手性控制的聚合诱导自组装,Chemical Science

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手性控制的聚合诱导自组装
Chemical Science ( IF 7.6 ) Pub Date : 2022-11-17 , DOI: 10.1039/d2sc05695j
Haolan Li ₁ , Erik Jan Cornel ₁ , Zhen Fan ₁ , Jianzhong Du _{1,

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Affiliation

最近的研究表明，可生物降解的纳米颗粒可以通过聚合N-羧酸酐诱导的自组装 (NCA-PISA)。然而，到目前为止，手性单体比例对此类 NCA-PISA 制剂和所得纳米粒子的影响尚未得到充分探索。在此，我们首次表明，可以通过改变成核单体的手性比来控制 PISA 纳米粒子的形态、二级结构和生物降解速率。这种手性控制的 PISA (CC-PISA) 方法允许制备更可调的纳米粒子，适用于未来的生物医学应用。此外，复杂的二级肽结构（α-螺旋与 β-折叠的比率）和 π-π 堆叠影响聚合物自组装过程。更具体地说，PEG ₄₅大分子引发剂用L - 和D-苯丙氨酸（L-和D -Phe-NCA）在无水 THF 中以各种摩尔比以 15 wt% 存在。这种开环聚合 (ROP) 允许制备原位自组装的同型和异型手性 Phe 肽嵌段共聚物成纳米粒子。对于均手性制剂，一旦获得足够高的苯丙氨酸聚合度 (DP)，聚合物就会自组装成囊泡。杂手性配方形成具有各种形态的较大纳米粒子，令我们惊讶的是，使用相等的对映异构体比例抑制了 PISA 并导致聚合物溶液。最后，表明这种 PISA 颗粒的酶促生物降解速率受聚合物手性的影响很大。这种 PISA 方法对于制造在疾病治疗中利用手性的纳米粒子具有重要价值。

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Chirality-controlled polymerization-induced self-assembly

Recent studies have shown that biodegradable nanoparticles can be efficiently prepared with polymerization of N-carboxyanhydrides-induced self-assembly (NCA-PISA). However, thus far, the effect of chiral monomer ratio on such NCA-PISA formulations and the resulting nanoparticles has not yet been fully explored. Herein, we show, for the first time, that the morphology, secondary structure, and biodegradation rate of PISA nanoparticles can be controlled by altering the chiral ratio of the core-forming monomers. This chirality-controlled PISA (CC-PISA) method allowed the preparation of nanoparticles that are more adjustable and applicable for future biomedical applications. Additionally, the complex secondary peptide structure (ratio of α-helix to β-sheet) and π–π stacking affect the polymer self-assembly process. More specifically, a PEG₄₅ macro-initiator was chain-extended with L- and D-phenylalanine (L- and D-Phe-NCA) in various molar ratios in dry THF at 15 wt%. This ring-opening polymerization (ROP) allowed the preparation of homo- and hetero-chiral Phe-peptide block copolymers that self-assembled in situ into nanoparticles. For homo-chiral formulations, polymers self-assembled into vesicles once a sufficiently high phenylalanine degree of polymerization (DP) was obtained. Hetero-chiral formulations formed larger nanoparticles with various morphologies and, much to our surprise, using an equal enantiomer ratio inhibited PISA and led to a polymer solution instead. Finally, it was shown that the enzymatic biodegradation rate of such PISA particles is greatly affected by the polymer chirality. This PISA approach could be of great value to fabricate nanoparticles that exploit chirality in disease treatment.

更新日期：2022-11-17

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