Chemically triggered life control of “smart” hydrogels through click and declick reactions

doi:10.1007/s11705-022-2149-z

Front. Chem. Sci. Eng.

2022, Vol. 16

Issue (9) : 1399-1406 https://doi.org/10.1007/s11705-022-2149-z

COMMUNICATION

Chemically triggered life control of “smart” hydrogels through click and declick reactions

Xing Feng¹, Meiqing Du¹, Hongbei Wei¹, Xiaoxiao Ruan¹, Tao Fu¹, Jie Zhang²(

), Xiaolong Sun¹(

)

¹. Key Laboratory of Biomedical Information Engineering of Ministry of Education, School of Life Science and Technology, Xi’an Jiaotong University, Xi’an 710049, China
². The Fourth Military Medical University, Xi’an 710032, China

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Abstract

The degradation of polymeric materials is recognized as one of the goals to be fulfilled for the sustainable economy. In this study, a novel methodology was presented to synthesize multiple highly cross-linked polymers (i.e., hydrogels) through amine–thiol scrambling under mild conditions. Amine-terminated poly(ethylene glycol) (PEG-NH₂) was reacted with the representative conjugate acceptors to synthesize hydrogels in organic and aqueous solutions, respectively. The materials above exhibited high water-swelling properties, distributed porous structures, as well as prominent mechanical strengths. It is noteworthy that the mentioned hydrogels could be degraded efficiently in hours to release the original coupling partner, which were induced by ethylene diamine at ambient temperature through amine-amine metathesis. The recovered PEG-NH₂ reagent could be employed again to regenerate hydrogels. Due to the multiple architectures and functions in polymeric synthesis, degradation and regeneration, a new generation of “smart” materials is revealed.

Keywords hydrogels degradation synthesis regeneration

Corresponding Author(s): Jie Zhang,Xiaolong Sun

About author:

Tongcan Cui and Yizhe Hou contributed equally to this work.

Online First Date: 22 April 2022 Issue Date: 20 September 2022

Cite this article:

Xing Feng,Meiqing Du,Hongbei Wei, et al. Chemically triggered life control of “smart” hydrogels through click and declick reactions[J]. Front. Chem. Sci. Eng., 2022, 16(9): 1399-1406.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2149-z
https://academic.hep.com.cn/fcse/EN/Y2022/V16/I9/1399

Fig.1 Recycling of soft materials through “amine–thiol coupling and amine–amine decoupling” reactions: materials of synthesis through the reactions between CAs 1, 2, 3 and 4-PEG amine 4 with releasing methyl mercaptan (CH₃SH); EDA-induced decoupling to release the original amine partner 4 and five-membered ring product 5, 6, 7. The recyclable monomer was employed again to regenerate soft materials.

Fig.2 (a) Formation of A-1, -2, -3 in acetonitrile; (b) Swelling properties for A-1, -2, -3 in water, size changes and swelling ratios; (c) SEM images for A-1, -2, -3. M = 15 k; (d) Raman spectra for A-1, -2, -3; (e) Storage modulus (G') and loss modulus (G'') for swelled A-1, -2, -3; (f) Stress-strain tension test for swelled A-1, -2, -3; (g) Maximum force, tensile strength and elastic modulus test for swelled A-1, -2, -3.

Fig.3 (a) Hydrogel formation for W-1, -2, -3 in water (10% acetonitrile as co-solvent) over time; (b) Swelling properties of W-1, -2 and -3 in water, size changes and swelling ratios; (c) SEM images of W-1, -2 and -3 after the swelling and the lyophilization. M = 15 k; (d) Raman spectra for W-1, -2 and -3; (e) Storage modulus (G') and loss modulus (G'') for W-1, -2 and -3 after the swelling; (f) Stress-strain tension test for W-1, -2 and -3 after the swelling; (g) Maximal force, tensile strength and elastic modulus test for the swelled samples of W-1, -2 and 3.

Tab.1 Comparison of hydrogels properties

Fig.4 (a) Degradation of all materials by EDA (Initial status of materials (left dishes); residue of materials after degradation for a certain amount of time (middle dishes); clear solutions after complete degradation (right dishes)); (b) Kinetics of degradation for all materials in EDA through measuring weight.

Fig.5 (a) Proton NMR for started and recycled 4-PEG amine in CDCl₃; (b) GPC for started and recycled 4-PEG amine in DMF; (c) Storage modulus (G') and loss modulus (G'') for ReA-1, -2, -3 after the swelling in the mode of time scan. Inset photos: regeneration of materials by using recycled 4-PEG amine in acetonitrile.

