Citation: Li-Jun Wang, Kai-Xiang Yang, Qiang Zhou, Hai-Yang Yang, Jia-Qing He, Xing-Yuan Zhang. Rhodamine Mechanophore Functionalized Mechanochromic Double Network Hydrogels with High Sensitivity to Stress[J]. Chinese Journal of Polymer Science, ;2020, 38(1): 24-36. doi: 10.1007/s10118-019-2293-1 shu

Rhodamine Mechanophore Functionalized Mechanochromic Double Network Hydrogels with High Sensitivity to Stress

School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China

Corresponding author: Hai-Yang Yang, yhy@ustc.edu.cn Xing-Yuan Zhang, zxym@ustc.edu.cn
Received Date: 26 April 2019
Revised Date: 10 May 2019
Available Online: 24 July 2019

Mechanochromic hydrogels, a new class of stimuli-responsive soft materials, have potential applications in a number of fields such as damage reporting and stress/strain sensing. We prepared a novel mechanochromic hydrogel using a strategy that has been developed to prepare dual-network (DN) hydrogels. A hydrophobic rhodamine derivative (Rh mechanophore) was covalently incorporated into a first network as a cross-linker. This first network embedded with Rh mechanophore within the DN hydrogel was pre-stretched. This guaranteed that the stress could be transferred extensively to the Rh-crosslinked first network once the hydrogel was under an applied force. Interestingly, we found that the threshold stress required to activate the mechanochromism of the hydrogel was less than 200 kPa, and much less than those in previous reports. Moreover, because of the excellent sensitivity of the hydrogel to stress, the DN hydrogel exhibited reversible freezing-induced mechanochromism. Benefiting from the sensitivity of Rh mechanophore to both pH and force, the DN hydrogel showed pH-regulated mechanochromic behavior. Our experimental results indicate that the preparation strategy we used introduces sensitive mechanochromism into the hydrogel and preserves the advantageous mechanical properties of the DN hydrogel. These results will be beneficial to the design and preparation of mechanochromic hydrogels with high stress sensitivity, and foster their practical applications in a number of fields such as damage reporting and stress/strain sensing.
- Rhodamine mechanophore,
- Mechanochromic,
- Dual-network hydrogel,
- Freezing-induced mechanochromism,
- pH-regulated,
- Stress sensitivity
1. [1]
  Raphael, M. O.; Kinam, P.; Teruo, O. In Biomedical applications of hydrogels handbook. Springer, New York, NY, 2010, pp. 19−43.
2. [2]
  Ahn, S. K.; Kasi, R. M.; Kim, S. C.; Sharma, N.; Zhou, Y. X. Stimuli-responsive polymer gels. Soft Matter 2008, 4, 1151−1157. doi: 10.1039/b714376a
3. [3]
  Koetting, M. C.; Peters, J. T.; Steichen, S. D.; Peppas, N. A. Stimulus-responsive hydrogels: theory, modern advances, and applications. Mater. Sci. Eng. R 2015, 93, 1−49. doi: 10.1016/j.mser.2015.04.001
4. [4]
  Ryu, J. H.; Lee, Y.; Kong, W. H.; Kim, T. G.; Park, T. G.; Lee, H. Catechol-functionalized chitosan/pluronic hydrogels for tissue adhesives and hemostatic materials. Biomacromolecules 2011, 12, 2653−2659. doi: 10.1021/bm200464x
