新型偶氮苯聚类肽的合成与自组装

李妙川; 金圣; 冯伟胜; 陶鑫峰; 林绍梁

doi:10.11777/j.issn1000-3304.2025.25100

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新型偶氮苯聚类肽的合成与自组装

研究论文 | 更新时间：2025-07-02

- 新型偶氮苯聚类肽的合成与自组装
- Synthesis and Self-assembly of Novel Polypeptoids with Azobenzene Side Chains
- 高分子学报 2025年页码：1-11
- 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 52325308);上海市自然科学基金(基金号 24ZR1416500)
- DOI：10.11777/j.issn1000-3304.2025.25100
  中图分类号：
- CSTR：32057.14.GFZXB.2025.7420
- 收稿日期：2025-04-14，
  
  录用日期：2025-05-17，
  
  网络出版日期：2025-07-02，
- 稿件说明：
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李妙川, 金圣, 冯伟胜, 陶鑫峰, 林绍梁. 新型偶氮苯聚类肽的合成与自组装. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25100

Li, M. C.; Jin, S.; Feng, W. S.; Tao, X. F.; Lin, S. L. Synthesis and self-assembly of novel polypeptoids with azobenzene side chains. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25100
李妙川, 金圣, 冯伟胜, 陶鑫峰, 林绍梁. 新型偶氮苯聚类肽的合成与自组装. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25100 DOI： CSTR： 32057.14.GFZXB.2025.7420.

Li, M. C.; Jin, S.; Feng, W. S.; Tao, X. F.; Lin, S. L. Synthesis and self-assembly of novel polypeptoids with azobenzene side chains. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25100 DOI： CSTR： 32057.14.GFZXB.2025.7420.

摘要

设计合成了4-异氰基偶氮苯(Azo-NC)单体和4-((2

11-四氧杂十三烷-13-基)氧基)苯甲醛(EG

-CHO)单体，并以4-氨基丁酸(AA

)、5-氨基戊酸(AA

)、6-氨基己酸(AA

)为氨基酸单体，通过Ugi多组分聚合成功制备了新型主链结构的偶氮苯功能化聚(

-类肽)、聚(

-类肽)和聚(

-类肽)，即P(AA

-Azo/EG

) (

=4、5和6). 通过核磁共振氢谱(

H-NMR)、红外光谱(FTIR)和体积排除色谱(SEC)表征了偶氮苯聚类肽的化学结构、分子量和分子量分布. 系统研究了P(AA

-Azo/EG

)的自组装行为，利用透射电子显微镜(TEM)对组装体的形貌进行了详细表征，获得了“松针”状和“竹叶”状等形貌的组装体. 紫外-可见光谱(UV-Vis)测试表明，随着氨基酸重复单元长度的增加，组装体中偶氮苯基团从

-型排列向

-型排列转变，且光致异构化速率加快. P(AA

-Azo/EG

)组装体具有良好的光响应性和温度响应性，“竹叶”形片状组装体在365 nm紫外光照后转变为纺锤形聚集体，在45 ℃热处理后转变为球形大复合胶束.

Abstract

Azobenzene-functionalized polypeptoids represent a significant class of photo-responsive smart materials

exhibiting remarkable application potential in biomimetics

medicine

and other fields because of their excellent biocompatibility

remotely controllable structure

and non-contact variable performance. However

reported azobenzene-functionalized polypeptoids are mainly poly(

α‍

-peptoid) synthesized by solid-phase synthesis and ring-opening polymerization of

-substituted glycine

-carboxyanhydride (NNCA) or

-substituted glycine

-thiocarboxyanhydride (NNTA). Azobenzene-functionalized polypeptoids with alternative main-chain structures have rarely been explored. In this study

novel azobenzene-functionalized polypeptoids were synthesized through Ugi multicomponent polymerization. First

4-isocyanoazobenzene (Azo-NC) and 4-((2

11-tetraoxatridecan-13-yl)oxy)benzaldehyde (EG

-CHO) were designed and synthesized

which could endow polypeptoids with photo-responsiveness and thermo-responsiveness. Azo-NC and EG

-CHO were polymerized with 4-aminobutyric acid (AA

)

