一种二苯乙烯羟胺类化合物的合成及其在糖类检测中的应用研究

以4-溴苯丙醇为初始原料,与苯乙烯经Heck反应得化合物2a;化合物2a在邻碘酰基苯甲酸的氧化作用下生成化合物3a;化合物3a在酸性条件下进行肟化反应得化合物4a;化合物4a在酸性条件下被氰基硼氢化钠还原,合成了一种二苯乙烯类羟胺化合物(5a,20.0%),其结构经1H NMR,13C NMR,IR和LC-MS(ESI)表征。化合物5a的光学性质研究结果表明:激发波长为312 nm,发射波长为357 nm,斯托克斯位移为45 nm,荧光量子产率为0.11。以类似方法合成了氘代标记的化合物5b,化合物5a和5b能在温和条件下与聚糖类物质快速发生衍生化反应,得到高强度质谱信号的衍生产物。通过比较“轻”、“重”同位素标记的聚糖衍生物相应的质谱峰强度,可以获得具有相同化学特征的聚糖的相对含量,实现聚糖的定量分析。

Synthesis of A Stilbenic Hydroxylamine and Its Application in Carbohydrate Detection

Compound 2a was synthesized by the Heck reaction of 4-bromophenylpropanol with styrene,which was oxidized by o-iodobenzoic acid to form compound 3a.It was converted to 4a by oxime reaction under acid conditions.Compound 4a was then reduced in acid condition by sodium cyanoborohydrate,and a stilbene hydroxylamine compound(5a,20.0%)was obtained.The structure was confirmed by 1H NMR,13C NMR,IR and LC-MS(ESI).The optical property of 5a was also studied.The results show that the excitation and emission wavelengths of compound 5a are 312 nm and 359 nm,respectively.The Stokes shift is 47 nm,and the quantum yield is 0.11.Deuterium modified-isotopic labeling reagents Compound 5b was synthesized in the same way.Compound 5a,5b can react rapidly with glycans under mild conditions,forming derivative products with high mass spectrum signal strength.By comparing the corresponding mass spectrometry peak strength of the polysaccharide derivatives marked with“light”and“heavy”isotopes,the relative content of polysaccharides with the same chemical characteristics can be obtained,and the quantitative analysis of polysaccharide can be achieved.