Abstract
Multicomponent supramolecular systems could be used to prepare exciting new functional materials, but it is often challenging to control the assembly across multiple length scales. Here we report a simple approach to forming patterned, spatially resolved multicomponent supramolecular hydrogels. A multicomponent gel is first formed from two low-molecular-weight gelators and consists of two types of fibre, each formed by only one gelator. One type of fibre in this ‘self-sorted network’ is then removed selectively by a light-triggered gel-to-sol transition. We show that the remaining network has the same mechanical properties as it would have done if it initially formed alone. The selective irradiation of sections of the gel through a mask leads to the formation of patterned multicomponent networks, in which either one or two networks can be present at a particular position with a high degree of spatial control.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Terech, P. & Weiss, R. G. Low molecular mass gelators of organic liquids and the properties of their gels. Chem. Rev. 97, 3133–3160 (1997).
Weiss, R. G. The past, present, and future of molecular gels. What is the status of the field, and where is it going? J. Am. Chem. Soc. 136, 7519–7530 (2014).
Raeburn, J. & Adams, D. J. Multicomponent low molecular weight gelators. Chem. Commun. 51, 5170–5180 (2015).
Buerkle, L. E. & Rowan, S. J. Supramolecular gels formed from multi-component low molecular weight species. Chem. Soc. Rev. 41, 6089–6102 (2012).
Hirst, A. R. et al. Self-assembly of two-component gels: stoichiometric control and component selection. Chem. Eur. J. 15, 372–379 (2009).
Adhikari, B., Nanda, J. & Banerjee, A. Multicomponent hydrogels from enantiomeric amino acid derivatives: helical nanofibers, handedness and self-sorting. Soft Matter 7, 8913–8922 (2011).
Sugiyasu, K., Kawano, S. I., Fujita, N. & Shinkai, S. Self-sorting organogels with p–n heterojunction points. Chem. Mater. 20, 2863–2865 (2008).
Raeburn, J., Zamith Cardoso, A. & Adams, D. J. The importance of the self-assembly process to control mechanical properties of low molecular weight hydrogels. Chem. Soc. Rev. 42, 5143–5156 (2013).
Molla, M. R., Das, A. & Ghosh, S. Chiral induction by helical neighbour: spectroscopic visualization of macroscopic-interaction among self-sorted donor and acceptor π-stacks. Chem. Commun. 47, 8934–8936 (2011).
Huang, Y. et al. Supramolecular hydrogels based on short peptides linked with conformational switch. Org. Biomol. Chem. 9, 2149–2155 (2011).
Li, X., Gao, Y., Kuang, Y. & Xu, B. Enzymatic formation of a photoresponsive supramolecular hydrogel. Chem. Commun. 46, 5364–5366 (2010).
Qiu, Z., Yu, H., Li, J., Wang, Y. & Zhang, Y. Spiropyran-linked dipeptide forms supramolecular hydrogel with dual responses to light and to ligand–receptor interaction. Chem. Commun. 3342–3344 (2009).
Sako, Y. & Takaguchi, Y. A photo-responsive hydrogelator having gluconamides at its peripheral branches. Org. Biomol. Chem. 6, 3843–3847 (2008).
Haines, L. A. et al. Light-activated hydrogel formation via the triggered folding and self-assembly of a designed peptide. J. Am. Chem. Soc. 127, 17025–17029 (2005).
Muraoka, T., Koh, C.-Y., Cui, H. & Stupp, S. I. Light-triggered bioactivity in three dimensions. Angew. Chem. Int. Ed. 48, 5946–5949 (2009).
Doran, T. M., Ryan, D. M. & Nilsson, B. L. Reversible photocontrol of self-assembled peptide hydrogel viscoelasticity. Polymer Chem. 5, 241–248 (2014).
Sahoo, J. K., Nalluri, S. K. M., Javid, N., Webb, H. & Ulijn, R. V. Biocatalytic amide condensation and gelation controlled by light. Chem. Commun. 50, 5462–5464 (2014).
He, M., Li, J., Tan, S., Wang, R. & Zhang, Y. Photodegradable supramolecular hydrogels with fluorescence turn-on reporter for photomodulation of cellular microenvironments. J. Am. Chem. Soc. 135, 18718–18721 (2013).
Yang, R., Peng, S., Wan, W. & Hughes, T. C. Azobenzene based multistimuli responsive supramolecular hydrogels. J. Mater. Chem. C 2, 9122–9131 (2014).
