天然环烯醚萜与蛋白质纤维的染色、交联反应特性(I)——4种天然环烯醚萜的制备及其对皮粉的染色—交联(鞣制)性能

Dyeing/Cross-linking Property of Natural Irioids to Protein Fibers(Ⅰ):preparation of four natural iridoids and their dyeing/cross-linking (tanning) property to hide powder

从栀子、忍冬、油橄榄、白花蛇舌草4种大宗植物的相应部位，分别制备了京尼平、马钱素苷元、橄榄苦苷苷元及E-6-O-香豆酰鸡屎藤次苷甲酯4种环烯醚萜化合物，采用电喷雾质谱（ESI—MS）、^1H NMR和^13C NMR确证了其结构；研究了它们对皮粉的染色和交联（鞣制）性能，初步探讨了其呈色、鞣制机理。结果表明：这4种环烯醚萜化合物都能在较小用量（质量分数1％-5％）、温和条件（pH=8．0，T=30～35℃）和较短时间（t≤12h）下，使皮粉呈现蓝黑、棕黄、黄、紫等一系列颜色，同时还能使皮粉的湿热变性温度提高20℃以上；其呈色-鞣制的机理在于环烯醚萜分子与皮胶原纤维分子链上的-NH2发生了交联反应。这一结果预示着，它们不仅作为一类全新的蛋白质材料专用“天然活性染料”，而且作为一类环境友好的皮革同步鞣制-染色材料，都有很好的应用前景。

roar iridoid compounds, namely genipin, loganin aglycone, oleuropein aglyeone and E - 6 - 0 - methoxycinnamoyl scandoside methyl ester aglycone were prepared from Gardenia jasminoides Ellis, Lonicera japonica Thunb, Olea europaea Linn and Hedyotis diffusa （Willd） Roxb respectively. Their structures were identified by electron spray ionization - mass spectrometry （ESI- MS）, ^1H NMR and ^13C NMR. The dyeing/tanning properties on hide powder was investigated, the relationship between dyeing/cross- lingking （tanning） property and the chemical structures were discussed. The results show that four natural iridoids could react with hide powder under a mild condition （35 ℃, pH = 7.5 - 8.0 ）, within a short time （ about 6 h） and at a low dosage （5% （w/w） of hide powder）. The hydrothermal stability of the reacted hide powder is 20 -25℃ higher than that of the control sample, and different colors, such as dark blue, brown - yellow, yellow and mauve, are induced to hide powder. The mechanism might be that, cross - linking reaction takes place between iridoids and -NH2 groups of collagen molecular chains. These results indicate that, natural iridoids might act as a completely noyel ＂natural reactive dyes＂ special for protein fibers and an environmental - friendly simultaeous tanning - dyeing agent for leather manufacture.