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61.
Collision-induced dissociation (CID) of 8-(4'-hydroxyphenyl)-2'-deoxyguanosine and 8-(2'-hydroxyphenyl)-2'-deoxyguanosine was investigated using sequential tandem mass spectrometry. These adducts represent biomarkers of DNA damage linked to phenolic radicals and were investigated to gain insight into the effects of chemical structure of a C-8 modification on fragmentation pathways of modified 2'-deoxyguanosine (dG). CID in MS(2) of the deprotonated molecules of both the isomers generated the same product ion having the same m/z values. CID in MS(3) of the product ion at m/z 242 and CID in MS(4) experiments carried out on the selected product ions at m/z 225 and m/z 218 afford distinct fragmentation patterns. The conformational properties of isomeric product ions from CID showed that the ortho-isomers possess the unique ability to tautomerize through an intramolecular proton transfer between the phenolic OH group and the imine nitrogen (N7). Tautomerization of ortho-isomers to their keto-tautomers led to differences in their system of conjugated double bonds compared with either their enol-tautomer or the para-isomer. The charge redistribution through the N-7 site on the imidazole ring is a critical step in guanosine adduct fragmentation which is disrupted by the formation of the keto-tautomer. For this reason, different reaction pathways are observed for 8-(4'-hydroxyphenyl)-2'-deoxyguanosine and 8-(2'-hydroxyphenyl)-2'-deoxyguanosine. We present herein the dissociation and the gas-phase ion-molecule reactions for highly conjugated ions involved in the CID ion chemistry of the investigated adducts. These will be useful for those using tandem mass spectrometry for structural elucidation of C-8 modified dG adducts. This study demonstrates that the modification at the C-8 site of dG has the potential to significantly alter the reactivity of adducts. We also show the ability of tandem mass spectrometry to completely differentiate between the isomeric dG adducts investigated. 相似文献
62.
Gerhard Simchen Günther Entenmann 《Angewandte Chemie (International ed. in English)》1973,12(2):119-126
Five-membered, six-membered, and seven-membered aza-, diaza-, and thiazaheterocycles can be prepared by cyclization of. ω-cyano carboxylic acid halides in the presence of hydrogen halides in aprotic solvents. Nitrile-hydrogen halide adducts occur as intermediates in this novel heterocycle synthesis of wide application. The acylating cyclizations of nitriles in protonic media, which proceed via imidic esters or amides, are not discussed. 相似文献
63.
64.
A density functional theory (DFT) study aimed at understanding structure–reactivity relationships in the oxidized metabolites of cyclopenta‐fused polycyclic aromatic hydrocarbons (CP‐PAHs) is reported. Epoxidation at various positions was examined in order to identify the most stable epoxide in each class of CP‐PAHs. Relative energies of the carbocations resulting from O‐protonation and epoxide ring opening were analyzed and compared, taking into account the available biological activity data on these compounds. Geometrical, electronic, and conformational issues were considered. Charge delocalization modes in the resulting carbocations were deduced via the natural population analysis (NPA)‐derived changes in charges. Computational results pointed to the importance of the unsaturated cyclopenta ring on the reactivity of these compounds. The reported bioactivity of this highly mutagenic/carcinogenic family of PAHs was observed to parallel their relative carbocation stabilities. A different behavior was observed in crowded non‐planar structures possessing a distorted aromatic system. A covalent adduct formed between a CP‐PAH epoxide and a purine base was computed inside a DNA fragment employing the ONIOM method. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
65.
Dipl.‐Chem. Andreas Kraft B. Sc. Patrick Roth Dr. David Schmidt M. Sc. Johannes Stangl Prof. Dr. Klaus Müller‐Buschbaum Dr. Florian Beuerle 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(17):5982-5987
Hexakis‐substituted [60]fullerene adducts with icosahedral symmetry provide an unprecedented scaffold for the spatial arrangement of twelve functional groups with high geometric precision. This unique molecular symmetry identifies such polyfunctional organic building blocks as potential highly connective linkers for coordination polymer and metal–organic framework synthesis. Hereby, the linker exhibits a higher connectivity than the metal ions and with the main connectivity based on the ligand, this can create a new type of inversely cross‐linked framework. Two hexakis adducts bearing either twelve glycolic acid or 3‐hydroxypropionic acid side chains attached to its malonate units were incorporated as organic connectivity centers in the first fullerene‐containing three‐dimensional frameworks by coordination with Zn2+. 相似文献
66.
