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Solubilization of poly{1,4-phenylene-[9,9-bis(4-phenoxy-butylsulfonate)]fluorene-2,7-diyl} in Water by Non-Ionic Amphiphiles

Burrows, Hugh D.; Tapia, Maria J.; Fonesca, Sofia M.; Pradhan, Swapna; Scherf, Ullrich; Silva, Cláudia L.; Pais, Alberto A. C. C.; Valente, Artur J. M.; Schillén, Karin LU and Alfredsson, Viveka LU , et al. (2009) In Langmuir 25(10). p.5545-5556
Abstract
In the presence of the nonionic alkyloxyethylene surfactant n-dodecylpentaoxyethylene glycol ether (C12E5), the

anionic conjugated polyelectrolyte (CPE) poly{1,4-phenylene-[9,9-bis(4-phenoxy-butylsulfonate)]fluorene-2,7-diyl}

(PBS-PFP) dissolves in water, leading to a blue shift in fluorescence and dramatic increases in fluorescence quantum

yields above the surfactant critical micelle concentration (cmc). No significant changes were seen with a poly(ethylene

oxide) of similar size to the surfactant headgroup, confirming that specific surfactant-polyelectrolyte interactions are

important. From UV-visible and fluorescence spectroscopy, dynamic light scattering (DLS), small-angle X-ray

... (More)
In the presence of the nonionic alkyloxyethylene surfactant n-dodecylpentaoxyethylene glycol ether (C12E5), the

anionic conjugated polyelectrolyte (CPE) poly{1,4-phenylene-[9,9-bis(4-phenoxy-butylsulfonate)]fluorene-2,7-diyl}

(PBS-PFP) dissolves in water, leading to a blue shift in fluorescence and dramatic increases in fluorescence quantum

yields above the surfactant critical micelle concentration (cmc). No significant changes were seen with a poly(ethylene

oxide) of similar size to the surfactant headgroup, confirming that specific surfactant-polyelectrolyte interactions are

important. From UV-visible and fluorescence spectroscopy, dynamic light scattering (DLS), small-angle X-ray

scattering (SAXS), cryogenic transmission electron microscopy (cryo-TEM), and electrical conductivity, together with

our published NMR and small-angle neutron scattering (SANS) results, we provide a coherent model for this behavior

in terms of breakup of PBS-PFP clusters through polymer-surfactant association leading to cylindrical aggregates

containing isolated polymer chains. This is supported by molecular dynamics simulations, which indicate stable

polymer-surfactant structures and also provide indications of the tendency of C12E5 to break up polymer clusters to

form these mixed polymer-surfactant aggregates. Radial electron density profiles of the cylindrical cross section

obtained from SAXS results reveal the internal structure of such inhomogeneous species. DLS and cryo-TEM results

show that at higher surfactant concentrations the micelles start to grow, possibly partially due to formation of long,

threadlike species. Other alkyloxyethylene surfactants, together with poly(propylene glycol) and hydrophobically

modified poly(ethylene glycol), also solubilize this polymer in water, and it is suggested that this results from a balance

between electrostatic (or ion-dipole), hydrophilic, and hydrophobic interactions. There is a small, but significant,

dependence of the emission maximum on the local environment. (Less)
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Langmuir
volume
25
issue
10
pages
5545 - 5556
publisher
The American Chemical Society
external identifiers
  • wos:000266081000022
  • scopus:66249122070
ISSN
0743-7463
DOI
10.1021/la8042044
language
English
LU publication?
yes
id
52bd35d4-dfe5-4095-abcd-0bb36057903f (old id 1405914)
date added to LUP
2009-05-29 08:28:46
date last changed
2017-12-10 03:49:51
@article{52bd35d4-dfe5-4095-abcd-0bb36057903f,
  abstract     = {In the presence of the nonionic alkyloxyethylene surfactant n-dodecylpentaoxyethylene glycol ether (C12E5), the<br/><br>
anionic conjugated polyelectrolyte (CPE) poly{1,4-phenylene-[9,9-bis(4-phenoxy-butylsulfonate)]fluorene-2,7-diyl}<br/><br>
(PBS-PFP) dissolves in water, leading to a blue shift in fluorescence and dramatic increases in fluorescence quantum<br/><br>
yields above the surfactant critical micelle concentration (cmc). No significant changes were seen with a poly(ethylene<br/><br>
oxide) of similar size to the surfactant headgroup, confirming that specific surfactant-polyelectrolyte interactions are<br/><br>
important. From UV-visible and fluorescence spectroscopy, dynamic light scattering (DLS), small-angle X-ray<br/><br>
scattering (SAXS), cryogenic transmission electron microscopy (cryo-TEM), and electrical conductivity, together with<br/><br>
our published NMR and small-angle neutron scattering (SANS) results, we provide a coherent model for this behavior<br/><br>
in terms of breakup of PBS-PFP clusters through polymer-surfactant association leading to cylindrical aggregates<br/><br>
containing isolated polymer chains. This is supported by molecular dynamics simulations, which indicate stable<br/><br>
polymer-surfactant structures and also provide indications of the tendency of C12E5 to break up polymer clusters to<br/><br>
form these mixed polymer-surfactant aggregates. Radial electron density profiles of the cylindrical cross section<br/><br>
obtained from SAXS results reveal the internal structure of such inhomogeneous species. DLS and cryo-TEM results<br/><br>
show that at higher surfactant concentrations the micelles start to grow, possibly partially due to formation of long,<br/><br>
threadlike species. Other alkyloxyethylene surfactants, together with poly(propylene glycol) and hydrophobically<br/><br>
modified poly(ethylene glycol), also solubilize this polymer in water, and it is suggested that this results from a balance<br/><br>
between electrostatic (or ion-dipole), hydrophilic, and hydrophobic interactions. There is a small, but significant,<br/><br>
dependence of the emission maximum on the local environment.},
  author       = {Burrows, Hugh D. and Tapia, Maria J. and Fonesca, Sofia M. and Pradhan, Swapna and Scherf, Ullrich and Silva, Cláudia L. and Pais, Alberto A. C. C. and Valente, Artur J. M. and Schillén, Karin and Alfredsson, Viveka and Carnerup, Anna and Tomšič, Matija and Jamnik, Andrej},
  issn         = {0743-7463},
  language     = {eng},
  number       = {10},
  pages        = {5545--5556},
  publisher    = {The American Chemical Society},
  series       = {Langmuir},
  title        = {Solubilization of poly{1,4-phenylene-[9,9-bis(4-phenoxy-butylsulfonate)]fluorene-2,7-diyl} in Water by Non-Ionic Amphiphiles},
  url          = {http://dx.doi.org/10.1021/la8042044},
  volume       = {25},
  year         = {2009},
}