Abstract
Photoresponsive supramolecular gels as intelligent non-invasive responsive materials can undergo changes in color, state, morphology and electronic properties upon photo irradiation, making them attractive for a variety of applications. Herein, a novel supramolecular hydrogelator DBE with 1,4-divinylbenzene as the central core, connected via amide linkage to l-phenylalanine and peripheral hydrophilic groups, was designed to evaluate the effect of [2 + 2] photocycloaddition reaction on supramolecular hydrogels. UV irradiation decreases the solubility of the hydrogelator DBE and hence, causes the destruction of the gel. SEM images clearly show that irradiation with UV light could induce disintegration of the right-handed helical nanofibers entangled network, which turns into nanoparticles and eventually massive crystals. Circular dichroism and vibrational circular dichroism data also indicate the formation of right-handed helical nanofibers in DBE gel. FTIR and MALDI–TOF–MS spectrum confirm that the variation of stability and aggregated morphology of DBE gel after UV irradiation is attributed to [2 + 2] cycloaddition reaction of vinyl units. This study presents a wonderful model for regulating the stability and aggregated morphology of supramolecular hydrogels via photo irradiation, as well as offers new ideas for designing novel photo responsive materials.
Graphic Abstract
Similar content being viewed by others
References
Aparicio F, Nieto-Ortega B, Najera F, Ramirez FJ, Navarrete JTL, Casado J, Sanchez L. Inversion of supramolecular helicity in oligo-p-phenylene-based supramolecular polymers: influence of molecular atropisomerism. Angew Chem Int Ed. 2014;53:1373.
Zhao D, van Leeuwen T, Cheng J, Feringa BL. Dynamic control of chirality and self-assembly of double-stranded helicates with light. Nat Chem. 2017;9:250.
Kim J, Lee J, Kim WY, Kim H, Lee S, Lee HC, Lee YS, Seo M, Kim SY. Induction and control of supramolecular chirality by light in self-assembled helical nanostructures. Nat Commun. 2015;6:6959.
Wood DM, Greenland BW, Acton AL, Rodriguez-Llansola F, Murray CA, Cardin CJ, Miravet JF, Escuder B, Hamley IW, Hayes W. pH-Tunable hydrogelators for water purification: structural optimisation and evaluation. Chem Eur J. 2012;18:2692.
Liu GF, Liu JY, Feng CL, Zhao YL. Unexpected right-handed helical nanostructures co-assembled from l-phenylalanine derivatives and achiral bipyridines. Chem Sci. 2017;8:1769.
Liu G-F, Zhu L-Y, Ji W, Feng C-L, Wei Z-X. Inversion of the supramolecular chirality of nanofibrous structures through co-assembly with achiral molecules. Angew Chem Int Ed. 2016;55:2411.
Yarimaga O, Yoon B, Ham D-Y, Lee J, Hara M, Choi Y-K, Kim J-M. Electrophoretic deposition of amphiphilic diacetylene supramolecules: polymerization, selective immobilization, pattern transfer and sensor applications. J Mater Chem. 2011;21:18605.
Postma SGJ, Vialshin IN, Gerritsen CY, Bao M, Huck WTS. Preprogramming complex hydrogel responses using enzymatic reaction networks. Angew Chem Int Ed. 2017;56:1794.
Liu S, Tang A, Xie M, Zhao Y, Jiang J, Liang G. Oligomeric hydrogels self-assembled from reduction-controlled condensation. Angew Chem Int Ed. 2015;54:3639.
Draper ER, Adams DJ. Photoresponsive gelators. Chem Commun. 2016;52:8196.
Chen L, Yao X, Gu Z, Zheng K, Zhao C, Lei W, Rong Q, Lin L, Wang J, Jiang L, Liu M. Covalent tethering of photo-responsive superficial layers on hydrogel surfaces for photo-controlled release. Chem Sci. 2010;2017:8.
Xu L, Sheybani N, Yeudall WA, Yang H. The effect of photoinitiators on intracellular AKT signaling pathway in tissue engineering application. Biomater Sci. 2015;3:250.
Sargeant TD, Aparicio C, Goldberger JE, Cui H, Stupp SI. Mineralization of peptide amphiphile nanofibers and its effect on the differentiation of human mesenchymal stem cells. Acta Biomater. 2012;8:2456.
