Aerobic oxidation of methyl p-tolyl sulfide catalyzed by a remarkably labile heteroscorpionate RuII-aqua complex,fac-[RuII(H2O)(dpp)(tppm)]2+

fac-[RuII(Cl)(dpp)(L3)]+ (L3 = tris(pyrid-2-yl)methoxymethane (tpmm) = [1A]+ and tris(pyrid-2-yl)pentoxymethane (tppm) = [1B]+ and dpp = di(pyrazol-1-yl)propane) rapidly undergo ligand substitution with water to form fac-[RuII(H2O)(dpp)(L3)]2+ (L3 = tpmm = [2A]2+ and tppm = [2B]2+). In the structure of [2A]2+, the distorted octahedral arrangement of ligands around Ru is evident by a long Ru(1)-O(40) of 2.172(3) A and a large angle O(40)-Ru(1)-N(51) of 96.95(14) degrees . The remarkably short distance between O(40) of H2O and H(45a) of dpp confirms the heteroscorpionate ligand effect of dpp on H2O. [2B]2+ aerobically catalyzes methyl p-tolyl sulfide to methyl p-tolyl sulfoxide in 1,2-dichlorobenzene at 25.0 +/- 0.1 degrees C under 11.4 psi of O2. Experimental facts in support of this aerobic sulfide oxidation are the absence of H2O2 and the oxidative reactivity of the putative Ru(IV)-oxo intermediate toward methyl p-tolyl sulfide, 2-propanol, and allyl alcohol. This study provides the first documented example of aerobic-sulfide oxidation catalyzed by the remarkably labile heteroscorpionate Ru(II)-aqua complex without the formation of a highly reactive peroxide as an intermediate.     

Effect of cost-free energy storage material and saline water depth on the performance of square pyramid solar still: a mathematical and experimental study

Journal of Thermal Analysis and Calorimetry - Low productivity of single-slope solar still is the main barrier for its worldwide usability. An attempt has been conducted to enhance the distillate...     

Impact of orientation and water depth on productivity of single-basin dual-slope solar still with Al2O3 and CuO nanoparticles

Journal of Thermal Analysis and Calorimetry - The thermal performance of solar still can be enhanced by means of nanoparticles. The core aim of the present work is to identify the influence of...     

Transition metal complexes enslaved in the supercages of zeolite-Y: DFT investigation and catalytic significance

A series of zeolite-Y encapsulated hybrid catalysts, [M(STCH)·xH₂O]-Y have been prepared by encapsulating Schiff base complexes [where M?=?Mn(II), Fe(II), Co(II), Ni(II); (x?=?3) and Cu(II); (x?=?1); H₂STCH?=?salicylaldehyde thiophene-2-carboxylic hydrazone] in zeolite-Y matrix by flexible ligand method. These hybrid materials have been characterized by various physico-chemical techniques such as ICP-OES, elemental analyses, (FT-IR and electronic) spectral studies, BET, scanning electron micrographs, thermal analysis and X-ray powder diffraction patterns. X-ray powder diffraction analysis reveals that the structural integrity of the mother zeolite in the hybrid material remained intact upon immobilization of the complex. Density functional theory is employed to calculate the relaxed structure, bond angle, bond distance, dihedral angle, difference of highest occupied molecular orbital and lowest unoccupied molecular orbital energies gap and electronic density of states of ligand and their neat transition metal complexes. The hybrid materials are active catalysts for the hydroxylation of phenol using hydrogen peroxide (30% H₂O₂) as an oxidant in order to selectively synthesize catechol or hydroquinone, amongst them [Cu(STCH)·H₂O]-Y shown the highest % of selectivity towards catechol (81.3%).     

Synthesis,spectral, thermal,and antibacterial investigation of mixed ligand complexes of oxovanadium(IV)

Novel mononuclear mixed-ligand oxovanadium(IV) complex [VO(PMFP)(Bipy)]ClO₄ was prepared by the condensation of VOSO₄ · 5H₂O with ligands 1-phenyl-3-methyl-4-formyl-2-pyrazolin-5one (PMFP) and 2,2′-bipyridyl (Bipy). The corresponding Schiff bases were prepared by the condensation of [VO(PMFP)(Bipy)]ClO₄ with ethylenediamine, ethanolamine, and glycine. All the compounds have been characterized by elemental analysis, magnetic susceptibility, X-ray crystallography, conductometry measurement, ¹H NMR, FT-IR, ESR, electronic spectra, and mass spectrometry. Electronic spectra and magnetic susceptibility measurements indicate distorted octahedral stereochemistry of the oxovanadium(IV) complexes. Thermal stability, kinetic order, heat capacity, and activation energy of thermal degradation of these complexes were determined by TGA and DSC. The presence of one coordinate water molecule is suggested from the IR and TGA studies. Hamiltonian and bonding parameters were found from ESR spectra, indicating that the metal-ligand bonding is partial covalent. Antibacterial screening is reported for the ligand and complexes of oxovanadium(IV). The text was submitted by the authors in English.     

