Klein R, Tatischeff I, Tham G, Mano N
Laboratoire de Physique et Chimie Biomoléculaires (UA 198, CNRS et Université P. et M. Curie), Institut Curie, Paris, France.
Chirality. 1994;6(7):564-71. doi: 10.1002/chir.530060709.
Optically active lumazines (biolumazine, dictyolumazine, monalumazine, and neolumazine) are prepared from the corresponding pterins by enzymatic reaction, using pterin deaminase excreted by Dictyostelium discoideum. The fluorescence properties, circular dichroism spectra, and chromatographic behavior of these lumazines are studied. D- and L-enantiomers of biolumazine, dictyolumazine, and monalumazine are separated using a chiral flavoprotein column. This column also separates the enantiomeric pterins of the threo form: monapterin and dictyopterin. However, the column does not separate the enantiomeric pterins of the erythro form: neopterin and biopterin. By coupling a reverse-phase column to the flavoprotein column, the separation of pterins and lumazines in function of their hydrophobicity, as well as the separation of the diastereomers, is achieved. This coupled achiral/chiral high-performance liquid chromatography method enables determination of the stereoconfiguration of natural lumazines by comparison with optically pure compounds. A lumazine derivative, present in the extracellular medium of Dictyostelium discoideum, is identified as D-dictyolumazine, i.e., 6-(D-threo-1,2-dihydroxypropyl)-lumazine.
旋光性的蝶啶（生物蝶啶、盘基网柄菌蝶啶、单蝶啶和新蝶啶）通过酶促反应由相应的蝶呤制备而成，该反应使用盘基网柄菌分泌的蝶呤脱氨酶。对这些蝶啶的荧光性质、圆二色光谱和色谱行为进行了研究。使用手性黄素蛋白柱分离生物蝶啶、盘基网柄菌蝶啶和单蝶啶的D-和L-对映体。该柱还能分离苏阿糖型对映体蝶呤：单蝶呤和盘基网柄菌蝶呤。然而，该柱不能分离赤藓糖型对映体蝶呤：新蝶呤和生物蝶呤。通过将反相柱与黄素蛋白柱联用，实现了根据蝶呤和蝶啶的疏水性进行分离，以及非对映异构体的分离。这种非手性/手性联用的高效液相色谱方法能够通过与光学纯化合物比较来确定天然蝶啶的立体构型。在盘基网柄菌细胞外培养基中存在的一种蝶啶衍生物被鉴定为D-盘基网柄菌蝶啶，即6-(D-苏阿糖-1,2-二羟基丙基)-蝶啶。
