Chain-Length-Dependent Hydrogen-Bonded Self-Assembly of Terminally Functionalized Discrete Polyketones
Chain-Length-Dependent Hydrogen-Bonded Self-Assembly of Terminally Functionalized Discrete Polyketones
复制标题
末端官能化离散聚酮的链长依赖性氢键自组装
DOI：
10.1021/prechem.3c00025
复制
发表时间：
2023
期刊：
影响因子：
--
通讯作者：
and Yasuhide Inokuma
中科院分区：
文献类型：
--
作者：
Kilingaru I. Shivakumar;Yumehiro Manabe;Tomoki Yoneda;Yuki Ide;and Yasuhide Inokuma
在这里，我们报道了离散二酮、四酮和六酮的合成和链长依赖的自组装行为，这些二酮末端被氢键羧基（C1、C2和c3）和3-酰基氨基吡啶基（P1、P2和p3）功能化。这些聚酮是由硅基化的3,3-二甲基戊烷-2,4-二酮和2,2-二甲基-3-氧丁酸丁酯偶联反应，然后与3-氨基吡啶水解或酰胺化制备的。单晶x射线衍射分析表明，c1和c2形成螺旋组合，其中组分通过末端羧基的二聚化连接，而较长的c3则以1,4-二氧六环作为结晶溶剂介导的无限氢键链。吡啶端化的p1由于在固态中存在多个NH···N（吡啶）氢键，呈现出三维氢键网络。p2在结晶状态下生成双螺旋状纤维结构。在以吡啶为末端的聚酮esp1 - p3中，只有lyp2在25℃的氯仿（100 mM浓度）中表现出胶凝行为。扫描电镜测量结果显示，xerogelp2形成棒状结构，厚度约为0.5 ~ 3.5 μm。这些结果表明，精确控制聚酮链长可以显著改变固态和溶液中氢键自组装，即使末端结构相同。
Here, we report the synthesis and the chain-length-dependent self-assembling behaviors of discrete di-, tetra-, and hexaketones terminally functionalized with hydrogen-bonding carboxyl (C1,C2, andC3) and 3-acylaminopyridine groups (P1,P2, andP3). These polyketones were prepared by the coupling reactions of silylated analogues of 3,3-dimethylpentane-2,4-dione andt-butyl 2,2-dimethyl-3-oxobutanoate and the subsequent hydrolysis or amidation with 3-aminopyridine. Single-crystal X-ray diffraction analysis revealed thatC1andC2form helical assemblies in which the components are connected by the dimerization of terminal carboxyl groups, whereas the longerC3showed infinite hydrogen-bonded chains mediated by 1,4-dioxane used as a crystallization solvent. Pyridine-terminatedP1exhibited a three-dimensional hydrogen-bonded network owing to multiple NH···N(pyridine) hydrogen bonds in the solid state.P2generated a double-helix-like fiber structure in the crystalline state. Among the pyridine-terminated polyketonesP1–P3, onlyP2showed gelation behavior in chloroform (100 mM concentration) at 25 °C. The scanning electron microscopy measurement of xerogelP2revealed the formation of rod-like structures with a thickness of approximately 0.5–3.5 μm. These results demonstrate that the precise control of the polyketone chain length can significantly alter hydrogen-bonded self-assembly in the solid state and in solution even with the same terminal structures.
登录
查看更多内容
影响因子：
15
作者：
Yang Yu;Soeun Gim;Dongyoon Kim;Zohar A. Arnon;E. Gazit;P. Seeberger;M. Delbianco
通讯作者：
Yang Yu;Soeun Gim;Dongyoon Kim;Zohar A. Arnon;E. Gazit;P. Seeberger;M. Delbianco
α/β 混合肽中 11/9 和 18/16 螺旋之间前所未有的链长度依赖性构象转换。
影响因子：
--
作者：
B. Legrand;C. André;Laure Moulat;E. Wenger;C. Didierjean;E. Aubert;Marie;Jean Martínez;M. Calmès;M. Amblard
通讯作者：
M. Amblard
影响因子：
18.3
作者：
George KL;Horne WS
通讯作者：
Horne WS
影响因子：
6.8
作者：
Bowie, James U.
通讯作者：
Bowie, James U.
影响因子：
16.6
作者：
Markiewicz G;Jenczak A;Kołodziejski M;Holstein JJ;Sanders JKM;Stefankiewicz AR
通讯作者：
Stefankiewicz AR