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31.
32.
Peter E. Kavanagh 《Journal of mass spectrometry : JMS》1980,15(7):334-335
A program, called ELANAL, has been written in basic which computes all possible empirical formulae for a molecular ion or a fragment ion containing up to eleven common elements. The program then calculates the expected intensities of the peaks following the molecular or fragment ion due to heavier isotopes in the formulae. These calculated intensities are compared with the intensities in an experimentally determined mass spectrum. 相似文献
33.
Goodwin JA Coor JL Kavanagh DF Sabbagh M Howard JW Adamec JR Parmley DJ Tarsis EM Kurtikyan TS Hovhannisyan AA Desrochers PJ Standard JM 《Inorganic chemistry》2008,47(17):7852-7862
Complexes of the (nitro)( meso-tetrakis(2- N-methylpyridyl)porphyinato)cobalt(III) cation, [LCoTMpyP(2)(NO 2)] (4+), in which L = water or ethanol have been immobilized through ionic attraction within Nafion films (Naf). These immobilized six-coordinate species, [LCoTMPyP(2)(NO 2)/Naf], have been found to catalyze the oxidation of triphenylphosphine in ethanol solution by dioxygen, therefore retaining the capacity to activate dioxygen catalytically without an additional reducing agent as was previously observed in nonaqueous solution for the non-ionic (nitro)cobalt porphyrin analogs. Heating these immobilized six-coordinate species under vacuum conditions results in the formation of the five-coordinate nitro derivatives, [CoTMPyP(2)(NO 2)/Naf] at 85 degrees C and [CoTMPyP(2)/Naf] at 110 degrees C. The catalytic oxidation of gas-phase cyclohexene with O 2 is supported only by the resulting immobilized five-coordinate nitro complex as was previously seen with the corresponding solution-phase catalyst in dichloromethane solution. The simultaneous catalytic oxidation of triphenylphosphine and cyclohexene with O 2 in the presence of the Nafion-bound six-coordinate ethanol nitro complex is also observed; however, this process is not seen for the CoTPP derivative in dichloromethane solution. The oxidation reactions do not occur with unmodified Nafion film or with Nafion-supported [BrCo(III)TmpyP]/Naf or [Co(II)TmpyP]/Naf, indicating the necessity for the nitro/nitrosyl ligand in the oxidation mechanism. The existence of a second reactive intermediate is indicated because the two simultaneous oxidation reactions depend on two distinct oxygen atom-transfer steps having different reactivity. The absence of homogeneous cyclohexene oxidation by the six-coordinate (H 2O)CoTPP(NO 2) derivatives in the presence of Ph 3P and O 2 in dichloromethane solution indicates that the second reactive intermediate is lost by an unidentified route only in solution, implying that the immobilization of it in Nafion allows it to react with cyclohexene. Although direct observation of this species has not been achieved, a comparitive DFT study of likely intermediates in several catalytic oxidation mechanisms at the BP 6-31G* level supports the possibility that this intermediate is a peroxynitro species on the basis of relative thermodynamic accessibility. The alternate intermediates evaluated include the reduced cobalt(II) porphyrin, the dioxygen adduct cobalt(III)-O 2 (-), the oxidized cobalt(II) pi-cation radical, and the nitrito complex, cobalt(III)-ONO. 相似文献
34.
Bunkoczi G Pasta S Joshi A Wu X Kavanagh KL Smith S Oppermann U 《Chemistry & biology》2007,14(11):1243-1253
Mammals utilize a single phosphopantetheinyl transferase for the posttranslational modification of at least three different apoproteins: the carrier protein components of cytosolic and mitochondrial fatty acid synthases and the aminoadipate semialdehyde reductase involved in lysine degradation. We determined the crystal structure of the human phosphopantetheinyl transferase, a eukaryotic phosphopantetheinyl transferase characterized, complexed with CoA and Mg(2+), and in ternary complex with CoA and ACP. The involvement of key residues in ligand binding and catalysis was confirmed by mutagenesis and kinetic analysis. Human phosphopantetheinyl transferase exhibits an alpha/beta fold and 2-fold pseudosymmetry similar to the Sfp phosphopantetheinyl transferase from Bacillus subtilis. Although the bound ACP exhibits a typical four-helix structure, its binding is unusual in that it is facilitated predominantly by hydrophobic interactions. A detailed mechanism is proposed describing the substrate binding and catalytic process. 相似文献
35.
