Chemistry, The University of Sheffield, Dainton Building, Brook Hill, Sheffield, S3 7HF, UK.
GEO Specialty Chemicals, Charleston Road, Hardley, Hythe, Southampton, SO45 3ZG, UK.
Angew Chem Int Ed Engl. 2021 May 17;60(21):12032-12037. doi: 10.1002/anie.202015298. Epub 2021 May 3.
Aldehyde groups enable facile conjugation to proteins, enzymes, oligonucleotides or fluorescent dyes, yet there are no literature examples of water-soluble aldehyde-functional vinyl monomers. We report the synthesis of a new hydrophilic cis-diol-based methacrylic monomer (GEO5MA) by transesterification of isopropylideneglycerol penta(ethylene glycol) using methyl methacrylate followed by acetone deprotection via acid hydrolysis. The corresponding water-soluble aldehyde monomer, AGEO5MA, is prepared by aqueous periodate oxidation of GEO5MA at 22 °C. RAFT polymerization of GEO5MA yields the water-soluble homopolymer, PGEO5MA. Aqueous periodate oxidation of the terminal cis-diol units on PGEO5MA at 22 °C affords a water-soluble aldehyde-functional homopolymer (PAGEO5MA). Moreover, a library of hydrophilic statistical copolymers bearing cis-diol and aldehyde groups was prepared using sub-stoichiometric periodate/cis-diol molar ratios. The aldehyde groups on PAGEO5MA homopolymer were reacted in turn with three amino acids to demonstrate synthetic utility.
醛基可使该化合物与蛋白质、酶、寡核苷酸或荧光染料轻松结合，但目前尚无水溶性醛基乙烯基单体的文献实例。我们通过使用甲基丙烯酸甲酯对异亚丙基甘油五（乙二醇）进行酯交换反应，然后通过酸水解进行丙酮脱保护，合成了一种新的基于顺-二醇的亲水性甲基丙烯酸单体（GEO5MA）。相应的水溶性醛单体 AGEO5MA 通过 GEO5MA 在 22°C 下的高碘酸盐氧化制备。GEO5MA 的 RAFT 聚合生成水溶性均聚物 PGEO5MA。在 22°C 下用高碘酸盐氧化 PGEO5MA 末端顺-二醇单元可得到水溶性醛功能均聚物（PAGEO5MA）。此外，使用亚化学计量的高碘酸盐/顺-二醇摩尔比制备了带有顺-二醇和醛基的亲水性统计共聚物库。PAGEO5MA 均聚物上的醛基依次与三种氨基酸反应，以证明其合成实用性。
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