Native Mannose-Dominant Extraction by Pyridine-Phenol Alternating Oligomers Having an Extremely Efficient Repeating Motif of Hydrogen-Bonding Acceptors and Donors
Native Mannose-Dominant Extraction by Pyridine-Phenol Alternating Oligomers Having an Extremely Efficient Repeating Motif of Hydrogen-Bonding Acceptors and Donors
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DOI：
10.1002/chem.201503149
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发表时间：
2015-11-09
影响因子：
4.3
通讯作者：
Inouye, Masahiko
中科院分区：
文献类型：
--
作者：
Ohishi, Yuki;Abe, Hajime;Inouye, Masahiko
设计并合成了吡啶-苯酚交替低聚物，其中的吡啶和苯酚部分通过芳环的2，6-位上的乙炔键交替连接。吡啶氮原子和邻近的酚羟基是定向的，因此它们不会形成分子内氢键，而是以推拉方式协同作用于糖羟基的氢键受体和供体。在1，2-二氯乙烷中，较长的齐聚物与亲脂性糖苷强烈结合，结合常数接近10(8)M(-1)。此外，低聚物从固相到非极性有机溶剂中提取天然糖的量达到了低聚物的等量，并且在天然丰富的己糖中表现出以甘露糖为主的提取。即使在含1，2-二氯乙烷的20%DMSO中，低聚物也能与天然糖结合，对D-甘露糖和D-葡萄糖的结合常数均大于10M(-1)。
Pyridine-phenol alternating oligomers in which pyridine and phenol moieties are alternatingly linked through acetylene bonds at the 2,6-positions of the aromatic rings were designed and synthesized. The pyridine nitrogen atom and the neighboring phenolic hydroxyl group were oriented so that they do not form an intramolecular hydrogen bond but cooperatively act as hydrogen-bonding acceptor and donor in a push-pull fashion for the hydroxyl group of saccharides. The longer oligomer strongly bound to lipophilic glycosides in 1,2-dichloroethane, and association constants approached 10(8)M(-1). Moreover, the oligomer extracted native saccharides from a solid phase to apolar organic solvents up to the extent of an equal amount of the oligomer and showed mannose-dominant extraction among naturally abundant hexoses. The oligomer bound to native saccharides even in 20% DMSO-containing 1,2-dichloroethane and exhibited association constants of greater than 10M(-1) for D-mannose and D-glucose.