Synthesis and Self-assembly Behavior of Porphyrin-based Polypeptides

Yin-chao Wang; Jia-hao Zheng; Wei-an Zhang; Chun-hua Cai; Jia-ping Lin

doi:10.11777/j.issn1000-3304.2023.23196

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Synthesis and Self-assembly Behavior of Porphyrin-based Polypeptides

Research Article | 更新时间：2024-01-19

- Synthesis and Self-assembly Behavior of Porphyrin-based Polypeptides
- Acta Polymerica Sinica Vol. 55, Issue 2, Pages: 172-181(2024)
- 作者机构：
  
  华东理工大学材料科学与工程学院上海 200237
- 作者简介：
  
  Wei-an Zhang, E-mail: wazhang@ecust.edu.cn
  Chun-hua Cai, E-mail: caichunhua@ecust.edu.cn
  Jia-ping Lin, E-mail: jlin@ecust.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2023.23196
  CLC：
- Published：20 February 2024，
  
  Published Online：27 October 2023，
  
  Received：25 July 2023，
  
  Accepted：13 September 2023
- 稿件说明：
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王寅超, 郑家豪, 张伟安, 蔡春华, 林嘉平. 含卟啉聚肽的合成及其自组装行为研究. 高分子学报, 2024, 55(2), 172-181

Wang, Y. C.; Zheng, J. H.; Zhang, W. A.; Cai, C. H.; Lin, J. P. Synthesis and self-assembly behavior of porphyrin-based polypeptides. Acta Polymerica Sinica, 2024, 55(2), 172-181
王寅超, 郑家豪, 张伟安, 蔡春华, 林嘉平. 含卟啉聚肽的合成及其自组装行为研究. 高分子学报, 2024, 55(2), 172-181 DOI： 10.11777/j.issn1000-3304.2023.23196.

Wang, Y. C.; Zheng, J. H.; Zhang, W. A.; Cai, C. H.; Lin, J. P. Synthesis and self-assembly behavior of porphyrin-based polypeptides. Acta Polymerica Sinica, 2024, 55(2), 172-181 DOI： 10.11777/j.issn1000-3304.2023.23196.

摘要

以带有炔丙基端基的聚(

-苄基-

-谷氨酸酯) (PBLG)和含单叠氮基团的卟啉衍生物(TFPP-N

)为反应物，利用点击反应，合成了含卟啉聚肽(TFPP-PBLG). 运用核磁共振氢谱(

H-NMR)、傅里叶变换红外光谱(FTIR)、紫外-可见光光度计(UV-Vis)和凝胶渗透色谱(GPC)表征了聚合物的结构、分子量及其分布. 采用有机共溶剂溶解、选择性溶剂(水)诱导组装并透析的方法，制备得到碗状胶束. 通过扫描电子显微镜(SEM)、原子力显微镜(AFM)、透射电子显微镜(TEM)、动态激光光散射(DLS)和小角X射线散射仪(SAXS)表征了组装体的形貌与结构，并探究其自组装机理. 结果表明，卟啉基团间的

堆叠作用使得胶束具有较为稳定结构；在透析过程中，胶束内部的溶剂向外扩散，导致胶束塌陷形成了纳米碗. 增加PBLG链段长度，会进一步提高初始胶束的结构稳定性，导致在透析过程中胶束结构保持完整不能得到纳米碗. 初始胶束的结构稳定性是决定其在后续溶剂交换过程中是否发生凹陷从而形成纳米碗的关键.

Abstract

Poly(

-benzyl-

-glutamate) (PBLG) with propargyl terminal group and porphyrin derivatives containing single azide group (TFPP-N

) were used as reactants to synthesize porphyrin-based polypeptide (TFPP-PBLG) using a click reaction. The molecular structures of the polymers

including molecular weight

polydispersity index

and composition were characterized by nuclear magnetic resonance spectroscopy (

H-NMR)

Fourier transform infrared spectroscopy (FTIR)

ultraviolet-visible spectrophotometer (UV-Vis)

and gel permeation chromatography (GPC). The critical water content (CWC) for the aggregation of the TFPP-PBLG polymers was determined by turbidity measurement (OD). By a selective precipitation method with water as the selective solvent

bowl-like aggregates with obvious pits were obtained. The solution self-assembly behavior was studied by scanning electron microscopy (SEM)

atomic force microscopy (AFM)

transmission electron microscopy (TEM)

dynamic laser light scattering (DLS) and small-angle X-ray scattering (SAXS). The results show that the TFPP-PBLG polymers can self-assemble into bowl-like aggregations when the PBLG chain is relatively short. Upon the addition of water

solubility of the solvent for polymers decreases

and the polymers aggregate into micelles. The

stacking effect contributed by porphyrin derivatives results in a relatively stable structure of the micelles. During the dialysis process

the solvent within the micelle diffuses outward while water is difficult into the micelles

causing the micelle to collapse and form a pit structure. As the solvent further diffuses

the pit becomes larger

ultimately leading to a bowl-like aggregate structure. Increasing the length of the PBLG makes the initial micelles more stable

which inhibits the collapse of the micelles under the dialysis process

as a result

ellipsoid micelles are maintained. The stability of the initial formed micelle is crucial in determining whether it undergoes depression during the subsequent dialysis process

ultimately resulting in the formation of nanobowls.

关键词

聚肽卟啉点击反应自组装碗状胶束

Keywords

PolypeptidesPorphyrinClick reactionSelf-assemblyNanobowls

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