Fan K, Yang J, Wang X, Song J. Rational construction of gel-based supramolecular logic gates by using a functional gelator with multiple-stimuli responsive properties. Soft Matter. 2014;10:8370.
Heilemann M, Margeat E, Kasper R, Sauer M, Tinnefeld P. Carbocyanine dyes as efficient reversible single-molecule optical switch. J Am Chem Soc. 2005;127:3801.
Khan M, Brunklaus G, Enkelmann V, Spiess H-W. Transient states in [2 + 2] photodimerization of cinnamic acid: correlation of solid-state NMR and X-ray analysis. J Am Chem Soc. 2008;130:1741.
Jiang H, Jiang Y, Han J, Zhang L, Liu M. Helical nanostructures: chirality transfer and a photodriven transformation from superhelix to nanokebab. Angew Chem Int Ed. 2019;58:785.
Liu JY, Yuan F, Ma XY, Auphedeous DIY, Zhao CL, Liu CT, Shen CY, Feng CL. The cooperative effect of both molecular and supramolecular chirality on cell adhesion. Angew Chem Int Ed. 2018;57:6475.
Jiang K, Zhang L, Hu Q, Zhang Q, Lin W, Cui Y, Yang Y, Qian G. Thermal stimuli-triggered drug release from a biocompatible porous metal–organic framework. Chem Eur J. 2017;23:10215.
Miura H, Takahashi S, Kasai H, Okada S, Yase K, Oikawa H, Nakanishi H. Fabrication of nanocrystals from diolefin derivatives and their solid-state photoreaction behavior. Cryst Growth Des. 2010;10:510.
Das D, Dasgupta A, Roy S, Mitra RN, Debnath S, Das PK. Water gelation of an amino acid-based amphiphile. Chem Eur J. 2006;12:5068.
Gratzer WB, Holzwarth GM, Doty P. Polarization of the ultraviolet absorption bands in α-helical polypeptides. Proc Natl Acad Sci U S A. 1961;47:1785.
Sato H, Yajima T, Yamagishi A. Helical inversion of gel fibrils by elongation of perfluoroalkyl chains as studied by vibrational circular dichroism. Chirality. 2016;28:361.
Dong Y, Xu B, Zhang J, Tan X, Wang L, Chen J, Lv H, Wen S, Li B, Ye L, Zou B, Tian W. Piezochromic luminescence based on the molecular aggregation of 9,10-Bis((E)-2-(pyrid-2-yl)vinyl)anthracene. Angew Chem Int Ed. 2012;51:10782.
Choudhury P, Mandal D, Brahmachari S, Das PK. Hydrophobic end-modulated amino-acid-based neutral hydrogelators: structure-specific inclusion of carbon nanomaterials. Chem Eur J. 2016;22:5160.
Wang X, Duan P, Liu M. Organogelation-controlled topochemical [2 + 2] cycloaddition and morphological changes: from nanofiber to peculiar coaxial hollow toruloid-like nanostructures. Chem Eur J. 2013;19:16072.
Liu L, Zhang L, Wang T, Liu M. Interfacial assembly of amphiphilic styrylquinoxalines: alkyl chain length tunable topochemical reactions and supramolecular chirality. Phys Chem Chem Phys. 2013;15:6243.
Zhao Y, Zhao J, Yan Y, Li Z, Huang J. Unprecedented parallel packing of unsymmetrical bolaamphiphiles driven by π–π stacking of cinnamoyl groups. Soft Matter. 2010;6:3282.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (NSFC 51833006), the Innovation Program of Shanghai Municipal Education Commission (201701070002E00061), start-up fund of Henan University for funding to J. Y. Liu (CX3050A0920135), and Program for Professors of Special Appointment (Eastern Scholar) at the Shanghai Institutions of Higher Learning.
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interests.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Peng, T., Dang-i, A.Y., Liu, J. et al. [2 + 2] Photocycloaddition Reaction Regulated the Stability and Morphology of Hydrogels. Adv. Fiber Mater. 1, 241–247 (2019). https://doi.org/10.1007/s42765-019-00014-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s42765-019-00014-x