Solubilization of polyelectrolytic hairy-rod polyfluorene in aqueous solutions of nonionic surfactant

Matti Knaapila, L. Almásy, Vasil M. Garamus, Christopher Pearson, Swapna Pradhan, Michael C. Petty, Ullrich Scherf, Hugh D. Burrows, Andrew P. Monkman

Research output: Contribution to journalArticle

49 Citations (Scopus)

Abstract

We report on the solubilization, phase behavior, and self-organized colloidal structure of a ternary water-polyfluorene - surfactant (amphiphile) system comprised of polyelectrolytic poly{1,4-phenylene[9,9- bis(4phenoxybutylsulfonate)]fluorene-2,7-diyl} (PBS-PFP) in nonionic pentaethylene glycol monododecyl ether (C12E5) at 20 °C. We show in particular how a high amount (milligrams per milliliter) of polyfluorene can be solubilized by aqueous C12E5 via aggregate formation. The PBS-PFP and C12E5 concentrations of 0.31 × 10-4-5 × 10-4 M and 2.5 × 10-4-75 × 10-4 M, respectively, were used. Under the studied conditions, the photoluminescence (PL), surface tension, static contact angle, and (π-A) isotherm measurements imply that D2O-PBS- PFP(C12E5)x realizes three phase regimes with an increasing molar ratio of surfactant over monomer unit (x). First, for x ≤ 0.5, the mixture is cloudy. In this regime polymer is only partially dissolved. Second, for 1 ≤ x ≤ 2, the solution is homogeneous. In this regime polymer is dissolved down to the colloidal level. Small-angle neutron scattering (SANS) patterns indicate rigid elongated (polymer-surfactant) aggregates with a diameter of 30 Å and mean length of ∼900 Å. The ratio between contour length and persistence length is less than 3. Third, for x ≥ 4, the solution is homogeneous and there is cooperative binding between polymer and surfactant. Surface tension, contact angle, and surface pressure remain essentially constant with increasing x. A PL spectrum characteristic of single separated polyfluorene molecules is observed. SANS curves show an interference maximum at q ∼ 0.015 Å-1, indicating an ordered phase. This ordering is suggested to be due to the electrostatic repulsion between polymer molecules adsorbed on or incorporated into the C12E5 aggregates (micelles). On dilution the distance between micelles increases via 3-dimensional packing. In this regime the polymer is potentially dissolved down to the molecular level. We show further that the aggregates (x = 2) form a floating layer at the air-water interface and can be transferred onto hydrophilic substrates.

Original languageEnglish
Pages (from-to)10248-10257
Number of pages10
JournalJournal of Physical Chemistry B
Volume110
Issue number21
DOIs
Publication statusPublished - Jun 1 2006

Fingerprint

Nonionic surfactants
Polymers
rods
surfactants
aqueous solutions
Surface-Active Agents
polymers
Surface active agents
Micelles
Neutron scattering
Contact angle
Surface tension
micelles
Photoluminescence
interfacial tension
neutron scattering
photoluminescence
Amphiphiles
Molecules
Water

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Knaapila, M., Almásy, L., Garamus, V. M., Pearson, C., Pradhan, S., Petty, M. C., ... Monkman, A. P. (2006). Solubilization of polyelectrolytic hairy-rod polyfluorene in aqueous solutions of nonionic surfactant. Journal of Physical Chemistry B, 110(21), 10248-10257. https://doi.org/10.1021/jp0560563

Solubilization of polyelectrolytic hairy-rod polyfluorene in aqueous solutions of nonionic surfactant. / Knaapila, Matti; Almásy, L.; Garamus, Vasil M.; Pearson, Christopher; Pradhan, Swapna; Petty, Michael C.; Scherf, Ullrich; Burrows, Hugh D.; Monkman, Andrew P.

In: Journal of Physical Chemistry B, Vol. 110, No. 21, 01.06.2006, p. 10248-10257.