5. [5]
  Dai, H. J.; Chen, Q.; Qin, H. L.; Guan, Y.; Shen, D. Y.; Hua, Y. Q.; Tang, Y. L.; Xu, J. A temperature-responsive copolymer hydrogel in controlled drug delivery. Macromolecules 2006, 39, 6584−6589. doi: 10.1021/ma060486p
6. [6]
  Tomatsu, I.; Peng, K.; Kros, A. Photoresponsive hydrogels for biomedical applications. Adv. Drug. Deliver. Rev. 2011, 63, 1257−1266. doi: 10.1016/j.addr.2011.06.009
7. [7]
  Yang, Y. Q.; Guan, L.; Gao, G. H. Low-cost, rapidly responsive, controllable, and reversible photochromic hydrogel for display and storage. ACS Appl. Mater. Interfaces 2018, 10, 13975−13984. doi: 10.1021/acsami.8b00235
8. [8]
  Holten-Andersen, N.; Harrington, M. J.; Birkedal, H.; Lee, B. P.; Messersmith, P. B.; Lee, K. Y. C.; Waite, J. H. pH-induced metal-ligand cross-links inspired by mussel yield self-healing polymer networks with near-covalent elastic moduli. Proc. Natl. Acad. Sci. 2011, 108, 2651−2655. doi: 10.1073/pnas.1015862108
9. [9]
  Milani, A. H.; Fielding, L. A.; Greensmith, P.; Saunders, B. R.; Adlam, D. J.; Freemont, A. J.; Hoyland, J. A.; Hodson, N. W.; Elsawy, M. A.; Miller, A. F.; Ratcliffe, L. P. D.; Mykhaylyk, O. O.; Armes, S. P. Anisotropic pH-responsive hydrogels containing soft or hard rod-like particles assembled using low shear. Chem. Mater. 2017, 29, 3100−3110. doi: 10.1021/acs.chemmater.7b00110
10. [10]
  Xiang, T.; Lu, T.; Zhao, W. F.; Zhao, C. S. Ionic-strength responsive zwitterionic copolymer hydrogels with tunable swelling and adsorption behaviors. Langmuir 2019, 35, 1146−1155. doi: 10.1021/acs.langmuir.8b01719
11. [11]
  Xiang, T.; Lu, T.; Zhao, W. F.; Zhao, C. S. Ionic strength- and thermo-responsive polyethersulfone composite membranes with enhanced antifouling properties. New J. Chem. 2018, 42, 5323−5333. doi: 10.1039/C8NJ00039E
12. [12]
  Ilg, P. Stimuli-responsive hydrogels cross-linked by magnetic nanoparticles. Soft Matter 2013, 9, 3465−3468. doi: 10.1039/c3sm27809c
13. [13]
  Liu, Q.; Li, H.; Lam, K. Y. Optimization of deformable magnetic-sensitive hydrogel-based targeting system in suspension fluid for site-specific drug delivery. Mol. Pharm. 2018, 15, 4632−4642. doi: 10.1021/acs.molpharmaceut.8b00626
14. [14]
  Mo, A. G.; Wang, Y. P.; Liu, Y. K.; Zhou, W. F. Zhou, Q. Yasin, A.; Yang, H. Y. Enhanced viscosity of poly(acrylamide) solution in the presence of chromium citrate triggered by release of CO₂. Chinese J. Chem. Phys. 2018, 31, 117−122. doi: 10.1063/1674-0068/31/cjcp1706128
15. [15]
  Park, J.; Pramanick, S.; Park, D.; Yeo, J.; Lee, J.; Lee, H.; Kim, W. J. Therapeutic-gas-responsive hydrogel. Adv. Mater. 2017, 29, 1702859. doi: 10.1002/adma.201702859
16. [16]
  Huebsch, N.; Kearney, C. J.; Zhao, X.; Kim, J.; Cezar, C. A.; Suo, Z.; Mooney, D. J. Ultrasound-triggered disruption and self-healing of reversibly cross-linked hydrogels for drug delivery and enhanced chemotherapy. Proc. Natl. Acad. Sci. 2014, 111, 9762−9767. doi: 10.1073/pnas.1405469111
