Issue 2, 2010

Intermolecular association and supramolecular structures of PNVF–LiPFN and PVP–LiPFN complexes in the aqueous phase

Abstract

A new polymersurfactant system, the poly(N-vinylformamide) (PNVF)–lithium perfluorononanoate (LiPFN) system, has been studied by a combination of the surface tension method and two-dimensional 1H-19F heteronuclear Overhauser effect NMR spectroscopy (2D 1H-19F HOESY). Using the surface tension method, we found that the critical aggregation concentration (cac) of LiPFN in the presence of PNVF is ca. 2 mM. In addition, the association behavior between LiPFN and PNVF is similar to that between poly(vinylpyrrolidone) (PVP) and LiPFN. The supramolecular structure of the PNVFLiPFN complex in the aqueous phase is revealed by means of the 2D 1H-19F HOESY experiment. On the basis of the intermolecular cross-relaxation between the PNVF protons and the LiPFN fluorines, we could conclude that the PNVF chain do penetrate into the LiPFN aggregate. The semi-quantitative analysis of the internuclear distance indicates that the PNVF chain is not located at the center core of the LiPFN aggregate, but the PNVF chain thread itself through the surface shell of the LiPFN aggregate instead. PNVF protons are nearest to the fluorines next to the carboxyl group, suggesting that the interaction between PNVF and LiPFN is mainly due to the dipole-ionic attraction. Moreover, we have reinvestigated the supramolecular structure of PVPLiPFN complex and have found that the PVP chain also penetrates into the LiPFN aggregate. In contrast with the PNVFLiPFN complex, the PVP chain in the PVP-LiPFN complex is rather close to the middle part of the LiPFN molecules which constitute the polymer-bound aggregate. This indicates that the formation of PVPLiPFN complex involves more or less fluorophilic interactions.

Graphical abstract: Intermolecular association and supramolecular structures of PNVF–LiPFN and PVP–LiPFN complexes in the aqueous phase

Article information

Article type
Paper
Submitted
06 Aug 2009
Accepted
19 Oct 2009
First published
20 Nov 2009

Soft Matter, 2010,6, 409-415

Intermolecular association and supramolecular structures of PNVFLiPFN and PVPLiPFN complexes in the aqueous phase

S. Hou, J. Tzeng and M. Chuang, Soft Matter, 2010, 6, 409 DOI: 10.1039/B913160D

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements