Catalytic activity of nanocrystalline ZnM2O4 (M = Fe,Co) prepared via simple and facile synthesis of thermal decomposition of mixed metal complexes of Schiff bases generated from α-ketobutyric acid and diaminoguanidine

Metal complexes ([ML₂], where M = Fe, Co, or Zn; HL = 2-[(6-ethyl-5-oxo-4,5-dihydro-2H-[1,2,4]triazin-3-ylidene)-hydrazono]-butyric acid, C₉H₁₃N₅O₃) of a Schiff base derived from α-ketobutyric acid (α-KBA) and diaminoguanidine (Damgu) were synthesized and characterized using elemental, spectral, and thermal studies. The metal complexes exhibited similar decomposition behavior, with a highly exothermic final decomposition step resulting in the formation of metal oxides. Isomorphism among the complexes was revealed using a powder X-ray diffraction (PXRD) technique. Solid solution precursors ([Zn_1/3M_2/3(L)₂], where M = Fe, Co) were synthesized and characterized using various physico-chemical techniques. A thermal decomposition technique was used to prepare spinel-type zinc cobaltite (ZnCo₂O₄) and zinc ferrite (ZnFe₂O₄) nanocrystalline particles with the synthesized single source precursors. Structural studies using PXRD ascertained the predominant crystal phase to be spinel. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) showed a mean nanoparticle size of 18 ± 2 nm. Magnetic measurements revealed a weak magnetic behavior in the synthesized spinels. In the aqueous phase, the spinels exhibited catalytic activity, reducing 4-nitrophenol (4-NP) in the presence of NaBH₄ at room temperature. Additionally, the study demonstrated that the catalyst can be recovered and reused for five cycles with a more than 85% conversion efficiency.     

Design,synthesis, and antibacterial studies of potent pyrazolinyltriazoles

Research on Chemical Intermediates - A library of pyrazolinyltriazole hybrids (3a–l, 4a–l) was synthesized via azide–alkyne dipolar (Huisgen) cycloaddition of azidoacetyl...     

Isolation,spectroscopic and thermal properties of hydrazinium tris(oxydiacetato)lanthanate(III) hemi(pentahydrate)

Oil-bath reaction of respective metal nitrate with an aqueous mixture of oxydiacetic acid (H₂oda) and hydrazine hydrate led to the formation of crystalline compounds with formula (N₂H₅)₃[Ln(oda)₃]·2.5H₂O (where Ln = La, Ce, Pr, Nd and Sm), which are stable for a week and undergo efflorescence. The resulting complexes were characterized by infrared spectral, thermal (air and nitrogen atmosphere), UV–visible and PXRD studies. From the thermal studies, both in air and nitrogen atmosphere, these compounds show endothermic dehydration below 100 °C to give anhydrous compounds. Next, the anhydrous compounds (in air) undergo endothermic decomposition between 190 and 225 °C to form Ln(Hoda)₃ intermediate, which further show exothermic decomposition to yield respective metal oxide as the end residue. But, in nitrogen atmosphere, the same anhydrous compounds exhibit endo-followed by exothermic decompositions to give respective metal as end product. This is observed as a continuous single step of decomposition in TG. The structure of (N₂H₅)₃[Nd(oda)₃]·2.5H₂O has been determined by single-crystal X-ray analysis. The neodymium atom is coordinated by nine oxygen atoms from three tridentate (O, O, O) oxydiacetate ions with tricapped trigonal prismatic geometry. In addition, both the parent acid and its compounds display strong fluorescent emission due to the ligand, which renders them as fluorescent materials at room temperature.     

A minimal composite theory for stability of non-parallel compressible boundary-layer flow

A new minimal composite theory that extends the approach of Govindarajan and Narasimha [1] is proposed here for 2D non-parallel compressible boundary-layer stability subject to 3D disturbances. The mean profiles are obtained from Hortons analysis, which provides a good approximation for a large range of Prandtl numbers at non-zero pressure gradients. In the lowest order, all effects of order lower than O(R^-2/3) anywhere in the boundary-layer are included, R being the local boundary-layer Reynolds number; the resulting non-parallel formulation yields a set of four ordinary differential equations, as compared to the five coupled equations of classical parallel flow theory of Mack [2]. The largest effect on stability of flow non-parallelism is found to be due to the wall-normal advection of velocity and temperature disturbance quantities by the mean flow. The present theory shows that the bulk viscosity, invariably included in compressible stability theories, is irrelevant at the lowest order. In comparison with the full [O(R^-1)] non-parallel theory, the present theory is marginally better than the parallel flow theory. PACS 03.50.De, 04.20-q, 42.65-k     

Selectivity switch in transformation of CO2 from ethanol to methanol on Cu embedded in the defect carbon

The copper-based catalysts have been generally regarded as high-performance catalysts for CO_2 hydrogenation toward methanol,while the production of ethanol via C–C coupling on the copper-based catalysts is still challenging. Herein, we report a new catalyst where Cu nanoparticles are embedded in the carbon support with abundant defect sites, achieving a high selectivity for ethanol in the CO_2 hydrogenation. The experiments coupled with the theoretical studies show a clear map where carbon defects serve as anchor sites that can stabilize interfacial copper species, and interfacial Cu sites with low coordination numbers can adsorb two C_1 species and later convert them to a C_2 species via a hydrogenation-induced coupling reaction. Further adjacent Cu atoms of interfacial Cu sites can facilitate OH reduction reactions via the Cu–Cu bridge adsorption to assist the formation of ethanol. Especially, those specific active sites easily disappear in the reducing conditions and during the reaction, the major product can transform from ethanol to methanol.     

