Photopatternable, Branched Polymer Hydrogels Based on Linear Macromonomers for 3D Cell Culture Applications

Tong, Ciqing; Wondergem, Joeri A. J.; Heinrich, Doris; Kieltyka, Roxanne E.

doi:10.1021/acsmacrolett.0c00175

Cited by 21 publications

(17 citation statements)

References 37 publications

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“…Although the disulfide bond is relatively strong (with a bond dissociation energy of roughly 60 kcal/mol), many disulfides are susceptible to cleavage by electrophiles, nucleophiles, reducing agents, free radicals, and even directly by specific wavelengths of light. − The unique chemistry surrounding disulfides has resulted in a recent surge of the incorporation of disulfides into polymeric systems. Polymers containing disulfides have been used for: stress relaxation, self-healing adaptable networks, controlled drug release, chain-transfer agents, increase of refractive index through the introduction of sulfur atoms, latent protection of thiols, and ring-opening polymerizations of 1,2-dithiolanes and 1,2-dithianes. ,− …”

Section: Introductionmentioning

confidence: 99%

Spatial and Temporal Control of Photomediated Disulfide–Ene and Thiol–Ene Chemistries for Two-Stage Polymerizations

et al. 2022

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A new strategy is reported for the design and synthesis of high sulfur-containing materials for potential use in covalent adaptable networks and optical materials by combining photomediated thiol–ene- and disulfide–ene-based polymerization reactions. Taking advantage of the relative reaction rates to differentiate sequentially between the thiol–ene and disulfide–ene conjugations, these reactions were performed semiorthogonally to produce polymer networks of controlled architecture. Kinetic analysis demonstrates that the thiol–ene reaction is approximately 30 times faster than the disulfide–ene reaction, enabling spatial and temporal manipulation of material properties via dual-cure networks and photopatterning. A two-stage polymerization approach was implemented with increases in modulus in the second stage of 2–3 orders of magnitude accompanied by increases in the glass-transition temperature of more than 15 °C. Additionally, the thiol–ene reaction in the presence of a disulfide yields materials capable of simultaneous network development and stress relaxation through dynamic bond exchange during in situ polymerization.

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Section: Introductionmentioning

confidence: 99%

Spatial and Temporal Control of Photomediated Disulfide–Ene and Thiol–Ene Chemistries for Two-Stage Polymerizations

et al. 2022

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“…UV irradiation-induced cross-linking of DT is likely responsible for the abrupt increase in hydrogel stiffness; the ring opening of the DT moiety with light in the multicomponent squaramide-based supramolecular materials was confirmed by solid-state NMR experiments against a covalent polymer PEGdiDT control ( Figures S13 and S14 ). 54 …”

Section: Results and Discussionmentioning

confidence: 99%

“…We further explored the possibility for spatiotemporal patterning of bioactive cues in supramolecular materials to mimic the heterogeneity of tissues in vivo. Fluorescent ( (fluorescein)GK(DT)GGGRGDS 54 and non-fluorescent ( (DT)GGGRGDS ( DT-RGD )) RGD peptides with a DT moiety were synthesized to enable photopatterning using either a photomask or direct laser writing (DLW) ( Figure 6 A). The efficiency of binding of the RGD peptide to SQ/10SQ-DT hydrogel by UV irradiation was found to be around 20% for samples of different RGD concentrations ( Figure S31 ), after homogenous UV exposure using a benchtop LED (5 min, ∼10 mW/cm 2 , 375 nm).…”

Section: Results and Discussionmentioning

confidence: 99%

Spatial and Temporal Modulation of Cell Instructive Cues in a Filamentous Supramolecular Biomaterial

