An Alternative Approach to the Surface Methacrylation of Non-stoichiometric Hydroxyapatite Nanoparticles for Use in Bone-Inspired Composites

Modification of the inorganic particle surface is one approach toward enhancing the mechanical and swelling properties of a bone-inspired composite. In this study we sought to manipulate the surface of non-stoichiometric nHA particles by utilizing a gentler methacrylation approach with two different...

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Main Authors: Patricia A. Comeau, Thomas Willett
Format: Article
Language:English
Published: Frontiers Media S.A. 2019-10-01
Series:Frontiers in Materials
Subjects:
Online Access:https://www.frontiersin.org/article/10.3389/fmats.2019.00263/full
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author Patricia A. Comeau
Thomas Willett
author_facet Patricia A. Comeau
Thomas Willett
author_sort Patricia A. Comeau
collection DOAJ
description Modification of the inorganic particle surface is one approach toward enhancing the mechanical and swelling properties of a bone-inspired composite. In this study we sought to manipulate the surface of non-stoichiometric nHA particles by utilizing a gentler methacrylation approach with two different methacrylates—methacrylic anhydride (MAh) and glycidyl methacrylate (GMA). While silanization of nHA (Si-nHA) is a recognized functionalization approach, one notable disadvantage is the need for relatively harsh reaction conditions. Here, ATR-FTIR and liquid state 13C-NMR provided evidence for a stronger affinity of the nHA surface for methacrylic anhydride compared to glycidyl methacrylate under the same reaction conditions; fewer GMA molecules reacted with the nHA surface. However, the affinity of MAh is more electrostatic in nature, whereas GMA attachment involves some covalent bond formation. In addition, while in water, there was no detectable dependence of particle settling on methacrylate choice, in ethanol, native nHA and nHA methacrylated with GMA each had detectably greater stability in suspension than the other sample groups. Lastly, the addition of GMA-nHA detectably increased the dynamic stiffness and did not impact the swelling in 37°C water of a GelMA-based composite compared to that observed upon adding native nHA. Overall, the GMA-based methacrylation approach was found to be a viable alternative to silanization and offers possibilities for future fabrication of bone-inspired composites.
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spelling doaj.art-be77b8b947434487af8b3abdd76cb6ab2022-12-21T17:18:04ZengFrontiers Media S.A.Frontiers in Materials2296-80162019-10-01610.3389/fmats.2019.00263481864An Alternative Approach to the Surface Methacrylation of Non-stoichiometric Hydroxyapatite Nanoparticles for Use in Bone-Inspired CompositesPatricia A. ComeauThomas WillettModification of the inorganic particle surface is one approach toward enhancing the mechanical and swelling properties of a bone-inspired composite. In this study we sought to manipulate the surface of non-stoichiometric nHA particles by utilizing a gentler methacrylation approach with two different methacrylates—methacrylic anhydride (MAh) and glycidyl methacrylate (GMA). While silanization of nHA (Si-nHA) is a recognized functionalization approach, one notable disadvantage is the need for relatively harsh reaction conditions. Here, ATR-FTIR and liquid state 13C-NMR provided evidence for a stronger affinity of the nHA surface for methacrylic anhydride compared to glycidyl methacrylate under the same reaction conditions; fewer GMA molecules reacted with the nHA surface. However, the affinity of MAh is more electrostatic in nature, whereas GMA attachment involves some covalent bond formation. In addition, while in water, there was no detectable dependence of particle settling on methacrylate choice, in ethanol, native nHA and nHA methacrylated with GMA each had detectably greater stability in suspension than the other sample groups. Lastly, the addition of GMA-nHA detectably increased the dynamic stiffness and did not impact the swelling in 37°C water of a GelMA-based composite compared to that observed upon adding native nHA. Overall, the GMA-based methacrylation approach was found to be a viable alternative to silanization and offers possibilities for future fabrication of bone-inspired composites.https://www.frontiersin.org/article/10.3389/fmats.2019.00263/fullnano-hydroxyapatitemethacrylationmethacrylic anhydrideglycidyl methacrylatesurface functionalizationnanocomposite
spellingShingle Patricia A. Comeau
Thomas Willett
An Alternative Approach to the Surface Methacrylation of Non-stoichiometric Hydroxyapatite Nanoparticles for Use in Bone-Inspired Composites
Frontiers in Materials
nano-hydroxyapatite
methacrylation
methacrylic anhydride
glycidyl methacrylate
surface functionalization
nanocomposite
title An Alternative Approach to the Surface Methacrylation of Non-stoichiometric Hydroxyapatite Nanoparticles for Use in Bone-Inspired Composites
title_full An Alternative Approach to the Surface Methacrylation of Non-stoichiometric Hydroxyapatite Nanoparticles for Use in Bone-Inspired Composites
title_fullStr An Alternative Approach to the Surface Methacrylation of Non-stoichiometric Hydroxyapatite Nanoparticles for Use in Bone-Inspired Composites
title_full_unstemmed An Alternative Approach to the Surface Methacrylation of Non-stoichiometric Hydroxyapatite Nanoparticles for Use in Bone-Inspired Composites
title_short An Alternative Approach to the Surface Methacrylation of Non-stoichiometric Hydroxyapatite Nanoparticles for Use in Bone-Inspired Composites
title_sort alternative approach to the surface methacrylation of non stoichiometric hydroxyapatite nanoparticles for use in bone inspired composites
topic nano-hydroxyapatite
methacrylation
methacrylic anhydride
glycidyl methacrylate
surface functionalization
nanocomposite
url https://www.frontiersin.org/article/10.3389/fmats.2019.00263/full
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