Metabolite assignment of ultrafiltered synovial fluid extracted from knee joints of reactive arthritis patients using high resolution NMR spectroscopy

Currently, there are no reliable biomarkers available that can aid early differential diagnosis of reactive arthritis (ReA) from other inflammatory joint diseases. Metabolic profiling of synovial fluid (SF)—obtained from joints affected in ReA—holds great promise in this regard and will further aid monitoring treatment and improving our understanding about disease mechanism. As a first step in this direction, we report here the metabolite specific assignment of ¹H and ¹³C resonances detected in the NMR spectra of SF samples extracted from human patients with established ReA. The metabolite characterization has been carried out on both normal and ultrafiltered (deproteinized) SF samples of eight ReA patients (n = 8) using high-resolution (800 MHz) ¹H and ¹H─¹³C NMR spectroscopy methods such as one-dimensional ¹H CPMG and two-dimensional J-resolved¹H NMR and homonuclear ¹H─¹H TOCSY and heteronuclear¹H─¹³C HSQC correlation spectra. Compared with normal SF samples, several distinctive ¹H NMR signals were identified and assigned to metabolites in the ¹H NMR spectra of ultrafiltered SF samples. Overall, we assigned 53 metabolites in normal filtered SF and 64 metabolites in filtered pooled SF sample compared with nonfiltered SF samples for which only 48 metabolites (including lipid/membrane metabolites as well) have been identified. The established NMR characterization of SF metabolites will serve to guide future metabolomics studies aiming to identify/evaluate the SF-based metabolic biomarkers of diagnostic/prognostic potential or seeking biochemical insights into disease mechanisms in a clinical perspective.     

Beyond Biological Chelation: Coordination of f-Block Elements by Polyhydroxamate Ligands

The promise of polyhydroxamic acid ligands for the selective chelation of the f-block elements is becoming increasingly more apparent. The initial studies of polyhydroxamic acid siderophores showed the formation of highly stable complexes with Pu^IV, but a higher preference for Fe^III hindered effective applications. The development of synthetic routes toward highly pure and customizable ligands containing multiple hydroxamic acids allowed for the growth of new classes of compounds. Although the first round of these ligands focused on the incorporation of siderophore-like frameworks, the new synthetic strategies led to small molecules of various frameworks and even resins for applications in the field of f-block element separations and biological desorption. Unfortunately, a lack of consistent stability-constant data makes direct comparisons across this body of work difficult. More studies into the stability constants and separations of the f-block elements in a variety of pH ranges is necessary to truly realize the potential for polyhydroxamic acid ligands.     

Dynamics of an array formed by three neutrally buoyant cylindrical cantilevers subjected to tensile follower forces

The flexural-rotational coupled motion of three identical flexible cylindrical cantilevers joined symmetrically to a central head is investigated. Effects of the tensile follower forces and inertia parameters on the natural frequencies of the system are studied. The analysis suggests two types of inplane motion: one corresponding to the oscillation of the cantilevers without any rotation of the central body, while the other involves coupled motion of the array. The former corresponds to the repeated eigenvalues which are identical to those of a single cantilever having the same axial tension parameter, P. Three sets of eigenvalues govern the out-of-plane motion: (a) the central head remaining stationary with no rolling motion of the array; (b) vertical motion of the central body without any rolling motion of the array; and (c) rigid body rolling motion without any vertical motion of the central head. There is a possibility of dynamic instability for small inertia parameters and large axial tension.     

Towards aflatoxins: a formal synthesis of aflatoxin B2

The development of a formal synthesis of aflatoxin B2 is described, which utilizes a Dötz benzannulation reaction as a key step.     

Novel Mn(III) heterochelates: synthesis,thermal, spectroscopic,and coordination aspects

This article describes the synthesis, structural features, and thermal studies of novel Mn(III) heterochelates of the type [Mn(SB _n )(L)(H₂O)]·xH₂O [H₂SB _n  = Nicotinic acid [1-(3-methyl-5-oxo-1-phenyl-4,5 dihydro-1H-pyrazol-4yl)-acylidene]-hydrazide where acyl = acetyl (H₂SB₁); benzoyl (H₂SB₂); propionyl (H₂SB₃); buteryl (H₂SB₄); phenyl acetyl (H₂SB₅); and HL = 5-Chloro-7-iodo-8-hydroxyquinoline (clioquinol)]. The heterochelates have been characterized on the basis of elemental analyses, magnetic susceptibility measurements, cyclic voltammetric studies, (FTIR and electronic) spectra, and thermal studies. The FAB mass spectrum of [Mn(SB₁)(L)H₂O]·3H₂O has been carried out. The cyclic voltammetric studies reveal that quasi-reversible reduction process of Mn(III)/Mn(II) coupled system suggesting that the ligands readily destabilize higher oxidation states of metal ion. Kinetic parameters such as order of reaction (n) and the energy of activation (Ea) were calculated using Freeman–Carroll method. The pre-exponential factor (A), the activation entropy (S*), the activation enthalpy (H*), and the free energy of activation (G*) were calculated using Horowitz–Metzger equations.