Schoevaart Rob, Kieboom Tom
Industrial Fermentative Chemistry, Leiden University, Einsteinweg 55, PO Box 9502, NL-2300 RA, Leiden, The Netherlands.
Carbohydr Res. 2002 May 13;337(10):899-904. doi: 10.1016/s0008-6215(02)00051-4.
Combined enzymatic oxidation of D-galactose by D-galactose oxidase [EC 1.1.3.9] in water, amination with butylamine, and oxalic acid catalyzed Amadori rearrangement in methanol yielded 1,6-bis(butylamino)-1,6-dideoxy-erythro-hexo-2,5-diulose, demonstrating how in situ formed galacto-hexodialdose can be used to cross-link protein residues. The various species formed during this three-step conversion are present as bicyclic structures in solution as established by 13C labeling and in situ NMR spectroscopy of the reaction mixtures. Using protein (gelatin) instead of butylamine, distinct Amadori product formation was observed using 99% enriched D-(1-(13)C)- and D-(2-(13)C)-galactose.
在水中，通过D-半乳糖氧化酶[EC 1.1.3.9]对D-半乳糖进行联合酶促氧化，与丁胺进行胺化反应，并在甲醇中由草酸催化阿玛多里重排反应，生成了1,6-双（丁基氨基）-1,6-二脱氧-赤藓糖己-2,5-二酮，这表明原位生成的半乳糖己二醛可用于交联蛋白质残基。通过13C标记和反应混合物的原位核磁共振光谱确定，在这三步转化过程中形成的各种物质在溶液中以双环结构存在。使用蛋白质（明胶）代替丁胺，使用99%富集的D-（1-（13）C）-和D-（2-（13）C）-半乳糖时，观察到了明显的阿玛多里产物形成。