Tab.2 Comparison of properties of A-1, -2, -3 and ReA-1, -2, -3

1	X Liu, J Liu, S Lin, X Zhao. Hydrogel machines. Materials Today, 2020, 36( 25): 102– 124 https://doi.org/10.1016/j.mattod.2019.12.026
2	L A Hockaday, K H Kang, N W Colangelo, P Y Cheung, B Duan, E Malone, J Wu, L N Girardi, L J Bonassar, H Lipson. et al.. Rapid 3D printing of anatomically accurate and mechanically heterogeneous aortic valve hydrogel scaffolds. Biofabrication, 2012, 4( 3): 035005– 035017 https://doi.org/10.1088/1758-5082/4/3/035005
3	S J Buwalda, K W Boere, P J Dijkstra, J Feijen, T Vermonden, W E Hennink. Hydrogels in a historical perspective: from simple networks to smart materials. Journal of Controlled Release, 2014, 190( 21): 254– 273 https://doi.org/10.1016/j.jconrel.2014.03.052
4	A Perez-San Vicente, M Peroglio, M Ernst, P Casuso, I Loinaz, H J Grande, M Alini, D Eglin, D Dupin. Self-healing dynamic hydrogel as injectable shock-absorbing artificial nucleus pulposus. Biomacromolecules, 2017, 18( 8): 2360– 2370 https://doi.org/10.1021/acs.biomac.7b00566
5	H Cheng, K Yue, M Kazemzadeh-Narbat, Y Liu, A Khalilpour, B Li, Y S Zhang, N Annabi, A Khademhosseini. Mussel-inspired multifunctional hydrogel coating for prevention of infections and enhanced osteogenesis. ACS Applied Materials & Interfaces, 2017, 9( 13): 11428– 11439 https://doi.org/10.1021/acsami.6b16779
6	X Zhao, H Wu, B Guo, R Dong, Y Qiu, P X Ma. Antibacterial anti-oxidant electroactive injectable hydrogel as self-healing wound dressing with hemostasis and adhesiveness for cutaneous wound healing. Biomaterials, 2017, 122( 4): 34– 47 https://doi.org/10.1016/j.biomaterials.2017.01.011
7	J Li, D J Mooney. Designing hydrogels for controlled drug delivery. Nature Reviews Materials, 2016, 1( 12): 1– 17 https://doi.org/10.1038/natrevmats.2016.71
8	M Choi, J W Choi, S Kim, S Nizamoglu, S K Hahn, S H Yun. Light-guiding hydrogels for cell-based sensing and optogenetic synthesis in vivo. Nature Photonics, 2013, 7( 12): 987– 994 https://doi.org/10.1038/nphoton.2013.278
9	L Xu, K Chen, G Q Chen, S E Kentish, G Li. Development of barium@alginate adsorbents for sulfate removal in lithium refining. Frontiers of Chemical Science and Engineering, 2020, 15( 1): 198– 207 https://doi.org/10.1007/s11705-020-1968-z
10	Y Huang, H Li, X He, X Yang, L Li, S Liu, Z Zou, K Wang, J Liu. Near-infrared photothermal release of hydrogen sulfide from nanocomposite hydrogels for anti-inflammation applications. Chinese Chemical Letters, 2020, 31( 3): 787– 791 https://doi.org/10.1016/j.cclet.2019.05.025
11	Y Guo, J Bae, Z Fang, P Li, F Zhao, G Yu. Hydrogels and hydrogel-derived materials for energy and water sustainability. Chemical Reviews, 2020, 120( 15): 7642– 7707 https://doi.org/10.1021/acs.chemrev.0c00345
12	M Choi, M Humar, S Kim, S H Yun. Step-index optical fiber made of biocompatible hydrogels. Advanced Materials, 2015, 27( 17): 4081– 4086 https://doi.org/10.1002/adma.201501603
13	D Yan, S Liu, Y G Jia, L Mo, D Qi, J Wang, Y Chen, L Ren. Responsive polypseudorotaxane hydrogels triggered by a compatible stimulus of CO2. Macromolecular Chemistry and Physics, 2019, 220( 12): 1900071– 1900076 https://doi.org/10.1002/macp.201900071
14	E Chalmers, Y Li, X Liu. Molecular tailoring to improve polypyrrole hydrogels’ stiffness and electrochemical energy storage capacity. Frontiers of Chemical Science and Engineering, 2019, 13( 4): 684– 694 https://doi.org/10.1007/s11705-019-1817-0
15	C Yang, Z Suo. Hydrogel ionotronics. Nature Reviews Materials, 2018, 3( 6): 125– 142 https://doi.org/10.1038/s41578-018-0018-7
16	H Arslan, A Nojoomi, J Jeon, K 3rd Yum. Printing of anisotropic hydrogels with bioinspired motion. Advancement of Science, 2019, 6( 2): 1800703– 1800711 https://doi.org/10.1002/advs.201800703
17	Y Gao, S Gu, F Jia, G Gao. A skin-matchable, recyclable and biofriendly strain sensor based on a hydrolyzed keratin-containing hydrogel. Journal of Materials Chemistry A, 2020, 8( 45): 24175– 24183 https://doi.org/10.1039/D0TA07883B
