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

Sheng-Shu Hou, Jung Kai Tzeng, Meng Han Chuang

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

A new polymer-surfactant 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 PNVF-LiPFN 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 PVP-LiPFN complex and have found that the PVP chain also penetrates into the LiPFN aggregate. In contrast with the PNVF-LiPFN 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 PVP-LiPFN complex involves more or less fluorophilic interactions.

Original languageEnglish
Pages (from-to)409-415
Number of pages7
JournalSoft Matter
Volume6
Issue number2
DOIs
Publication statusPublished - 2010 Dec 1

Fingerprint

Lithium
lithium
Association reactions
Fluorine
hexadecafluoro-nonanoic acid
poly(N-vinylformamide)
fluorine
Surface tension
Protons
Polymers
interfacial tension
Overhauser effect
cross relaxation
protons
threads
polymers
carboxyl group
Surface-Active Agents
quantitative analysis
Nuclear magnetic resonance spectroscopy

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Condensed Matter Physics

Cite this

@article{12b9027d4df24a969670a443dbce0a55,
title = "Intermolecular association and supramolecular structures of PNVF-LiPFN and PVP-LiPFN complexes in the aqueous phase",
abstract = "A new polymer-surfactant 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 PNVF-LiPFN 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 PVP-LiPFN complex and have found that the PVP chain also penetrates into the LiPFN aggregate. In contrast with the PNVF-LiPFN 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 PVP-LiPFN complex involves more or less fluorophilic interactions.",
author = "Sheng-Shu Hou and Tzeng, {Jung Kai} and Chuang, {Meng Han}",
year = "2010",
month = "12",
day = "1",
doi = "10.1039/b913160d",
language = "English",
volume = "6",
pages = "409--415",
journal = "Soft Matter",
issn = "1744-683X",
publisher = "Royal Society of Chemistry",
number = "2",

}

Intermolecular association and supramolecular structures of PNVF-LiPFN and PVP-LiPFN complexes in the aqueous phase. / Hou, Sheng-Shu; Tzeng, Jung Kai; Chuang, Meng Han.

In: Soft Matter, Vol. 6, No. 2, 01.12.2010, p. 409-415.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Intermolecular association and supramolecular structures of PNVF-LiPFN and PVP-LiPFN complexes in the aqueous phase

AU - Hou, Sheng-Shu

AU - Tzeng, Jung Kai

AU - Chuang, Meng Han

PY - 2010/12/1

Y1 - 2010/12/1

N2 - A new polymer-surfactant 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 PNVF-LiPFN 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 PVP-LiPFN complex and have found that the PVP chain also penetrates into the LiPFN aggregate. In contrast with the PNVF-LiPFN 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 PVP-LiPFN complex involves more or less fluorophilic interactions.

AB - A new polymer-surfactant 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 PNVF-LiPFN 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 PVP-LiPFN complex and have found that the PVP chain also penetrates into the LiPFN aggregate. In contrast with the PNVF-LiPFN 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 PVP-LiPFN complex involves more or less fluorophilic interactions.

UR - http://www.scopus.com/inward/record.url?scp=79951634035&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=79951634035&partnerID=8YFLogxK

U2 - 10.1039/b913160d

DO - 10.1039/b913160d

M3 - Article

AN - SCOPUS:79951634035

VL - 6

SP - 409

EP - 415

JO - Soft Matter

JF - Soft Matter

SN - 1744-683X

IS - 2

ER -