5-aminovaleric acid (AA

)

and 6-aminocaproic acid (AA

) respectively in trifluoroethanol at 50 ℃ for 96 h

yielding azobenzene-functionalized poly(

-peptoid) (P(AA

-Azo/EG

))

poly(

-peptoid) (P(AA

-Azo/EG

))

and poly(

-peptoid) (P(AA

-Azo/EG

)) with high yields (

86%). The chemical structures

molecular weights (MWs)

and MW distributions of P(AA

-Azo/EG

) were confirmed using

H-NMR

FTIR

and SEC analyses. The self-assembly behavior of P(AA

-Azo/EG

) in an aqueous solution was systematically investigated

and the resulting morphologies were characterized by TEM. At an initial water content of 33%

P(AA

-Azo/EG

) formed "pine leaf"-like assemblies

whereas P(AA

-Azo/EG

) and P(AA

-Azo/EG

) formed "bamboo leaf"-like assemblies

which indicated that aspect ratio of the assemblies decreased with increasing lengths of the amino acid repeat unit. As the initial water content was increased

spherical composite micelles gradually appeared. UV-Vis spectroscopy measurements revealed that P(AA

-Azo/EG

) and its assemblies showed excellent photo-isomerization properties. Notably

with longer amino acid repeat units

the azobenzene groups within the assemblies changed from an

-type to a

-type arrangement

accompanied by an accelerated rate of photo-induced

trans

-to-

cis

isomerization. The P(AA

-Azo/EG

) assemblies exhibited excellent photo-responsiveness and thermo-responsiveness. Specifically

the "bamboo leaf"-like assemblies of P(AA

-Azo/EG

) transformed into spindle-shaped aggregates after 6 h irradiation of 365 nm ultraviolet light. The "bamboo leaf"-like assemblies of P(AA

-Azo/EG

) reorganized into spherical composite micelles after 4 h heat treatment at 45 ℃.

关键词

Keywords

references

Zhang D. H. ; Lahasky S. H. ; Guo L. ; Lee C. U. ; Lavan M. Polypeptoid materials: current status and future perspectives . Macromolecules , 2012 , 45 ( 15 ), 5833 - 5841 . doi: 10.1021/ma202319g http://dx.doi.org/10.1021/ma202319g

Gangloff N. ; Ulbricht J. ; Lorson T. ; Schlaad H. ; Luxenhofer R. Peptoids and polypeptoids at the frontier of supra- and macromolecular engineering . Chem. Rev. , 2016 , 116 ( 4 ), 1753 - 1802 . doi: 10.1021/acs.chemrev.5b00201 http://dx.doi.org/10.1021/acs.chemrev.5b00201

Tao Y. ; Tao Y. H. Ugi reaction of amino acids: from facile synthesis of polypeptoids to sequence-defined macromolecules . Macromol. Rapid Commun. , 2021 , 42 ( 6 ), e 2000515 . doi: 10.1002/marc.202000515 http://dx.doi.org/10.1002/marc.202000515

Fetsch C. ; Grossmann A. ; Holz L. ; Nawroth J. F. ; Luxenhofer R. Polypeptoids from N -substituted glycine N -carboxyanhydrides: hydrophilic, hydrophobic, and amphiphilic polymers with Poisson distribution . Macromolecules , 2011 , 44 ( 17 ), 6746 - 6758 . doi: 10.1021/ma201015y http://dx.doi.org/10.1021/ma201015y

Fetsch C. ; Luxenhofer R. Thermal properties of aliphatic polypeptoids . Polymers , 2013 , 5 ( 1 ), 112 - 127 . doi: 10.3390/polym5010112 http://dx.doi.org/10.3390/polym5010112

Lee C. U. ; Li A. ; Ghale K. ; Zhang D. H. Crystallization and melting behaviors of cyclic and linear polypeptoids with alkyl side chains . Macromolecules , 2013 , 46 ( 20 ), 8213 - 8223 . doi: 10.1021/ma401067f http://dx.doi.org/10.1021/ma401067f

Chan B. A. ; Xuan S. T. ; Li A. ; Simpson J. M. ; Sternhagen G. L. ; Yu T. Y. ; Darvish O. A. ; Jiang N. S. ; Zhang D. H. Polypeptoid polymers: synthesis, characterization, and properties . Biopolymers , 2018 , 109 ( 1 ). e 23070 . doi: 10.1002/bip.23070 http://dx.doi.org/10.1002/bip.23070

