Thermally-induced softening of PNIPAm-based nanopillar arrays

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The surface properties of soft nanostructured hydrogels are crucial in the design of responsive materials that can be used as platforms to create adaptive devices. The lower critical solution temperature (LCST) of thermo-responsive hydrogels such as poly(N-isopropylacrylamide) (PNIPAm) can be modifi...

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Autor principal: Sanz, B.
Otros Autores: Von Bilderling, C., Tuninetti, J.S, Pietrasanta, L., Mijangos, C., Longo, G.S, Azzaroni, O., Giussi, J.M
Formato: Capítulo de libro
Lenguaje:Inglés
Publicado: Royal Society of Chemistry 2017
Acceso en línea:Registro en Scopus
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100 1 |a Sanz, B. 
245 1 0 |a Thermally-induced softening of PNIPAm-based nanopillar arrays 
260 |b Royal Society of Chemistry  |c 2017 
270 1 0 |m Giussi, J.M.; Instituto de Investigaciones Fisicoquimicas Teoricas y Aplicadas (INIFTA), Departamento de Quimica, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CONICETArgentina; email: jmgiussi@inifta.unlp.edu.ar 
506 |2 openaire  |e Política editorial 
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520 3 |a The surface properties of soft nanostructured hydrogels are crucial in the design of responsive materials that can be used as platforms to create adaptive devices. The lower critical solution temperature (LCST) of thermo-responsive hydrogels such as poly(N-isopropylacrylamide) (PNIPAm) can be modified by introducing a hydrophilic monomer to create a wide range of thermo-responsive micro-/nano-structures in a large temperature range. Using surface initiation atom-transfer radical polymerization in synthesized anodized aluminum oxide templates, we designed, fabricated, and characterized thermo-responsive nanopillars based on PNIPAm hydrogels with tunable mechanical properties by incorporating acrylamide monomers (AAm). In addition to their LCST, the incorporation of a hydrophilic entity in the nanopillars based on PNIPAm has abruptly changed the topological and mechanical properties of our system. To gain an insight into the mechanical properties of the nanostructure, its hydrophilic/hydrophobic behavior and topological characteristics, atomic force microscopy, molecular dynamics simulations and water contact angle studies were combined. When changing the nanopillar composition, a significant and opposite variation was observed in their mechanical properties. As temperature increased above the LCST, the stiffness of PNIPAm nanopillars, as expected, did so too, in contrast to the stiffness of PNIPAm-AAm nanopillars that decreased significantly. The molecular dynamics simulations proposed a local molecular rearrangement in our nanosystems at the LCST. The local aggregation of NIPAm segments near the center of the nanopillars displaced the hydrophilic AAm units towards the surface of the structure leading to contact with the aqueous environment. This behavior was confirmed via contact angle measurements below and above the LCST. © The Royal Society of Chemistry.  |l eng 
536 |a Detalles de la financiación: Austrian Institute of Technology, 4947/11, 3911 
536 |a Detalles de la financiación: PICT-2015-0346, PICT-2014-3377 
536 |a Detalles de la financiación: Universidad Nacional de La Plata, UNLP 
536 |a Detalles de la financiación: Agencia Nacional de Promoción Científica y Tecnológica, PICT-2010-2554, PICT-2013-0905 
536 |a Detalles de la financiación: Ministerio de Economía y Competitividad, MAT 2014-53437 
536 |a Detalles de la financiación: Consejo Nacional de Investigaciones Científicas y Técnicas 
536 |a Detalles de la financiación: J. T., G. S. L., O. A. and J. M. G. acknowledge the financial support from CONICET, ANPCyT (PICT-2010-2554, PICT-2013-0905), UNLP, Fundaci?n Petruzza and the Austrian Institute of Technology GmbH (AIT-CONICET Partner Group: ?Exploratory Research for Advanced Technologies in Supramolecular Materials Science?-Exp. 4947/11, Res. No. 3911, 28-12-2011). G. S. L. is thankful for the support from ANCyT (PICT-2014-3377). J. M. G. is thankful for the support from ANCyT (PICT-2015-0346). B. Z., C. M, and J. M. G. acknowledge MINECO for its financial support (MAT 2014-53437). The authors would like to thank to D. G?mez for SEM measurements and I. Mu?oz Ochando for Raman measurements. 
593 |a Instituto de Ciencia y Tecnologia de Polimeros, CSIC, Juan de la Cierva 3, Madrid, 28006, Spain 
593 |a Instituto de Fisica de Buenos Aires (IFIBA-CONICET), Departamento de Fisica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Buenos Aires, C1428EHA, Argentina 
593 |a Instituto de Investigaciones Fisicoquimicas Teoricas y Aplicadas (INIFTA), Departamento de Quimica, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CONICET, La Plata, 1900, Argentina 
593 |a Centro de Microscopias Avanzadas, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Buenos Aires, C1428EHA, Argentina 
690 1 0 |a ACRYLIC MONOMERS 
690 1 0 |a AMIDES 
690 1 0 |a ATOM TRANSFER RADICAL POLYMERIZATION 
690 1 0 |a ATOMIC FORCE MICROSCOPY 
690 1 0 |a CONTACT ANGLE 
690 1 0 |a FREE RADICAL REACTIONS 
690 1 0 |a HYDROGELS 
690 1 0 |a HYDROPHILICITY 
690 1 0 |a MECHANICAL PROPERTIES 
690 1 0 |a MOLECULAR DYNAMICS 
690 1 0 |a MONOMERS 
690 1 0 |a NANOSYSTEMS 
690 1 0 |a STIFFNESS 
690 1 0 |a TOPOLOGY 
690 1 0 |a ANODIZED ALUMINUM OXIDE 
690 1 0 |a HYDROPHILIC/HYDROPHOBIC 
690 1 0 |a LOWER CRITICAL SOLUTION TEMPERATURE 
690 1 0 |a MOLECULAR DYNAMICS SIMULATIONS 
690 1 0 |a NANOSTRUCTURED HYDROGELS 
690 1 0 |a POLY(N-ISOPROPYL ACRYLAMIDE) (PNIPAM) 
690 1 0 |a THERMO-RESPONSIVE HYDROGELS 
690 1 0 |a TOPOLOGICAL CHARACTERISTICS 
690 1 0 |a NANOSTRUCTURES 
700 1 |a Von Bilderling, C. 
700 1 |a Tuninetti, J.S. 
700 1 |a Pietrasanta, L. 
700 1 |a Mijangos, C. 
700 1 |a Longo, G.S. 
700 1 |a Azzaroni, O. 
700 1 |a Giussi, J.M. 
773 0 |d Royal Society of Chemistry, 2017  |g v. 13  |h pp. 2453-2464  |k n. 13  |p Soft Matter  |x 1744683X  |w (AR-BaUEN)CENRE-3021  |t Soft Matter 
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856 4 0 |u https://doi.org/10.1039/c7sm00206h  |y DOI 
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