Amphipathic Substrates Based on Crosslinker-Free Poly(ε-Caprolactone):Poly(2-Hydroxyethyl Methacrylate) Semi-Interpenetrated Networks Promote Serum Protein Adsorption

A simple procedure has been developed to synthesize uncrosslinked soluble poly(hydroxyethyl methacrylate) (PHEMA) gels, ready for use in a subsequent fabrication stage. The presence of 75 wt % methanol (MetOH) or dimethylformamide (DMF) impedes lateral hydroxyl–hydroxyl hydrogen bonds between PHEMA...

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Main Authors: Guillermo Vilariño-Feltrer, Alfredo Salgado-Gallegos, Joan de-la-Concepción-Ausina, José Carlos Rodríguez-Hernández, Mohsen Shahrousvand, Ana Vallés-Lluch
Format: Article
Language:English
Published: MDPI AG 2020-05-01
Series:Polymers
Subjects:
Online Access:https://www.mdpi.com/2073-4360/12/6/1256
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author Guillermo Vilariño-Feltrer
Alfredo Salgado-Gallegos
Joan de-la-Concepción-Ausina
José Carlos Rodríguez-Hernández
Mohsen Shahrousvand
Ana Vallés-Lluch
author_facet Guillermo Vilariño-Feltrer
Alfredo Salgado-Gallegos
Joan de-la-Concepción-Ausina
José Carlos Rodríguez-Hernández
Mohsen Shahrousvand
Ana Vallés-Lluch
author_sort Guillermo Vilariño-Feltrer
collection DOAJ
description A simple procedure has been developed to synthesize uncrosslinked soluble poly(hydroxyethyl methacrylate) (PHEMA) gels, ready for use in a subsequent fabrication stage. The presence of 75 wt % methanol (MetOH) or dimethylformamide (DMF) impedes lateral hydroxyl–hydroxyl hydrogen bonds between PHEMA macromers to form during their solution polymerization at 60 °C, up to 24 h. These gels remain soluble when properly stored in closed containers under cold conditions and, when needed, yield by solvent evaporation spontaneous physically-crosslinked PHEMA adapted to the mould used. Moreover, this two-step procedure allows obtaining multicomponent systems where a stable and water-affine PHEMA network would be of interest. In particular, amphiphilic polycaprolactone (PCL):PHEMA semi-interpenetrated (sIPN) substrates have been developed, from quaternary metastable solutions in chloroform (CHCl<sub>3</sub>):MetOH 3:1 wt. and PCL ranging from 50 to 90 wt % in the polymer fraction (thus determining the composition of the solution). The coexistence of these countered molecules, uniformly distributed at the nanoscale, has proven to enhance the number and interactions of serum protein adsorbed from the acellular medium as compared to the homopolymers, the sIPN containing 80 wt % PCL showing an outstanding development. In accordance to the quaternary diagram presented, this protocol can be adapted for the development of polymer substrates, coatings or scaffolds for biomedical applications, not relying upon phase separation, such as the electrospun mats here proposed herein (12 wt % polymer solutions were used for this purpose, with PCL ranging from 50% to 100% in the polymer fraction).
