Vibrational Study on Structure and Bioactivity of Protein Fibers Grafted with Phosphorylated Methacrylates

In the last decades, silk fibroin and wool keratin have been considered functional materials for biomedical applications. In this study, fabrics containing silk fibers from <i>Bombyx mori</i> and Tussah silk fibers from <i>Antheraea pernyi</i>, as well as wool keratin fabrics...

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Autores principales: Michele Di Foggia, Masuhiro Tsukada, Paola Taddei
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Publicado: MDPI AG 2021
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spelling oai:doaj.org-article:face50b3e4c948558c599bac74d0dc6d2021-11-11T18:29:11ZVibrational Study on Structure and Bioactivity of Protein Fibers Grafted with Phosphorylated Methacrylates10.3390/molecules262164871420-3049https://doaj.org/article/face50b3e4c948558c599bac74d0dc6d2021-10-01T00:00:00Zhttps://www.mdpi.com/1420-3049/26/21/6487https://doaj.org/toc/1420-3049In the last decades, silk fibroin and wool keratin have been considered functional materials for biomedical applications. In this study, fabrics containing silk fibers from <i>Bombyx mori</i> and Tussah silk fibers from <i>Antheraea pernyi</i>, as well as wool keratin fabrics, were grafted with phosmer CL and phosmer M (commercial names, i.e., methacrylate monomers containing phosphate groups in the molecular side chain) with different weight gains. Both phosmers were recently proposed as flame retarding agents, and their chemical composition suggested a possible application in bone tissue engineering. IR and Raman spectroscopy were used to disclose the possible structural changes induced by grafting and identify the most reactive amino acids towards the phosmers. The same techniques were used to investigate the nucleation of a calcium phosphate phase on the surface of the samples (i.e., bioactivity) after ageing in simulated body fluid (SBF). The phosmers were found to polymerize onto the biopolymers efficiently, and tyrosine and serine underwent phosphorylation (monitored through the strengthening of the Raman band at 1600 cm<sup>−1</sup> and the weakening of the Raman band at 1400 cm<sup>−1</sup>, respectively). In grafted wool keratin, cysteic acid and other oxidation products of disulphide bridges were detected together with sulphated residues. Only slight conformational changes were observed upon grafting, generally towards an enrichment in ordered domains, suggesting that the amorphous regions were more prone to react (and, sometimes, degrade). All samples were shown to be bioactive, with a weight gain of up to 8%. The most bioactive samples contained the highest phosmers amounts, i.e., the highest amounts of phosphate nucleating sites. The sulphate/sulphonate groups present in grafted wool samples appeared to increase bioactivity, as shown by the five-fold increase of the IR phosphate band at 1040 cm<sup>−1</sup>.Michele Di FoggiaMasuhiro TsukadaPaola TaddeiMDPI AGarticlesilk fibroin<i>Bombyx mori</i>Tussahwool keratingraftingphosmerOrganic chemistryQD241-441ENMolecules, Vol 26, Iss 6487, p 6487 (2021)
institution DOAJ
collection DOAJ
language EN
topic silk fibroin
<i>Bombyx mori</i>
Tussah
wool keratin
grafting
phosmer
Organic chemistry
QD241-441
spellingShingle silk fibroin
<i>Bombyx mori</i>
Tussah
wool keratin
grafting
phosmer
Organic chemistry
QD241-441
Michele Di Foggia
Masuhiro Tsukada
Paola Taddei
Vibrational Study on Structure and Bioactivity of Protein Fibers Grafted with Phosphorylated Methacrylates
description In the last decades, silk fibroin and wool keratin have been considered functional materials for biomedical applications. In this study, fabrics containing silk fibers from <i>Bombyx mori</i> and Tussah silk fibers from <i>Antheraea pernyi</i>, as well as wool keratin fabrics, were grafted with phosmer CL and phosmer M (commercial names, i.e., methacrylate monomers containing phosphate groups in the molecular side chain) with different weight gains. Both phosmers were recently proposed as flame retarding agents, and their chemical composition suggested a possible application in bone tissue engineering. IR and Raman spectroscopy were used to disclose the possible structural changes induced by grafting and identify the most reactive amino acids towards the phosmers. The same techniques were used to investigate the nucleation of a calcium phosphate phase on the surface of the samples (i.e., bioactivity) after ageing in simulated body fluid (SBF). The phosmers were found to polymerize onto the biopolymers efficiently, and tyrosine and serine underwent phosphorylation (monitored through the strengthening of the Raman band at 1600 cm<sup>−1</sup> and the weakening of the Raman band at 1400 cm<sup>−1</sup>, respectively). In grafted wool keratin, cysteic acid and other oxidation products of disulphide bridges were detected together with sulphated residues. Only slight conformational changes were observed upon grafting, generally towards an enrichment in ordered domains, suggesting that the amorphous regions were more prone to react (and, sometimes, degrade). All samples were shown to be bioactive, with a weight gain of up to 8%. The most bioactive samples contained the highest phosmers amounts, i.e., the highest amounts of phosphate nucleating sites. The sulphate/sulphonate groups present in grafted wool samples appeared to increase bioactivity, as shown by the five-fold increase of the IR phosphate band at 1040 cm<sup>−1</sup>.
format article
author Michele Di Foggia
Masuhiro Tsukada
Paola Taddei
author_facet Michele Di Foggia
Masuhiro Tsukada
Paola Taddei
author_sort Michele Di Foggia
title Vibrational Study on Structure and Bioactivity of Protein Fibers Grafted with Phosphorylated Methacrylates
title_short Vibrational Study on Structure and Bioactivity of Protein Fibers Grafted with Phosphorylated Methacrylates
title_full Vibrational Study on Structure and Bioactivity of Protein Fibers Grafted with Phosphorylated Methacrylates
title_fullStr Vibrational Study on Structure and Bioactivity of Protein Fibers Grafted with Phosphorylated Methacrylates
title_full_unstemmed Vibrational Study on Structure and Bioactivity of Protein Fibers Grafted with Phosphorylated Methacrylates
title_sort vibrational study on structure and bioactivity of protein fibers grafted with phosphorylated methacrylates
publisher MDPI AG
publishDate 2021
url https://doaj.org/article/face50b3e4c948558c599bac74d0dc6d
work_keys_str_mv AT micheledifoggia vibrationalstudyonstructureandbioactivityofproteinfibersgraftedwithphosphorylatedmethacrylates
AT masuhirotsukada vibrationalstudyonstructureandbioactivityofproteinfibersgraftedwithphosphorylatedmethacrylates
AT paolataddei vibrationalstudyonstructureandbioactivityofproteinfibersgraftedwithphosphorylatedmethacrylates
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