Investigation of the salting-in/-out, hydrotropic and surface-active behavior of plant-based hormone and phenolic acid salts.

HYPOTHESIS: The role of hormones and polyphenolic acids in communication and regulation of biological processes can be linked to their physical-chemical interaction with target compounds and water. Further, the variety of polyphenolic acids suggests adjustable hydrotropic properties of these natural compounds. EXPERIMENTS: Phase transition temperature (PTT) measurements of binary water/di(propylene glycol) n-propyl ether (DPnP) or propylene glycol n-propyl ether (PnP) systems with sodium dehydroepiandrosterone sulfate (NaDHEAS), indole-3-acetate (NaIAA), indole-3-butyrate (NaIBA) - common hormones -, and sodium polyphenolates should unravel their salting-in/-out properties. Their salting-in/-out behavior was compared to the compounds' surface-active and structuring properties via surface tension, dynamic light scattering (DLS) and Nuclear magnetic resonance (NMR) experiments. FINDINGS: All hormone salts were revealed as salting-in agents. PTT, surface tension and DLS measurements indicated surfactant-like behavior of the hormone NaDHEAS, and hydrotropic behavior of NaIAA and NaIBA. The salting-in/-out properties of sodium polyphenolates - in an (anti-)hydrotrope range - are adjustable with functional groups. The (i) absence of nano-structuring in pure water, (ii) the reduction of the DPnP nano-structuring in water in presence of sodium polyphenolates and (iii) the absence of a slope change of the PTT curves at the critical aggregation concentration showed that the DPnP/polyphenolate interactions are of molecular hydrotropic and not of micellar/aggregative nature.

Potential Dependence of Surfactant Adsorption at the Graphite Electrode/Deep Eutectic Solvent Interface.

Atomic force microscopy and cyclic voltammetry are used to probe how ionic surfactant adsorbed layer structure affects redox processes at deep eutectic solvent (DES)/graphite interfaces. Unlike its behavior in water, sodium dodecyl sulfate (SDS) in DESs only adsorbs as a complete layer of hemicylindrical hemimicelles far above its critical micelle concentration (CMC). Near the CMC it forms a tail-to-tail monolayer at open-circuit potential (OCP) and positive potentials, and it desorbs at negative potentials. In contrast, cetyltrimethylammonium bromide (CTAB) adsorbs as hemimicelles at low concentrations and remains adsorbed at both positive and negative potentials. The SDS horizontal monolayer has little overall effect on redox processes at the graphite interface, but hemimicelles form an effective and stable barrier. The stronger solvophobic interactions between the C16 versus C12 alkyl chains in the DES allow CTAB to self-assemble into a robust coating at low concentrations and illustrate how the structure of the DES/electrode interface and electrochemical response can be engineered by controlling surfactant structure.

Carnitine alkyl ester bromides as novel biosourced ionic liquids, cationic hydrotropes and surfactants.

HYPOTHESIS: In contrast to anionic and nonionic amphiphilic substances, bio-based cationic ones are very rare. Cationic amphiphiles are mostly based on quaternary ammonium, pyridinium or imidazolium groups that are either badly biodegradable or have toxic residues even after degradation. In the search for green alternatives to cationic hydrotropes and amphiphiles, natural l-carnitine could be a promising candidate for a cationic headgroup. EXPERIMENTS: By esterification of carnitine in one step and with low cost, cationic molecules with alkyl chain length of n=2-14 could be obtained. Their thermal properties, aggregation behaviour and cytotoxicity were determined. Hydrophobic compounds were solubilized in their aqueous solutions and the PIT-slope method was applied to determine a relative hydrophilicity. FINDINGS: It was found that some pure carnitine ester bromides were liquid at room temperature and thus can be classified as ionic liquids. They are highly water-soluble, and in aqueous solutions, they showed hydrotrope or surfactant behaviour depending on their alkyl chain length. Their high hydrotropic efficiency was demonstrated by solubilizing Disperse Red 13, while also biomolecules, like vanillin, could be dissolved in reasonable amounts. In all tests, they performed at least as good as the tested reference substances, while showing similar cytotoxicity towards human skin keratinocytes, thus demonstrating their potential as green functional amphiphilic molecules of positive charge.