17. [17]
  Weng, G. S.; Thanneeru, S.; He, J. Dynamic coordination of Eu-iminodiacetate to control fluorochromic response of polymer hydrogels to multistimuli. Adv. Mater. 2018, 30, 1706526. doi: 10.1002/adma.201706526
18. [18]
  Chan, E. P.; Walish, J. J.; Urbas, A. M.; Thomas, E. L. Mechanochromic photonic gels. Adv. Mater. 2013, 25, 3934−3947. doi: 10.1002/adma.v25.29
19. [19]
  Yue, Y. F.; Kurokawa, T.; Haque, M. A.; Nakajima, T.; Nonoyama, T.; Li, X. F.; Kajiwara, I.; Gong, J. P. Mechano-actuated ultrafast full-colour switching in layered photonic hydrogels. Nat. Commun. 2014, 5, 4659. doi: 10.1038/ncomms5659
20. [20]
  Wang, X. Q.; Wang, C. F.; Zhou, Z. F.; Chen, S. Robust mechanochromic elastic one-dimensional photonic hydrogels for touch sensing and flexible displays. Adv. Optic. Mater. 2014, 2, 652−662. doi: 10.1002/adom.201300538
21. [21]
  Haque, M. A.; Kamita, G.; Kurokawa, T.; Tsujii, K.; Gong, J. P. Unidirectional alignment of lamellar bilayer in hydrogel: one-dimensional swelling, anisotropic modulus, and stress/strain tunable structural color. Adv. Mater. 2010, 22, 5110−5114. doi: 10.1002/adma.201002509
22. [22]
  Cellini, F.; Block, L.; Li, J.; Khapli, S.; Peterson, S. D.; Porfiri, M. Mechanochromic response of pyrene functionalized nanocomposite hydrogels. Sens. Actuators B 2016, 234, 510−520. doi: 10.1016/j.snb.2016.04.149
23. [23]
  Davis, D. A.; Hamilton, A.; Yang, J.; Cremar, L. D.; van Gough, D.; Potisek, S. L.; Ong, M. T.; Braun, P. V.; Martinez, T. J.; White, S. R.; Moore, J. S.; Sottos, N. R. Force-induced activation of covalent bonds in mechanoresponsive polymeric materials. Nature 2009, 459, 68−72. doi: 10.1038/nature07970
24. [24]
  Wang, Z.; Ma, Z.; Wang, Y.; Xu, Z.; Luo, Y.; Wei, Y.; Jia, X. A novel mechanochromic and photochromic polymer film: when rhodamine joins polyurethane. Adv. Mater. 2015, 27, 6469−6474. doi: 10.1002/adma.201503424
25. [25]
  Imato, K.; Kanehara, T.; Ohishi, T.; Nishihara, M.; Yajima, H.; Ito, M.; Takahara, A.; Otsuka, H. Mechanochromic dynamic covalent elastomers: quantitative stress evaluation and autonomous recovery. ACS Macro Lett. 2015, 4, 1307−1311. doi: 10.1021/acsmacrolett.5b00717
26. [26]
  Verstraeten, F.; Gostl, R.; Sijbesma, R. P. Stress-induced colouration and crosslinking of polymeric materials by mechanochemical formation of triphenylimidazolyl radicals. Chem. Commun. 2016, 52, 8608−8611. doi: 10.1039/C6CC04312G
27. [27]
  Chen, H.; Yang, F.; Chen, Q.; Zheng, J. A novel design of multi-mechanoresponsive and mechanically strong hydrogels. Adv. Mater. 2017, 29, 1606900. doi: 10.1002/adma.201606900
28. [28]
  Wang, L.; Zhou, W.; Tang, Q.; Yang, H.; Zhou, Q.; Zhang, X. Rhodamine-functionalized mechanochromic and mechanofluorescent hydrogels with enhanced mechanoresponsive sensitivity. Polymers 2018, 10, 994. doi: 10.3390/polym10090994
29. [29]
