Pluskota-Karwatka Donata, Le Curieux Frank, Munter Tony, Sjöholm Rainer, Kronberg Leif
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland.
Chem Res Toxicol. 2005 Feb;18(2):300-7. doi: 10.1021/tx0498455.
The reactions of guanosine with malonaldehyde in buffered aqueous solutions in the presence of acetaldehyde or formaldehyde were studied. The reaction mixtures were analyzed by RP-HPLC. Two adducts were formed in the reaction of malonaldehyde and acetaldehyde and one in the reaction of malonaldehyde and formaldehyde. The products were isolated and purified by preparative C-18 chromatography and structurally characterized by UV absorbance, 1H NMR, and 13C NMR spectroscopy and mass spectrometry. The adducts formed in the reaction of malonaldehyde and acetaldehyde were identified as 7-(2,2-diformyl-1-methylethyl)-3-(beta-D-ribofuranosyl)pyrimido[1,2-a]-purin-10(3H)-one (M2AA-Guo I) and 2-(3,5-diformyl-4-methyl-1,4-dihydro-1-pyridyl)-9-(beta-D-ribofuranosyl)-purin-6(9H)-one (M2AA-Guo II). In the reaction of malonaldehyde and formaldehyde, the major product was identified as 7-formyl-3-(beta-D-ribofuranosyl)pyrimido[1,2-a]purin-10(8H)-one (M1FA-Guo). The highest yields of M2AA-Guo I and M2AA-Guo II, 7 and 2 mol %, respectively, were obtained in the reaction performed at pH 7.4 and 37 degrees C for 6 days, while M1FA-Guo was produced at a yield of 0.3 mol % after 3 days of reaction at pH 7.4 and 37 degrees C. The products are formed by reactions of malonaldehyde-acetaldehyde and malonaldehyde-formaldehyde condensation products with guanosine and are analogous to the previously identified condensation products formed with adenosine, cytidine, and proteins.
研究了在乙醛或甲醛存在下，鸟苷在缓冲水溶液中与丙二醛的反应。反应混合物通过反相高效液相色谱（RP-HPLC）进行分析。丙二醛与乙醛反应形成了两种加合物，丙二醛与甲醛反应形成了一种加合物。通过制备型C-18色谱法分离和纯化产物，并通过紫外吸收光谱、1H核磁共振（1H NMR）、13C核磁共振（13C NMR）光谱和质谱对其结构进行表征。丙二醛与乙醛反应形成的加合物被鉴定为7-(2,2-二甲酰基-1-甲基乙基)-3-(β-D-呋喃核糖基)嘧啶并[1,2-a]嘌呤-10(3H)-酮（M2AA-Guo I）和2-(3,5-二甲酰基-4-甲基-1,4-二氢-1-吡啶基)-9-(β-D-呋喃核糖基)嘌呤-6(9H)-酮（M2AA-Guo II）。在丙二醛与甲醛的反应中，主要产物被鉴定为7-甲酰基-3-(β-D-呋喃核糖基)嘧啶并[1,2-a]嘌呤-10(8H)-酮（M1FA-Guo）。在pH 7.4和37℃下反应6天，M2AA-Guo I和M2AA-Guo II的最高产率分别为7 mol%和2 mol%，而在pH 7.4和37℃下反应3天后，M1FA-Guo的产率为0.3 mol%。这些产物是由丙二醛-乙醛和丙二醛-甲醛缩合产物与鸟苷反应形成的，与先前鉴定的与腺苷、胞苷和蛋白质形成的缩合产物类似。
