Controlled synthesis of β-cyclodextrin-based starlike helical poly(phenyl isocyanide) and its application in chiral resolution

IF 10.7 1区化学 Q1 CHEMISTRY, APPLIED

Carbohydrate Polymers Pub Date : 2025-02-27 DOI:10.1016/j.carbpol.2025.123456

Benfa Chu , Feiyang Song , Hui Zou

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Abstract

In an effort to expand the diversity of helical polymers exhibiting intricate structures, a strategy for the precise fabrication of β-cyclodextrin-based star polymers adorned with helical poly(phenyl isocyanide) (PPI) arms has been successfully realized through the integration of isocyanide polymerization and atom transfer radical polymerization (ATRP). An elegant β-cyclodextrin embellished with 7 Pd(II) complexes on one side and 14 bromine groups on the other side, denoted as ((Pd(II))₇-CD-(Br)₁₄), was initially synthesized. Subsequently, the (PPI)₇-CD-(Br)₁₄ was synthesized through the polymerization of the phenyl isocyanide monomer initiated with (Pd(II))₇-CD-(Br)₁₄. Finally, starlike PPI was obtained by ATRP of 1,2-diacrylyl ethane initiated via the macro-initiator of (PPI)₇-CD-(Br)₁₄. Circular dichroism measurement analysis indicated that the obtained starlike PPI exhibited a consistent helical conformation with a preferred handedness, and it was revealed that the helical structure of starlike PPI originated from the PPI backbone, rather than intermolecular aggregation in solutions. Furthermore, the starlike PPI demonstrated excellent efficacy in the chiral resolution of racemic compounds, achieving an enantiomeric excess (e.e.) of 92 % for threonine racemates when used as a chiral resolution agent.

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基于β-环糊精的星形螺旋聚苯基异氰酸酯的受控合成及其在手性拆分中的应用

为了扩大具有复杂结构的螺旋聚合物的多样性，通过将异氰酸酯聚合和原子转移自由基聚合（ATRP）相结合，成功地制备了螺旋聚苯基异氰酸酯（PPI）臂修饰的β-环糊精基星形聚合物。初步合成了一侧有7个Pd（II）配合物，另一侧有14个溴基团修饰的精致β-环糊精，标记为((Pd（II))7- cd -(Br)14）。随后，通过（Pd(II)）7-CD-(Br)14引发的苯基异氰化物单体聚合合成了（PPI）7-CD-(Br)14。最后，以（PPI）7-CD-(Br)14为宏观引发剂，对1,2-二丙基乙烷进行ATRP，得到了星形PPI。圆二色性分析表明，得到的星形PPI具有一致的螺旋构象，具有优先的手性，揭示了星形PPI的螺旋结构来源于PPI主链，而不是溶液中的分子间聚集。此外，星形PPI在外消旋化合物的手性拆分方面表现出优异的功效，当用作手性拆分剂时，苏氨酸外消旋物的对映体过剩（例如）达到92%。

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来源期刊

Carbohydrate Polymers 化学-高分子科学

CiteScore

22.40

自引率

8.00%

发文量

1286

审稿时长

47 days

期刊介绍： Carbohydrate Polymers stands as a prominent journal in the glycoscience field, dedicated to exploring and harnessing the potential of polysaccharides with applications spanning bioenergy, bioplastics, biomaterials, biorefining, chemistry, drug delivery, food, health, nanotechnology, packaging, paper, pharmaceuticals, medicine, oil recovery, textiles, tissue engineering, wood, and various aspects of glycoscience. The journal emphasizes the central role of well-characterized carbohydrate polymers, highlighting their significance as the primary focus rather than a peripheral topic. Each paper must prominently feature at least one named carbohydrate polymer, evident in both citation and title, with a commitment to innovative research that advances scientific knowledge.