Tong

Wondergem

Brink

et al. 2022

ACS Appl. Mater. Interfaces

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Supramolecular materials provide unique opportunities to mimic both the structure and mechanics of the biopolymer networks that compose the extracellular matrix. However, strategies to modify their filamentous structures in space and time in 3D cell culture to study cell behavior as encountered in development and disease are lacking. We herein disclose a multicomponent squaramide-based supramolecular material whose mechanics and bioactivity can be controlled by light through co-assembly of a 1,2-dithiolane (DT) monomer that forms disulfide cross-links. Remarkably, increases in storage modulus from ∼200 Pa to >10 kPa after stepwise photo-cross-linking can be realized without an initiator while retaining colorlessness and clarity. Moreover, viscoelasticity and plasticity of the supramolecular networks decrease upon photo-irradiation, reducing cellular protrusion formation and motility when performed at the onset of cell culture. When applied during 3D cell culture, force-mediated manipulation is impeded and cells move primarily along earlier formed channels in the materials. Additionally, we show photopatterning of peptide cues in 3D using either a photomask or direct laser writing. We demonstrate that these squaramide-based filamentous materials can be applied to the development of synthetic and biomimetic 3D in vitro cell and disease models, where their secondary cross-linking enables mechanical heterogeneity and shaping at multiple length scales.

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“…The self-healing, biocompatibility, photocontrolled viscoelastic properties, as well as gel-to-sol transition, make these hydrogels interesting for release of a molecular cargo in the presence of living cells. Tong and co-workers reported that UV irradiation of DT- and norbornene (NB)-terminated PEG in the presence of LAP led to production of a hydrogel containing reversible dynamic S–S as well as irreversible thioether bonds . Light irradiation and ring opening of DT produced thiyl radicals, which could be added to the disulfide and double bonds of DT or NB to form reversible and irreversible cross-links, respectively.…”

Section: Light-responsive Homolytically Cleavable Dynamic Covalent Bondsmentioning

confidence: 99%

Stimuli-Responsive Covalent Adaptable Hydrogels Based on Homolytic Bond Dissociation and Chain Transfer Reactions

et al. 2022

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Covalent adaptable hydrogels containing dynamic covalent bonds are gaining significant interest based on their ability of stimuli-controlled reversible bond dissociation, structural reorganization, color change, and self-healing through covalent bond exchange or dissociation. Potential applications of such hydrogels have been explored in coatings, sealants, tissue adhesives, soft robotics, tissue engineering, and stimuli-responsive lithography. Stimuli-induced homolytic bond cleavage leads to the formation of radicals with the ability of recombination or transfer to induce bond exchange and color variation. The incorporation of such stimuli-responsive homolytically cleavable bonds in hydrogels can lead to stimuli-controlled plasticity, stress relaxation, self-healing, structural reorganization, mechanochromism, and mechanoluminescence. The resultant smart materials are interesting for different applications, ranging from patterning and shape-shifting, cell encapsulation and culturing, and protein binding to strain sensing and damage reporting. The recent progress in the preparation of covalently adaptable hydrogels based on stimuli-responsive homolytical bond dissociation and recombination or chain transfer will be discussed in this review. More specifically, the different types of chemistry that can be used for development of covalent adaptable hydrogels based on light-induced, temperature-induced, and mechanically induced homolytic bond dissociation will be discussed. Moreover, the applications of the resultant covalent adaptable hydrogels will be highlighted, focusing on stress sensing and damage reporting, tissue engineering, and self-healable hydrogels, as well as stimuli-controlled patterning and shape-shifting.

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Photopatternable, Branched Polymer Hydrogels Based on Linear Macromonomers for 3D Cell Culture Applications

Cited by 21 publications

References 37 publications

Spatial and Temporal Control of Photomediated Disulfide–Ene and Thiol–Ene Chemistries for Two-Stage Polymerizations

Spatial and Temporal Control of Photomediated Disulfide–Ene and Thiol–Ene Chemistries for Two-Stage Polymerizations

Spatial and Temporal Modulation of Cell Instructive Cues in a Filamentous Supramolecular Biomaterial

Stimuli-Responsive Covalent Adaptable Hydrogels Based on Homolytic Bond Dissociation and Chain Transfer Reactions

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