Positive Synergy between the Helical Poly(phenylacetylene) Backbones and the Helical L-Proline Oligopeptide Pendants for Enhanced Enantioseparation Properties,Analytical Chemistry

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Positive Synergy between the Helical Poly(phenylacetylene) Backbones and the Helical L-Proline Oligopeptide Pendants for Enhanced Enantioseparation Properties
Analytical Chemistry ( IF 6.7 ) Pub Date : 2024-01-23 , DOI: 10.1021/acs.analchem.3c04755
Yanli Zhou _{1,

2} , Chunhong Zhang _{1,

3} , Jiahe Huang ₁ , Lijia Liu _{1,

3} , Jianwei Bai ₁ , Junqing Li ₁ , Toshifumi Satoh ₄ , Yoshio Okamoto _{1,

5}

Affiliation

A series of optically active helical poly(phenylacetylene)s (PPA-Pro₁, PPA-Pro₃, PPA-Pro₆, PPA-Pro₉, and PPA-Pro₁₂) bearing different chain lengths of L-proline oligopeptide in the side chains were obtained by polymerizing the corresponding novel phenylacetylene monomers. The monomer adopted a trans-rich helix structure when the L-proline oligopeptide chain length was longer, according to the optical activities and 2D-NMR analysis. The helical structure could be maintained and significantly influenced the polymers’ helical conformation by introducing the L-proline oligopeptide to the pendants. By the way, the morphology of PPA-Pro₃ was observed by atomic force microscope (AFM) on highly oriented pyrolytic graphite (HOPG), and the information on the helix direction, pitch, and chain arrangement was obtained. Also, the chiral separation properties of these polymer-based chiral stationary phases (CSPs) were investigated using high-performance liquid chromatography (HPLC). The poly(phenylacetylene)s showed enhanced enantioseparation properties toward various racemates depending on the longer chain length of the L-proline oligopeptide in the pendants and the positive synergy between the helical backbone and helical side chains. Particularly, PPA-Pro₉ showed comparable or even superior enantioseparation properties for racemates 2 and 9 to four commercial columns (Daicel Chiralpak or Chiralcel AD, AS, OD, and OT), indicating that these poly(phenylacetylene)-based CSPs have potential practical values. This work presented here provides inspiration for the further development of CSPs based on a new paradigm.

中文翻译：

螺旋聚苯乙炔主链和螺旋 L-脯氨酸寡肽悬垂物之间的正协同作用可增强对映体分离性能

一系列光学活性螺旋聚苯乙炔（ PPA-Pro ₁ 、 PPA-Pro ₃ 、 PPA-Pro ₆ 、 PPA-Pro ₉和PPA-Pro ₁₂ ），侧面带有不同链长的L-脯氨酸寡肽链是通过聚合相应的新型苯乙炔单体获得的。根据光学活性和2D-NMR分析，当L-脯氨酸寡肽链长较长时，单体采用富含反式的螺旋结构。通过将L-脯氨酸寡肽引入到悬垂物中，可以保持螺旋结构并显着影响聚合物的螺旋构象。顺便说一下，通过原子力显微镜（AFM）在高取向热解石墨（HOPG）上观察PPA-Pro ₃的形貌，获得了螺旋方向、螺距和链排列的信息。此外，还使用高效液相色谱 (HPLC) 研究了这些聚合物基手性固定相 (CSP) 的手性分离特性。聚苯乙炔对各种外消旋体表现出增强的对映体分离特性，这取决于侧链中L-脯氨酸寡肽的较长链长以及螺旋主链和螺旋侧链之间的正协同作用。特别是，对于外消旋体 2 和 9 ，PPA-Pro ₉显示出与四种商业色谱柱（Daicel Chiralpak 或 Chiralcel AD、AS、OD 和 OT）相当甚至更优异的对映体分离性能，表明这些基于聚苯乙炔的 CSP 具有潜在的实用价值。价值观。这里介绍的这项工作为基于新范式的 CSP 的进一步发展提供了灵感。

更新日期：2024-01-23

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