Modular engineering of H-bonded supramolecular polymers for reversible functionalization of carbon nanotubes

A. Llanes-Pallas, D. Bonifazi, K. Yoosaf, J. Mohanraj, N. Armaroli, H. Traboulsi, T. Seldrum, J. Dumont, A. Minoia, R. Lazzaroni

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

A H-bond-driven, noncovalent, reversible solubilization/functionalization of multiwalled carbon nanotubes (MWCNTs) in apolar organic solvents (CHCl , CH Cl , and toluene) has been accomplished through a dynamic combination of self-assembly and self-organization processes leading to the formation of supramolecular polymers, which enfold around the outer wall of the MWCNTs. To this end, a library of phenylacetylene molecular scaffolds with complementary recognition sites at their extremities has been synthesized. They exhibit triple parallel H-bonds between the NH-N-NH (DAD) functions of 2,6-di(acetylamino)pyridine and the CO-NH-CO (ADA) imidic groups of uracil derivatives. These residues are placed at 180° relative to each other (linear systems) or at 60°/120° (angular modules), in order to tune their ability of wrapping around MWCNTs. Molecular Dynamics (MD) simulations showed that the formation of the hybrid assembly MWCNT•[X•Y] (where X = 1a or 1b -DAD- and Y = 2, 3, or 4 -ADA-) is attributed to π-π and CH-π interactions between the graphitic walls of the carbon materials and the oligophenyleneethynylene polymer backbones along with its alkyl groups, respectively. Addition of polar or protic solvents, such as DMSO or MeOH, causes the disruption of the H-bonds with partial detachment of the polymer from the CNTs, followed by precipitation. Taking advantage of the chromophoric and luminescence properties of the molecular subunits, the solubilization/precipitation processes have been monitored by UV-vis absorption and luminescence spectroscopies. All hybrid MWCNTs-polymer materials have been also structurally characterized via thermogravimetric analysis (TGA), transmission electron microscopy (TEM), atomic force microscopy (AFM), scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS).
langue originaleAnglais
Pages (de - à)15412-15424
Nombre de pages13
journalJournal of the American Chemical Society
Volume133
Numéro de publication39
Les DOIs
étatPublié - 5 oct. 2011

Empreinte digitale

Carbon Nanotubes
Multiwalled carbon nanotubes (MWCN)
Carbon nanotubes
Polymers
Carbon Monoxide
Luminescence
Scanning Tunnelling Microscopy
Photoelectron Spectroscopy
Uracil
Atomic Force Microscopy
Toluene
Scanning tunneling microscopy
Molecular Dynamics Simulation
Dimethyl Sulfoxide
Transmission Electron Microscopy
Scaffolds
Pyridine
Organic solvents
Self assembly
Libraries

Citer ceci

Llanes-Pallas, A. ; Bonifazi, D. ; Yoosaf, K. ; Mohanraj, J. ; Armaroli, N. ; Traboulsi, H. ; Seldrum, T. ; Dumont, J. ; Minoia, A. ; Lazzaroni, R. / Modular engineering of H-bonded supramolecular polymers for reversible functionalization of carbon nanotubes. Dans: Journal of the American Chemical Society. 2011 ; Vol 133, Numéro 39. p. 15412-15424.
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abstract = "A H-bond-driven, noncovalent, reversible solubilization/functionalization of multiwalled carbon nanotubes (MWCNTs) in apolar organic solvents (CHCl , CH Cl , and toluene) has been accomplished through a dynamic combination of self-assembly and self-organization processes leading to the formation of supramolecular polymers, which enfold around the outer wall of the MWCNTs. To this end, a library of phenylacetylene molecular scaffolds with complementary recognition sites at their extremities has been synthesized. They exhibit triple parallel H-bonds between the NH-N-NH (DAD) functions of 2,6-di(acetylamino)pyridine and the CO-NH-CO (ADA) imidic groups of uracil derivatives. These residues are placed at 180° relative to each other (linear systems) or at 60°/120° (angular modules), in order to tune their ability of wrapping around MWCNTs. Molecular Dynamics (MD) simulations showed that the formation of the hybrid assembly MWCNT•[X•Y] (where X = 1a or 1b -DAD- and Y = 2, 3, or 4 -ADA-) is attributed to π-π and CH-π interactions between the graphitic walls of the carbon materials and the oligophenyleneethynylene polymer backbones along with its alkyl groups, respectively. Addition of polar or protic solvents, such as DMSO or MeOH, causes the disruption of the H-bonds with partial detachment of the polymer from the CNTs, followed by precipitation. Taking advantage of the chromophoric and luminescence properties of the molecular subunits, the solubilization/precipitation processes have been monitored by UV-vis absorption and luminescence spectroscopies. All hybrid MWCNTs-polymer materials have been also structurally characterized via thermogravimetric analysis (TGA), transmission electron microscopy (TEM), atomic force microscopy (AFM), scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS).",
author = "A. Llanes-Pallas and D. Bonifazi and K. Yoosaf and J. Mohanraj and N. Armaroli and H. Traboulsi and T. Seldrum and J. Dumont and A. Minoia and R. Lazzaroni",
note = "Copyright 2011 Elsevier B.V., All rights reserved.",
year = "2011",
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Modular engineering of H-bonded supramolecular polymers for reversible functionalization of carbon nanotubes. / Llanes-Pallas, A.; Bonifazi, D.; Yoosaf, K.; Mohanraj, J.; Armaroli, N.; Traboulsi, H.; Seldrum, T.; Dumont, J.; Minoia, A.; Lazzaroni, R.

