Synthesis of sugar-substituted poly(phenylenevinylene)s.
Synthesis of sugar-substituted poly(phenylenevinylene)s.
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DOI：
10.1021/bm0506849
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发表时间：
2006-01
影响因子：
6.2
通讯作者：
A. Takasu;K. Iso;T. Dohmae;T. Hirabayashi
中科院分区：
文献类型：
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作者：
A. Takasu;K. Iso;T. Dohmae;T. Hirabayashi
含糖PPV，聚{2-[O-(2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖基)]-5-甲氧基-对亚苯基亚乙烯基-alt-对亚苯基亚乙烯基} (PPV-GlcNAc) 和 聚{2,5-双-[O-(β-d-吡喃葡萄糖基)]-对亚苯基亚乙烯基-alt-对亚苯基亚乙烯基} (PPV-Glc(2))，通过对二乙烯基苯 (DVB) 与 O-糖基化氢醌的 Heck 反应合成， 分别为 2,5-二溴-4-甲氧基苯基 2-乙酰胺基-3,4,6-三-O-乙酰基-2-脱氧-β-D-吡喃葡萄糖苷 (3) 和 1,4-双(O-2,3,4,6-四-O-乙酰基-β-D-吡喃葡萄糖基)-2,5-二溴苯 (6)。 PPV 的乙酰基保护基团在温和条件下可完全去除（产率 69-87%）。使用(1)H NMR和IR光谱证实了结构。尺寸排阻色谱(SEC)(洗脱液：DMF，聚苯乙烯标准品)测量表明所得聚合物的M(n)和M(w)/M(n)值分别为4.49×10(3)和2.3(5)(PPV-GlcNAc)和3.86×10(3)和1.3(9)(PPV-Glc(2))。这些含糖 PPV 可溶于水/DMF (8/2，v/v)，并被 D-葡萄糖结合蛋白伴刀豆球蛋白 A (Con A) 识别。当葡萄糖取代的 PPV 与 Con A 相互作用时，证实了共轭聚合物主链 lambda(max) 的蓝移。基于这些结合特性，这些结果表明所获得的带有侧糖的 PPV 具有检测生物刺激的能力。
Sugar-containing PPVs, poly{2-[O-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)]-5-methoxy-p-phenylenevinylene-alt-p-phenylenevinylene} (PPV-GlcNAc) and poly{2,5-bis-[O-(beta-d-glucopyranosyl)]-p-phenylenevinylene-alt-p-phenylenevinylene} (PPV-Glc(2)), were synthesized via Heck reaction of p-divinylbenzene (DVB) with O-glycosylated hydroquinones, 2,5-dibromo-4-methoxyphenyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-beta-D-glucopyranoside (3) and 1,4-bis(O-2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)-2,5-dibromobenzene (6), respectively. Acetyl protecting groups of the PPVs are completely removable under mild conditions (yield 69-87%). The structures were confirmed using (1)H NMR and IR spectra. Size exclusion chromatography (SEC) (eluent: DMF, polystyrene standards) measurements indicated that respective M(n) and M(w)/M(n) values of the obtained polymers are 4.49 x 10(3) and 2.3(5) (PPV-GlcNAc) and 3.86 x 10(3) and 1.3(9) (PPV-Glc(2)). These sugar-containing PPVs are soluble in water/DMF (8/2, v/v) and are recognized by Concanavalin A (Con A), D-glucose-binding protein. Blue shift of lambda(max) of the conjugated polymer backbone was confirmed when the glucose-substituted PPV interacts with Con A. Based on those binding properties, these results revealed that the obtained PPVs with pendant sugars have capabilities for detection of biological stimuli.