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81.
Peltier P Beláňová M Dianišková P Zhou R Zheng RB Pearcey JA Joe M Brennan PJ Nugier-Chauvin C Ferrières V Lowary TL Daniellou R Mikušová K 《Chemistry & biology》2010,17(12):1356-1366
UDP-galactofuranose (UDP-Galf) is a substrate for two types of enzymes, UDP-galactopyranose mutase and galactofuranosyltransferases, which are present in many pathogenic organisms but absent from mammals. In particular, these enzymes are involved in the biosynthesis of cell wall galactan, a polymer essential for the survival of the causative agent of tuberculosis, Mycobacterium tuberculosis. We describe here the synthesis of derivatives of UDP-Galf modified at C-5 and C-6 using a chemoenzymatic route. In cell-free assays, these compounds prevented the formation of mycobacterial galactan, via the production of short "dead-end" intermediates resulting from their incorporation into the growing oligosaccharide chain. Modified UDP-furanoses thus constitute novel probes for the study of the two classes of enzymes involved in mycobacterial galactan assembly, and studies with these compounds may ultimately facilitate the future development of new therapeutic agents against tuberculosis. 相似文献
82.
83.
Berwyck L. J. Poad Huong T. Pham Michael C. Thomas Jessica R. Nealon J. Larry Campbell Todd W. Mitchell Stephen J. Blanksby 《Journal of the American Society for Mass Spectrometry》2010,21(12):1989-1999
Ozone-induced dissociation (OzID) exploits the gas-phase reaction between mass-selected lipid ions and ozone vapor to determine
the position(s) of unsaturation. In this contribution, we describe the modification of a tandem linear ion-trap mass spectrometer
specifically for OzID analyses wherein ozone vapor is supplied to the collision cell. This instrumental configuration provides
spatial separation between mass-selection, the ozonolysis reaction, and mass-analysis steps in the OzID process and thus delivers
significant enhancements in speed and sensitivity (ca. 30-fold). These improvements allow spectra revealing the double-bond
position(s) within unsaturated lipids to be acquired within 1 s: significantly enhancing the utility of OzID in high-throughput
lipidomic protocols. The stable ozone concentration afforded by this modified instrument also allows direct comparison of
relative reactivity of isomeric lipids and reveals reactivity trends related to (1) double-bond position, (2) substitution
position on the glycerol backbone, and (3) stereochemistry. For cis- and trans-isomers, differences were also observed in the branching ratio of product ions arising from the gas-phase ozonolysis reaction,
suggesting that relative ion abundances could be exploited as markers for double-bond geometry. Additional activation energy
applied to mass-selected lipid ions during injection into the collision cell (with ozone present) was found to yield spectra
containing both OzID and classical-CID fragment ions. This combination CID-OzID acquisition on an ostensibly simple monounsaturated
phosphatidylcholine within a cow brain lipid extract provided evidence for up to four structurally distinct phospholipids
differing in both double-bond position and sn-substitution. 相似文献
84.
A highly convergent synthesis of (-)-okilactomycin is described. Key reactions of this synthesis include a strategy-level diastereoselective oxy-Cope rearrangement/oxidation sequence, a Petasis-Ferrier union/rearrangement tactic, and an efficient RCM reaction to construct the 13-membered macrocyclic ring. 相似文献
85.
The use of solution 17O NMR spectroscopy in verifying the mechanism of trialkyl phosphite hydrolysis is presented. Trimethyl phosphite was reacted with 17O-labeled H2O at different temperatures and two reactant concentrations, with the reaction being monitored by 17O NMR. Kinetic details elucidated from the NMR spectra are also discussed. 相似文献
86.
Todd JF Barber SJ Wright IP Morgan GH Morse AD Sheridan S Leese MR Maynard J Evans ST Pillinger CT Drummond DL Heys SC Huq SE Kent BJ Sawyer EC Whalley MS Waltham NR 《Journal of mass spectrometry : JMS》2007,42(1):1-10
In May 2014, the Rosetta spacecraft is scheduled to rendezvous with the comet Churyumov-Gerasimenko ('67P'). One of the instruments on board the 'Lander' which will descend on to the surface of the comet is a miniaturised GC/MS system that incorporates an ion trap mass spectrometer, specially developed for isotope ratio analysis. This article describes the development and optimisation of the ion trap for this unique application, and presents a summary of the range of pre-programmed experiments that will contribute to the characterisation of the solid and volatile cometary materials. 相似文献
87.
Gogichaeva NV Williams T Alterman MA 《Journal of the American Society for Mass Spectrometry》2007,18(2):279-284
This is the first report of an application of collisionally induced fragmentation of amino acids (AA) and their derivatives by MALDI TOF/TOF tandem mass spectrometry (MS). In this work, we collected the data on high-energy fragmentation reactions of a large group of protonated amino acids and their derivatives with the goal of determining which product ions are analyte specific and if yields of these fragment could be used for quantitative analysis. From 34 different amino acids (20 alpha-amino acids, beta-amino acids, homocysteine, GABA, and modified AA Met sulfone and sulfoxide, hydroxyproline, etc.) we observed that high yields of the target specific immonium ions and fragmentation patterns are most similar to EI or FAB CID on sector instruments. The major exceptions were two highly basic amino acids, Arg and Orn. It is noted that neither beta-, gamma-, nor delta-amino acids produce immonium ions. As might be predicted from high-energy CID work on peptides from the sectors and TOF/TOF, the presence of specific indicator ions in MALDI tandem MS allows distinguishing isomeric and isobaric amino acids. These indicator ions, in combination with careful control of data acquisition, ensure quantitative analysis of amino acids. We believe our data provide strong basis for the application of MALDI TOF/TOF MS/MS in qualitative and quantitative analysis of amino and organic acids, including application in clinical medicine. 相似文献
88.
Todd B. Kreutzian Khalid S. A. Seraj Larry G. Anderson Donald C. Zapien 《Electroanalysis》2007,19(23):2479-2482
In this work, long optical path length thin‐layer electrochemical cell was constructed using indium‐tin oxide on glass as the electrode material. Iron release from ferritin adsorbed on the electrode was induced by applying a negative potential sweep in the presence of 1,10‐phenanthroline. The usefulness of spectroelectrochemistry as a means of determining the quantity of iron released from an adsorbed layer of ferritin is demonstrated. 相似文献
89.
The thermally stable, terminal phosphinidene complexes [CpM(CO)2(eta1-PNiPr2)]AlCl4(Cp= Cp, Cp*; M = Fe) and [Cp*M(CO)3(eta1-PNiPr2)]AlCl4 (M = Cr, Mo, W) react with Ph2C=N=N to form terminal P-coordinated eta1-phosphaazine and eta3-diazaphosphaallene ligands, respectively, whereas [CpFe(CO)2(eta1-PNiPr2)]AlCl4 reacts with Me3SiCHN2 affording a terminal phosphorus bound eta1-phosphaalkene complex. 相似文献
90.
Bob Boyd Gareth Brenton Eddie Clayton Jonathan Curtis R. M. Elliott G. A. Errock B. N. Green R. H. Bateman Simon J. Gaskell Iwan Griffiths Zdenek Herman Philip Jonathan Rich Kondrat Mila Laušević Chris Lock Deepak Mathur John F. J. Todd Károly Vékey 《Rapid communications in mass spectrometry : RCM》2016,30(11):1253-1264