Polyelectrolytes Carrying Pendant (Cyanobiphenylyl)oxy Chromophores. Synthesis, Behavior in Aqueous Solution, and Interactions with Surfactants

Abstract

Poly(sulfonylethylmaleic acid monoamide-co-alkyl vinyl ether)s carrying both a sulfonic acid and a carboxylic acid moiety are obtained by reacting the corresponding poly(maleic anhydride-co-alkyl vinyl ether)s with 2-aminoethanesulfonic acid. The alkyl vinyl ethers have a n-hexyl or n-dodecyl group or the alkyl groups have a terminal (cyanobiphenylyl)oxy chromophore and spacer lengths of 6−12 methylene units. Dynamic light scattering experiments show that all polymers form large aggregates in water in which the polymer chains are entangled. The formed aggregates are highly ordered as can be deduced from the blue shift of the absorption maxima of the chromophores by UV spectroscopy. When the charge density on the polyelectrolyte backbones is increased by varying the pH or the hydrophobicity of the polyelectrolyte is decreased by variation of the spacer length, the aggregates become more open and less ordered. The interaction between the polyelectrolytes and n-dodecyltrimethylammonium bromide (DTAB) has been investigated by potentiometry using a DTAB-selective electrode and surface tension measurements. The binding already has begun at very low DTAB concentrations and has been shown to be noncooperative. This is caused by the presence of hydrophobic microdomains formed by the polyelectrolytes. With small amounts of DTAB the polyelectrolytes form highly surface active complexes. These complexes are more hydrophobic than the individual components, resulting in an accumulation of the complexes at the air−solution interface. UV spectroscopy was used to investigate the interactions between the polyelectrolytes and DTAB, n-hexadecyltrimethylammonium bromide, poly(oxyethylene(4)lauryl ether), and sodium dodecyl sulfate.

Ultrathin polymer coatings by complexation of polyelectrolytes at interfaces: suitable materials, structure and properties

“…14. Examples of charged hydrophobically associative polymers used for ESA 54,135,[376][377][378] films and an extremely high roughness. Studies on the use of amphiphilic block copolymers reported poor quality for thicker ESA-films, too, if the hydrophobic block becomes large 374,375) .…”

Characterization of Solvation Environment Provided by Dilute Poly(sulfonyl maleic anhydride‐co‐dodecyl vinyl ether) Solutions at Various pH Using Pyrene and 1,3‐Bis(1‐pyrenyl)propane as Fluorescence Probes

“…[11] Sodium dodecyl sulfate (SDS, 99.7%) was purchased from Fisher Scientific and was used as received. Background electrolyte buffers for electrokinetic chromatography were prepared at pH 4.0 (10 mM acetate, Aldrich), 7.0 (20 mM TRIS, Sigma) and 9.0 (50 mM Borate, Aldrich).…”

“…[1][2][3][4][5][6][7][8][9][10][11][12] In many cases, these polymers have properties similar to those of conventional surfactant micelles in that they can solubilize compounds with otherwise low water solubility. [13,14] Applications for such materials have been developed or proposed in drug delivery, detergency, oil recovery and analytical chemistry.…”

“…[13,14] Applications for such materials have been developed or proposed in drug delivery, detergency, oil recovery and analytical chemistry. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] In recent years, polymers of this type have received significant attention for application in analytical chemistry as pseudo-stationary phases in electrokinetic chromatography. [13,14] The polymers provide several advantages relative to conventional micelles for this application, including stability in the presence of organic solvents, applicability with mass spectrometric detection, and unique and varied chemical separation selectivity.…”

“…Nieuwkerk et al have demonstrated that a polymer of similar structure can be obtained via reaction of taurine with maleic anhydride groups on the backbone of the precursor polymer to yield sulfonylethyl groups. [11] This yields polymers with the basic structure shown in Figure 1. The presence of the sulfonic acid group substantially increases the solubility of the polymers, especially at pH < 7, and significantly alters the extent to which pH affects the ionization of the polymer.…”