Synthesis and Self-assembly of Poly (ethylene glycol)-<italic style="font-style: italic">g</italic>-Poly (<italic style="font-style: italic">γ</italic>-benzyl-L-glutamate) Rod-Coil Graft Copolymers

Shuo Zhang; Qing Li; Jia-ping Lin; Chun-hua Cai; Li-quan Wang

doi:10.11777/j.issn1000-3304.2017.16258

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Synthesis and Self-assembly of Poly (ethylene glycol)-g-Poly (γ-benzyl-L-glutamate) Rod-Coil Graft Copolymers

Research Article | 更新时间：2021-05-18

- Synthesis and Self-assembly of Poly (ethylene glycol)-g-Poly (γ-benzyl-L-glutamate) Rod-Coil Graft Copolymers
- Acta Polymerica Sinica Issue 2, Pages: 294-305(2017)
- 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重点实验室上海 200237
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2017.16258
  CLC：
- Published：20 February 2017，
  
  Received：22 August 2016，
  
  Revised：30 September 2016，
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Shuo Zhang, Qing Li, Jia-ping Lin, Chun-hua Cai, Li-quan Wang. Synthesis and Self-assembly of Poly (ethylene glycol)-g-Poly (γ-benzyl-L-glutamate) Rod-Coil Graft Copolymers. [J]. Acta Polymerica Sinica (2):294-305(2017)
DOI：

Shuo Zhang, Qing Li, Jia-ping Lin, Chun-hua Cai, Li-quan Wang. Synthesis and Self-assembly of Poly (ethylene glycol)-g-Poly (γ-benzyl-L-glutamate) Rod-Coil Graft Copolymers. [J]. Acta Polymerica Sinica (2):294-305(2017) DOI： 10.11777/j.issn1000-3304.2017.16258.

摘要

通过负离子开环聚合，合成了以柔性亲水的聚乙二醇（PEG）为主链，刚性疏水的聚（

-苄基L-谷氨酸酯）（PBLG）为侧链的PEG-

-PBLG刚-柔接枝共聚物.运用核磁共振氢谱（

H-NMR）、傅里叶变换红外光谱（FTIR）和凝胶渗透色谱（GPC）等表征了共聚物的结构、分子量及其分布.以共溶剂溶解、选择性溶剂透析的方法制备了自组装聚集体.利用扫描电子显微镜（SEM）、透射电子显微镜（TEM）、原子力显微镜（AFM）和激光光散射（LLS）等表征了共聚物自组装体的形貌和结构.研究发现，基于其特殊的拓扑结构，接枝共聚物的自组装行为表现出与一般规律不同的变化趋势.具有较短疏水PBLG侧链的PEG-

-PBLG可以自组装形成球形复合胶束，随着疏水PBLG侧链的增长，聚集体逐渐由复合胶束转变为囊泡，这种现象在已有的研究中鲜有报道.此外，降低初始聚合物溶液的浓度，共聚物自组装得到的聚集体的尺寸变小而分布变宽；反之，聚集体的尺寸增大而分布变窄.还利用耗散粒子动力学方法，验证了实验中聚集体的形貌变化，并给出了聚集体中的链段分布等在实验中较难得到的信息.

Abstract

Poly (ethylene glyco1)-

-poly (

-benzyl-L-glutamate) (PEG-

-PBLG) graft copolymers

bearing hydrophilic PEG backbone and hydrophobic PBLG side chain

were synthesized

via

ring opening polymerization of

-benzyl-L-glutamate-

-carboxyanhydride (BLG-NCA) using PEG-

-NH

as the initiator. The molecular weight and polydispersity index of the graft copolymers as well as conformation of PBLG chains were characterized by proton nuclear magnetic resonance (

H-NMR)

gel permeation chromatography (GPC)

and Fourier transform infrared spectrum (FTIR)

respectively. Self-assemblies were prepared by a selective solvent method with tetrahydrofuran (THF) as the initial common solvent and water as the selective solvent. The critical water content (CWC) for the graft copolymer aggregation was determined by turbidity measurement (OD). The CWC value decreases from 17.3 wt% to 12.8 wt% gradually with the increase in PBLG length (the initial concentration is 0.5 g L

-1

). The morphologies and structures of the formed aggregates were investigated by scanning electron microscopy (SEM)

transmission electron microscopy (TEM)

atom force microscopy (AFM)

and laser light scattering measurements (LLS). The results show that the graft copolymers are able to self-assemble into spherical compound micelles when the PBLG side chain is relatively short. As the PBLG length increases

the aggregates gradually transform to rod-like aggregates and vesicles. In addition to the experiments

the self-assembly of the graft copolymers was investigated using dissipative particle dynamics (DPD) simulation based on a coarse-grained coil-

-rod graft copolymer model. The simulation results were in agreement with the experimental findings

and additional information such as chain distribution of copolymers in aggregates was obtained. Besides

it was found that the initial polymer concentration affected the aggregate size but no significant influence was observed on the aggregate morphology. When prepared at higher initial polymer concentration (1.0 g L

-1

)

the aggregates obtained were much larger in size and narrower in size distribution. Finally

based on both the experimental and the simulation results

a mechanism for the self-assembly of PEG-

-PBLG graft copolymers was proposed.

关键词

接枝共聚物聚肽刚性链段囊泡耗散粒子动力学

Keywords

Graft copolymerPolypeptideRigid chainVesicleDissipative particle dynamics simulation

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State Key Laboratory of Chemical Resources Engineering, Beijing Laboratory of Biomedical Materials, Beijing University of Chemical Technology

State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing Laboratory of Biomedical Materials

State Key Laboratory of Chemical Resource Engineering, Beijing Laboratory of Biomedical Materials, Beijing University of Chemical Technology

School of Chemistry and Molecular Engineering, East China Normal University

College of Chemistry, State Key Laboratory of Polymer Materials Engineering, National Engineering Laboratory of Eco-Friendly Polymeric Materials (Sichuan), Sichuan University

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⁰

Synthesis and Self-assembly of Poly (ethylene glycol)-g-Poly (γ-benzyl-L-glutamate) Rod-Coil Graft Copolymers

DOI：10.11777/j.issn1000-3304.2017.16258

摘要

Abstract

关键词

Keywords

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