Dans: Journal of the American Chemical Society, Vol 133, Numéro 39, 05.10.2011, p. 15412-15424.

Résultats de recherche: Contribution à un journal/une revueArticle

TY - JOUR

T1 - Modular engineering of H-bonded supramolecular polymers for reversible functionalization of carbon nanotubes

AU - Llanes-Pallas, A.

AU - Bonifazi, D.

AU - Yoosaf, K.

AU - Mohanraj, J.

AU - Armaroli, N.

AU - Traboulsi, H.

AU - Seldrum, T.

AU - Dumont, J.

AU - Minoia, A.

AU - Lazzaroni, R.

N1 - Copyright 2011 Elsevier B.V., All rights reserved.

PY - 2011/10/5

Y1 - 2011/10/5

N2 - A H-bond-driven, noncovalent, reversible solubilization/functionalization of multiwalled carbon nanotubes (MWCNTs) in apolar organic solvents (CHCl , CH Cl , and toluene) has been accomplished through a dynamic combination of self-assembly and self-organization processes leading to the formation of supramolecular polymers, which enfold around the outer wall of the MWCNTs. To this end, a library of phenylacetylene molecular scaffolds with complementary recognition sites at their extremities has been synthesized. They exhibit triple parallel H-bonds between the NH-N-NH (DAD) functions of 2,6-di(acetylamino)pyridine and the CO-NH-CO (ADA) imidic groups of uracil derivatives. These residues are placed at 180° relative to each other (linear systems) or at 60°/120° (angular modules), in order to tune their ability of wrapping around MWCNTs. Molecular Dynamics (MD) simulations showed that the formation of the hybrid assembly MWCNT•[X•Y] (where X = 1a or 1b -DAD- and Y = 2, 3, or 4 -ADA-) is attributed to π-π and CH-π interactions between the graphitic walls of the carbon materials and the oligophenyleneethynylene polymer backbones along with its alkyl groups, respectively. Addition of polar or protic solvents, such as DMSO or MeOH, causes the disruption of the H-bonds with partial detachment of the polymer from the CNTs, followed by precipitation. Taking advantage of the chromophoric and luminescence properties of the molecular subunits, the solubilization/precipitation processes have been monitored by UV-vis absorption and luminescence spectroscopies. All hybrid MWCNTs-polymer materials have been also structurally characterized via thermogravimetric analysis (TGA), transmission electron microscopy (TEM), atomic force microscopy (AFM), scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS).

AB - A H-bond-driven, noncovalent, reversible solubilization/functionalization of multiwalled carbon nanotubes (MWCNTs) in apolar organic solvents (CHCl , CH Cl , and toluene) has been accomplished through a dynamic combination of self-assembly and self-organization processes leading to the formation of supramolecular polymers, which enfold around the outer wall of the MWCNTs. To this end, a library of phenylacetylene molecular scaffolds with complementary recognition sites at their extremities has been synthesized. They exhibit triple parallel H-bonds between the NH-N-NH (DAD) functions of 2,6-di(acetylamino)pyridine and the CO-NH-CO (ADA) imidic groups of uracil derivatives. These residues are placed at 180° relative to each other (linear systems) or at 60°/120° (angular modules), in order to tune their ability of wrapping around MWCNTs. Molecular Dynamics (MD) simulations showed that the formation of the hybrid assembly MWCNT•[X•Y] (where X = 1a or 1b -DAD- and Y = 2, 3, or 4 -ADA-) is attributed to π-π and CH-π interactions between the graphitic walls of the carbon materials and the oligophenyleneethynylene polymer backbones along with its alkyl groups, respectively. Addition of polar or protic solvents, such as DMSO or MeOH, causes the disruption of the H-bonds with partial detachment of the polymer from the CNTs, followed by precipitation. Taking advantage of the chromophoric and luminescence properties of the molecular subunits, the solubilization/precipitation processes have been monitored by UV-vis absorption and luminescence spectroscopies. All hybrid MWCNTs-polymer materials have been also structurally characterized via thermogravimetric analysis (TGA), transmission electron microscopy (TEM), atomic force microscopy (AFM), scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS).

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