18	S Correa, A K Grosskopf, H Lopez Hernandez, D Chan, A C Yu, L M Stapleton, E A Appel. Translational applications of hydrogels. Chemical Reviews, 2021, 18( 14): 11385– 11457 https://doi.org/10.1021/acs.chemrev.0c01177
19	J Glowacki, S Mizuno. Collagen scaffolds for tissue engineering. Biopolymers, 2008, 89( 5): 338– 344 https://doi.org/10.1002/bip.20871
20	M A Haque, T Kurokawa, J P Gong. Super tough double network hydrogels and their application as biomaterials. Polymer, 2012, 53( 9): 1805– 1822 https://doi.org/10.1016/j.polymer.2012.03.013
21	Y Yue, X Wang, Q Wu, J Han, J Jiang. Highly recyclable and super-tough hydrogel mediated by dual-functional TiO2 nanoparticles toward efficient photodegradation of organic water pollutants. Journal of Colloid and Interface Science, 2020, 564( 5): 99– 112 https://doi.org/10.1016/j.jcis.2019.12.069
22	Y Liu, Q Sun, X Yang, J Liang, B Wang, A Koo, R Li, J Li, X Sun. High-performance and recyclable Al-air coin cells based on eco-friendly chitosan hydrogel membranes. ACS Applied Materials & Interfaces, 2018, 10( 23): 19730– 19738 https://doi.org/10.1021/acsami.8b04974
23	T Yuan, X Qu, X Cui, J Sun. Self-healing and recyclable hydrogels reinforced with in situ-formed organic nanofibrils exhibit simultaneously enhanced mechanical strength and stretchability. ACS Applied Materials & Interfaces, 2019, 11( 35): 32346– 32353 https://doi.org/10.1021/acsami.9b08208
24	A Chamas, H Moon, J Zheng, Y Qiu, T Tabassum, J H Jang, M Abu-Omar, S L Scott, S Suh. Degradation rates of plastics in the environment. ACS Sustainable Chemistry & Engineering, 2020, 8( 9): 3494– 3511 https://doi.org/10.1021/acssuschemeng.9b06635
25	V Delplace, J Nicolas. Degradable vinyl polymers for biomedical applications. Nature Chemistry, 2015, 7( 10): 771– 784 https://doi.org/10.1038/nchem.2343
26	A Ben Cheikh, J Chuche, N Manisse, J C Pommelet, K P Netsch, P Lorencak, C Wentrup. Synthesis of α-cyano carbonyl compounds by flash vacuum thermolysis of (alkylamino)methylene derivatives of meldrum’s acid. Evidence for facile 1,3-shifts of alkylamino and alkylthio groups in imidoylketene intermediates. Journal of Organic Chemistry, 1991, 56( 3): 970– 975 https://doi.org/10.1021/jo00003a014
27	K Sweidan, Q Abu-Salem, A Al-Sheikh, G Sheikha. Novel derivatives of 1,3-dimethyl-5-methylenebarbituric acid. Letters in Organic Chemistry, 2009, 6( 8): 669– 672 https://doi.org/10.2174/157017809790442934
28	B M El-Zaatari, J S A Ishibashi, J A Kalow. Cross-linker control of vitrimer flow. Polymer Chemistry, 2020, 11( 33): 5339– 5345 https://doi.org/10.1039/D0PY00233J
29	K L Diehl, I V Kolesnichenko, S A Robotham, J L Bachman, Y Zhong, J S Brodbelt, E V Anslyn. Click and chemically triggered declick reactions through reversible amine and thiol coupling via a conjugate acceptor. Nature Chemistry, 2016, 8( 10): 968– 973 https://doi.org/10.1038/nchem.2601
30	M K Meadows, X Sun, I V Kolesnichenko, C M Hinson, K A Johnson, E V Anslyn. Mechanistic studies of a “declick” reaction. Chemical Science (Cambridge), 2019, 10( 38): 8817– 8824 https://doi.org/10.1039/C9SC00690G
31	X Sun, M Chwatko, D H Lee, J L Bachman, J F Reuther, N A Lynd, E V Anslyn. Chemically triggered synthesis, remodeling, and degradation of soft materials. Journal of the American Chemical Society, 2020, 142( 8): 3913– 3922 https://doi.org/10.1021/jacs.9b12122
32	L Chang, C Wang, S Han, X Sun, F Xu. Chemically triggered hydrogel transformations through covalent adaptable networks and applications in cell culture. ACS Macro Letters, 2021, 10( 7): 901– 906 https://doi.org/10.1021/acsmacrolett.1c00276
33	T Wu, T Liang, W Hu, M Du, S Zhang, Y Zhang, E V Anslyn, X Sun. Chemically triggered click and declick reactions: application in synthesis and degradation of thermosetting plastics. ACS Macro Letters, 2021, 10( 9): 1125– 1131 https://doi.org/10.1021/acsmacrolett.1c00548
34	Y Fang, J Xu, F Gao, X Du, Z Du, X Cheng, H Wang. Self-healable and recyclable polyurethane-polyaniline hydrogel toward flexible strain sensor. Composites Part B: Engineering, 2021, 219( 22): 108965– 108974 https://doi.org/10.1016/j.compositesb.2021.108965

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