Davis C Gordon N Murphy S Singh I Kavanagh K Carberry S Doyle S 《Analytical and bioanalytical chemistry》2011,401(8):2519-2529
Gliotoxin is produced by non-ribosomal peptide synthesis and secreted from certain fungi, including Aspergillus fumigatus. It is an epipolythiodioxopiperazine that contains an intact disulphide bridge and is the focus of intense research as a
consequence of its negative immunomodulatory properties. Gliotoxin detection is generally enabled by reversed-phase–high-performance
liquid chromatography (RP-HPLC), with absorbance detection (220–280 nm), or liquid chromatography-mass spectrometry, yet detection
is not readily achievable by matrix-assisted laser desorption ionisation–time-of-flight mass spectrometry (MALDI-ToF MS).
We have developed a single-pot derivatisation strategy which uses sodium borohydride-mediated reduction of gliotoxin followed
by immediate alkylation of exposed thiols by 5′-iodoacetamidofluorescein to yield a stable product, diacetamidofluorescein-gliotoxin
(GT-(AF)2), of molecular mass 1103.931 Da ((M + H)+). This product is readily detectable by RP-HPLC and exhibits a 6.8-fold increase
in molar absorptivity compared with gliotoxin, which results in a higher sensitivity of detection (40 ng; 125 pmoL). GT-(AF)2 also fluoresces (excitation/emission, 492:518 nm). Unlike free gliotoxin, the product (>800 fmol) is detectable by MALDI-ToF
MS. Sporidesmin A can also be detected by RP-HPLC and MALDI-ToF MS (>530 fmol) using this strategy. We also demonstrate that
the strategy facilitates detection of gliotoxin (mean ± SD = 3.55 ± 0.07 μg 100 μL−1; n = 2) produced by A. fumigatus, without the requirement for organic extraction of culture supernatants and associated solvent removal. GT-(AF)2 is also detectable (150 ng; 460 pmol) by thin-layer chromatography. 相似文献
36.
Rengaraj S Mani V Kavanagh P Rusling J Leech D 《Chemical communications (Cambridge, England)》2011,47(43):11861-11863
Layer-by-layer (LBL) assembly of alternate osmium redox polymers and glucose oxidase, at anode, and laccase, at cathode, using graphite electrodes form a membrane-less glucose/O(2) enzymatic fuel cell providing a power density of 103 μW cm(-2) at pH 5.5. 相似文献
37.
38.
LUDVÍK BENEŠ KLÁRA MELÁNOVÁ JAN SVOBODA VÍTĚZSLAV ZIMA 《Journal of inclusion phenomena and macrocyclic chemistry》2006,55(3-4):289-293
Intercalates of o-, m-, and p-toluidine into α-Zr(HPO4)2 · H2O were prepared and characterized by powder X-ray diffraction, thermogravimetric analysis and infrared spectroscopy. As follows from IR, toludine molecules are protonated in the interlayer space. Toluidine molecules are arranged in a bimolecular way in the intercalates containing more than 1.5 toluidine molecules per Zr atom. On the other hand, a monolayer of the toluidine molecules is supposed in the intercalates with less than one toluidine molecule per Zr atom. 相似文献
39.
M. E. Farago P. Kavanagh R. Blanks J. Kelly G. Kazantzis I. Thornton P. R. Simpson J. M. Cook S. Parry G. M. Hall 《Fresenius' Journal of Analytical Chemistry》1996,354(5-6):660-663
Concentrations of Pt, Pd, Rh and Au in soils and road dusts taken from areas of high and low traffic flows in the London Borough of Richmond and from a section of the Kingston bypass (A3) at New Malden, Surrey, have been measured. High concentrations of platinum are associated with high traffic densities. Samples taken from streets of lower traffic flows were found to contain the lower concentrations of the ranges. These values correlated well with the levels of lead which were also high at roundabouts. If the preliminary results obtained in this study apply more generally throughout the UK, then the potential for exposure to enhanced levels of Pt would appear to be higher for road users and for those living in urban environments or along major highways. 相似文献
40.
Suaad Abuskhuna Malachy McCann John Briody Michael Devereux Kevin Kavanagh Nijhuma Kayal Vickie McKee 《Polyhedron》2007
Cu(II) and Zn(II) complexes of N-hydroxyimidazoles were synthesised by reacting simple metal perchlorate salts with the imidazole ligand in alcohol and formulated with a metal:ligand ratio of 1:2. The X-ray crystal structures of five complexes (four Cu(II) and one Zn(II)) were obtained and each showed the two trans, N-hydroxyimidazole ligands forming six-membered, chelate rings with the metal. Both of the NO chelating, neutral N-hydroxyimidazole ligands are in the zwitterion form, with the uncoordinated imidazole imine N atom being protonated and the oxime O atom deprotonated. In the solid state the complexes form hydrogen-bonded supramolecular structures. 相似文献