Molecularly Engineered Supramolecular Thermoresponsive Hydrogels with Tunable Mechanical and Dynamic Properties

Biomacromolecules, vol. 25, pp. 4686–4696

Abstract

High Resolution Image Download MS PowerPoint Slide Synthetic supramolecular polymers and hydrogels in water are emerging as promising biomaterials due to their modularity and intrinsic dynamics. Here, we introduce temperature sensitivity into the nonfunctionalized benzene-1,3,5-tricarboxamide ( BTA-EG 4 ) supramolecular system by incorporating a poly( N -isopropylacrylamide)-functionalized ( BTA-PNIPAM) moiety, enabling 3D cell encapsulation applications. The viscous and structural properties in the solution state as well as the mechanical and dynamic features in the gel state of BTA-PNIPAM/BTA-EG 4 mixtures were investigated and modulated. In the dilute state ( c ∼μM), BTA-PNIPAM acted as a chain capper below the cloud point temperature ( T cp = 24 °C) but served as a cross-linker above T cp . At higher concentrations ( c ∼mM), weak or stiff hydrogels were obtained, depending on the BTA-PNIPAM/BTA-EG 4 ratio. The mixture with the highest BTA-PNIPAM ratio was ∼100 times stiffer and ∼10 times less dynamic than BTA-EG 4 hydrogel. Facile cell encapsulation in 3D was realized by leveraging the temperature-sensitive sol–gel transition, opening opportunities for utilizing this hydrogel as an extracellular matrix mimic.

Authors 7

1. Laura Rijns

   Eindhoven University of Technology

   Affiliation as printed

   Department of Biomedical Engineering, Institute for Complex Molecular Systems (ICMS), Eindhoven University of Technology, Eindhoven 5600 MB, The Netherlands

2. Heleen Duijs Aachen Leiden Academic Centre for Drug Research

   Leiden University

   Affiliation as printed

   Leiden Academic Centre for Drug Research (LACDR), Leiden University, Wassenaarseweg 76, Leiden 2333 AL, The Netherlands

3. René P. M. Lafleur

   Eindhoven University of Technology

   Affiliation as printed

   Laboratory of Macromolecular and Organic Chemistry, Institute for Complex Molecular Systems (ICMS), Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven 5600 MB, The Netherlands

4. Ruth Cardinaels

   Eindhoven University of Technology · KU Leuven

   Affiliation as printed

   Processing and Performance of Materials, Institute for Complex Molecular Systems (ICMS), Department of Mechanical Engineering, Eindhoven University of Technology, Eindhoven 5600 MB, The Netherlands

   Soft Matter, Rheology and Technology, Department of Chemical Engineering, KU Leuven, Leuven 3001, Belgium

5. Anja R. A. Palmans

   Eindhoven University of Technology

   Affiliation as printed

   Laboratory of Macromolecular and Organic Chemistry, Institute for Complex Molecular Systems (ICMS), Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven 5600 MB, The Netherlands

6. Patricia Y. W. Dankers

   Eindhoven University of Technology

   Affiliation as printed

   Department of Biomedical Engineering, Institute for Complex Molecular Systems (ICMS), Eindhoven University of Technology, Eindhoven 5600 MB, The Netherlands

7. Lu Su corresponding Aachen Leiden Academic Centre for Drug Research

   Leiden University

   Affiliation as printed

   Leiden Academic Centre for Drug Research (LACDR), Leiden University, Wassenaarseweg 76, Leiden 2333 AL, The Netherlands