孙静 , 李志波 . 聚类肽高分子材料及其结构与性能的研究 . 高分子学报 , 2018 , ( 1 ), 1 - 8 . doi: 10.11777/j.issn1000-3304.2018.17220 http://dx.doi.org/10.11777/j.issn1000-3304.2018.17220

Ma A. Y. ; Yu X. Y. ; Liao M. Z. ; Liu W. X. ; Xuan S. T. ; Zhang Z. B. Research progress in polypeptoids prepared by controlled ring-opening polymerizations . Macromol. Rapid Commun. , 2023 , 44 ( 1 ), 2200301 . doi: 10.1002/marc.202200301 http://dx.doi.org/10.1002/marc.202200301

戚家乐 , 姚远 , 陶鑫峰 , 林绍梁 . 含芳香侧链聚类肽的合成与自组装 . 高分子学报 , 2022 , 53 ( 12 ), 1475 - 1483 . doi: 10.11777/j.issn1000-3304.2022.22195 http://dx.doi.org/10.11777/j.issn1000-3304.2022.22195

Liu D. D. ; Lin M. ; Shu L. L. ; Sun J. ; Chen X. S. A versatile supramolecular assembly platform for tumor microenvironment motivated drug release and ferroptosis synergistic therapy . Nano Lett. , 2023 , 23 ( 12 ), 5713 - 5721 . doi: 10.1021/acs.nanolett.3c01440 http://dx.doi.org/10.1021/acs.nanolett.3c01440

Heller P. ; Mohr N. ; Birke A. ; Weber B. ; Reske-Kunz A. ; Bros M. ; Barz M. Directed interactions of block copolypept(o)ides with mannose-binding receptors: peptoMicelles targeted to cells of the innate immune system . Macromol. Biosci. , 2015 , 15 ( 1 ), 63 - 73 . doi: 10.1002/mabi.201400417 http://dx.doi.org/10.1002/mabi.201400417

Hao K. ; Cui R. L. ; Fang L. F. ; Ling J. ; Zhu B. K. Lysine-sarcosine PiPo functionalized surface with excellent hemocompatibility . ACS Appl. Mater. Interfaces , 2023 , 15 ( 25 ), 29700 - 29712 . doi: 10.1021/acsami.2c19677 http://dx.doi.org/10.1021/acsami.2c19677

Sun J. ; Li M. ; Lin M. ; Zhang B. ; Chen X. S. High antibacterial activity and selectivity of the versatile polysulfoniums that combat drug resistance . Adv. Mater. , 2021 , 33 ( 41 ), e 2104402 . doi: 10.1002/adma.202104402 http://dx.doi.org/10.1002/adma.202104402

颜舒婷 , 姚远 , 陶鑫峰 , 林绍梁 . 含硫正离子聚类肽水凝胶的合成与性能 . 高等学校化学学报 , 2022 , 43 ( 11 ), 222 - 230 . doi: 10.7503/cjcu20220381 http://dx.doi.org/10.7503/cjcu20220381

Ma X. T. ; Lin M. ; Sun J. ; Chen X. S. Fabrication of antifouling/antimicrobial polysulfonium-coated surface against biofilms and water bacterial contamination . Adv. NanoBiomed Res. , 2023 , 3 ( 7 ), 2200150 . doi: 10.1002/anbr.202200150 http://dx.doi.org/10.1002/anbr.202200150

Fang R. ; Pi J. W. ; Wei T. T. ; Ali A. ; Guo L. Stimulus-responsive polymers based on polypeptoid skeletons . Polymers , 2021 , 13 ( 13 ), 2089 . doi: 10.3390/polym13132089 http://dx.doi.org/10.3390/polym13132089

Okuno Y. ; Iwasaki Y. Well-defined anisotropic self-assembly from peptoids and their biomedical applications . ChemMedChem , 2023 , 18 ( 15 ), e 202300217 . doi: 10.1002/cmdc.202300217 http://dx.doi.org/10.1002/cmdc.202300217

Xuan S. T. ; Zuckermann R. N. Diblock copolypeptoids: a review of phase separation, crystallization, self-assembly and biological applications . J. Mater. Chem. B , 2020 , 8 ( 25 ), 5380 - 5394 . doi: 10.1039/d0tb00477d http://dx.doi.org/10.1039/d0tb00477d

Zhao M. F. Hierarchical assemblies of polypeptoids for rational design of advanced functional nanomaterials . Biopolymers , 2021 , 112 ( 9 ), e 23469 . doi: 10.1002/bip.23469 http://dx.doi.org/10.1002/bip.23469

