Molecular self-diffusion in micellar and discrete cubic phases of an ionic surfactant with mixed monovalent/polymeric counterions
(2003) In The Journal of Physical Chemistry Part B 107(47). p.13241-13250- Abstract
- The molecular self-diffusion in concentrated aqueous mixtures based on an oppositely charged po
ymer-surfactant pair has been investigated by NMR pulsed field gradient techniques. The investigated structures were an ordered cubic Pm3n phase (ca. 50 wt % water) and a disordered micellar phase, both containing cetyltrimethylammonium (CTA(+)) micelles with mixed acetate (Ac-) and polyacrylate (PA(-)) counterions. In the cubic phase, CTA(+) gave broad lines in the H-1 NMR spectrum, which made it possible to use the pulsed field gradient (PFG) spin echo (SE) technique to measure the PA(-) diffusion. The observed diffusion coefficients for the four different molecular species covered 4 orders of magnitude with the rate of diffusion... (More) - The molecular self-diffusion in concentrated aqueous mixtures based on an oppositely charged po
ymer-surfactant pair has been investigated by NMR pulsed field gradient techniques. The investigated structures were an ordered cubic Pm3n phase (ca. 50 wt % water) and a disordered micellar phase, both containing cetyltrimethylammonium (CTA(+)) micelles with mixed acetate (Ac-) and polyacrylate (PA(-)) counterions. In the cubic phase, CTA(+) gave broad lines in the H-1 NMR spectrum, which made it possible to use the pulsed field gradient (PFG) spin echo (SE) technique to measure the PA(-) diffusion. The observed diffusion coefficients for the four different molecular species covered 4 orders of magnitude with the rate of diffusion decreasing in the order water > Ac- > PA(-) > CTA(+). For all species, the diffusion coefficients were largely insensitive to the counterion composition. A model considering obstruction effects and binding to the micelles could account for the reduced diffusion of Ac- and CTA(+) compared to dilute reference solutions. For water, the reduction of the diffusion was mainly
ue to obstruction effects. The PA(-) diffusion was much more retarded than the
Ac- diffusion in the cubic phase; moreover, the molecular weight
dependence of the diffusion was dramatically enhanced for the
polydisperse polyion. Both effects are attributed to electrostatic
attractions and obstruction effects experienced by polyions diffusing
in a concentrated matrix of stationary
micelles. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/122236
- author
- Svensson, Anna LU ; Topgaard, Daniel LU ; Piculell, Lennart LU and Söderman, Olle LU
- organization
- publishing date
- 2003
- type
- Contribution to journal
- publication status
- published
- subject
- in
- The Journal of Physical Chemistry Part B
- volume
- 107
- issue
- 47
- pages
- 13241 - 13250
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000186762200045
- scopus:0344272197
- ISSN
- 1520-5207
- DOI
- 10.1021/jp0348225
- language
- English
- LU publication?
- yes
- id
- 7c6f4eb1-aff1-4224-a905-db43d552810c (old id 122236)
- date added to LUP
- 2016-04-01 15:20:39
- date last changed
- 2025-04-04 15:28:28
@article{7c6f4eb1-aff1-4224-a905-db43d552810c, abstract = {{The molecular self-diffusion in concentrated aqueous mixtures based on an oppositely charged po<br/><br> ymer-surfactant pair has been investigated by NMR pulsed field gradient techniques. The investigated structures were an ordered cubic Pm3n phase (ca. 50 wt % water) and a disordered micellar phase, both containing cetyltrimethylammonium (CTA(+)) micelles with mixed acetate (Ac-) and polyacrylate (PA(-)) counterions. In the cubic phase, CTA(+) gave broad lines in the H-1 NMR spectrum, which made it possible to use the pulsed field gradient (PFG) spin echo (SE) technique to measure the PA(-) diffusion. The observed diffusion coefficients for the four different molecular species covered 4 orders of magnitude with the rate of diffusion decreasing in the order water > Ac- > PA(-) > CTA(+). For all species, the diffusion coefficients were largely insensitive to the counterion composition. A model considering obstruction effects and binding to the micelles could account for the reduced diffusion of Ac- and CTA(+) compared to dilute reference solutions. For water, the reduction of the diffusion was mainly <br/><br> ue to obstruction effects. The PA(-) diffusion was much more retarded than the<br/><br> Ac- diffusion in the cubic phase; moreover, the molecular weight<br/><br> dependence of the diffusion was dramatically enhanced for the<br/><br> polydisperse polyion. Both effects are attributed to electrostatic<br/><br> attractions and obstruction effects experienced by polyions diffusing<br/><br> in a concentrated matrix of stationary<br/><br> micelles.}}, author = {{Svensson, Anna and Topgaard, Daniel and Piculell, Lennart and Söderman, Olle}}, issn = {{1520-5207}}, language = {{eng}}, number = {{47}}, pages = {{13241--13250}}, publisher = {{The American Chemical Society (ACS)}}, series = {{The Journal of Physical Chemistry Part B}}, title = {{Molecular self-diffusion in micellar and discrete cubic phases of an ionic surfactant with mixed monovalent/polymeric counterions}}, url = {{http://dx.doi.org/10.1021/jp0348225}}, doi = {{10.1021/jp0348225}}, volume = {{107}}, year = {{2003}}, }