Layer-by-layer adsorption of polyelectrolyte and surfactant and adsorption of their complexes on solid surface

Sergeeva, I. P.; Соболев, В. Д.; Дибров, Г. А.; Churaev, N. V.

doi:10.1134/s1061933x11020116

Cited by 4 publications

(3 citation statements)

References 27 publications

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“…135 As stated in the introduction, the lamellar structure is also common in the CPEsurfactant and PE-surfactant literature with a wide range of surfactants showing these effects. [136][137][138]141 With these publications and our observed results, it is proposed that the aggregation and ordered cross-linking effects in the solution phase are transferred in the casting process. The resulting thin film would then be composed of a disordered array of ordered surfactant cross-linked CPE aggregates resulting in a quenched fluorescence intensity.…”

Section: Solid Phasesupporting

confidence: 69%

“…The formation of lamellar phases within a film has also been noted within PE and CPE-surfactant systems in the solid phase with many studies showing this effect. [136][137][138] The electrostatic interactions of CPEs allows for an easy casting process for ultrathin films known as the layer-by-layer (LBL) techniques. Once a single CPE layer is cast onto a substrate, direct layering of oppositely charged CPEs can be completed through simple dip processes into a solution of the oppositely charged CPE.…”

Section: Introductionmentioning

confidence: 99%

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Control of the Optical and Physical Characteristics of Conjugated Polyelectrolytes in the Solution and Solid Phase

Heeley¹

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<p>Conjugated Polyelectrolytes (CPEs) are a branch of conducting polymers that combine the electronic and solution processability of conjugated polymers (CPs) with the ionic and self-assembling nature of polyelectrolytes. These systems have been shown to exhibit high sensitivity with changes in aggregation state and optical character dependant on the local environment. The ionic character of the CPEs can be used as scaffolds for post-synthetic alterations allowing for control of the optical and physical characteristics. In this thesis, the control of the optical and physical characteristics of the conjugated polyelectrolytes (CPEs) sodium poly[2-(3-thienyl)ethoxyl-4-butylsulfonate] (PTEBS) and poly(9,9-bis[6-(N,N,N-trimethylammonium)hexyl]fluorine-co-altphenylene] (FPQ-X, where X denotes the various counter-ions of the polymers) is investigated though the addition of various extrinsic ions to dilute solutions and concentrated solutions used for film casting, with the main focus being in the solution phase behavior. The CPE characteristics were studied primarily through UV/Vis absorption and fluorescence spectroscopy coupled with dynamic light scattering and surface tension techniques. Controlling the solution phase characteristics of the CPE was investigated through a study of through of solvent composition effects, monovalent and divalent ion addition, organic salt addition, and surfactant additions to dilute aqueous solutions of the CPEs. Solvent composition effects were shown to result in fluorescence enhancement with changes in the polarity of the solvent, while the addition of monovalent and divalent ions was shown to induce fluorescence quenching through ionic strength, ion condensation, and cross-linking of CPE molecules dependant on the concentration and valency of the metal ion. Organic salt additions of a range of concentrations were shown to result in both concentration and alkyl chain length dependant fluorescence intensity enhancements with little changes in the particle size of aggregates in solution. The lack of change in particle size suggested that the effects were localized to the aggregate surface with the size of the organic salt inducing a steric prying effect on the CPE aggregate. A proposed model of this was created to this effect. Large changes in the optical and physical characteristics of the CPEs were found with addition of surfactants to the CPE solutions. Fluorescence quenching and enhancements, particle size increases and decreases, and absorption hypsochromic shifts have been noted, with surfactant structure and concentration dependence. The resulting effects are shown to be hydrophobically, electrostatically, and self-assembly driven. Concentration control of the CPE aggregate size and optical characteristics is completed with surfactant micelles being noted at pre-CMC concentrations within the solutions. A model of interactions at the various concentration levels of surfactant has been developed explaining these results. Transferring this system to the solid state has been shown to exhibit both bathochromic and hypsochromic shifts in absorption and have two optically active phases. The dual phase absorption and emission was attributed to a CPE-surfactant complex where the CPE backbone and surfactant self assemblies result in lamellar type structures within the cast films. The optical overlap of the emission and absorption of the CPEs used was also shown to be favorable for FRET based transfer from FPQ-X to PTEBS. Films created by the layer-by-layer technique showed FRET based signal of PTEBS via excitation of FPQ-Br showing effective FRET based energy transfer between the two species. The absorption signatures of the films with multiple layer-by-layer processes showed that the films do not result in unique layers but rather interdigitated mixtures within the film. Proof of concept P3HT with DOD addition OFET devices were then created in the attempt to alter the electrode potentials using mobile ions. The devices were found to be less efficient than that of the controls due to the disruption of self assembled structures within the devices hampering electron movement.</p>