Hexamerin a Novel Protein Associated with Bacillus sphaericus Resistance in Culex quinquefasciatus

Bacterial insecticides like, Bacillus sphaericus and Bacillus thuringiensis serovar israelensis, have been used for the control of nuisance and vector mosquitoes for more than two decades. For many years, it was assumed that the use of microbial larvicides based on B. sphaericus would not lead to resistance in mosquitoes. However, recent reports have shown that B. sphaericus toxins are not free from this problem. Therefore, the resistance of mosquito populations to be will seriously threaten the sustainability of current mosquito control programme using these microbial insecticides. In the present study, we have characterised a novel protein responsible for resistance development in the filariasis vector of Culex quinquefasciatus. Laboratory selection experiments with B. sphaericus against the larvae were carried out up to 17 generations, and the occurrence of resistance was reported (resistance ratio (RR) at lethal concentration (LC)₅₀ and LC₉₀?=?1,987 and 2,051 folds, respectively). The protein profiles of B. sphaericus-resistant and susceptible population have confirmed with the expression of a new polypeptide (80 kDa) in the resistant strain only. Sequence result revealed that the newly expressed protein was ‘hexamerin’, and this factor might conceivably be responsible for the inheritance of resistance. This study is therefore valuable for comprehending the underlining factor and management of B. sphaericus resistance problem in mosquito population.     

Synthesis and Characterization of Homoleptic and Heteroleptic Complexes Involving Dithiocarbamates,Triphenylphosphine, and Nickel(II)

Abstract

Six new nickel complexes of two dithiocarbamate ligands (cyfdtc = N-cyclohexyl-N- furfuryldithiocarbamate and bztpedtc = N-benzyl-N-[2-thiophenylethyl]dithiocarbamate) namely, (Ni[cyfdtc]₂) (1), (Ni[bztpedtc]₂) (2), (Ni[cyfdtc][NCS][PPh₃]) (3), (Ni[bztpedtc] [NCS][PPh₃]) (4), (Ni[cyfdtc][PPh₃]₂)ClO₄ (5), and (Ni[bztpedtc][PPh₃]₂)ClO₄ (6) have been prepared and characterized using IR, electronic, and NMR (¹H and ¹³C) spectra. A single crystal X-ray structural analysis was carried out for complex 3 and showed that nickel is in a distorted square planar arrangement with the NiS₂PN chromophore. The shift in ν_C?N of the heteroleptic complexes to higher frequencies compared with the parent complex is assigned to mesomeric delocalization of electron density from the

dithiocarbamate ligand toward the metal atom, which increases the contribution of polar thioureide form in mixed ligand complexes. Electronic spectral studies suggest square planar geometry for the complexes. In the ¹³C NMR spectra, the upfield shift of NCS₂ carbon signal for 3 and 4 from the chemical shift value of 1 and 2 is due to effect of PPh₃ on the mesomeric drift of electron density toward nickel throughout thioureide C?N bond.     

Experimental and Theoretical Insights into the Optical Properties and Intermolecular Interactions in Push-Pull Bromide Salts

Experimental and theoretical insights into the nature of intermolecular interactions and their effect on optical properties of 1-allyl-4-(1-cyano-2-(4-dialkylaminophenyl)vinyl)pyridin-1-ium bromide salts ( I and II ) are reported. A comparison of optical properties in solution and in the solid-state of the salts ( I and II ) with their precursors ( Ia and IIa ) is made. The experimental absorption maxima (λ_max) in CHCl₃ is at 528 nm for I and at 542 nm for II , and a strong bathochromic shift of ∼110 nm is observed for salts I and II compared with their precursors. The absorption bands in solid-state at ∼627 nm for I and at ∼615 nm for II that are assigned to charge transfer (CT) effect. The optical properties and single crystal structural features of I and II are explored by experimental and computational tools. The calculated λ_max and the CT are in good agreement with the experimental results. The intermolecular interactions existing in the crystal structures and their energies are quantified for various dimers by PIXEL, QTAIM and DFT approaches. Three types of interactions, (i) the cation⋅⋅⋅cation interactions, (ii) cation⋅⋅⋅anion interactions and (iii) anion⋅⋅⋅anion interactions are observed. The cationic moiety is mainly destabilized by C−H⋅⋅⋅N/π and π⋅⋅⋅π interactions whereas the cation and anion moiety is predominantly stabilized by strong C−H⋅⋅⋅Br⁻ interactions in both structures. The existence of charge transfer between cation and anion moieties in these structures is established through NBO analysis.