Light-Responsive Self-Assembled Materials by Supramolecular Post-Functionalization via Hydrogen Bonding of Amphiphilic Block Copolymers

Alberto  Concellon; Eva Blasco; Alfonso Martinez-Felipe; Juan Carlos  Martínez; Igor  Šics; Tiberio A.  Ezquerra; Aurora  Nogales; Milagros Piñ ol; Luis Oriol

doi:10.1021/acs.macromol.6b01112

Light-Responsive Self-Assembled Materials by Supramolecular Post-Functionalization via Hydrogen Bonding of Amphiphilic Block Copolymers

Alberto Concellon, Eva Blasco, Alfonso Martinez-Felipe, Juan Carlos Martínez, Igor Šics, Tiberio A. Ezquerra, Aurora Nogales (Corresponding Author), Milagros Piñ ol (Corresponding Author), Luis Oriol (Corresponding Author)

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Abstract

A new class of light-responsive supramolecular amphiphilic block copolymers (BCs) based on the association through multiple H-bonding between 4-isobutyloxyazobenzene motifs and 2,6-diacylaminepyridine units is reported. Block copolymers containing 2,6-diacylaminopyridine side units, as hydrophobic block, and poly(ethylene glycol), as a hydrophilic segment, were functionalized with either a carboxylic acid azodendron, via double H-bonding, or a thymine azobenzene, via triple H-bonding. The structural and thermal characterization of these supramolecular azo-copolymers in bulk and solution is presented. The work emphasizes the self-assembly of these supramolecular polymers in water and the study of their UV-light responsive properties by UV–vis spectroscopy, dynamic light scattering (DLS), transmission electron microscopy (TEM), and synchrotron small-angle X-ray (SAXS). The present noncovalent postpolymerization functionalization strategy has provided stable self-assemblies in water with light responsive properties that can be used to load and trigger the delivery of small fluorescent molecules.

Original language	English
Pages (from-to)	7825-7836
Number of pages	12
Journal	Macromolecules
Volume	49
Issue number	20
Early online date	4 Oct 2016
DOIs	https://doi.org/10.1021/acs.macromol.6b01112
Publication status	Published - 25 Oct 2016

Bibliographical note

This work was supported by the MINECO, Spain, under Projects MAT2014-59187-R and MAT2014-55205-P, FEDER funding, and Aragon Government. A.C. acknowledges MINE- ́ CO for his Ph.D. grant. A.M.-F. expresses thanks for the financial support of the Generalitat Valenciana for his
APOSTD/2013/054 grant. The authors would like to acknowledge the Servicio General de Apoyo a la Investigacion (SAI) ́ and the Advanced Microscopy Laboratory (LMA) of the Universidad de Zaragoza and the Servei de Microscopia of the ̀ Universitat Autonoma de Barcelona for the TEM and cryo- ̀TEM observations. The authors additionally acknowledge the use of the CEQMA Services of the Universidad de ZaragozaCSIC. The authors also thank the IACS (Aragon Health ́ Sciences Institute) for the confocal microscope studies

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10.1021/acs.macromol.6b01112Licence: Unspecified

Concellon_etal_Macromol_Light_responsive_AAM
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.macromol.6b01112
Accepted author manuscript, 2.44 MBLicence: Unspecified
Supplementary_info_AAMAccepted author manuscript, 1.68 MBLicence: Unspecified

Alfonso Martinez-Felipe
- Engineering, Engineering - Senior Lecturer
- Centre for Energy Transition
Person: Academic

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@article{a91bb33d9e1c4bf3a6285d2872e18d93,

title = "Light-Responsive Self-Assembled Materials by Supramolecular Post-Functionalization via Hydrogen Bonding of Amphiphilic Block Copolymers",

abstract = "A new class of light-responsive supramolecular amphiphilic block copolymers (BCs) based on the association through multiple H-bonding between 4-isobutyloxyazobenzene motifs and 2,6-diacylaminepyridine units is reported. Block copolymers containing 2,6-diacylaminopyridine side units, as hydrophobic block, and poly(ethylene glycol), as a hydrophilic segment, were functionalized with either a carboxylic acid azodendron, via double H-bonding, or a thymine azobenzene, via triple H-bonding. The structural and thermal characterization of these supramolecular azo-copolymers in bulk and solution is presented. The work emphasizes the self-assembly of these supramolecular polymers in water and the study of their UV-light responsive properties by UV–vis spectroscopy, dynamic light scattering (DLS), transmission electron microscopy (TEM), and synchrotron small-angle X-ray (SAXS). The present noncovalent postpolymerization functionalization strategy has provided stable self-assemblies in water with light responsive properties that can be used to load and trigger the delivery of small fluorescent molecules.",

