X=Y-ZH systems as potential 1,3-dipoles. Cycloadditions of thiominoethers and thioiminocarbonates

Thioiminoethers and thioiminocarbonates of α-amino acid esters undergo acetic acid catalysed cycloaddition reaction with N-phenylmaleimide via their 1,3-dipolar tautomers.     

Flow-rate dependence of gel permeation chromatography

Analysis of polystyrene standards by gel permeation chromatography over a wide range of flow rates revealed two sources of error in volume measurement. These errors arise from solvent evaporation in the siphon chamber and from solvent continuing to flow into the siphon during discharge. Appropriate corrections are discussed, and a vapor feedback loop to eliminate the solvent evaporation error is described. The flow rate dependence of the GPC calibration curve, expressed in the corrected elution volumes, appears different from that reported in the literature. The corrected flow rate dependence of peak elution volumes is in agreement with the expectation of diffusion and exclusion theories.     

Determination of eleven coccidiostats in animal feed by liquid chromatography-tandem mass spectrometry at cross contamination levels

A confirmatory multi-residue method has been developed to allow for the detection, confirmation and quantification of eleven coccidiostats in animal feed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The method can be used to determine halofuginone, robenidine, nicarbazin, diclazuril, decoquinate, semduramicin, lasalocid, monensin, salinomycin, narasin, maduramicin at levels relating to unavoidable carry over as stated in Regulation 2009/8/EC. Feed samples are extracted with water and acetonitrile with the addition of anhydrous magnesium sulphate and sodium chloride. The extract then undergoes a freezing out step before being diluted and injected onto the LC-MS/MS system. The LC-MS/MS system is run in MRM mode with both positive and negative electrospray ionisation and can confirm all eleven analytes in a run time of 19 min. The sensitivity of the method allows quantification and confirmation for all coccidiostats at a 0.5% carry over level. The method was validated over three days in accordance with of European legislation; Commission Decision 2002/657/EC. Validation criteria of accuracy, precision, decision limit (CCα), and detection capability (CCβ) along with measurement uncertainty are calculated for all analytes. The method was then successfully used to analyse a number of feed samples that contained various coccidiostat substances.     

ac Conductivity of mixed spinel NiAl0.7Cr0.7Fe0.6O4

ac Conductivity measurements are carried out across the metal to insulator transition in NiAl_0.7Cr_0.7Fe_0.6O₄. The low frequency data is analyzed using Summerfield scaling theory for hopping conductivity. The exponent of the scaling behavior has significantly different values in the conducting and insulating regimes. The hopping frequency and the zero frequency conductivity are found to increase with temperature, slowly in the metallic regime and rapidly in the insulating regime.     

Enzyme-catalysed synthesis and reactions of benzene oxide/oxepine derivatives of methyl benzoates

A series of twelve benzoate esters was metabolised, by species of the Phellinus genus of wood-rotting fungi, to yield the corresponding benzyl alcohol derivatives and eight salicylates. The isolation of a stable oxepine metabolite, from methyl benzoate, allied to evidence of the migration and retention of a carbomethoxy group (the NIH Shift), during enzyme-catalysed ortho-hydroxylation of alkyl benzoates to form salicylates, is consistent with a mechanism involving an initial arene epoxidation step. This mechanism was confirmed by the isolation of a remarkably stable, optically active, substituted benzene oxide metabolite of methyl 2-(trifluoromethyl)benzoate, which slowly converted into the racemic form. The arene oxide was found to undergo a cycloaddition reaction with 4-phenyl-1,2,4-triazoline-3,5-dione to yield a crystalline cycloadduct whose structure and racemic nature was established by X-ray crystallography. The metabolite was also found to undergo some novel benzene oxide reactions, including epoxidation to give an anti-diepoxide, base-catalysed hydrolysis to form a trans-dihydrodiol and acid-catalysed aromatisation to yield a salicylate derivative via the NIH Shift of a carbomethoxy group.     

Regioselectivity and stereoselectivity of dioxygenase catalysed cis-dihydroxylation of mono- and tri-cyclic azaarene substrates

cis-Dihydrodiol metabolites were obtained from dioxygenase-catalysed asymmetric dihydroxylations of five monocyclic (azabiphenyl) and four tricyclic (azaphenanthrene) azaarene substrates. Enantiopurity values and absolute configuration assignments were determined using a combination of stereochemical correlation, X-ray crystallography and spectroscopy methods. The degree of regioselectivity found during cis-dihydroxylation of monocyclic azaarenes (2,3 bond > 3,4 bond) and of tricyclic azaarenes (bay region > non-bay region bonds) was dependent on the type of dioxygenase used. The cis-dihydrodiol metabolite from an azaarene (3-phenylpyridine) was utilised in the chemoenzymatic synthesis of the corresponding trans-dihydrodiol.     

The role of molecular chaperonins in warm ischemia and reperfusion injury in the steatotic liver: A proteomic study

ABSTRACT: BACKGROUND: The molecular basis of the increased susceptibility of steatotic livers to warm ischemia/reperfusion (I/R) injury during transplantation remains undefined. Animal model for warm I/R injury was induced in obese Zucker rats. Lean Zucker rats provided controls. Two dimensional differential gel electrophoresis was performed with liver protein extracts. Protein features with significant abundance ratios (p < 0.01) between the two cohorts were selected and analyzed with HPLC/MS. Proteins were identified by Uniprot database. Interactive protein networks were generated using Ingenuity Pathway Analysis and GRANITE software. RESULTS: The relative abundance of 105 proteins was observed in warm I/R injury. Functional grouping revealed four categories of importance: molecular chaperones/endoplasmic reticulum (ER) stress, oxidative stress, metabolism, and cell structure. Hypoxia up-regulated 1, calcium binding protein 1, calreticulin, heat shock protein (HSP) 60, HSP-90, and protein disulfide isomerase 3 were chaperonins significantly (p < 0.01) down-regulated and only one chaperonin, HSP-1was significantly upregulated in steatotic liver following I/R. CONCLUSION: Down-regulation of the chaperones identified in this analysis may contribute to the increased ER stress and, consequently, apoptosis and necrosis. This study provides an initial platform for future investigation of the role of chaperones and therapeutic targets for increasing the viability of steatotic liver allografts.     

Local canted spin behaviour in Co1.4−x Zn x Ge0.4Fe1.2O4 spinels: A macroscopic, mesoscopic and microscopic study

DC magnetization, neutron depolarization and neutron diffraction (with both polarized and unpolarized neutrons) measurements have been reported for the Co_1.1−x Zn _x Ge_0.1Fe_1.2O₁ spinels with x=0.5, 0.6 and 0.7. Neutron depolarization and neutron diffraction measurements confirm the presence of a long range ferrimagnetic ordering of the local canted spins in these ferrite samples. The observed features of low field magnetization have been explained under the framework of thermally activated domain wall movement of ferrimagnetic arrangement of local canted spins. An important role of magnetic anisotropy (due to the presence of Co²⁺ ions) in establishing the magnetic ordering and domain kinetics in these ferrites has been observed.