Cholesterol side groups in Helical Poly(3-alkylesterfurans)
Cholesterol side groups in Helical Poly(3-alkylesterfurans)
复制标题
螺旋聚（3-烷基酯呋喃）中的胆固醇侧基
DOI：
10.1038/s41428-022-00741-w
复制
发表时间：
2023
期刊：
影响因子：
2.8
通讯作者：
Noonan, Kevin J.
中科院分区：
文献类型：
--
作者：
Kawakami, Manami;Downey, Payton;Peteanu, Linda;Bernhard, Stefan;Noonan, Kevin J.
聚（3-烷基酯呋喃）折叠成螺旋构象，这是由于聚合物主链中相邻呋喃重复单元优先采用双构象，其中呋喃环的氧原子以相同方向取向。在这方面的贡献，一个新的手性螺旋聚（3-烷基酯呋喃）的报告，其中胆固醇基团已连接到骨干，以确保过量的单手螺旋手性。这种刚性侧基促进了聚合物在氯仿中的折叠构象，如1H NMR、吸收和圆二色性研究所证明。这在先前报道的具有S-3-辛醇侧链的螺旋聚（3-烷基酯呋喃）中是独特的，因为这些聚合物在相同溶剂中更加无序。圆偏振发光的研究也表明了手性的性质是如何影响这些螺旋聚合物的分子间聚集。该研究揭示了通过精确选择手性侧链来调整螺旋聚呋喃的性质的潜力，该手性侧链可以在单体合成期间通过2-溴-3-糠酸的Steglich修饰来安装。当使用市售的PEPPSI-IPent催化剂催化交叉偶联时，Suzuki-Miyaura交叉偶联聚合以合理的产率产生所需的手性螺旋聚合物，分子量高于10 kg/mol。
Poly(3-alkylesterfurans) fold into helical conformations due to a preference for adjacent furan repeat units in the polymer backbone to adopt asynconformation in which the oxygen atoms of the furan rings are oriented in the same direction. In this contribution, a new chiral helical poly(3-alkylesterfuran) is reported in which a cholesterol group has been attached to the backbone to ensure excess single-handed helix chirality. This rigid side group promotes a folded conformation of the polymer in chloroform, as evidenced by1H NMR, absorption, and circular dichroism studies. This is unique among previously reported helical poly(3-alkylesterfurans) withS-3-octanol side chains, as those polymers are much more disordered in the same solvent. Circularly polarized luminescence studies also indicated how the chiroptical properties are impacted by intermolecular aggregation of these helical polymers. The study reveals the potential for tuning the properties of helical polyfurans via precise choice of the chiral side chain, which can be installed during monomer synthesis via a Steglich modification of 2-bromo-3-furoic acid. Suzuki-Miyaura cross-coupling polymerization produces the desired chiral helical polymers in reasonable yields with molecular weights above 10 kg/mol when the commercially available PEPPSI-IPent catalyst is used to catalyze cross-coupling.
登录
查看更多内容
影响因子：
4.6
作者：
Michiel Verswyvel;G. Koeckelberghs
通讯作者：
Michiel Verswyvel;G. Koeckelberghs
影响因子：
--
作者：
Valentina Topolskaia;Adam A. Pollit;Susan Cheng;D. Seferos
通讯作者：
Valentina Topolskaia;Adam A. Pollit;Susan Cheng;D. Seferos
影响因子：
5.5
作者：
Pieter Leysen;J. Teyssandier;S. D. Feyter;G. Koeckelberghs
通讯作者：
G. Koeckelberghs
影响因子：
5.5
作者：
Wang, Yue;Harada, Takunori;Nakano, Tamaki
通讯作者：
Nakano, Tamaki
聚噻吩的手性：综述。
影响因子：
2
作者：
Kun Wang;Yin Xiao
通讯作者：
Yin Xiao