Homeostasis as regulated by activated macrophage. II. LPS of plant origin other than wheat flour and their concomitant bacteria.

In order to seek a macrophage-activating substance, lipopolysaccharide (LPS) of plant origin other than that of wheat flour was surveyed. A large amount of LPS (10-100 micrograms/g) was detected in Laminaria japonica (kelp), Curcuma longa (turmeric), Undaria pinnatifida and other substances. Since concomitant bacteria possibly existing in root of farm products can be considered to contribute to LPS of plant origin, a count was taken of bacterial cells both dead and alive. This count revealed that some LPS were derived from concomitant bacteria which had probably come from root. Few concomitant bacterial cells were found in seaweed, while stem-root contained enough bacterial cells. Three predominant bacteria have been isolated and identified; Pantoea agglomerans, Enterobacter cloacae, and Serratia ficaria. These LPSs were purified and their chemical compositions were examined. They are similar to that of Escherichia coli except that their molecular sizes are smaller. Since LPS is non-toxic when taken orally or percutaneously, these LPSs may also be advantageous in the cure of intractable diseases.     

Kinetics and mechanism of dissociation of some tri- and tetra-dentate complexes of copper(II) in acid media

Summary Kinetics of the dissociation ofm-phenylene-dibiguanidecopper(II) ion,N-salicylideneglycyl-glycinatocuprate(II) ion andN-salicylideneglycinato-aquocopper(II) in acid media, forming aquo-copper(II) ion, have been studied by the stopped-flow spectrophotometric technique. Dissociation of the complexes occurs in two consecutive steps, the first being faster than the second. For them-phenylenedibiguanide complex each step exhibits second order acid dependance,k _x=k _x [H⁺]² wherek _x is the observed pseudo-first order rate constant. However, the Schiff base complexes show first order acid dependance,k _x=k _x [H⁺], for both steps. The results, with relatively low H and highly negative S values, are consistent with a solvent-assisted dissociative process.     

Resolution, quantification and confirmation of betamethasone and dexamethasone in equine plasma by liquid chromatography/tandem mass spectrometry

This method describes the simultaneous separation, identification, quantification and confirmation of betamethasone (BTM) and dexamethasone (DXM) in equine plasma by liquid chromatography (LC) integrated with multidimensional tandem mass spectrometry. Analytes were directly extracted from equine plasma by methyl tert-butyl ether (MTBE). The residues were reconstituted with sample solvent. LC separation of the analytes was performed on a Hypercarb column using acetonitrile/water/formic acid (95:5:0.5, v/v/v) as the mobile phase. Sample screening, quantification and confirmation were performed in multiple reaction monitoring (MRM) mode. The method was linear over the concentration range of 0.1-75 ng/mL for both analytes. Limit of detection (LOD) was 50 pg/mL and that of quantification (LOQ) was 100 pg/mL for both analytes. The limit of confirmation (LOC) for the presence of BTM or DXM by MRM was 0.5 ng/mL. The intra-and inter-day precisions expressed as coefficient of variation (CV) for quantification of DXM and BTM from 0.1 to 50 ng/mL were less than 7% and the accuracy was in the range of 97-105%. This method is capable of distinguishing BTM from DXM when both analytes are simultaneously present in equine plasma. Measurement uncertainty for both analytes was estimated at less than 16%. The method is rapid, specific, selective, sensitive, simple and reliable. The importance of this method is its usefulness in directly identifying and differentiating BTM from DXM without derivatization.     

Synthesis and structural characterization of a novel dinuclear complex compound formed by the aerial oxidation of cobalt(II) having an interligand C-C sigma-bond

The aerial oxidation of cobalt(II) salt, in a methanolic solution, containing a hydrazone ligand, (E)-N'-(4-oxo-4-phenylbutan-2-ylidene)benzohydrazide (condensation product of benzoyl acetone and benzhydrazide, LH2) leads to the coupling of two such ligand units through the formation of a rather long C-C bond [1.601(6) A] giving rise to a dinuclear Co (III) hydrazone complex, [Co2(L)2(L')(].0.25H2O (L' = C-C coupled hydrazone ligand). The structure of the complex has been determined by X-ray crystallography and IR, UV-Vis spectroscopy and elemental analysis have characterized the complex.     

Structural and spectral studies of a new copper(II) complex with a tridentate thiosemicarbazone ligand

The reaction of copper(II) chloride dihydrate with 2-hydroxy-3-methoxybenzaldehydethiosemicarbazone (HL) ligand in a 1:1 ratio forms the complex [Cu(L)(Cl)] · H₂O. The complex is characterized by spectroscopic, electrochemical, and thermal analysis. X-ray crystallographic analysis reveals that the central copper atom displays the distorted square planar geometry. The water molecule present in the lattice participates in a strong hydrogen bonding network, which leads to a 2D supramolecular arrangement.     

Square planar complexes of Cu(II) and Ni(II) with N<Subscript>2</Subscript>O donor set of two Schiff base ligands: synthesis and structural aspects

Abstract Two new square planar Cu(II) and Ni(II) complexes, [CuL¹(NCO)] (1) and [NiL²(N₃)] (2) have been synthesized with two different tridentate N₂O donor Schiff base ligands L ¹ H (1:1 condensation product of benzoylacetone and 2-diethylaminoethylamine) and L ² H (1:1 condensation product of benzoylacetone and 2-dimethylaminoethylamine), respectively. Both the complexes 1 and 2 have been characterized by elemental analysis, IR, UV-Vis spectroscopy, room temperature magnetic susceptibility measurement, electrochemical, thermal, and single crystal X-ray diffraction studies. Structural studies reveal that in both the complexes metal centers have square planar environment with N₂O donor set of Schiff base ligands and terminal pseudohalide anions (isocyanate for 1 and azide for 2) at four coordination sites of square plane. Graphical abstract Square planar complexes of Cu(II) and Ni(II) with N ₂ O donor set of two Schiff base ligands: synthesis and structural aspects Subhra Basak, Soma Sen, Samiran Mitra, C. Marschner, W. S. Sheldrick Two new square planar Cu(II) and Ni(II) complexes, [CuL¹(NCO)] (1) and [NiL²(N₃)] (2) have been synthesized with two different tridentate N₂O donor Schiff base ligands L ¹ H and L ² H respectively. Both the complexes 1 and 2 have been characterized by elemental analysis, IR, UV-Vis spectroscopy, room temperature magnetic susceptibility measurement, electrochemical, thermal and single crystal X-ray diffraction studies.      

