DFG-DST Project: Stimuli-Responsive Microgels with Permanent and Dynamic Ionic Crosslinks: Chemical Design and Behavior in Aqueous Solutions

DFG-DST 项目：具有永久和动态离子交联的刺激响应微凝胶：水溶液中的化学设计和行为

• 批准号: 323308141
• 负责人: Professor Dr. Andrij Pich
• 金额: --
• 依托单位: DWI - Leibniz-Institut für Interaktive Materialien e.V.
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2017
• 资助国家: 德国
• 起止时间: 2016-12-31 至 2019-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/323308141?language=en
• 关键词: DFG; DST; Project; Stimuli; Responsive

In this project we propose to design a molecular toolbox of zwitterionic building blocks and to elaborate new synthesis protocols to obtain microgels with a controlled distribution and a high loading of zwitterionic groups. For these zwitterionic microgels a comprehensive picture to show the relationship between the molecular structure and the stimuli-responsive behavior in aqueous solutions is going to be developed.We aim to synthesize zwitterionic reactive building blocks with precisely controlled molecular architecture (chemical structure of zwitterionic group) and tunable size (monomers vs. macromonomers). Using different polymerisation approaches we will synthesize temperature-responsive microgels based on N-vinylcaprolactam (VCL), N-vinylpiperidone (VPP) and N-vinylpyrolidone (VPR) with tunable amount and controlled distribution of zwitterionic groups in the microgels (random vs. core-shell). The synthesized microgels will exhibit two unique features: They will have both, an upper critical solution temperature (UCST) (due to the presence of zwitterionic groups in polymer chains) and a lower critical solution temperature (LCST) (due to the presence of lactam groups in polymer chains). They will also have two types of crosslinks, ionic dynamic crosslinks generated by zwitterionic groups and covalent crosslinks generated by a crosslinker.To understand the properties of the synthesized zwitterionic microgels we will perform their characterization using different analytical methods to understand the internal structure and behavior in aquous solutions. Specifically, we will focus on following questions:-Which amount of zwitterionic groups in the microgels is required for the formation of ionic (dynamic) crosslinks?;-How do the structure of the zwitterionic building blocks (monomers vs. macromonomers) and the amphiphilic properties of the polymer chains (size of the lactam rings) influence the formation of ionic (dynamic) crosslinks?; -Can we tune the volume phase transition temperatures (UCST and LCST), swelling degree and colloidal stability of the microgels with high contents of zwitterionic groups?The scientific outcome of this project will be an elaborated synthesis to design a toolbox of temperature-responsive zwitterionic microgels with covalent and ionic (dynamic) crosslinks and an understanding of their behavior in aqueous solutions. Based on this knowledge new application perspectives for such microgels, as candidates for drug delivery vehicles and building blocks for self-healing and protein-repelling coatings, will be generated.

在这个项目中，我们建议设计一个两性离子构建块的分子工具箱，并制定新的合成方案，以获得具有受控分布和高负载两性离子基团的微凝胶。对于这些两性离子微凝胶，我们将开发一幅全面的图像来展示分子结构和水溶液中刺激响应行为之间的关系。我们的目标是合成具有精确控制的分子结构(两性离子基团的化学结构)和可调大小(单体与大单体)的两性离子反应构建块。使用不同的聚合方法，我们将合成基于N-乙烯基己内酰胺(VCL)、N-乙烯基哌啶酮(VPP)和N-乙烯基吡咯烷酮(VPR)的温度响应型微凝胶，微凝胶中两性离子基团的数量和分布(随机和核壳)可调。合成的微凝胶将表现出两个独特的特征：它们都具有较高的临界溶解温度(UCST)(由于聚合物链中存在两性离子基团)和较低的临界溶解温度(LCST)(由于聚合物链中存在内酰胺基团)。它们还将有两种类型的交联物，由两性离子基团产生的离子动态交联物和由交联剂产生的共价交联物。为了了解合成的两性离子微凝胶的性质，我们将使用不同的分析方法对其进行表征，以了解其在水溶液中的内部结构和行为。具体地说，我们将着重于以下问题：-微凝胶中需要多少两性离子基团才能形成离子(动态)交联物？-两性离子构建块(单体与大单体)的结构和聚合物链的两亲性(内酰胺环的尺寸)如何影响离子(动态)交联物的形成？-我们能否调节高含量两性离子微凝胶的体积相变温度(UCST和LCST)、溶胀度和胶体稳定性？该项目的科学成果将是一项精心设计的合成，旨在设计一种具有共价和离子(动态)交联的温度响应性两性离子微凝胶工具箱，并了解它们在水溶液中的行为。基于这一知识，这种微凝胶将产生新的应用前景，作为药物输送载体的候选者，以及用于自我修复和蛋白质排斥涂层的构建块。

项目成果

Aqueous solution behavior of thermoresponsive polyzwitterionic microgels based on poly(N-vinylcaprolactam) synthesized via RAFT precipitation polymerization

• DOI: 10.1016/j.eurpolymj.2019.05.063
• 发表时间: 2019-09
• 期刊: European Polymer Journal
• 影响因子: 6
• 作者: Pabitra Saha;Michael Kather;S. L. Banerjee;N. Singha;A. Pich

A dual thermoresponsive and antifouling zwitterionic microgel with pH triggered fluorescent "on-off" core.

• DOI: 10.1016/j.jcis.2020.12.018
• 发表时间: 2020-12
• 期刊: Journal of colloid and interface science
• 影响因子: 9.9
• 作者: S. L. Banerjee;Pabitra Saha;Ritabrata Ganguly;Koushik Bhattacharya;Uddhab Kalita;A. Pich;N. Singha

Dual Stimuli‐Responsive Self‐Assembly Behavior of a Tailor‐Made ABC‐Type Amphiphilic Tri‐Block Copolymer

定制 ABC 型两亲性三嵌段共聚物的双刺激响应自组装行为

• DOI: 10.1002/pol.20190200
• 发表时间: 2020
• 期刊: Journal of Polymer Science
• 影响因子: 3.4
• 作者: Sanjay Pal;Michael Kather;Sovan Lal Banerjee;Pabitra Saha;Andrij Pich;Nikhil K. Singha
• 通讯作者: Nikhil K. Singha