Magnetic behaviour of the orthochromite La0.5Gd0.5CrO3

Magnetic behaviour of the perovskite La_0.5Gd_0.5CrO₃ has been studied. The orthochromite orders canted antiferromagnetically below Neel temperature T_N of ～225 K. Reversal of magnetization is observed in temperature dependence of magnetization measured in field cooled mode under external fields upto 500 Oe. In the field dependence of magnetization below T_N, a small hysteresis is observed with the magnetic anisotropy continuously increasing with lowering of temperature. Estimated values of Cr³⁺ moments, internal field due to sub-lattice of canted ordered Cr³⁺ and the paramagnetic Curie temperature of Gd³⁺ sub-lattice are found to be smaller than reported for GdCrO₃. Compared with Pr substituted analogue La_0.5Pr_0.5CrO₃, Cr³⁺ moment is about the same but the internal field at the Gd³⁺ sub-lattice is much smaller.     

Thermodynamic Parameters for the Association of Fluorinated Benzenesulfonamides with Bovine Carbonic Anhydrase II

This paper describes a calorimetric study of the association of a series of seven fluorinated benzenesulfonamide ligands (C₆H_nF_5?nSO₂NH₂) with bovine carbonic anhydrase II (BCA). Quantitative structure–activity relationships between the free energy, enthalpy, and entropy of binding and pK_a and log P of the ligands allowed the evaluation of the thermodynamic parameters in terms of the two independent effects of fluorination on the ligand: its electrostatic potential and its hydrophobicity. The parameters were partitioned to the three different structural interactions between the ligand and BCA: the Zn^II cofactor–sulfonamide bond (≈65 % of the free energy of binding), the hydrogen bonds between the ligand and BCA (≈10 %), and the contacts between the phenyl ring of the ligand and BCA (≈25 %). Calorimetry revealed that all of the ligands studied bind in a 1:1 stoichiometry with BCA; this result was confirmed by ¹⁹F NMR spectroscopy and X‐ray crystallography (for complexes with human carbonic anhydrase II).     

Structure and solution dynamics of a “P–N–P” ligand attached to calix[4]arene scaffold and its palladium dichloride complex

A new diphosphazane ligand, Ph₂PN(CHMe₂)P(Ph){1,3-dimethoxycalix[4]arene} (2), in which the P–N–P unit is appended to calix[4]arene backbone, and its PdCl₂ complex (3) have been synthesized. The structures of the conformers of both the compounds in solution have been elucidated with the help of two-dimensional NMR experiments. Single crystal X-ray diffraction studies reveal the partial cone and cone conformations of the calixarene unit in the ligand (2) and the Pd-complex (3), respectively.     

Expedient synthesis of substituted imidazoles from nitriles

Expedient and practical new methodology for the synthesis of substituted imidazoles was developed to provide a rapid access to a variety of 2-substituted, 1,2-disubstituted and 1,2,4-trisubstituted imidazoles by the direct CuCl-mediated reaction of nitriles with α-amino acetals in an intermolecular as well as intramolecular fashion.     

Ultrasound-assisted analyte extraction for the determination of sulfate and elemental sulfur in zinc sulfide by different liquid chromatography techniques

The speciation and determination of sulfate (SO4(2-)) and elemental sulfur (S degree) in zinc sulfide (ZnS) using ion-chromatography (IC) and reversed-phase liquid chromatography (RPLC) respectively is described. Three sample pretreatment approaches were employed with the aim of determining sulfate: (i) conventional water extraction of the analyte; (ii) solid-liquid aqueous extraction with an ultrasonic probe; and (iii) elimination of the zinc sulfide matrix via ion-exchange dissolution (IED). The separation of sulfate was carried out by an anion-exchange column (IonPac AS17), followed by suppressed conductivity detection. Elemental sulfur was extracted ultrasonically from the acid treated sample solution into chloroform and separated on a reversed phase HPLC column equipped with a diode array detector (DAD) at 264 nm. The achievable solid detection limits for sulfate and sulfur were 35 and 10 microg g(-1) respectively.     

Mass spectral investigations on trichothecene mycotoxins. III. Synthesis, characterization and applications of pentafluoropropionyl and trifluoroacetyl esters of simple trichothecenes

The pentafluoropropionyl, (PFP) and trifluoroacetyl (TFA) esters of several naturally occurring and synthetically modified simple trichothecenes were synthesized in nanogram amounts and characterized. Optimum conditions for the gas chromatographic (GC) separation of these derivatives and their analysis by negative ion chemical ionization (NICI) mass spectrometric technique were determined. These perfluoroacyl derivatives under the NICI conditions undergo limited but characteristic fragmentations similar to the fragmentations of heptafluorobutyryl esters of trichothecenes under the same conditions. Characteristic ions for the specific detection and accurate quantification of these PFP and TFA derivatives were chosen. Preliminary results indicated that the PFP derivatives are better suited for the analysis of simple trichothecenes by GC-NICI-MS technique. Ultra trace (0.5-2.0 pg) amounts of these PFP derivatives were detected by the developed procedure.     

