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Stereocomplexation of Poly(Lactic Acid)s on Graphite Nanoplatelets: From Functionalized Nanoparticles to Self-assembled Nanostructures

The control of nanostructuration of graphene and graphene related materials (GRM) into self-assembled structures is strictly related to the nanoflakes chemical functionalization, which may be obtained via covalent grafting of non-covalent interactions, mostly exploiting π-stacking. As the non-covale...

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Autores principales: Eleuteri, Matteo, Bernal, Mar, Milanesio, Marco, Monticelli, Orietta, Fina, Alberto
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Frontiers Media S.A. 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6450084/
https://www.ncbi.nlm.nih.gov/pubmed/30984744
http://dx.doi.org/10.3389/fchem.2019.00176
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author Eleuteri, Matteo
Bernal, Mar
Milanesio, Marco
Monticelli, Orietta
Fina, Alberto
author_facet Eleuteri, Matteo
Bernal, Mar
Milanesio, Marco
Monticelli, Orietta
Fina, Alberto
author_sort Eleuteri, Matteo
collection PubMed
description The control of nanostructuration of graphene and graphene related materials (GRM) into self-assembled structures is strictly related to the nanoflakes chemical functionalization, which may be obtained via covalent grafting of non-covalent interactions, mostly exploiting π-stacking. As the non-covalent functionalization does not affect the sp(2) carbon structure, this is often exploited to preserve the thermal and electrical properties of the GRM and it is a well-known route to tailor the interaction between GRM and organic media. In this work, non-covalent functionalization of graphite nanoplatelets (GnP) was carried out with ad-hoc synthesized pyrene-terminated oligomers of polylactic acid (PLA), aiming at the modification of GnP nanopapers thermal properties. PLA was selected based on the possibility to self-assemble in crystalline domains via stereocomplexation of complementary poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) enantiomers. Pyrene-initiated PLLA and PDLA were indeed demonstrated to anchor to the GnP surface. Calorimetric and X-ray diffraction investigations highlighted the enantiomeric PLAs adsorbed on the surface of the nanoplatelets self-organize to produce highly crystalline stereocomplex domains. Most importantly, PLLA/PDLA stereocomplexation delivered a significantly higher efficiency in nanopapers heat transfer, in particular through the thickness of the nanopaper. This is explained by a thermal bridging effect of crystalline domains between overlapped GnP, promoting heat transfer across the nanoparticles contacts. This work demonstrates the possibility to enhance the physical properties of contacts within a percolating network of GRM via the self-assembly of macromolecules and opens a new way for the engineering of GRM-based nanostructures.
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spelling pubmed-64500842019-04-12 Stereocomplexation of Poly(Lactic Acid)s on Graphite Nanoplatelets: From Functionalized Nanoparticles to Self-assembled Nanostructures Eleuteri, Matteo Bernal, Mar Milanesio, Marco Monticelli, Orietta Fina, Alberto Front Chem Chemistry The control of nanostructuration of graphene and graphene related materials (GRM) into self-assembled structures is strictly related to the nanoflakes chemical functionalization, which may be obtained via covalent grafting of non-covalent interactions, mostly exploiting π-stacking. As the non-covalent functionalization does not affect the sp(2) carbon structure, this is often exploited to preserve the thermal and electrical properties of the GRM and it is a well-known route to tailor the interaction between GRM and organic media. In this work, non-covalent functionalization of graphite nanoplatelets (GnP) was carried out with ad-hoc synthesized pyrene-terminated oligomers of polylactic acid (PLA), aiming at the modification of GnP nanopapers thermal properties. PLA was selected based on the possibility to self-assemble in crystalline domains via stereocomplexation of complementary poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) enantiomers. Pyrene-initiated PLLA and PDLA were indeed demonstrated to anchor to the GnP surface. Calorimetric and X-ray diffraction investigations highlighted the enantiomeric PLAs adsorbed on the surface of the nanoplatelets self-organize to produce highly crystalline stereocomplex domains. Most importantly, PLLA/PDLA stereocomplexation delivered a significantly higher efficiency in nanopapers heat transfer, in particular through the thickness of the nanopaper. This is explained by a thermal bridging effect of crystalline domains between overlapped GnP, promoting heat transfer across the nanoparticles contacts. This work demonstrates the possibility to enhance the physical properties of contacts within a percolating network of GRM via the self-assembly of macromolecules and opens a new way for the engineering of GRM-based nanostructures. Frontiers Media S.A. 2019-03-29 /pmc/articles/PMC6450084/ /pubmed/30984744 http://dx.doi.org/10.3389/fchem.2019.00176 Text en Copyright © 2019 Eleuteri, Bernal, Milanesio, Monticelli and Fina. http://creativecommons.org/licenses/by/4.0/ This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
spellingShingle Chemistry
Eleuteri, Matteo
Bernal, Mar
Milanesio, Marco
Monticelli, Orietta
Fina, Alberto
Stereocomplexation of Poly(Lactic Acid)s on Graphite Nanoplatelets: From Functionalized Nanoparticles to Self-assembled Nanostructures
title Stereocomplexation of Poly(Lactic Acid)s on Graphite Nanoplatelets: From Functionalized Nanoparticles to Self-assembled Nanostructures
title_full Stereocomplexation of Poly(Lactic Acid)s on Graphite Nanoplatelets: From Functionalized Nanoparticles to Self-assembled Nanostructures
title_fullStr Stereocomplexation of Poly(Lactic Acid)s on Graphite Nanoplatelets: From Functionalized Nanoparticles to Self-assembled Nanostructures
title_full_unstemmed Stereocomplexation of Poly(Lactic Acid)s on Graphite Nanoplatelets: From Functionalized Nanoparticles to Self-assembled Nanostructures
title_short Stereocomplexation of Poly(Lactic Acid)s on Graphite Nanoplatelets: From Functionalized Nanoparticles to Self-assembled Nanostructures
title_sort stereocomplexation of poly(lactic acid)s on graphite nanoplatelets: from functionalized nanoparticles to self-assembled nanostructures
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6450084/
https://www.ncbi.nlm.nih.gov/pubmed/30984744
http://dx.doi.org/10.3389/fchem.2019.00176
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