Maity, C., Hendriksen, W. E., van Esch, J. H. & Eelkema, R. Spatial structuring of a supramolecular hydrogel by using a visible-light triggered catalyst. Angew. Chem. Int. Ed. 54, 998–1001 (2015).
Sun, Z. et al. Multistimuli-responsive supramolecular gels: design rationale, recent advances, and perspectives. ChemPhysChem 15, 2421–2430 (2014).
van Herpt, J. T., Stuart, M. C. A., Browne, W. R. & Feringa, B. L. A dithienylethene-based rewritable hydrogelator. Chem. Eur. J. 20, 3077–3083 (2014).
Kloxin, A. M., Kasko, A. M., Salinas, C. N. & Anseth, K. S. Photodegradable hydrogels for dynamic tuning of physical and chemical properties. Science 324, 59–63 (2009).
Yan, B., Boyer, J.-C., Habault, D., Branda, N. R. & Zhao, Y. Near infrared light triggered release of biomacromolecules from hydrogels loaded with upconversion nanoparticles. J. Am. Chem. Soc. 134, 16558–16561 (2012).
Morris, K. L. et al. Chemically programmed self-sorting of gelator networks. Nature Commun. 4, 1480 (2013).
Colquhoun, C. et al. The effect of self-sorting and co-assembly on the mechanical properties of low molecular weight hydrogels. Nanoscale 6, 13719–13725 (2014).
Raeburn, J. et al. Electrochemically-triggered spatially and temporally resolved multi-component gels. Mater. Horiz. 1, 241–246 (2014).
Pocker, Y. & Green, E. Hydrolysis of D-glucono-δ-lactone. I. General acid–base catalysis, solvent deuterium isotope effects, and transition state characterization. J. Am. Chem. Soc. 95, 113–119 (1973).
Adams, D. J. et al. A new method for maintaining homogeneity during liquid–hydrogel transitions using low molecular weight hydrogelators. Soft Matter 5, 1856–1862 (2009).
Chen, L., Revel, S., Morris, K., Serpell, L. C. & Adams, D. J. Effect of molecular structure on the properties of naphthalene–dipeptide hydrogelators. Langmuir 26, 13466–13471 (2010).
Houton, K. A. et al. On crystal versus fiber formation in dipeptide hydrogelator systems. Langmuir 28, 9797–9806 (2012).
Chen, L. et al. Self-assembly mechanism for a naphthalene–dipeptide leading to hydrogelation. Langmuir 26, 5232–5242 (2010).
Fleming, S., Debnath, S., Frederix, P. W. J. M., Hunt, N. T. & Ulijn, R. V. Insights into the coassembly of hydrogelators and surfactants based on aromatic peptide amphiphiles. Biomacromolecules 15, 1171–1184 (2014).
Haque, M. A., Kurokawa, T. & Gong, J. P. Super tough double network hydrogels and their application as biomaterials. Polymer 53, 1805–1822 (2012).
Acknowledgements
E.R.D. thanks the Engineering and Physical Sciences Research Council (EPSRC) for a Doctorial Training Accounts studentship. D.A. thanks the EPSRC for a Fellowship (EP/L021978/1).
Author information
Authors and Affiliations
Contributions
E.R.D. and D.J.A. conceived the project and synthesized the gelators. E.R.D. and D.J.A. designed the experiments. E.R.D. carried out the gelation, irradiation and rheological experiments. E.G.B.E. carried out the NMR experiments. T.O.M. carried out the SEM experiments. All the authors contributed to writing the paper.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Supplementary information
Supplementary information
Supplementary information (PDF 1459 kb)
Rights and permissions
About this article
Cite this article
Draper, E., Eden, E., McDonald, T. et al. Spatially resolved multicomponent gels. Nature Chem 7, 848–852 (2015). https://doi.org/10.1038/nchem.2347
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nchem.2347
This article is cited by
-
Four distinct network patterns of supramolecular/polymer composite hydrogels controlled by formation kinetics and interfiber interactions
Nature Communications (2023)
-
Self-sorting double network hydrogels with photo-definable biochemical cues as artificial synthetic extracellular matrix
Nano Research (2022)
-
Micro-structural investigations on oppositely charged mixed surfactant gels with potential dermal applications
Scientific Reports (2021)
-
Control of seed formation allows two distinct self-sorting patterns of supramolecular nanofibers
Nature Communications (2020)
-
Protein-responsive protein release of supramolecular/polymer hydrogel composite integrating enzyme activation systems
Nature Communications (2020)