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spelling doaj.art-40c05c6f7e8544dabc76b9558ec4a7312023-11-20T02:16:35ZengMDPI AGPolymers2073-43602020-05-01126125610.3390/polym12061256Amphipathic Substrates Based on Crosslinker-Free Poly(ε-Caprolactone):Poly(2-Hydroxyethyl Methacrylate) Semi-Interpenetrated Networks Promote Serum Protein AdsorptionGuillermo Vilariño-Feltrer0Alfredo Salgado-Gallegos1Joan de-la-Concepción-Ausina2José Carlos Rodríguez-Hernández3Mohsen Shahrousvand4Ana Vallés-Lluch5Centre for Biomaterials and Tissue Engineering, Universitat Politècnica de València, 46022 Valencia, SpainCentre for Biomaterials and Tissue Engineering, Universitat Politècnica de València, 46022 Valencia, SpainCentre for Biomaterials and Tissue Engineering, Universitat Politècnica de València, 46022 Valencia, SpainCentre for Biomaterials and Tissue Engineering, Universitat Politècnica de València, 46022 Valencia, SpainCaspian Faculty of Engineering, College of Engineering, University of Tehran, P.O. Box 119-43841 Rezvanshahr, IranCentre for Biomaterials and Tissue Engineering, Universitat Politècnica de València, 46022 Valencia, SpainA simple procedure has been developed to synthesize uncrosslinked soluble poly(hydroxyethyl methacrylate) (PHEMA) gels, ready for use in a subsequent fabrication stage. The presence of 75 wt % methanol (MetOH) or dimethylformamide (DMF) impedes lateral hydroxyl–hydroxyl hydrogen bonds between PHEMA macromers to form during their solution polymerization at 60 °C, up to 24 h. These gels remain soluble when properly stored in closed containers under cold conditions and, when needed, yield by solvent evaporation spontaneous physically-crosslinked PHEMA adapted to the mould used. Moreover, this two-step procedure allows obtaining multicomponent systems where a stable and water-affine PHEMA network would be of interest. In particular, amphiphilic polycaprolactone (PCL):PHEMA semi-interpenetrated (sIPN) substrates have been developed, from quaternary metastable solutions in chloroform (CHCl<sub>3</sub>):MetOH 3:1 wt. and PCL ranging from 50 to 90 wt % in the polymer fraction (thus determining the composition of the solution). The coexistence of these countered molecules, uniformly distributed at the nanoscale, has proven to enhance the number and interactions of serum protein adsorbed from the acellular medium as compared to the homopolymers, the sIPN containing 80 wt % PCL showing an outstanding development. In accordance to the quaternary diagram presented, this protocol can be adapted for the development of polymer substrates, coatings or scaffolds for biomedical applications, not relying upon phase separation, such as the electrospun mats here proposed herein (12 wt % polymer solutions were used for this purpose, with PCL ranging from 50% to 100% in the polymer fraction).https://www.mdpi.com/2073-4360/12/6/1256poly(ε-caprolactone)poly(2-hydroxyethyl methacrylate)amphipathicamphiphiliccrosslinker-freesemi-interpenetrated network
spellingShingle Guillermo Vilariño-Feltrer
Alfredo Salgado-Gallegos
Joan de-la-Concepción-Ausina
José Carlos Rodríguez-Hernández
Mohsen Shahrousvand
Ana Vallés-Lluch
Amphipathic Substrates Based on Crosslinker-Free Poly(ε-Caprolactone):Poly(2-Hydroxyethyl Methacrylate) Semi-Interpenetrated Networks Promote Serum Protein Adsorption
Polymers
poly(ε-caprolactone)
poly(2-hydroxyethyl methacrylate)
amphipathic
amphiphilic
crosslinker-free
semi-interpenetrated network
title Amphipathic Substrates Based on Crosslinker-Free Poly(ε-Caprolactone):Poly(2-Hydroxyethyl Methacrylate) Semi-Interpenetrated Networks Promote Serum Protein Adsorption
title_full Amphipathic Substrates Based on Crosslinker-Free Poly(ε-Caprolactone):Poly(2-Hydroxyethyl Methacrylate) Semi-Interpenetrated Networks Promote Serum Protein Adsorption
title_fullStr Amphipathic Substrates Based on Crosslinker-Free Poly(ε-Caprolactone):Poly(2-Hydroxyethyl Methacrylate) Semi-Interpenetrated Networks Promote Serum Protein Adsorption
title_full_unstemmed Amphipathic Substrates Based on Crosslinker-Free Poly(ε-Caprolactone):Poly(2-Hydroxyethyl Methacrylate) Semi-Interpenetrated Networks Promote Serum Protein Adsorption
title_short Amphipathic Substrates Based on Crosslinker-Free Poly(ε-Caprolactone):Poly(2-Hydroxyethyl Methacrylate) Semi-Interpenetrated Networks Promote Serum Protein Adsorption
title_sort amphipathic substrates based on crosslinker free poly ε caprolactone poly 2 hydroxyethyl methacrylate semi interpenetrated networks promote serum protein adsorption
topic poly(ε-caprolactone)
poly(2-hydroxyethyl methacrylate)
amphipathic
amphiphilic
crosslinker-free
semi-interpenetrated network
url https://www.mdpi.com/2073-4360/12/6/1256
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