Synthesis and Self-assembly of Amphiphilic Alternating Azopolymers

Sheng Jin; Yun-kai Lu; Xin-feng Tao; Shao-liang Lin

doi:10.11777/j.issn1000-3304.2026.26109

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Synthesis and Self-assembly of Amphiphilic Alternating Azopolymers

Research Article | 更新时间：2026-07-30

- Synthesis and Self-assembly of Amphiphilic Alternating Azopolymers
- Acta Polymerica Sinica Vol. 57, Issue 8, Pages: 1740-1750(2026)
- 作者机构：
  
  华东理工大学材料科学与工程学院上海市先进聚合物材料重点实验室上海 200237
- 作者简介：
  
  Xin-feng Tao, E-mail: taoxinfeng@ecust.edu.cn
  Shao-liang Lin, E-mail: slin@ecust.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26109
  CLC：
- CSTR：32057.14.GFZXB.2026.7630
- Received：07 April 2026，
  
  Accepted：18 May 2026，
  
  Online First：10 July 2026，
  
  Published：20 August 2026
- 稿件说明：
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金圣, 陆云凯, 陶鑫峰, 林绍梁. 两亲性偶氮苯交替共聚物的合成与自组装. 高分子学报, 2026, 57(8), 1740-1750.

Jin, S.; Lu, Y. K.; Tao, X. F.; Lin, S. L. Synthesis and self-assembly of amphiphilic alternating azopolymers. Acta Polymerica Sinica (in Chinese), 2026, 57(8), 1740-1750.
金圣, 陆云凯, 陶鑫峰, 林绍梁. 两亲性偶氮苯交替共聚物的合成与自组装. 高分子学报, 2026, 57(8), 1740-1750. DOI： 10.11777/j.issn1000-3304.2026.26109. CSTR： 32057.14.GFZXB.2026.7630.

Jin, S.; Lu, Y. K.; Tao, X. F.; Lin, S. L. Synthesis and self-assembly of amphiphilic alternating azopolymers. Acta Polymerica Sinica (in Chinese), 2026, 57(8), 1740-1750. DOI： 10.11777/j.issn1000-3304.2026.26109. CSTR： 32057.14.GFZXB.2026.7630.

摘要

以偶氮苯-4

4'-二羧酸(Azo)，低聚乙二醇二胺(EG

)，苯甲醛和叔丁基异腈为单体，通过Ugi多组分聚合合成了主链刚-柔交替的两亲性偶氮苯共聚物，简称为P(Azo-

alt

-EG

) (

=2、3、4和5). 利用核磁共振氢谱(

H-NMR)、体积排除色谱(SEC)和紫外-可见光谱(UV-Vis)，对偶氮苯交替共聚物的化学结构、分子量、分子量分布和光致顺反异构化特性进行了表征. 系统研究了P(Azo-

alt

-EG

)在醇类溶剂中的热退火自组装行为，利用透射电子显微镜(TEM)、动态光散射(DLS)和静态光散射(SLS)对组装体的形貌和尺寸进行了详细表征. 在乙醇和正丙醇中，P(Azo-

alt

-EG

)分别自组装得到了囊泡和梭形片状组装体，且组装体的尺寸随EG链长的增长而增大. P(Azo-

alt

-EG

)组装体具有良好的光响应性，囊泡在365 nm紫外光照后瓦解为不规则聚集体，在450 nm可见光照后回复为尺寸更大的囊泡；梭形片状组装体在365 nm紫外光照后转变为球形胶束，在450 nm可见光照后转变为细长的“竹叶”形纳米片.

Abstract

Alternating azopolymers are prominent in the field of smart material design due to their distinctive self-assembly behavior

which originates from the precisely regulated solvophilic/solvophobic balance and their responsiveness to stimuli. However

the azobenzene-functionalized alternating copolymers reported thus far are predominantly synthesized through complex and time-consuming methods. In this work

novel amphiphilic alternating azopolymers

P(Azo-

alt

-EG

) (

and 5)

were prepared

via

Ugi multicomponent polymerization using commercially available monomers

including azobenzene-4

4'-dicarboxylic acid (Azo)

oligo(ethylene glycol) diamines (EG

)

benzaldehyde

and

tert

-butyl isocyanide. The polymerizations proceeded successfully

affording relatively high yields (

74%). The chemical structures

molecular weights (MWs) and MW distributions were verified through ¹H-NMR and SEC analyses. The resulting copolymers exhibited a comparable MW range

spanning from 11.9 kg/mol to 13.3 kg/mol. UV-Vis spectroscopy demonstrated that P(Azo-

alt

-EG

) possessed excellent photo-isomerization properties. As the value of

increased from 2 to 5

the rates of photo-induced

trans

-to-

cis

isomerization of P(Azo-

alt

-EG

) were (0.418±0.023)

(0.461±0.011)

(0.528±0.043)

and (0.660±0.013) s

-1

respectively. This trend was attributed to the longer EG chains providing more free space for the azobenzene groups to move. The thermal annealing-induced self-assembly behaviors of P(Azo-

alt

-EG

) in alcoholic solvents were systematically investigated. Firstly

P(Azo-

alt

-EG

) was dissolved in ethanol at 70 ℃ and maintained for 4 h

followed by incubating at 25 ℃ for 24 h. This process led to the formation of uniform polymersomes with hydrodynamic radius (

) ranging from 95.4 nm to 148.0 nm

depending on the increasing length of EG chains. Meanwhile

when annealed from 90 ℃ in

-propanol

P(Azo-

alt

-EG

) formed fusiform nanosheets

with sizes tunable according to the length of the EG chains. In both polymersomes and nanosheets

P(Azo-

alt

-EG

) chains are orderly arranged following a folded chain model

adopting a monolayer core-shell structure. UV-Vis spectroscopy revealed that the azobenzene groups within the assemblies had a H-aggregation. These assemblies exhibited remarkable photo-responsiveness

undergoing morphological transitions under ultraviolet/visible light irradiation. Specifically

polymersomes disintegrated into irregular aggregates under 365 nm UV light irradiation and reformed into larger polymersomes under 450 nm visible light irradiation

while fusiform nanosheets transformed into spherical micelles and subsequently into elongated "bamboo leaf"-like nanosheets. These findings indicate promising applications for P(Azo-

alt

-EG

) assemblies in the fields of smart materials and biomedicine.

关键词

Keywords

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