author = "Alberto Concellon and Eva Blasco and Alfonso Martinez-Felipe and Mart{\'i}nez, {Juan Carlos} and Igor {\v S}ics and Ezquerra, {Tiberio A.} and Aurora Nogales and {Pi{\~n} ol}, Milagros and Luis Oriol",

note = "This work was supported by the MINECO, Spain, under Projects MAT2014-59187-R and MAT2014-55205-P, FEDER funding, and Aragon Government. A.C. acknowledges MINE-{\' } CO for his Ph.D. grant. A.M.-F. expresses thanks for the financial support of the Generalitat Valenciana for his APOSTD/2013/054 grant. The authors would like to acknowledge the Servicio General de Apoyo a la Investigacion (SAI){\' } and the Advanced Microscopy Laboratory (LMA) of the Universidad de Zaragoza and the Servei de Microscopia of the{\` } Universitat Autonoma de Barcelona for the TEM and cryo-{\` }TEM observations. The authors additionally acknowledge the use of the CEQMA Services of the Universidad de ZaragozaCSIC. The authors also thank the IACS (Aragon Health{\' } Sciences Institute) for the confocal microscope studies",

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T1 - Light-Responsive Self-Assembled Materials by Supramolecular Post-Functionalization via Hydrogen Bonding of Amphiphilic Block Copolymers

AU - Concellon, Alberto

AU - Blasco, Eva

AU - Martinez-Felipe, Alfonso

AU - Martínez, Juan Carlos

AU - Šics, Igor

AU - Ezquerra, Tiberio A.

AU - Nogales, Aurora

AU - Piñ ol, Milagros

AU - Oriol, Luis

N1 - This work was supported by the MINECO, Spain, under Projects MAT2014-59187-R and MAT2014-55205-P, FEDER funding, and Aragon Government. A.C. acknowledges MINE- ́ CO for his Ph.D. grant. A.M.-F. expresses thanks for the financial support of the Generalitat Valenciana for his APOSTD/2013/054 grant. The authors would like to acknowledge the Servicio General de Apoyo a la Investigacion (SAI) ́ and the Advanced Microscopy Laboratory (LMA) of the Universidad de Zaragoza and the Servei de Microscopia of the ̀ Universitat Autonoma de Barcelona for the TEM and cryo- ̀TEM observations. The authors additionally acknowledge the use of the CEQMA Services of the Universidad de ZaragozaCSIC. The authors also thank the IACS (Aragon Health ́ Sciences Institute) for the confocal microscope studies

PY - 2016/10/25

Y1 - 2016/10/25

N2 - A new class of light-responsive supramolecular amphiphilic block copolymers (BCs) based on the association through multiple H-bonding between 4-isobutyloxyazobenzene motifs and 2,6-diacylaminepyridine units is reported. Block copolymers containing 2,6-diacylaminopyridine side units, as hydrophobic block, and poly(ethylene glycol), as a hydrophilic segment, were functionalized with either a carboxylic acid azodendron, via double H-bonding, or a thymine azobenzene, via triple H-bonding. The structural and thermal characterization of these supramolecular azo-copolymers in bulk and solution is presented. The work emphasizes the self-assembly of these supramolecular polymers in water and the study of their UV-light responsive properties by UV–vis spectroscopy, dynamic light scattering (DLS), transmission electron microscopy (TEM), and synchrotron small-angle X-ray (SAXS). The present noncovalent postpolymerization functionalization strategy has provided stable self-assemblies in water with light responsive properties that can be used to load and trigger the delivery of small fluorescent molecules.

AB - A new class of light-responsive supramolecular amphiphilic block copolymers (BCs) based on the association through multiple H-bonding between 4-isobutyloxyazobenzene motifs and 2,6-diacylaminepyridine units is reported. Block copolymers containing 2,6-diacylaminopyridine side units, as hydrophobic block, and poly(ethylene glycol), as a hydrophilic segment, were functionalized with either a carboxylic acid azodendron, via double H-bonding, or a thymine azobenzene, via triple H-bonding. The structural and thermal characterization of these supramolecular azo-copolymers in bulk and solution is presented. The work emphasizes the self-assembly of these supramolecular polymers in water and the study of their UV-light responsive properties by UV–vis spectroscopy, dynamic light scattering (DLS), transmission electron microscopy (TEM), and synchrotron small-angle X-ray (SAXS). The present noncovalent postpolymerization functionalization strategy has provided stable self-assemblies in water with light responsive properties that can be used to load and trigger the delivery of small fluorescent molecules.

U2 - 10.1021/acs.macromol.6b01112

DO - 10.1021/acs.macromol.6b01112

M3 - Article

SN - 0024-9297

VL - 49

SP - 7825

EP - 7836

JO - Macromolecules

JF - Macromolecules

IS - 20

ER -

Light-Responsive Self-Assembled Materials by Supramolecular Post-Functionalization via Hydrogen Bonding of Amphiphilic Block Copolymers

Abstract

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Alfonso Martinez-Felipe

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