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Section: Solid Phasesupporting

confidence: 69%

Section: Introductionmentioning

confidence: 99%

Control of the Optical and Physical Characteristics of Conjugated Polyelectrolytes in the Solution and Solid Phase

Heeley¹

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“…Despite the attractive features of surfactant–polyelectrolyte complexes there appears to be extremely few examples of surfactant-based LbL assemblies in the literature 43 and, to our knowledge, functionally mesostructured surfactant–polyelectrolyte LbL assemblies have not been previously anchored onto electrode supports. In addition, although some functional films have been fabricated by the LbL assembly of polyelectrolyte–surfactant complexes, 44 the structural tailoring of LbL-assembled films using surfactants as building blocks is far from being well investigated.…”

Section: Introductionmentioning

confidence: 99%

Hydrophobic interactions leading to a complex interplay between bioelectrocatalytic properties and multilayer meso-organization in layer-by-layer assemblies

Cortez

Matteis

Ceolı́n

et al. 2014

Phys. Chem. Chem. Phys.

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The present study explores the development of mesostructured bioelectrochemical interfaces with accurate compositional and topological control of the supramolecular architecture through the layer-by-layer assembly of ternary systems based on poly(allylamine) containing an osmium polypyridyl complex (OsPA), an anionic surfactant, sodium dodecyl sulfate (SDS) or sodium octodecyl sulfate (ODS), and glucose oxidase (GOx). We show that the introduction of the anionic surfactant allows a sensitive increase of the polyelectrolyte and the enzyme uptake at pH 7.0, enhancing its catalytic behavior in the presence of glucose as compared to the surfactant-free system (OsPA/GOx)n constructed at the same pH. Structural characterization of the multilayer films was performed by means of grazing-incidence small-angle X-ray scattering (GISAXS), which showed the formation of mesostructured domains within the composite assemblies. Experimental results indicate that the balance between ionic and hydrophobic interactions plays a leading role not only in the construction of the self-assembled system but also in the functional properties of the bioactive interface. The structure of the ternary multilayered films depends largely on the length of the alkyl chain of the surfactant. We show that surfactants incorporated into the film also play a role as chemical entities capable of tuning the hydrophobicity of the whole assembly. In this way, the deliberate introduction of short-range hydrophobic forces was exploited as an additional variable to manipulate the adsorption and coverage of protein during each assembly step. However, the integration of long-chain surfactants may lead to the formation of very well-organized interfacial architectures with poor electron transfer properties. This, in turn, leads to a complex trade-off between enzyme coverage and redox wiring that is governed by the meso-organization and the hydrophobic characteristics of the multilayer assembly.

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The effect of surfactants in the silsesquioxane solution for LbL films assembly

et al. 2017

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Layer-by-layer adsorption of polyelectrolyte and surfactant and adsorption of their complexes on solid surface

Cited by 4 publications

References 27 publications

Control of the Optical and Physical Characteristics of Conjugated Polyelectrolytes in the Solution and Solid Phase

Control of the Optical and Physical Characteristics of Conjugated Polyelectrolytes in the Solution and Solid Phase

Hydrophobic interactions leading to a complex interplay between bioelectrocatalytic properties and multilayer meso-organization in layer-by-layer assemblies

The effect of surfactants in the silsesquioxane solution for LbL films assembly

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