Research output: Contribution to journalArticle

Knaapila, M, Almásy, L, Garamus, VM, Pearson, C, Pradhan, S, Petty, MC, Scherf, U, Burrows, HD & Monkman, AP 2006, 'Solubilization of polyelectrolytic hairy-rod polyfluorene in aqueous solutions of nonionic surfactant', Journal of Physical Chemistry B, vol. 110, no. 21, pp. 10248-10257. https://doi.org/10.1021/jp0560563
Knaapila, Matti ; Almásy, L. ; Garamus, Vasil M. ; Pearson, Christopher ; Pradhan, Swapna ; Petty, Michael C. ; Scherf, Ullrich ; Burrows, Hugh D. ; Monkman, Andrew P. / Solubilization of polyelectrolytic hairy-rod polyfluorene in aqueous solutions of nonionic surfactant. In: Journal of Physical Chemistry B. 2006 ; Vol. 110, No. 21. pp. 10248-10257.
@article{2859a87cf3b640689eafd71e6d23d479,
title = "Solubilization of polyelectrolytic hairy-rod polyfluorene in aqueous solutions of nonionic surfactant",
abstract = "We report on the solubilization, phase behavior, and self-organized colloidal structure of a ternary water-polyfluorene - surfactant (amphiphile) system comprised of polyelectrolytic poly{1,4-phenylene[9,9- bis(4phenoxybutylsulfonate)]fluorene-2,7-diyl} (PBS-PFP) in nonionic pentaethylene glycol monododecyl ether (C12E5) at 20 °C. We show in particular how a high amount (milligrams per milliliter) of polyfluorene can be solubilized by aqueous C12E5 via aggregate formation. The PBS-PFP and C12E5 concentrations of 0.31 × 10-4-5 × 10-4 M and 2.5 × 10-4-75 × 10-4 M, respectively, were used. Under the studied conditions, the photoluminescence (PL), surface tension, static contact angle, and (π-A) isotherm measurements imply that D2O-PBS- PFP(C12E5)x realizes three phase regimes with an increasing molar ratio of surfactant over monomer unit (x). First, for x ≤ 0.5, the mixture is cloudy. In this regime polymer is only partially dissolved. Second, for 1 ≤ x ≤ 2, the solution is homogeneous. In this regime polymer is dissolved down to the colloidal level. Small-angle neutron scattering (SANS) patterns indicate rigid elongated (polymer-surfactant) aggregates with a diameter of 30 {\AA} and mean length of ∼900 {\AA}. The ratio between contour length and persistence length is less than 3. Third, for x ≥ 4, the solution is homogeneous and there is cooperative binding between polymer and surfactant. Surface tension, contact angle, and surface pressure remain essentially constant with increasing x. A PL spectrum characteristic of single separated polyfluorene molecules is observed. SANS curves show an interference maximum at q ∼ 0.015 {\AA}-1, indicating an ordered phase. This ordering is suggested to be due to the electrostatic repulsion between polymer molecules adsorbed on or incorporated into the C12E5 aggregates (micelles). On dilution the distance between micelles increases via 3-dimensional packing. In this regime the polymer is potentially dissolved down to the molecular level. We show further that the aggregates (x = 2) form a floating layer at the air-water interface and can be transferred onto hydrophilic substrates.",
author = "Matti Knaapila and L. Alm{\'a}sy and Garamus, {Vasil M.} and Christopher Pearson and Swapna Pradhan and Petty, {Michael C.} and Ullrich Scherf and Burrows, {Hugh D.} and Monkman, {Andrew P.}",
year = "2006",
month = "6",
day = "1",
doi = "10.1021/jp0560563",
language = "English",
volume = "110",
pages = "10248--10257",
journal = "Journal of Physical Chemistry B Materials",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "21",

}

TY - JOUR

T1 - Solubilization of polyelectrolytic hairy-rod polyfluorene in aqueous solutions of nonionic surfactant

AU - Knaapila, Matti

AU - Almásy, L.

AU - Garamus, Vasil M.

AU - Pearson, Christopher

AU - Pradhan, Swapna

AU - Petty, Michael C.

AU - Scherf, Ullrich

AU - Burrows, Hugh D.

AU - Monkman, Andrew P.

