resumo
The formation of hydrogels by photosensitized oxidation and crosslinking of histidine-derived polymers is demonstrated for the first time. The photooxidation of pendant His mediated by singlet oxygen was used to promote covalent coupling by its dimerization. As a proof-of-concept, two systems were studied: (i) chondroitin sulfate (CS) functionalized with His, and (ii) an elastin-like peptide (ELP) containing His produced by recombinant techniques. Both materials were crosslinked by irradiation at 425 nm in the presence of Zn-porphyrin derivatives yielding His-based hydrogels. The molecular structure and physicochemical properties of ELP-His and other 5 ELPs with photooxidizable amino acids were studied in silica by computer simulation. A correlation between the protein conformation and its elastic properties is discussed. CS-His hydrogels demonstrate larger storage moduli than ELPs with other amino acids. The obtained results show the potential use of photooxidation to create a new type of His-based hydrogels.
palavras-chave
CROSS-LINKING; MECHANICAL-PROPERTIES; STABILITY; POLYMER; COMPOSITES; PROTEINS; DNA
categoria
Chemistry, Physical; Materials Science, Multidisciplinary; Physics, Multidisciplinary; Polymer Science
autores
Liberato, MS; Cavalcante, NGS; Sindu, PA; Rodrigues-Jesus, MJ; Zelenovskii, P; Carreira, ACO; Baptista, MS; Sogayar, MC; Ferreira, LCS; Catalani, LH
Grupos
agradecimentos
The work was funded by the Sao Paulo Research Foundation (FAPESP, grants 2018/13492-2, 2019/10789-7, 2019/08975-7). Part of this work was developed within the scope of project CICECO-Aveiro Institute of Materials (UIDB/50011/2020 & UIDP/50011/2020) financed by national funds through the FCT -Fundacao para a Ciencia e a Tecnologia, I.P. (Portugal). Authors are grateful to Prof. Cristiano L. P. Oliveira and Ms Arnaldo G. de Oliveira Filho for their help with SAXS measurements and interpretation, and to Prof. Fabiana A. Perrechil for the rheology measurements.