Topologically-Interlocked Minicircles as Probes of DNA Topology and DNA-Protein Interactions

DNA minicircles exist in biological contexts, such as kinetoplast DNA, and are promising components for creating functional nanodevices. They have been used to mimic the topological features of nucleosomal DNA and to probe DNA-protein interactions such as HIV-1 and PFV integrases, and DNA gyrase. Here, we synthesized the topologically-interlocked minicircle rotaxane and catenane inside a frame-shaped DNA origami. These minicircles are 183 bp in length, constitute six individual single-stranded DNAs that are ligated to realize duplex interlocking, and adopt temporary base pairing of single strands for interlocking. To probe the DNA-protein interactions, restriction reactions were carried out on DNAs with different topologies such as free linear duplex or duplex constrained inside origami and free or topologically-interlocked minicircles. Except the free linear duplex, all tested structures were resistant to restriction digestion, indicating that the topological features of DNA, such as flexibility, curvature, and groove orientation, play a major role in DNA-protein interactions.     

Unusual reactivity of a sterically hindered diphosphazane ligand, EtN{P(OR)(2)}(2), (R = C(6)H(3)(Pr(I))(2)-2,6) towards (eta(3)-allyl)palladium precursors

The reactivity of (eta(3)-allyl)palladium chloro dimers [(1-R-eta(3)-C(3)H(4))PdCl](2) (R = H or Me) towards a sterically hindered diphosphazane ligand [EtN{P(OR)(2)}(2)] (R = C(6)H(3)(Pr(i))(2)-2,6), has been investigated under different reaction conditions. When the reaction is carried out using NH(4)PF(6) as the halide scavenger, the cationic complex [(1-R-eta(3)-C(3)H(4))Pd{EtN(P(OR)(2))(2)}]PF(6) (R = H or Me) is formed as the sole product. In the absence of NH(4)PF(6), the initially formed cationic complex, [(eta(3)-C(3)H(5))Pd{EtN(P(OR)(2))(2)}]Cl, is transformed into a mixture of chloro bridged complexes over a period of 4 days. The dinuclear complexes, [(eta(3)-C(3)H(5))Pd(2)(mu-Cl)(2){P(O)(OR)(2)}{P(OR)(2)(NHEt)}] and [Pd(mu-Cl){P(O)(OR)(2)}{P(OR)(2)(NHEt)}](2) are formed by P-N bond hydrolysis, whereas the octa-palladium complex [(eta(3)-C(3)H(5))(2-Cl-eta(3)-C(3)H(4))Pd(4)(mu-Cl)(4)(mu-EtN{P(OR)(2)}(2))](2), is formed as a result of nucleophilic substitution by a chloride ligand at the central carbon of an allyl fragment. The reaction of [EtN{P(OR)(2)}(2)] with [(eta(3)-C(3)H(5))PdCl](2) in the presence of K(2)CO(3) yields a stable dinuclear (eta(3)-allyl)palladium(I) diphosphazane complex, [(eta(3)-C(3)H(5))[mu-EtN{P(OR)(2)}(2)Pd(2)Cl] which contains a coordinatively unsaturated T-shaped palladium center. This complex exhibits high catalytic activity and high TON's in the catalytic hydrophenylation of norbornene.     

Tuning the properties of a black TiO2-Ag visible light photocatalyst produced by a rapid one-pot chemical reduction

A highly efficient black TiO₂-Ag photocatalytic nanocomposite, active under both UV and visible light illumination, was synthesized by decorating the surface of 25 nm TiO₂ particles with Ag nanoparticles. The material was obtained via a rapid, one-pot, simple (surfactant and complexing agent free) chemical reduction method using silver nitrate and formaldehyde as a metal salt and reducing agent, respectively. The nanocomposite shows an increase of over 800% in the rate of photocatalytic methylene blue dye degradation, compared to commercial unmodified TiO_2, under UV-VIS illumination. Unlike pure TiO₂, the nanocomposite exhibits visible light activation, with a corresponding drop in optical reflectance from 100% to less than 10%. The photocatalytic properties were shown to be strongly enhanced by post-reduction annealing heat treatments in air, which were observed to decrease, rather than coarsen, silver particle size, and increase particle distribution. This, accompanied by a variation in the silver surface oxidation states, appear to dramatically affect the photocatalytic efficiency under both UV and visible light. This highly active photocatalyst could have wide ranging applications in water and air pollution remediation and solar fuel production.     

A highly efficient and general N-monomethylation of functionalized primary amines via formylation--borane:methyl sulfide reduction

Formylation of functionalized primary aromatic and aliphatic amines with acetic formic anhydride (AFA) followed by borane:methyl sulfide reduction in the same pot affords the corresponding $\text{N}$-methylamines in excellent isolated yields, uncontaminated bybis alkylation; the reaction sequence is applicable to even very weakly basic and sterically hindered amines.