Reaction of Mucochloric Acid with Adenosine: Formation of 8-(N6-Adenosinyl)ethenoadenosine Derivatives

Abstract

The bacterial mutagen mucochloric acid was reacted with adenosine in aqueous solutions at 37 degrees C. In the HPLC chromatograms of the reaction mixtures two peaks of unidentified products were observed at longer retention times than the previously characterized "etheno" and "ethenocarbaldehyde" adducts. Following isolation and purification with chromatographic methods, the products were characterized by UV absorbance, 1H and 13C NMR spectroscopy, and thermospray mass spectrometry. The products were found to consist of ethenoadenosine derivatives which bonded an additional adenosine unit to C-8 in the etheno bridge. In one of the products a formyl group and in the other an oxalo group was localized at C-7 in the etheno bridge. The yield of the products was about 0.04 mol% (calculated from the original amount of adenosine) in the reaction mixture held for 4 days at pH 7.4. It was concluded that mucochloric acid acts as an oxidative agent during the course of formation of the products.

Thiol-Activated DNA Damage by α-Bromo-2-cyclopentenone

“…A number of studies have characterized adducts formed by the direct, in vitro reaction between α-haloacrolyl derivatives and DNA (in the absence of thiols) (85–88). The products resulting from these direct reactions are distinct from those described here.…”

“…The products resulting from these direct reactions are distinct from those described here. For example, the reaction of 2-bromoacrolein with 2'-deoxycytidine yields a cyclic, bromine-containing adduct resulting from addition of the exocyclic N 4 -nitrogen to the carbonyl carbon and 1,4-addition of the endocyclic N3 nitrogen to the olefin (85–88). Rate constants for these thiol-independent DNA alkylation reactions have not been reported.…”

Analytics of MX and NDMA, two disinfection byproducts, in water

“…Andrzejewski (Andrzejewski, 1999) investigated other alternative methods, based on the concentration of the sample through water evaporation under vacuum. MX stability at 60 o C and pH 2 yielded positive results (Asplund et al, 1995). Research on the recovery of MX and other chlorinated hydroxyfuranones was first carried out using high quality pure water modified with a mixture of hydroxyfuranones (the standard used: MCA, MCF, CMCF, MBA and MX) and following positive results, with tap water and standard added.…”

Genotoxic halofuranones in water: isomerization and acidity of mucohalic acids

“…Mucochloric acid (MCA, 3,4‐dichloro‐5‐hydroxyfuran‐2(5 H )‐one) and mucobromic acid (MBA, 3,4‐dibromo‐5‐hydroxyfuran‐2(5 H )‐one) are two halohydroxyfuranones that have been shown to be direct genotoxins and potential carcinogens 7–14. DNA adducts of mucohalic acids (MXA) are known, with the isolation of etheno, oxalo etheno, and halopropenal derivatives of guanosine, adenosine, and cytosine 15–22…”

“…[7][8][9][10][11][12][13][14] DNA adducts of mucohalic acids (MXA) are known, with the isolation of etheno, oxalo etheno, and halopropenal derivatives of guanosine, adenosine, and cytosine. [15][16][17][18][19][20][21][22] In recent years, MXA have also attracted much attention in organic synthesis owing to their high functionalization and availability, and they have been used in the synthesis of heterocycles such as gamma-substituted gamma-butenolides and gamma-lactams, and other furanone derivatives. [23][24][25][26][27][28][29][30][31][32][33][34][35] MXA exist in solution as an equilibrium between two species: [36][37][38][39][40] the cyclic lactone-lactol form ðMXA cl Þ and the openchain aldehyde-acid form ðMXA o op Þ.…”