基于NNTA可控聚合的环形聚类肽合成与表征

胡祖佳; 颜舒婷; 戚家乐; 陶鑫峰; 林绍梁

doi:10.11777/j.issn1000-3304.2020.20284

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基于NNTA可控聚合的环形聚类肽合成与表征

研究论文 | 更新时间：2024-02-20

- 基于NNTA可控聚合的环形聚类肽合成与表征
- Synthesis and Characterization of Cyclic Polypeptoids Based on Controlled Polymerizations of NNTA
- 高分子学报 2021年52卷第7期页码：708-716
- 作者机构：
  
  上海市先进聚合物材料重点实验室华东理工大学材料科学与工程学院上海 200237
- 作者简介：
  
  E-mail: taoxinfeng@ecust.edu.cn
  slin@ecust.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 ┣21901073);52073092┫;上海市自然科学基金(基金号19ZR1412100);上海市晨光计划(18CG32)
- DOI：10.11777/j.issn1000-3304.2020.20284
  中图分类号：
- 纸质出版日期：2021-07-20，
  
  网络出版日期：2021-05-18，
  
  收稿日期：2020-12-26，
  
  修回日期：2021-01-10，
扫描看全文
胡祖佳,颜舒婷,戚家乐等.基于NNTA可控聚合的环形聚类肽合成与表征[J].高分子学报,2021,52(07):708-716.

Zu-jia Hu, Shu-ting Yan, Jia-le Qi, Xin-feng Tao, Shao-liang Lin. Synthesis and Characterization of Cyclic Polypeptoids Based on Controlled Polymerizations of NNTA[J]. ACTA POLYMERICA SINICA, 2021,52(7):708-716.
胡祖佳,颜舒婷,戚家乐等.基于NNTA可控聚合的环形聚类肽合成与表征[J].高分子学报,2021,52(07):708-716. DOI： 10.11777/j.issn1000-3304.2020.20284.

Zu-jia Hu, Shu-ting Yan, Jia-le Qi, Xin-feng Tao, Shao-liang Lin. Synthesis and Characterization of Cyclic Polypeptoids Based on Controlled Polymerizations of NNTA[J]. ACTA POLYMERICA SINICA, 2021,52(7):708-716. DOI： 10.11777/j.issn1000-3304.2020.20284.

摘要

研究了1

8-二氮杂二环十一碳-7-烯(DBU)引发的

-取代甘氨酸-

-硫代羧酸酐(NNTA)开环聚合. 聚合通过两性离子开环聚合机理进行，表现出良好的可控性，聚合产率高(

86%)，分子量可控(900~7500 g/mol)，分子量分布较窄(1.13~1.25). 通过

H-NMR、

C-NMR谱图、MALDI-ToF质谱和红外光谱等表征手段，证明所得聚合产物具有环形结构，且聚合物链上带有DBU残基和硫代氨基甲酸酯基团. 与苄胺(BA)引发所得的线形聚类肽相比，DBU引发所得的聚类肽具有更小的流体力学体积，进一步证明了其环形结构. 扩链反应表明，加入新单体后聚合反应仍可以继续进行，产物分子量显著增加，表明了DBU引发的NNTA聚合具有活性特征. DBU引发的NNTA两性离子开环聚合是一种简便、高效的环形聚类肽合成方法.

Abstract

The ring-opening polymerizations of

-substituted glycine

-thiocarboxyanhydrides (NNTAs) initiated by 1

8-diazabicycloundec-7-ene (DBU) were investigated. Homo- and co-polymerizations of

-ethylglycine

-thiocarboxyanhydride (NEG-NTA) and

-butylglycine

-thiocarboxyanhydride (NBG-NTA) initiated by DBU were carried out in THF at 60 ℃

which produced corresponding poly(

-ethylglycine) (PNEG)

poly(

-butylglycine) (PNBG) and poly(

-ethylglycine-

-butylglycine) (P(NEG-

-NBG)) with high yield (

86%) and narrow dispersities (1.13-1.25). By adjusting monomer to initiator feed molar ratios ranging from 10 to 100

the molecular weights of PNEGs could be tuned from 900 g/mol to 7500 g/mol

which showed the good controllability of the polymerizations.

H-NMR and MALDI-ToF mass analyses revealed the structures of cyclic polypeptoids bearing one DBU moiety and one thiocarbamate group. The DBU moiety would be eliminated by potassium trifluoroacetate during the MALDI-ToF analysis and DBU-free cyclic polypeptoids were formed. The existence of thiocarbamate group was further proven by

C-NMR and FTIR analyses. To further confirm the cyclic structures of the products obtained by using DBU initiator

linear polypeptoids were synthesized as comparisons by benzylamine (BA)‍-initiated NNTA polymerizations. With the same degree of polymerizations (DPs)

polypeptoids obtained by DBU initiator had lower hydrodynamic volumes

which indicated their cyclic structures. The living characteristics of DBU-initiated NNTA polymerizations were finally supported by the chain extension reaction. The polymer chain could continue propagating after the addition of another batch of monomers

and the molecular weight of the product increased significantly while the dispersity kept narrow (

=1.23). DBU-initiated NNTA polymerizations went through zwitterionic ring-opening polymerization mechanism. Attack of DBU on NNTA would generate a zwitterionic propagating intermediate

in which DBU cation and thiocarbamate anion interacted strongly with each another by electrostatic interaction. The chain propagation caused by NNTA monomer addition at the thiocarbamate end of zwitterionic propagating intermediate. And then

end-to-end macrocyclization between DBU cation and thiocarbamate anion formed cyclic polypeptoids. Since NNTAs are more stable monomers compared to NNCAs

and DBU is an accessible initiator

DBU-initiated NNTA zwitterionic ring-opening polymerization is a simple and facile method for the synthesis of cyclic polypeptoids.

关键词

聚类肽两性离子开环聚合环形聚合物N-硫代羧酸酐有机碱

Keywords

PolypeptoidsZwitterionic ring-opening polymerizationCyclic polymersN-ThiocarboxyanhydridesOrganic bases

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