  Wang, T.; Zhang, N.; Dai, J.; Li, Z.; Bai, W.; Bai, R. Novel reversible mechanochromic elastomer with high sensitivity: bond scission and bending-induced multicolor switching. ACS Appl. Mater. Interfaces 2017, 9, 11874−11881. doi: 10.1021/acsami.7b00176
30. [30]
  Woodcock, J. W.; Beams, R.; Davis, C. S.; Chen, N.; Stranick, S. J.; Shah, D. U.; Vollrath, F.; Gilman, J. W. Observation of interfacial damage in a silk-epoxy composite, using a simple mechanoresponsive fluorescent probe. Adv. Mater. Interfaces 2017, 4, 1601018. doi: 10.1002/admi.201601018
31. [31]
  Ducrot, E.; Chen, Y.; Bulters, M.; Sijbesma, R. P.; Creton, C. Toughening elastomers with sacrificial bonds and watching them break. Science 2014, 344, 186−189. doi: 10.1126/science.1248494
32. [32]
  Nakajima, T.; Sato, H.; Zhao, Y.; Kawahara, S.; Kurokawa, T.; Sugahara, K.; Gong, J. P. A universal molecular stent method to toughen any hydrogels based on double network concept. Adv. Funct. Mater. 2012, 22, 4426−4432. doi: 10.1002/adfm.v22.21
33. [33]
  Gong, J. P. Why are double network hydrogels so tough? Soft Matter 2010, 6, 2583−2590. doi: 10.1039/b924290b
34. [34]
  Li, Z.; Wu, S.; Han, J.; Han, S. Imaging of intracellular acidic compartments with a sensitive rhodamine based fluorogenic pH sensor. Analyst 2011, 136, 3698−3706. doi: 10.1039/c1an15108h
35. [35]
  Zhang, W.; Tang, B.; Liu, X.; Liu, Y.; Xu, K.; Ma, J.; Tong, L.; Yang, G. A highly sensitive acidic pH fluorescent probe and its application to HepG2 cells. Analyst 2009, 134, 367−371. doi: 10.1039/B807581F
36. [36]
  Matsuda, T.; Nakajima, T.; Fukuda, Y.; Hong, W.; Sakai, T.; Kurokawa, T.; Chung, U. I.; Gong, J. P. Yielding criteria of double network hydrogels. Macromolecules 2016, 49, 1865−1872. doi: 10.1021/acs.macromol.5b02592
37. [37]
  Liu, X. X.; Tong, Z.; Hu, O. Swelling equilibria of hydrogels with sulfonate groups in water and in aqueous salt-solutions. Macromolecules 1995, 28, 3813−3817. doi: 10.1021/ma00115a010
38. [38]
  Beiermann, B. A.; Kramer, S. L. B.; May, P. A.; Moore, J. S.; White, S. R.; Sottos, N. R. The effect of polymer chain alignment and relaxation on force-induced chemical reactions in an elastomer. Adv. Funct. Mater. 2014, 24, 1529−1537. doi: 10.1002/adfm.v24.11
39. [39]
  Kato, S.; Ishizuki, K.; Aoki, D.; Goseki, R.; Otsuka, H. Freezing-induced mechanoluminescence of polymer gels. ACS Macro Lett. 2018, 7, 1087−1091. doi: 10.1021/acsmacrolett.8b00521
40. [40]
  Imato, K.; Irie, A.; Kosuge, T.; Ohishi, T.; Nishihara, M.; Takahara, A.; Otsuka, H. Mechanophores with a reversible radical system and freezing-induced mechanochemistry in polymer solutions and gels. Angew. Chem. Int. Ed. 2015, 54, 6168−6172. doi: 10.1002/anie.201412413
41. [41]
  Li, M.; Zhang, Q.; Zhu, S. Photo-inactive divinyl spiropyran mechanophore cross-linker for real-time stress sensing. Polymer 2016, 99, 521−528. doi: 10.1016/j.polymer.2016.07.057
1. [1]