pH induced interaction of DPPC with a fluorescent dye in Langmuir and Langmuir Blodgett (LB) films

This communication reports the investigation of the pH effects on the interaction of a well-known lung surfactant, Dipalmitoylphosphatidylcholine (DPPC) with water soluble highly fluorescent dye Rhodamine B (RhB) in complex Langmuir monolayers at the air–water interface. The ionic nature of DPPC changes with the pH of the subphase in the Langmuir trough. At sufficiently low pH it becomes cationic whereas at higher pH it can be presented with a negative net charge and at normal pH it is zwitterionic. Being zwitterionic, RhB molecules can interact with DPPC at normal and higher pH, whereas at lower pH the interaction becomes less probable. This has been investigated in details at the air–water interface in Langmuir trough as well as in Langmuir Blodgett (LB) film by employing surface pressure versus area per molecule (π–A) isotherms, compressibility study, in-situ Fluorescence Imaging Microscopy (FIM), UV-vis absorption spectroscopy and Atomic Force Microscopy (AFM) study.     

A new luminescent sulfate bridged dimeric copper(II) complex with DNA binding and SO2 fixation ability: Synthesis and structure

New luminescent mononuclear and dinuclear copper(II) (S = 1/2) complexes [Cu(HL)(H₂O)₂](ClO₄)₂ (1a) and [Cu₂(HL)₂(μ-SO₄)₂]·2H₂O (1b) were synthesized with the acyclic tridentate pyridine-2-carboxaldehyde-2-pyridylhydrazone ligand, HL (1). Interestingly, the mononuclear complex 1a can be converted into the disulfate bridged dimeric copper(II) complex 1b by passing freshly prepared SO₂ through the basic medium. On excitation at 290 nm, the ligand fluoresces at 364 nm due to an intraligand ¹(π–π1) transition. Upon complexation with copper(II), the emission peak is slightly blue shifted (356 nm, F/F₀ 0.76 for 1a and 354 nm, F/F₀ 0.89 for 1b) with a little quenching in the emission intensity. The association constants (K_ass (5.06 ± 0.004) × 10⁴ for 1a and K_ass (5.46 ± 0.006) × 10⁴ for 1b at 298 K) and the thermodynamic parameters have been determined by UV–Vis spectroscopy. The molecular structure of the complex 1b (Cu?Cu 4.456 Å) has been determined by single crystal X-ray diffraction studies. The complex 1b exhibits a strong interaction towards DNA as revealed from the K_b (intrinsic binding constant) 6.3 × 10⁴ M^?1 and K_sv (Stern–Volmer quenching constant) 2.93 values.     

Monitoring of the electrochemical degradation of PEDOT films on gold using the bending beam method

Electrochemical and mechanical properties of thin poly(3,4-ethylenedioxythiophene) films deposited on gold have been investigated in aqueous sulfuric acid and sodium-sulfate solutions. It has been shown that at sufficiently positive electrode potentials, overoxidation of the polymer takes place. In some cases, only small changes could be observed in the shape of cyclic voltammograms taken in the “stability region” before and after overoxidation. In contrast to this, the impedance spectra recorded after overoxidation differed considerably from the impedance spectra of a freshly made electrode. Morphological changes of the polymer caused by overoxidation (degradation) could be detected by using the bending beam method.

     

Numerical investigation of laminar cross-flow non-premixed flames in the presence of a bluff-body

A knowledge of flame stability regimes in the presence of cylindrical bluff-bodies of various dimensions is essential to design non-premixed burners. The reacting flow field in such cases is reported to be three-dimensional and unsteady. In the literature, only a few experimental investigations with limited measurements are available. Therefore, in this work, a detailed numerical study of laminar cross-flow non-premixed methane–air flames in the presence of a square cylinder is presented. The flow, temperature, species and reaction fields have been predicted using a comprehensive transient three-dimensional reacting flow model with detailed chemical kinetics and variable thermo-physical properties, in order to get a good insight into the flame stabilisation phenomena. Further, analyses of quantities such as local equivalence ratio, cell Damköhler number, species velocity, net consumption rate of methane, which are not easily obtained through experiments even with detailed diagnostics, have been carried out. The influence of the flow field due to varying inlet velocity of the oxidiser, in the presence of the bluff-body, on flame anchoring location has been analysed in detail. Local equivalence ratio contours obtained from non-reacting flow calculations are seen to be quite useful in analysing the mixing process and in the prediction of flame anchoring locations when the flames are not separated. Cell Damköhler number has been calculated using cell size, species velocity of the fuel, which is a derived quantity, and the net reaction rate of the fuel. The flame zone, which is customarily inferred from the contours of temperature, CO and OH, is also shown to be predicted well by the contour line corresponding to a Damköhler number equal to unity. The net reaction rate of CH₄ and the net rates of two dominant reactions, which consume methane, show clearly the variation in the flame anchoring locations in these three cases. Further, the three-dimensionality of these flames are analysed by plotting the mean temperature contours in y–z planes. Finally, the unsteadiness in the separated flame case is analysed.