Eur. Phys. J. E (2009) 29: 73-85
https://doi.org/10.1140/epje/i2009-10451-5

Regular Article

Individual bottle brush molecules in dense 2D layers restoring high degree of extension after collapse-decollapse cycle: Directly measured scaling exponent

¹ Faculty of Physics, M. V. Lomonosov Moscow State University, Leninskie gory 1-2, GSP-1, 119991, Moscow, Russia
² Organische Chemie III, Universität Ulm, Albert-Einstein-Allee 11, D-89069, Ulm, Germany
³ Institute of Polymer Science, Universität Ulm, Albert-Einstein-Allee 47, D-89069, Ulm, Germany
⁴ Department of Chemistry, Mellon Institute, Carnegie Mellon University, 4400 Fifth Avenue, 15213, Pittsburgh, PA, USA
⁵ Department of Colloid Chemistry, Max Planck Institute of Colloids and Interfaces, D-14424, Potsdam-Golm, Germany
⁶ Institute of Technical and Macromolecular Chemistry, RWTH Aachen and DWI at the RWTH Aachen e.V., Pauwelsstr. 8, D-52056, Aachen, Germany

^* e-mail: glm@spm.phys.msu.ru
^** e-mail: igor@polly.phys.msu.ru

Received: 27 November 2008
Revised: 2 February 2009
Accepted: 10 March 2009
Published online: 6 May 2009

Abstract

We prepared dense films of adsorbed brush-like macromolecules on mica substrate by transfer of compressed Langmuir monolayers from water subphase. The main macromolecular contours in the dense films were clearly resolved by SFM. The films were subjected to successive treatments by ethanol and water vapours. In accordance with previous results for isolated macromolecules, the films underwent collapse and subsequent decollapse morphological transformations in the changing vapour environment. Statistical analysis of the macromolecular dimensions in the films allowed us to measure the values of the scaling exponent determining the correlation between mean lateral and linear dimensions of the macromolecules. The analysis showed that the macromolecular conformations in the film as transferred were similar to the previously described conformations of the same macromolecules deposited directly on mica as isolated chains at much lower surface densities. The determined was close to the 0.75 value corresponding to the 2D SAW statistics. We assumed that the molecules retained the high degree of extension during the compression step due to suppressed reorganisation of the side chains. Differently from previous observations for isolated macromolecules, the restored conformations in the dense films after collapse-decollapse cycle were more extended with the of about 0.73 value. A theoretical explanation of the high degree of re-extension is proposed.