PMID- 38101558 OWN - NLM STAT- MEDLINE DCOM- 20240102 LR - 20240106 IS - 1878-7568 (Electronic) IS - 1742-7061 (Linking) VI - 174 DP - 2024 Jan 15 TI - Liquid crystalline composite hydrogels with large pH-triggered anisotropic swelling for embolotherapy. PG - 206-216 LID - S1742-7061(23)00720-1 [pii] LID - 10.1016/j.actbio.2023.12.016 [doi] AB - Inspired by the anisotropic structure of biological tissues, anisotropic hydrogels have been developed using various nanofillers, however, it remains a big challenge to synthesize hydrogels with large swelling anisotropy. Herein a single molecule filler, alpha-helical polypeptide, instead of nanoscale fillers, was used to synthesize anisotropic hydrogels. First nematic liquid crystal of poly(gamma-benzyl l-glutamate) (PBLG) was prepared by shearing and stabilized by embedding in a crosslinked polymer matrix. The resulting PBLG composite gels were then converted to poly(L-glutamic acid) (PLGA) composite gels by debenzylation. The rigid rod-like structure of alpha-helical PBLG chains makes them easy to be orientated. The pH-sensitivity of PLGA makes the resulting composite gels pH-sensitive without the need to couple with a stimuli-responsive hydrogel matrix. In response to pH change PLGA composite gels swell anisotropically with a much larger swelling degree in the radial direction than in the axial direction. The swelling anisotropy (3.43) is much higher than most anisotropic hydrogels, particularly the stimuli-responsive ones reported previously. The composite gel also exhibits anisotropic mechanical properties with a larger Young's modulus in the axial direction than that in the radial direction. Preliminary test demonstrated that the composite gels have potential in embolotherapy thanks to its large pH-triggered anisotropic swelling. STATEMENT OF SIGNIFICANCE: Anisotropic hydrogels have important biomedical applications. Introduction of oriented nanofillers has been demonstrated a popular and versatile method for their synthesis, however, it remains a big challenge to achieve large swelling anisotropy. Herein a single molecule filler, alpha-helical polypeptide, instead of nanoscale fillers, was used to synthesize anisotropic hydrogels. This filler can be easily oriented by shearing. More importantly, as single molecule filler, it can constrain the swelling of hydrogel matrix more effectively. Using this filler, a pH-sensitive hydrogel with large swelling anisotropy (3.43) was successfully synthesized. Thanks to its large pH-triggered anisotropic swelling the hydrogel was successfully used as embolic agent to occlude vessels. CI - Copyright (c) 2023 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved. FAU - Zhang, Yujie AU - Zhang Y AD - State Key Laboratory of Separation Membranes and Membrane Processes, School of Pharmaceutical Sciences, Tiangong University, Tianjin 300387, China. FAU - Luo, Ying AU - Luo Y AD - State Key Laboratory of Separation Membranes and Membrane Processes, School of Pharmaceutical Sciences, Tiangong University, Tianjin 300387, China. FAU - Gao, Sijia AU - Gao S AD - State Key Laboratory of Separation Membranes and Membrane Processes, School of Pharmaceutical Sciences, Tiangong University, Tianjin 300387, China. FAU - Zou, Lei AU - Zou L AD - State Key Laboratory of Separation Membranes and Membrane Processes, School of Pharmaceutical Sciences, Tiangong University, Tianjin 300387, China. FAU - Guan, Ying AU - Guan Y AD - Institute of Polymer Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China. Electronic address: yingguan@nankai.edu.cn. FAU - Zhang, Yongjun AU - Zhang Y AD - State Key Laboratory of Separation Membranes and Membrane Processes, School of Pharmaceutical Sciences, Tiangong University, Tianjin 300387, China; Cangzhou Institute of Tiangong University, Cangzhou 061000, China. Electronic address: zhangyj@tiangong.edu.cn. LA - eng PT - Journal Article DEP - 20231214 PL - England TA - Acta Biomater JT - Acta biomaterialia JID - 101233144 RN - 0 (Hydrogels) RN - 0 (Peptides) SB - IM MH - Hydrogels/chemistry MH - Anisotropy MH - *Liquid Crystals MH - *Embolization, Therapeutic MH - Hydrogen-Ion Concentration MH - Peptides OTO - NOTNLM OT - Anisotropic swelling OT - Embolotherapy OT - Hydrogels OT - Peptide OT - alpha-helix COIS- Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. EDAT- 2023/12/16 11:43 MHDA- 2024/01/02 11:45 CRDT- 2023/12/15 19:28 PHST- 2023/08/31 00:00 [received] PHST- 2023/12/07 00:00 [revised] PHST- 2023/12/07 00:00 [accepted] PHST- 2024/01/02 11:45 [medline] PHST- 2023/12/16 11:43 [pubmed] PHST- 2023/12/15 19:28 [entrez] AID - S1742-7061(23)00720-1 [pii] AID - 10.1016/j.actbio.2023.12.016 [doi] PST - ppublish SO - Acta Biomater. 2024 Jan 15;174:206-216. doi: 10.1016/j.actbio.2023.12.016. Epub 2023 Dec 14.