  Yanbing Shen , Yuan Yuan , Yaxin Wang , Xiaonan Ma , Wensheng Yang , Yulan Chen . Dihydroanthracene bridged bis-naphthopyrans: A multimodal chromophore with mechano- and photo-chromic properties. Chinese Chemical Letters, 2024, 35(5): 108949-. doi: 10.1016/j.cclet.2023.108949
2. [2]
  Qinwen Zheng , Xin Liu , Lintao Tian , Yi Zhou , Libing Liao , Guocheng Lv . Mechanism of Fenton catalytic degradation of Rhodamine B induced by microwave and Fe₃O₄. Chinese Chemical Letters, 2025, 36(4): 109771-. doi: 10.1016/j.cclet.2024.109771
3. [3]
  Di ZHANG , Tianxiang XIE , Xu HE , Wanyu WEI , Qi FAN , Jie QIAO , Gang JIN , Ningbo LI . Construction and antitumor activity of pH/GSH dual-responsive magnetic nanodrug. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 786-796. doi: 10.11862/CJIC.20240329
4. [4]
  Jianye Kang , Xinyu Yang , Xuhao Yang , Jiahui Sun , Yuhang Liu , Shutao Wang , Wenlong Song . Carbon dots-enhanced pH-responsive lubricating hydrogel based on reversible dynamic covalent bondings. Chinese Chemical Letters, 2024, 35(5): 109297-. doi: 10.1016/j.cclet.2023.109297
5. [5]
  Rui Wang , He Qi , Haijiao Zheng , Qiong Jia . Light/pH dual-responsive magnetic metal-organic frameworks composites for phosphorylated peptide enrichment. Chinese Chemical Letters, 2024, 35(7): 109215-. doi: 10.1016/j.cclet.2023.109215
6. [6]
  Yuan CONG , Yunhao WANG , Wanping LI , Zhicheng ZHANG , Shuo LIU , Huiyuan GUO , Hongyu YUAN , Zhiping ZHOU . Construction and photocatalytic properties toward rhodamine B of CdS/Fe₃O₄ heterojunction. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2241-2249. doi: 10.11862/CJIC.20240219
7. [7]
  Chuyu Huang , Zhishan Liu , Linping Zhao , Zuxiao Chen , Rongrong Zheng , Xiaona Rao , Yuxuan Wei , Xin Chen , Shiying Li . Metal-coordinated oxidative stress amplifier to suppress tumor growth combined with M2 macrophage elimination. Chinese Chemical Letters, 2024, 35(12): 109696-. doi: 10.1016/j.cclet.2024.109696
8. [8]
  Zhong-Hui Sun , Yu-Qi Zhang , Zhen-Yi Gu , Dong-Yang Qu , Hong-Yu Guan , Xing-Long Wu . CoPSe nanoparticles confined in nitrogen-doped dual carbon network towards high-performance lithium/potassium ion batteries. Chinese Chemical Letters, 2025, 36(1): 109590-. doi: 10.1016/j.cclet.2024.109590
9. [9]
  Xiangdong Lai , Tengfei Liu , Zengchao Guo , Yihan Wang , Jiang Xiao , Qingxiu Xia , Xiaohui Liu , Hui Jiang , Xuemei Wang . In situ formed fluorescent gold nanoclusters inhibit hair follicle regeneration in oxidative stress microenvironment via suppressing NFκB signal pathway. Chinese Chemical Letters, 2025, 36(2): 109762-. doi: 10.1016/j.cclet.2024.109762
10. [10]
  Ruru Li , Qian Liu , Hui Li , Fengbin Sun , Zhurui Shen . Rational design of dual sites induced local electron rearrangement for enhanced photocatalytic oxygen activation. Chinese Chemical Letters, 2024, 35(11): 109679-. doi: 10.1016/j.cclet.2024.109679
11. [11]
  Weijian Zhang , Xianyu Deng , Liying Wang , Jian Wang , Xiuting Guo , Lianggui Huang , Xinyi Wang , Jun Wu , Linjia Jiang . Poly(ferulic acid) nanocarrier enhances chemotherapy sensitivity of acute myeloid leukemia by selectively targeting inflammatory macrophages. Chinese Chemical Letters, 2024, 35(9): 109422-. doi: 10.1016/j.cclet.2023.109422
