Byrne C J, Marshallsay L V, Ward A D
Department of Organic Chemistry, University of Adelaide, Australia.
J Photochem Photobiol B. 1990 Jun;6(1-2):13-27. doi: 10.1016/1011-1344(90)85070-d.
The compositions of Photofrin II and haematoporphyrin derivative (HPD) were examined. Dihaematoporphyrin ester was unambiguously synthesized and shown by high performance liquid chromatography (HPLC) not to be a significant component of Photofrin II. Hydrolysis studies showed the presence of an acid-stable oligomer in Photofrin II which comprised about 40% of of an acid-stable oligomer in Photofrin II which comprised about 40% of the total sample. A dimer derivative was isolated from this oligomeric material by fully dehydrating the methyl-esterified acidic hydrolysis product of Photofrin II. The structure of this dimer, in which two porphyrin units are linked by a three-carbon bridge containing a double bond and a methyl group, was determined by nuclear magnetic resonance (NMR) and fast atom bombardment (FAB) mass spectrometry. An analogous trimer was also isolated and identified. Structures for the hydroxyl-containing precursors to the dimer and trimer, and for the acid-stable oligomeric material in Photofrin II, are suggested. The acid-stable oligomeric material is produced in the sodium hydroxide polymerization step of the preparation of Photofrin II.
对血卟啉衍生物（HPD）和光卟啉II的成分进行了研究。明确合成了双血卟啉酯，并通过高效液相色谱（HPLC）表明其不是光卟啉II的主要成分。水解研究表明，光卟啉II中存在一种酸稳定的低聚物，其占总样品的约40%。通过对光卟啉II的甲酯化酸性水解产物进行完全脱水，从这种低聚材料中分离出一种二聚体衍生物。通过核磁共振（NMR）和快原子轰击（FAB）质谱法确定了这种二聚体的结构，其中两个卟啉单元通过一个含有双键和甲基的三碳桥相连。还分离并鉴定了一种类似的三聚体。提出了二聚体和三聚体含羟基前体以及光卟啉II中酸稳定低聚材料的结构。酸稳定的低聚材料是在光卟啉II制备的氢氧化钠聚合步骤中产生的。