Meriam Jebari Nabil Bouazizi Radhouane Bargougui Farhat Rezgui Jacques Maddaluno Franck Le Derf Julien Vieillard Julien Legros 《Tetrahedron letters》2018,59(45):4044-4046
Several iron oxides nanoparticles (Fe2O3@Fe2O3, Fe°@Fe2O3, GO@Fe2O3 and calcinated Fe2O3) have been assessed as catalysts in the 1,4-addition of a cyclic β-ketoester onto methyl vinyl ketone under neat conditions. It appeared that calcinated Fe2O3NP are efficient catalysts at 1?mol% loading for the Michael addition of 1,3-dicarbonyl compounds onto various enones. 相似文献
67.
The compound bis(1,3-diphenyl-1,3-propanedionato-O,O′) (1,10-phenanthroline-N, N′)cobalt(II) (Co(DBM)2(1,10-phe)) was investigated as a potential host component for functional inclusion materials. The molecules of the complex in the crystal (a=21.015(5) ?, b=17.456(5) ?, c=9.503(3) ?, β=107.04(2)°, s.g. C 2/c) are centrosymmetric and assemble by way of C–H···O and C–H···π hydrogen bonds as well as π···π stacking interactions to provide a supramolecular ladder-like motif that is accompanied by a variant of the six phenyl-embrace synthon. 相似文献
68.
The first example of the one-pot oxidative conjugate addition of sulfur-centred nucleophiles to Baylis-Hillman adducts is reported. The reaction involves oxidation of Baylis-Hillman adducts with NaNO3 in the Brønsted acidic ionic liquid [Hmim]HSO4 to give [E]-α-cyanocinnamaldehydes followed by conjugate hydrothiocyanation/hydrosulfenylation with NH4SCN/PhSH to afford the corresponding β-thiocyanato (or β-phenylsulfenyl)-α-cyanohydrocinnamaldehydes diastereoselectively in 76-89% yields in a one-pot procedure. After isolation of the product, the ionic liquid [Hmim]HSO4 could be easily recycled for further use. 相似文献
69.
Roshanak Aslebagh Bruce A. Pfeffer Steven J. Fliesler Costel C. Darie 《Electrophoresis》2016,37(20):2615-2623
Modification of proteins by 4‐hydroxy‐2‐nonenal (HNE), a reactive by‐product of ω6 polyunsaturated fatty acid oxidation, on specific amino acid residues is considered a biomarker for oxidative stress, as occurs in many metabolic, hereditary, and age‐related diseases. HNE modification of amino acids can occur either via Michael addition or by formation of Schiff‐base adducts. These modifications typically occur on cysteine (Cys), histidine (His), and/or lysine (Lys) residues, resulting in an increase of 156 Da (Michael addition) or 138 Da (Schiff‐base adducts), respectively, in the mass of the residue. Here, we employed biochemical and mass spectrometry (MS) approaches to determine the MS “signatures” of HNE‐modified amino acids, using lysozyme and BSA as model proteins. Using direct infusion of unmodified and HNE‐modified lysozyme into an electrospray quadrupole time‐of‐flight mass spectrometer, we were able to detect up to seven HNE modifications per molecule of lysozyme. Using nanoLC‐MS/MS, we found that, in addition to N‐terminal amino acids, Cys, His, and Lys residues, HNE modification of arginine (Arg), threonine (Thr), tryptophan (Trp), and histidine (His) residues can also occur. These sensitive and specific methods can be applied to the study of oxidative stress to evaluate HNE modification of proteins in complex mixtures from cells and tissues under diseased versus normal conditions. 相似文献
70.
Yu Huilan Dong Junjun Hu Zhen Pei Chengxin Liu Shilei Xiang Yu 《Phosphorus, sulfur, and silicon and the related elements》2016,191(1):111-116
A new method for the synthesis of organophosphorylated adducts of the nonapeptide FGESAGAAS is presented. The adducts were obtained by using sarin (GB) or soman (GD) as the organophosphorylating reagents and cesium carbonate as the acid scavenger. Greater than 50% of the peptide was modified on serine 4. MS/MS spectra acquired on an Agilent 6520 quadrupole time of flight mass spectrometer demonstrated that serine 4, but not serine 9 in the nonapeptide, was modified. The adducts included the characteristic isopropyl group of sarin and the pinacolyl group of soman, indicating that aging had not occurred. It was concluded that the new synthetic method yielded sarin and soman-modified peptides that could be used as references when analyzing human exposure to these nerve agents. 相似文献