Ikuta K, Shibata N, Blake J S, Dahl M V, Nelson R D, Hisamichi K, Kobayashi H, Suzuki S, Okawa Y
Second Department of Hygienic Chemistry, Tohoku College of Pharmacy, 4-4-1 Komatsushima, Aoba-ku, Sendai, Miyagi 981, Japan.
Biochem J. 1997 Apr 1;323 ( Pt 1)(Pt 1):297-305. doi: 10.1042/bj3230297.
Around 90% of chronic dermatophyte infections are caused by the fungi Trichophyton mentagrophytes and Trichophyton rubrum. One of the causes of the chronic infection resides in the immunosuppressive effects of the cell-wall components of these organisms. Therefore we have attempted to identify the chemical structure of galactomannan, one of the major cell-wall components. The cell-wall polysaccharides secreted by T. mentagrophytes and T. rubrum were isolated from the culture medium and fractionated into three subfractions by DEAE-Sephadex chromatography. Analysis of each subfraction by NMR indicated that there are two kinds of polysaccharides present, i.e. mannan and galactomannan. The mannan has a linear backbone consisting of alpha1,6-linked mannose units, with alpha1,2-linked mannose units as side chains. The core mannan moiety of the galactomannan was analysed by a sequential NMR assignment method after removing the galactofuranose units by acid treatment. The result indicates that the mannan moiety has a linear repeating structure of alpha1,2-linked mannotetraose units connected by an alpha1,6 linkage. The H-1 signals of the two intermediary alpha1, 2-linked mannoses of the tetraose unit showed a significant upfield shift (Deltadelta=0.05-0.08 p.p.m.), due to the steric effect of an alpha1,6-linked mannose unit. The attachment point of the galactofuranose units was determined at C-3 of the core mannan by the assignment of the downfield-shifted 13C signals of the galactomannan compared with those of the acid-modified product. In these galactomannans there were no polygalactofuranosyl chains which have been found in Penicillium charlesii and Aspergillus fumigatus.
约90%的慢性皮肤癣菌感染由须癣毛癣菌和红色毛癣菌引起。慢性感染的原因之一在于这些生物体细胞壁成分的免疫抑制作用。因此,我们试图确定半乳甘露聚糖(主要细胞壁成分之一)的化学结构。从培养基中分离出须癣毛癣菌和红色毛癣菌分泌的细胞壁多糖,并通过DEAE-葡聚糖凝胶色谱法将其分为三个亚组分。通过核磁共振对每个亚组分进行分析表明,存在两种多糖,即甘露聚糖和半乳甘露聚糖。甘露聚糖具有由α1,6-连接的甘露糖单元组成的线性主链,以α1,2-连接的甘露糖单元作为侧链。在通过酸处理去除呋喃半乳糖单元后,采用顺序核磁共振归属方法对半乳甘露聚糖的核心甘露聚糖部分进行了分析。结果表明,甘露聚糖部分具有由α1,6-连接的α1,2-连接的甘露四糖单元组成的线性重复结构。由于α1,6-连接的甘露糖单元的空间效应,四糖单元中两个中间α1,2-连接的甘露糖的H-1信号显示出明显的高场位移(Δδ = 0.05 - 0.08 ppm)。通过与酸修饰产物相比,对半乳甘露聚糖中向低场位移的13C信号进行归属,确定了呋喃半乳糖单元的连接点在核心甘露聚糖的C-3处。在这些半乳甘露聚糖中,没有发现像在拟青霉和烟曲霉中存在的聚呋喃半乳糖链。