Self-Assembly of Polyelectrolyte Rods in Polymer Gel and in Solution:  Small-Angle Neutron Scattering Study

Zaroslov, Yuri D.; Gordeliy, Valentin; Куклин, А. И.; Islamov, Akhmed; Philippova, Olga E.; Khokhlov, Alexei R.; Wegner, Gerhard

doi:10.1021/ma0120207

Cited by 40 publications

(44 citation statements)

References 8 publications

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“…32 Therefore, the observed ordering in the considered dilute solutions (∼1 wt %) is certainly not caused by steric effects but rather by the electrostatic repulsive interactions induced by the charged PBS-PFP molecules. This ordering should not be a surprise as the counterion sensitive order and a reflection at low q due to electrostatic repulsion have been reported also for example for aqueous PPP [8][9][10] and MBL-PPV 11 polyelectrolytes.…”

Section: Discussionsupporting

confidence: 66%

Solubilization of Polyelectrolytic Hairy-Rod Polyfluorene in Aqueous Solutions of Nonionic Surfactant

Knaapila¹,

Garamus²,

Pearson³

et al. 2006

J. Phys. Chem. B

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We report on the solubilization, phase behavior, and self-organized colloidal structure of a ternary waterpolyfluorene-surfactant (amphiphile) system comprised of polyelectrolytic poly{1,4-phenylene[9,9-bis(4-phenoxybutylsulfonate)]fluorene-2,7-diyl} (PBS-PFP) in nonionic pentaethylene glycol monododecyl ether (C 12 E 5 ) at 20°C. We show in particular how a high amount (milligrams per milliliter) of polyfluorene can be solubilized by aqueous C 12 E 5 via aggregate formation. The PBS-PFP and C 12 E 5 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 D 2 O-PBS-PFP(C 12 E 5 ) x realizes three phase regimes with an increasing molar ratio of surfactant over monomer unit (x). First, for x e 0.5, the mixture is cloudy. In this regime polymer is only partially dissolved. Second, for 1 e x e 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 g 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 C 12 E 5 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.

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Section: Discussionsupporting

confidence: 66%

Solubilization of Polyelectrolytic Hairy-Rod Polyfluorene in Aqueous Solutions of Nonionic Surfactant

Knaapila¹,

Garamus²,

Pearson³

et al. 2006

J. Phys. Chem. B

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“…41−43 Hydrated membrane studies have primarily focused on microphase-separated morphologies in ionomer−water mixtures of Nafion. Atomistic molecular dynamics (MD) simulations [27][28][29][30][31][32]34,37 have served as the focal point of membrane simulation studies. Other approaches such dissipative particle dynamics (DPD) simulations 50,53,55 and mean-field approaches 56 have helped expanding the time and length scale of atomistic simulations.…”

Section: ■ Introductionmentioning

confidence: 99%

Ionomer Self-Assembly in Dilute Solution Studied by Coarse-Grained Molecular Dynamics

2016

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Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions? Contact the NRC Publications Archive team atPublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://doi.org/10.1021/acs.macromol.5b02158Access and use of this website and the material on it are subject to the Terms and Conditions set forth at Ionomer self-assembly in dilute solution studied by coarse-grained molecular dynamics Ghelichi, Mahdi; Malek, Kourosh; Eikerling, Michael H. NRC Publications Record / Notice d'Archives des publications de CNRC:http://nparc.cisti-icist.nrc-cnrc.gc.ca/eng/view/object/?id=2aeba8dc-9a31-4a12-83a6-c0e4356cbc1e http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/voir/objet/?id=2aeba8dc-9a31-4a12-83a6-c0e4356cbc1e Bundles have a core of backbones surrounded by a surface layer of charged anionic headgroups and a diffuse halo of counterions. Parametric studies of bundle properties unravel the interplay of backbone hydrophobicity, strength of electrostatic interactions between charged moieties, side chain content, and counterion valence: expectedly, the size of bundles increases with backbone hydrophobicity; the aggregate size depends nonmonotonically on the Bjerrum length; increasing the grafting density of pendant side chains results in smaller bundles; and the counterion valence exerts a strong effect on bundle size and counterion localization in the near-bundle region. Results reveal how the ionomer architecture and solvent properties influence the ionomer aggregation and associated electrostatic and mechanical bundle properties. These properties of ionomer aggregates are vital for rationalizing the water sorption behavior and transport phenomena as well as the chemical and mechanical stability of ionomer membranes.

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“…[1][2][3][4][5] -see Figure 1). The visco-elastic properties of the network are characterized by the friction coefficient of network junctions z N0 and by elasticity constant, K N0 , characterizing the entropic elasticity of network strands (Figure 1).…”

Section: Model Of a Polymer Network With Included Rods And Main Equatmentioning

confidence: 99%

“…In the last years, polymer network gels containing rod-like particles were synthesized and experimentally investigated [1][2][3][4][5] . The ability of gels with included rods to change drastically and reversibly their volume in response to variation of the external stimulus (temperature, pH etc.)…”

Section: Introductionmentioning

confidence: 99%

“…The long enough rigid rods in these systems are not covalently attached to the network but they are effectively retained inside the gel and cannot diffuse up to long distance from their average positions [5] . The rods can be quasi-elastically involved into long-scale network motions (due to topological entanglements) and therefore should move together with network fragments.…”

Section: Introductionmentioning

confidence: 99%

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The Local and Collective Mobility in Polymer Chains and Networks with Included Rigid Particles Elastically Connected with the Network

Gotlib

Torchinskii

Toshchevikov

et al. 2006

Macromolecular Symposia

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Summary:The theory of molecular mobility of a polymer network with included rodlike particles is developed. The case is considered when the length of rods is comparable or greater than the average distance between neighboring cross-links of the primary network. The long-scale dynamics of the network is described by means of a regular cubic ''coarse-grained'' model. The junctions of this model describe the great network fragments (domains) the sizes of which are near to the average distance between neighboring rods.The quasi-elastic interactions between rods and network fragments lead to a broad relaxation spectrum for included rods as compared with free rods which are characterized by a single relaxation time of rotational diffusion. The frequency dependence of the dielectric loss factor of included rods is calculated for rods with permanent dipole moments directed parallel to the long axes of the rods chaotically distributed in the network. The frequency dependence of dynamic modulus of a polymer network with included rods is obtained. The increment in the dynamic modulus of the relatively short network motions (smaller than the distance between rods) also is taken into account. The broad relaxation spectrum of included rods leads to appearance of several maximums on the frequency dependences of both the dielectric loss factor and dynamical modulus.

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Self-Assembly of Polyelectrolyte Rods in Polymer Gel and in Solution: Small-Angle Neutron Scattering Study

Cited by 40 publications

References 8 publications

Solubilization of Polyelectrolytic Hairy-Rod Polyfluorene in Aqueous Solutions of Nonionic Surfactant

Solubilization of Polyelectrolytic Hairy-Rod Polyfluorene in Aqueous Solutions of Nonionic Surfactant

Ionomer Self-Assembly in Dilute Solution Studied by Coarse-Grained Molecular Dynamics

The Local and Collective Mobility in Polymer Chains and Networks with Included Rigid Particles Elastically Connected with the Network

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