Gohy J. F. ; Zhao Y. Photo-responsive block copolymer micelles: design and behavior . Chem. Soc. Rev. , 2013 , 42 ( 17 ), 7117 - 7129 . doi: 10.1039/c3cs35469e http://dx.doi.org/10.1039/c3cs35469e

Li Y. ; Tom J. C. ; Biehl P. ; Ling J. ; Schacher F. H. Block polypeptoids: synthesis, characterization, and response toward irradiation with UV light and temperature . Macromolecules , 2020 , 53 ( 13 ), 5218 - 5226 . doi: 10.1021/acs.macromol.0c00654 http://dx.doi.org/10.1021/acs.macromol.0c00654

Lin M. ; Ding J. ; Sun J. Photo‐triggered polymeric antimicrobial peptide mimics with excellent selectivity and antifouling and antimicrobial hydrogels . Giant , 2022 , 10 , 100097 . doi: 10.1016/j.giant.2022.100097 http://dx.doi.org/10.1016/j.giant.2022.100097

Yang X. ; Lin M. S. ; Wei J. R. ; Sun J. A self-crosslinking nanogel scaffold for enhanced catalytic efficiency and stability . Polym. Chem. , 2023 , 14 ( 3 ), 284 - 294 . doi: 10.1039/d2py01272c http://dx.doi.org/10.1039/d2py01272c

Jerca F. A. ; Jerca V. V. ; Hoogenboom R. Advances and opportunities in the exciting world of azobenzenes . Nat. Rev. Chem. , 2022 , 6 ( 1 ), 51 - 69 . doi: 10.1038/s41570-021-00334-w http://dx.doi.org/10.1038/s41570-021-00334-w

Xu B. B. ; Qian H. Y. ; Zhang L. ; Lin S. L. Branched aggregates with tunable morphology via hierarchic al self-assembly of azobenzene-derived molecular double brushes . Angew. Chem. Int. Ed , 2021 , 60 ( 32 ), 17707 - 17713 . doi: 10.1002/anie.202106321 http://dx.doi.org/10.1002/anie.202106321

Zhao Y. L. ; Tao X. F. ; Lin J. P. ; Lin S. L. Azobenzene functionalized organic covalent frameworks: controlled morphologies and photo-regulated adsorption . Adv. Funct. Mater. , 2023 , 33 ( 38 ), 2302225 . doi: 10.1002/adfm.202302225 http://dx.doi.org/10.1002/adfm.202302225

Zhao Y. L. ; Tao X. F. ; Xu B. B. ; Liu W. B. ; Lin S. L. Robust thiazole-linked covalent organic frameworks with post-modified azobenzene groups: photo-regulated dye adsorption and separation . Adv. Funct. Mater. , 2024 , 34 ( 34 ), 2401895 . doi: 10.1002/adfm.202401895 http://dx.doi.org/10.1002/adfm.202401895

Peng G. P. ; Jin H. B. ; Liu F. ; Yang X. Y. ; Sui P. L. ; Lin S. L. Biomimetic ultrathin pepsomes for photo-controllable catalysis . Sci. China Chem. , 2022 , 65 ( 12 ), 2444 - 2449 . doi: 10.1007/s11426-022-1353-4 http://dx.doi.org/10.1007/s11426-022-1353-4

Zhang Y. X. ; Huang J. ; Zhang J. ; Zhu X. Y. ; Tong G. S. Synthesis and self-assembly of photo-responsive polypeptoid-based copolymers containing azobenzene side chains . Polym. Chem. , 2021 , 12 ( 12 ), 1823 - 1829 . doi: 10.1039/d0py01723j http://dx.doi.org/10.1039/d0py01723j

Zhang Y. X. ; Huang J. ; Zhang J. ; Ren N. ; Tong G. S. ; Zhu X. Y. Dual photo/thermo-responsive polypeptoids . Chinese J. Polym. Sci. , 2023 , 41 ( 1 ), 24 - 31 . doi: 10.1007/s10118-022-2837-7 http://dx.doi.org/10.1007/s10118-022-2837-7

胡祖佳 , 颜舒婷 , 戚家乐 , 陶鑫峰 , 林绍梁 . 基于NNTA可控聚合的环形聚类肽合成与表征 . 高分子学报 , 2021 , 52 ( 7 ), 708 - 716 . doi: 10.11777/j.issn1000-3304.2020.20284 http://dx.doi.org/10.11777/j.issn1000-3304.2020.20284

