Probe for bio-oligomers and elucidation of their function

本研究实现了多功能化生物低聚物衍生化的一般步骤，并开发了新的功能来捕获连接光可切割分子标签的目标分子。在实验的基础上，以2,6 -二甲基苯基酯的Fries反应为关键反应，建立了激光解吸电离质谱（LDI-MS）光裂解分子标签的合成新途径。氯化锆是促进反应的唯一有效佐剂。该分子标记无需色谱纯化，共5步得到。并且，在叔胺的存在下羟基的苄基化被建立。二异丙基乙胺醇和苄基卤化物的混合物，在二异丙基乙胺的存在下，以良好或极好的产率产生相应的苄基醚指出了无溶剂条件的重要性。该反应对包括苯甲酸酯在内的许多官能团具有较高的耐受性，即使在150℃的反应温度下也是如此。发现碘化钠是一种有效的加速反应的催化剂。操作简单，成功应用于LDI-MS分析的前处理。然后，通过缩醛生成反应，研究出了一种新的靶向1,2 -二醇基序的糖捕获剂。设计并合成了具有α -二酮功能的光可切割分子标签。由于该化合物没有多余的系链子结构，因此其灵敏度可与先前制备的化合物相媲美。

General procedures for derivatization of multi functionalized bio-oligomers and exploitation of new function to capture a target molecules connecting photocleavable molecular tag were achieved in this research.Along with the experiment, a new synthetic route for the photocleavable molecular tag for laser desorption ionization mass spectrometry(LDI-MS) was achieved using Fries reaction of 2, 6-dimethylphenyl ester as its key reaction. Zirconium chloride was found as uniquely efficient adjuvant to promote the reaction. The molecular tag was obtained in 5 steps without chromatographic purification.And, the Benzylation of hydroxyl groups in the presence of tertiary amines is established. A mixture of an alcohol and a benzyl halide afforded the corresponding benzyl ether in good to excellent yields in the presence of diisopropylethylamine. The importance of solventless conditions was observed. The reaction showed high tolerance to many functional groups including benzoate, even at a reaction temperature of 150°C. Sodium iodide was found to be an efficient catalyst to accelerate the reaction. The simple operation was successfully applied for pre-treatment of LDI-MS analysis.Then, new trapping agent for sugars targeting 1, 2-diol motif by mean of ketal formation reaction. Photocleavable molecular tag bearing alpha diketone functioality was designed and synthesized. Since the compound does not have redundant tether substructure, high sensitivity is comparable with compounds previously prepared.