TPPMS) were used as catalyst precursors for a comparative study of the catalytic hydroformylation of several C6 alkenes and alkene mixtures under moderate reaction conditions in homogeneous (PPh₃) and aqueous-biphasic (TPPTS, TPPMS) media. The biphasic systems are efficient for the hydroformylation of hex-1-ene, 2,3-dimethyl-1-butene, styrene, cyclohexene, and mixtures thereof, in water/n-heptane at 80 °C. The main problem associated with these catalysts is their tendency to promote alkene isomerization if the effective syngas concentration in the liquid phases is low, but this side-reaction can be suppressed by using higher CO/H₂ pressures (54 atm). The selectivity of both water-soluble catalysts for linear products of hex-1-ene and for branched products of styrene is modest in comparison with the homogeneous system, which may limit their utility for classical oxo uses, but this is not a disadvantage for other interesting applications related to the hydroformylation of alkene mixtures and particularly to naphtha upgrading where linear and branched products are equally useful. The catalysts can be recycled without significant loss of activity and are resistant to the presence of benzothiophene in the mixture.     

Influence of aromatic substituents on metal(II)salen catalysed, asymmetric synthesis of α-methyl α-amino acids

The influence of substituents on both the aromatic rings of the catalyst, and the benzylidene unit of the substrate are investigated in the (salen)copper(II) catalysed asymmetric benzylation of alanine derivatives. Catalysts with electron-donating, and electron-withdrawing substituents of various sizes and at various locations on the aromatic rings of the salen ligand were prepared, but all exhibited inferior enantioselectivity to the parent (salen)copper(II) complex. In contrast, the introduction of halogenated substituents onto the aromatic ring of the N-benzylidene alanine methyl ester substrate was found to enhance the enantioselectivity of the alkylation with a para-chloro substituent giving optimal results. A new procedure for the preparation of the catalysts which avoids the need for chromatography on sephadex LH20 is reported, and the optimal catalyst obtained in this way was found to be a cobalt(salen) complex.     

Mass spectra of some 2-methyl-3-(o- and p;-R-phenyl)-3,3a,4,5,6,7-hexahydro-2H-indazoles

The mass spectra of twelve 2-methyl-3-(o- and p-R-phenyl)-3,3a,4,5,6,7-hexahydro-2H-indazoles which have potentially useful pharmacological properties are presented.     

Structure of a de novo designed protein model of radical enzymes

The use of side chains as catalytic cofactors for protein mediated redox chemistry raises significant mechanistic issues as to how these amino acids are activated toward radical chemistry in a controlled manner. De novo protein design has been used to examine the structural basis for the creation and maintenance of a tryptophanyl radical in a three-helix bundle protein maquette. Here we report the detailed structural analysis of the protein by multidimensional NMR methods. An interesting feature of the structure is an apparent pi-cation interaction involving the sole tryptophan and a lysine side chain. Hybrid density functional calculations support the notion that this interaction raises the reduction potential of the W degrees /WH redox pair and helps explain the redox characteristics of the protein. This model protein system therefore provides a powerful model for exploring the structural basis for controlled radical chemistry in protein.     

Stereoselective syntheses of 1,4-dideoxy-1,4-imino-octitols and novel tetrahydroxyindolizidines

A new route for the preparation of four new indolizidines, (1R,2S,6S,7S,8aS)- and (1R,2S,6R,7R,8aS)-1,2,6,7-tetrahydroxyindolizidine (30 and 32) and (1S,2R,7S,8S,8aR)- and (1S,2R,7R,8R,8aR)-1,2,7,8-tetrahydroxyindolizidine (44 and 46), is reported. The synthesis is based on Knoevenagel homologation of the readily available enantiomerically pure pyrrolidin-carbaldehydes 13 and 37followed by asymmetric dihydroxylation of the subsequent alkenyl pyrrolidines and cyclization of the corresponding imino-octitols. The new indolizidines and their precursors (imino-octitols 20, 25, 26) and indolizidinones 28a and 28b have been tested for inhibitory activities toward 26 glycosidases. The enzymatic inhibition of trans-7-hydroxy-d-(-)-swainsonine (44) toward alpha-mannosidases is similar to that described for trans-7-hydroxy-l-(+)-swainsonine (11b) toward naringinase (alpha-l-rhamnosidase from Penicillium decumbens).     

Fractionation and redox speciation of antimony in agricultural soils by hydride generation--atomic fluorescence spectrometry and stability of Sb(III) and Sb(V) during extraction with different extractant solutions

This stability of Sb(III) and Sb(V) species was studied during single extraction from soils by water. EDTA, diluted H2SO4 and H3PO4, and oxalic acid/oxalate solutions, with and without ascorbic acid, were used as stabilizing reagent of both Sb species. Antimony redox speciation in soil extracts was performed by selective hydride generation-atomic fluorescence spectrometry. Simulated extraction procedures (without soil) showed that, except in oxalate medium, Sb(III) was oxidized to Sb(V), and this reaction was avoided with ascorbic acid. Recovery studies from a spiked agricultural soil showed that no oxidation but sorption of Sb(III) occurred during the extraction process in water and H2SO4 medium, and quantitative oxidation in EDTA and oxalate medium. With ascorbic acid, this oxidation was totally avoided in EDTA and partially avoided in oxalate solution. A new sequential extraction procedure was proposed and applied to the fractionation and redox speciation of antimony in agricultural soils, using EDTA + ascorbic acid, pH 7 (available under complexing and moderately reducible conditions); oxalic acid/oxalate + ascorbic acid (extractable in reducible conditions) and HNO3 + HCl + HF (residual fraction). The proposed extraction scheme can provide information about the availability and mobility of antimony redox species in agricultural soils.     

A facile access to ureido sugars. Synthesis of urea-bridged β-cyclodextrins

The preparation of a urea-bridged β-cyclodextrin dimer and of a 6-monodeoxy-6-mono[3-(β-d-glucopyranos-2-yl)ureido]-β-cyclodextrin has been developed, using triphosgene as the isocyanation agent in an aqueous two-phase system. Per-O-acetylated β-d-gluco and mannopyranosylamines and 2-amino-2-deoxy-α- and β-d-glucose were also transformed into the corresponding isocyanates and converted in situ into ureas by coupling with aromatic and aliphatic amines.