PY - 2006/6/1

Y1 - 2006/6/1

N2 - We report on the solubilization, phase behavior, and self-organized colloidal structure of a ternary water-polyfluorene - surfactant (amphiphile) system comprised of polyelectrolytic poly{1,4-phenylene[9,9- bis(4phenoxybutylsulfonate)]fluorene-2,7-diyl} (PBS-PFP) in nonionic pentaethylene glycol monododecyl ether (C12E5) at 20 °C. We show in particular how a high amount (milligrams per milliliter) of polyfluorene can be solubilized by aqueous C12E5 via aggregate formation. The PBS-PFP and C12E5 concentrations of 0.31 × 10-4-5 × 10-4 M and 2.5 × 10-4-75 × 10-4 M, respectively, were used. Under the studied conditions, the photoluminescence (PL), surface tension, static contact angle, and (π-A) isotherm measurements imply that D2O-PBS- PFP(C12E5)x realizes three phase regimes with an increasing molar ratio of surfactant over monomer unit (x). First, for x ≤ 0.5, the mixture is cloudy. In this regime polymer is only partially dissolved. Second, for 1 ≤ x ≤ 2, the solution is homogeneous. In this regime polymer is dissolved down to the colloidal level. Small-angle neutron scattering (SANS) patterns indicate rigid elongated (polymer-surfactant) aggregates with a diameter of 30 Å and mean length of ∼900 Å. The ratio between contour length and persistence length is less than 3. Third, for x ≥ 4, the solution is homogeneous and there is cooperative binding between polymer and surfactant. Surface tension, contact angle, and surface pressure remain essentially constant with increasing x. A PL spectrum characteristic of single separated polyfluorene molecules is observed. SANS curves show an interference maximum at q ∼ 0.015 Å-1, indicating an ordered phase. This ordering is suggested to be due to the electrostatic repulsion between polymer molecules adsorbed on or incorporated into the C12E5 aggregates (micelles). On dilution the distance between micelles increases via 3-dimensional packing. In this regime the polymer is potentially dissolved down to the molecular level. We show further that the aggregates (x = 2) form a floating layer at the air-water interface and can be transferred onto hydrophilic substrates.

AB - We report on the solubilization, phase behavior, and self-organized colloidal structure of a ternary water-polyfluorene - surfactant (amphiphile) system comprised of polyelectrolytic poly{1,4-phenylene[9,9- bis(4phenoxybutylsulfonate)]fluorene-2,7-diyl} (PBS-PFP) in nonionic pentaethylene glycol monododecyl ether (C12E5) at 20 °C. We show in particular how a high amount (milligrams per milliliter) of polyfluorene can be solubilized by aqueous C12E5 via aggregate formation. The PBS-PFP and C12E5 concentrations of 0.31 × 10-4-5 × 10-4 M and 2.5 × 10-4-75 × 10-4 M, respectively, were used. Under the studied conditions, the photoluminescence (PL), surface tension, static contact angle, and (π-A) isotherm measurements imply that D2O-PBS- PFP(C12E5)x realizes three phase regimes with an increasing molar ratio of surfactant over monomer unit (x). First, for x ≤ 0.5, the mixture is cloudy. In this regime polymer is only partially dissolved. Second, for 1 ≤ x ≤ 2, the solution is homogeneous. In this regime polymer is dissolved down to the colloidal level. Small-angle neutron scattering (SANS) patterns indicate rigid elongated (polymer-surfactant) aggregates with a diameter of 30 Å and mean length of ∼900 Å. The ratio between contour length and persistence length is less than 3. Third, for x ≥ 4, the solution is homogeneous and there is cooperative binding between polymer and surfactant. Surface tension, contact angle, and surface pressure remain essentially constant with increasing x. A PL spectrum characteristic of single separated polyfluorene molecules is observed. SANS curves show an interference maximum at q ∼ 0.015 Å-1, indicating an ordered phase. This ordering is suggested to be due to the electrostatic repulsion between polymer molecules adsorbed on or incorporated into the C12E5 aggregates (micelles). On dilution the distance between micelles increases via 3-dimensional packing. In this regime the polymer is potentially dissolved down to the molecular level. We show further that the aggregates (x = 2) form a floating layer at the air-water interface and can be transferred onto hydrophilic substrates.

UR - http://www.scopus.com/inward/record.url?scp=33745509237&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33745509237&partnerID=8YFLogxK

U2 - 10.1021/jp0560563

DO - 10.1021/jp0560563

M3 - Article

C2 - 16722726

AN - SCOPUS:33745509237

VL - 110

SP - 10248

EP - 10257

JO - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

IS - 21

ER -