Development of Synthetic Oligomers Forming Higher-Order Structures by Self- and Molecular-Recognition Striving for Promotion of Chemical Reactions

2014 Fiscal Year Final Research Report

• Project/Area Number: 25620129
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Bio-related chemistry
• Research Institution: University of Toyama
• Principal Investigator: INOUYE Masahiko 富山大学, 大学院医学薬学研究部(薬学), 教授 (60211752)
• Co-Investigator(Kenkyū-buntansha): ABE Hajime 富山大学, 大学院医学薬学研究部(薬学), 准教授 (10324055)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Keywords: ピリジン / フェノール / らせん構造 / 水素結合 / 自己会合 / 糖認識

Outline of Final Research Achievements

We have developed "pyridine/phenol oligomer"s consisted of pyridine and phenol units linked at their 2,6-positions with acetylene bonds. The pyridine/phenol alternating 12- and 6-meric oligomers were prepared by Sonogashira reactions and their self-association and saccharide recognition were investigated.
In CDCl3, concentration dependence on 1H NMR spectra revealed that those oligomers show self-association of moderate strength. The Kdim were 350 and 34 M-1 for the 12- and 6-mer, respectively. The 12-mer exhibited much strong saccharide recognition ability. When octyl beta-D-glucopyranoside was added to a DCE solution of the 12-mer, a strong negative CD band was induced, and the Ka was 2.4 x 10^7 M-1. While, the shorter substrate 6-mer showed weaker saccaride recognition, showing a CD band of opposite sign.
These association are based on multipoint hydrogen bonding in a push-pull fashion, which was supported by the X-ray structure of a model compound binding with methanol.

Free Research Field

生体関連化学