DNA‐Responsive Polyisocyanopeptide Hydrogels with Stress‐Stiffening Capacity

Deshpande, Swapneel R.; Hammink, Roel; Das, Rajat K.; Nelissen, Frank H. T.; Blank, Kerstin; Rowan, Alan E.; Heus, Hans A.

doi:10.1002/adfm.201602461

Cited by 46 publications

(59 citation statements)

References 47 publications

(41 reference statements)

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“…For the synthesis of PIC hydrogels, tetra(ethylene glycol) functionalized monomers were used. The resulting polymers possess a gelation temperature (T gel = LCST) of approximately 39 °C in PBS (Deshpande et al, 2016), which is well below the T m of CC-A4B4. A fraction of monomers (1:100) was equipped with a terminal azide functional group to allow peptide coupling via a heterobifunctional DBCO-EG 4 -maleimide crosslinker ( Figure 1B).…”

Section: Design and Synthesis Of Coiled Coil-crosslinked Pic And Peg mentioning

confidence: 91%

“…Subsequently, the DBCOfunctionalized CC was added to the azide-containing PIC to allow CC-mediated crosslinking via a strain-promoted azide alkyne cycloaddition reaction (N 3 :DBCO = 1:1). The yield of this reaction was previously quantified for a similar system (PIC crosslinked with DNA) and was determined to be 90 % (Deshpande et al, 2016). Considering the yield of both reactions, it can be assumed that approximately 80 % of CC-forming peptides are coupled to the PIC polymer.…”

Section: Design and Synthesis Of Coiled Coil-crosslinked Pic And Peg mentioning

confidence: 99%

“…To fully utilize the potential of PIC hydrogels as cytoskeleton and ECM mimics, several types of crosslinks have previously been introduced into PIC networks. These include short double-stranded DNA oligonucleotides (Deshpande et al, 2016) and stimuli-responsive DNA motifs (Deshpande et al, 2017) as well as self-assembled virus capsids (Schoenmakers et al, 2018b) and covalent triazole crosslinks (Schoenmakers et al, 2018a). In the majority of these studies, the focus was placed on understanding the effect of these crosslinks on the non-linear stress-stiffening response.…”

Section: Introductionmentioning

confidence: 99%

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Influence of Network Topology on the Viscoelastic Properties of Dynamically Crosslinked Hydrogels

Grad¹,

Tunn²,

Voerman³

et al. 2020

Preprint

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Biological materials combine stress relaxation and self-healing with non-linear stress-strain responses. These characteristic features are a direct result of hierarchical self-assembly, which often results in fiber-like architectures. Even though structural knowledge is rapidly increasing, it has remained a challenge to establish relationships between microscopic and macroscopic structure and function. Here, we focus on understanding how network topology determines the viscoelastic properties, i.e. stress relaxation, of biomimetic hydrogels. We have dynamically crosslinked two different synthetic polymers with one and the same crosslink. The first polymer, a polyisocyanopeptide (PIC), self-assembles into semi-flexible, fiber-like bundles and thus displays stress-stiffening, similar to many biopolymer networks. The second polymer, 4-arm poly(ethylene glycol) (starPEG), serves as a reference network with well-characterized structural and viscoelastic properties. Using one and the same coiled coil crosslink allows us to decouple the effects of crosslink kinetics and network topology on the stress relaxation behavior of the resulting hydrogel networks. We show that the fiber-containing PIC network displays a relaxation time approximately two orders of magnitude slower than the starPEG network. This reveals that crosslink kinetics is not the only determinant for stress relaxation. Instead, we propose that the different network topologies determine the ability of elastically active network chains to relax stress. In the starPEG network, each elastically active chain contains exactly one crosslink. In the absence of entanglements, crosslink dissociation thus relaxes the entire chain. In contrast, each polymer is crosslinked to the fiber bundle in multiple positions in the PIC hydrogel. The dissociation of a single crosslink is thus not sufficient for chain relaxation. This suggests that tuning the number of crosslinks per elastically active chain in combination with crosslink kinetics is a powerful design principle for tuning stress relaxation in polymeric materials. The presence of a higher number of crosslinks per elastically active chain thus yields materials with a slow macroscopic relaxation time but fast dynamics at the microscopic level. Using this principle for the design of synthetic cell culture matrices will yield materials with excellent long-term stability combined with the ability to locally reorganize, thus facilitating cell motility, spreading and growth.

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Section: Design and Synthesis Of Coiled Coil-crosslinked Pic And Peg mentioning

confidence: 91%

Section: Design and Synthesis Of Coiled Coil-crosslinked Pic And Peg mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Influence of Network Topology on the Viscoelastic Properties of Dynamically Crosslinked Hydrogels

Grad¹,

Tunn²,

Voerman³

et al. 2020

Preprint

Self Cite

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show abstract

“…Furthermore, hybrid hydrogels formed by PIC and fibrin were also constructed to investigate their structural and mechanical effects on cell spreading and differentiation . However, the reported PIC‐based supramolecular polymer networks were only responsive to single or dual stimuli, and the development of multiple‐stimuli‐responsive hybrid hydrogels to tailor PIC‐based mechanical responsiveness remains challenging …”

Section: Introductionmentioning

confidence: 99%

A Multiple‐Stimulus‐Responsive Biomimetic Assembly Based on a Polyisocyanopeptide and Conjugated Polymer

Meng

Xing

Yuan

et al. 2017

Chemistry An Asian Journal

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An assembly was fabricated and was revealed to be a multiple-stimulus-responsive biomimetic hybrid polymer architecture. It was constructed by the hydrophobic interactions between a conjugated polyfluorene that contained 2,1,3-benzothiadiazole units (PFBT) and a tri(ethylene glycol)-functionalized polyisocyanopeptide (3OEG-PIC). The introduction of PFBT to the polyisocyanopeptide (PIC) network allowed for the incorporation of responsiveness to multiple stimuli including temperature, CO , carbonic anhydrase, and nonlinear mechanics, which mimics natural processes and interactions. Furthermore, the light-harvesting and signal amplification characteristics of PFBT endowed the supramolecular assembly with the essential function of fluorescence monitoring for biological processes.

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“…13). 26 The helical polymer is soluble in water thanks 15 to the oligo(ethylene oxide) strands that are appended to amino acid residues that are responsible for the rigid secondary structure through amide hydrogen bonding between the sidechains. They form gels at extremely low concentration, down to 0.006 wt%, an order of magnitude less concentrated than 20 other synthetic supergelators.…”

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confidence: 99%