4.7 Review

Crosslinkers for polysaccharides and proteins: Synthesis conditions, mechanisms, and crosslinking efficiency, a review

Journal

INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
Volume 202, Issue -, Pages 558-596

Publisher

ELSEVIER
DOI: 10.1016/j.ijbiomac.2022.01.029

Keywords

Crosslinkers; Hydrogels; Polysaccharides; Proteins

Funding

  1. Sao Paulo Research Foundation (FAPESP) [2018/13492-2, 2019/22671-0, 2020/01907-3, 2020/05632-9, 2020/03248-7]
  2. Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq) [306848/2017, 421014/2018]
  3. Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior -Brasil (CAPES) [001, 88882.328247/2019-01]
  4. FNRS-Fonds de la Recherche Scientifique [R.M014.19, 35704283]

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Polysaccharides and proteins are essential macromolecules for biomedical hydrogels. Chemical hydrogels, which have chemical bonds mediated by crosslinkers, offer better chemical, mechanical, and dimensional stability compared to physical hydrogels. This review revisits the crosslinking reactions between synthetic or natural crosslinkers and polysaccharides or proteins. It discusses the mechanisms, evaluation methods, and challenges in creating safe chemical hydrogels for biomedical applications.
Polysaccharides and proteins are important macromolecules for developing hydrogels devoted to biomedical applications. Chemical hydrogels offer chemical, mechanical, and dimensional stability than physical hydrogels due to the chemical bonds among the chains mediated by crosslinkers. There are many crosslinkers to synthesize polysaccharides and proteins based on hydrogels. In this review, we revisited the crosslinking reaction mechanisms between synthetic or natural crosslinkers and polysaccharides or proteins. The selected synthetic cross linkers were glutaraldehyde, carbodiimide, boric acid, sodium trimetaphosphate, N,N'-methylene bisacrylamide, and polycarboxylic acid, whereas the selected natural crosslinkers included transglutaminase, tyrosinase, horseradish peroxidase, laccase, sortase A, genipin, vanillin, tannic acid, and phytic acid. No less important are the reactions involving click chemistry and the macromolecular crosslinkers for polysaccharides and proteins. Literature examples of polysaccharides or proteins crosslinked by the different strategies were presented along with the corresponding highlights. The general mechanism involved in chemical crosslinking mediated by gamma and UV radiation was discussed, with particular attention to materials commonly used in digital light processing. The evaluation of crosslinking efficiency by gravimetric measurements, rheology, and spectroscopic techniques was presented. Finally, we presented the challenges and opportunities to create safe chemical hydrogels for biomedical applications.

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