Issue 15, 2011

Interparticle distance in monolayers controlled by soft spacers

Abstract

This paper addresses the use of graft polymer layers as spacers to control interparticle distance in 2-dimensional monolayers. Gold nanoparticles grafted with thermosensitive PNIPAM-based polymers with a large range of molecular mass and different degrees of hydrophobicity have been studied. The hydrophobicity of the polymer is adjusted by incorporation of a comonomer n-propylamine. The resulting copolymer, PNIPAM-co-NPAM, exhibits lower collapse transition temperature and increased cooperativity in the collapse process with n ≈ 150 compared to n ≈ 100 for PNIPAM, n being the number of monomers per collapse domain. Langmuir isotherms of these polymers under moderate compression follow closely a πc3 behavior with corresponding critical exponent ν = 3/4 as predicted for 2-dimensional polymer conformation in good solvent. Nanoparticles grafted with these polymers form stable Langmuir monolayers where the graft polymer chains adopt a 2-D stretched conformation that tethers the nanoparticles to the interface. The nanoparticle cores are thus isolated by the polymer shells resulting in nanoparticle areas that increase with polymer chain length. Correspondingly, the interparticle distance is found to vary with chain length as DpN0.8. For the Au-PNIPAM-NPAM, a moderate increase in temperature to near-θ conditions decreases the nanoparticle area by about 30% through lateral collapse of the polymer layer. This thermally induced molecular collapse in a 2-D monolayer is an unusual and novel observation that may be attributed to cooperative effects of the collapse transition of the new copolymer PNIPAM-co-NPAM.

Graphical abstract: Interparticle distance in monolayers controlled by soft spacers

Article information

Article type
Paper
Submitted
07 Mar 2011
Accepted
11 May 2011
First published
24 Jun 2011

Soft Matter, 2011,7, 7112-7122

Interparticle distance in monolayers controlled by soft spacers

C. Said-Mohamed, J. Niskanen, M. Karesoja, P. Pulkkinen, H. Tenhu, M. Daoud and L. Lee, Soft Matter, 2011, 7, 7112 DOI: 10.1039/C1SM05397C

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