12. [12]
  Lan Yang , Yu Li , Mou Jiang , Rui Zhou , Hengjiang Cong , Minghui Yang , Lei Zhang , Shenhui Li , Yunhuang Yang , Maili Liu , Xin Zhou , Zhong-Xing Jiang , Shizhen Chen . Fluorinated [2]rotaxanes as sensitive ¹⁹F MRI agents: Threading for higher sensitivity. Chinese Chemical Letters, 2024, 35(10): 109512-. doi: 10.1016/j.cclet.2024.109512
13. [13]
  Junmei FAN , Wei LIU , Ruitao ZHU , Chenxi QIN , Xiaoling LEI , Haotian WANG , Jiao WANG , Hongfei HAN . High sensitivity detection of baicalein by N, S co-doped carbon dots and their application in biofluids. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 2009-2020. doi: 10.11862/CJIC.20240120
14. [14]
  Huihui LIU , Baichuan ZHAO , Chuanhui WANG , Zhi WANG , Congyun ZHANG . Green synthesis of MIL-101/Au composite particles and their sensitivity to Raman detection of thiram. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 2021-2030. doi: 10.11862/CJIC.20240059
15. [15]
  Shangda Qu , Yiming Yuan , Xu Ye , Wentao Xu . High sensitivity artificial synapses using printed high-transmittance ITO fibers for neuromorphic computing. Chinese Chemical Letters, 2024, 35(12): 110030-. doi: 10.1016/j.cclet.2024.110030
16. [16]
  Zhenfei Tang , Yunwu Zhang , Zhiyuan Yang , Haifeng Yuan , Tong Wu , Yue Li , Guixiang Zhang , Xingzhi Wang , Bin Chang , Dehui Sun , Hong Liu , Lili Zhao , Weijia Zhou . Iron-doping regulated light absorption and active sites in LiTaO₃ single crystal for photocatalytic nitrogen reduction. Chinese Chemical Letters, 2025, 36(3): 110107-. doi: 10.1016/j.cclet.2024.110107
17. [17]
  Xiaxia LIU , Xiaofang MA , Luxia GUO , Xianda HAN , Sisi FENG . Structure and magnetic properties of Mn(Ⅱ) coordination polymers regulated by N-auxiliary ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 587-596. doi: 10.11862/CJIC.20240269
18. [18]
  Kangmin Wang , Liqiu Wan , Jingyu Wang , Chunlin Zhou , Ke Yang , Liang Zhou , Bijin Li . Multifunctional 2-(2′-hydroxyphenyl)benzoxazoles: Ready synthesis, mechanochromism, fluorescence imaging, and OLEDs. Chinese Chemical Letters, 2024, 35(10): 109554-. doi: 10.1016/j.cclet.2024.109554
19. [19]
  Lei Shen , Hongmei Liu , Ming Jin , Jinchao Zhang , Caixia Yin , Shuxiang Wang , Yutao Yang . “Three-in-one” strategy of trifluoromethyl regulated blood-brain barrier permeable fluorescent probe for peroxynitrite and antiepileptic evaluation of edaravone. Chinese Chemical Letters, 2024, 35(10): 109572-. doi: 10.1016/j.cclet.2024.109572
20. [20]
  Xi Chen , Xue Zhang , Shuai Yang , Jie Wang , Tian Tang , Maling Gou . An adhesive hydrogel for the treatment of oral ulcers. Chinese Chemical Letters, 2025, 36(3): 110021-. doi: 10.1016/j.cclet.2024.110021

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(808)
HTML views(10)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142