王永秀 , 赵崇浩 , 陶鑫峰 , 林绍梁 . 环形偶氮苯功能化聚类肽的合成与自组装 . 功能高分子学报 , 2024 , 37 ( 1 ), 5 - 14 . doi: 10.14133/j.cnki.1008-9357.20231213001 http://dx.doi.org/10.14133/j.cnki.1008-9357.20231213001

Yang B. ; Zhao Y. ; Wei Y. ; Fu C. K. ; Tao L. The Ugi reaction in polymer chemistry: syntheses, applications and perspectives . Polym. Chem. , 2015 , 6 ( 48 ), 8233 - 8239 . doi: 10.1039/c5py01398d http://dx.doi.org/10.1039/c5py01398d

陶磊 , 赵原 , 杨斌 , 危岩 , 吴海波 . 以多组分点击化学为基础的高分子合成: 高分子合成的新机遇 . 高分子学报 , 2016 , ( 11 ), 1482 - 1494 . doi: 10.11777/j.issn1000-3304.2016.16218 http://dx.doi.org/10.11777/j.issn1000-3304.2016.16218

Tao Y. ; Wang Z. ; Tao Y. H. Polypeptoids synthesis based on Ugi reaction: advances and perspectives . Biopolymers , 2019 , 110 ( 6 ), e 23288 . doi: 10.1002/bip.23288 http://dx.doi.org/10.1002/bip.23288

Zhang X. J. ; Wang S. X. ; Liu J. ; Xie Z. G. ; Luan S. F. ; Xiao C. S. ; Tao Y. H. ; Wang X. H. Ugi reaction of natural amino acids: a general route toward facile synthesis of polypeptoids for bioapplications . ACS Macro Lett. , 2016 , 5 ( 9 ), 1049 - 1054 . doi: 10.1021/acsmacrolett.6b00530 http://dx.doi.org/10.1021/acsmacrolett.6b00530

陶月 , 陈金龙 , 王士学 , 陶友华 . 基于Ugi多组分反应的赖氨酸与糠醛的直接聚合 . 高分子学报 , 2020 , 51 ( 7 ), 738 - 743 . doi: 10.11777/j.issn1000-3304.2020.20025 http://dx.doi.org/10.11777/j.issn1000-3304.2020.20025

Stiernet P. ; Couturaud B. ; Bertrand V. ; Eppe G. ; De Winter J. ; Debuigne A. Ugi four-component polymerization of amino acid derivatives: a combinatorial tool for the design of polypeptoids . Polym. Chem. , 2021 , 12 ( 14 ), 2141 - 2151 . doi: 10.1039/d1py00109d http://dx.doi.org/10.1039/d1py00109d

Liu H. ; Zhang S. W. ; Yan X. Q. ; Song C. ; Chen J. P. ; Dong Y. P. ; Li X. F. Silylium cation initiated sergeants-and-soldiers type chiral amplification of helical aryl isocyanide copolymers . Polym. Chem. , 2020 , 11 ( 37 ), 6017 - 6028 . doi: 10.1039/d0py00808g http://dx.doi.org/10.1039/d0py00808g

Tao X. F. ; Shen C. Y. ; Hua Q. X. ; Jin S. ; Yao Y. ; Lin S. L. Poly(acetylene azobenzene oligoethylene glycol) with concurrently reversible photomechanical and photoelectric responsiveness upon ultraviolet irradiation . ACS Appl. Polym. Mater. , 2025 , 7 ( 8 ), 5212 - 5220 . doi: 10.1021/acsapm.5c00543 http://dx.doi.org/10.1021/acsapm.5c00543

Rocha R. O. ; Rodrigues M. O. ; Neto B. A. D. Review on the ugi multicomponent reaction mechanism and the use of fluorescent derivatives as functional chromophores . ACS Omega , 2020 , 5 ( 2 ), 972 - 979 . doi: 10.1021/acsomega.9b03684 http://dx.doi.org/10.1021/acsomega.9b03684

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 .

任许乐 , 蔡春华 , 林嘉平‍ . 聚肽三嵌段共聚物棒状胶束的超分子环化行为研究 . 高分子学报 , 2024 , 55 ( 12 ), 1668 - 1679 .

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