The association behavior of polyelectrolyte block copolymers in aqueous solution as a function of polymer and salt concentration is investigated for poly(ethylethylene-b-styrenesulfonic acid) (PEE-PSSH). This copolymer combines a soft hydrophobic block with a highly charged polyelectrolyte block that allows direct dissolution in aqueous solutions to investigate micellization under equilibrium conditions. Increasing polymer and salt concentration leads to the fusion of polyelectrolyte micelles into vesicles and fractal toroid-micronetworks. Association structures were characterized by static light scattering (SLS), small-angle neutron scattering (SANS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). At high salt concentrations the solution phase separates into a dilute micellar phase and a concentrated gel phase.

The morphology of the J-aggregates formed after the addition of ionic surfactants into solutions of the 3,3‘-bis(3-carboxypropyl)-5,5‘,6,6‘-tetrachloro-1,1‘-dioctylbenzimidacarbocyanine dye (C8O3) was characterized by absorption and circular dichroism spectroscopy, cryogenic temperature transmission electron microscopy, scanning force microscopy, and small-angle neutron scattering. The optical activity of the C8O3 J-aggregates, existing in aqueous solution as superhelices composed of tubular single strands, disappears upon addition of both cationic and anionic surfactants. This is accompanied by distinct spectral changes in the visible region as well as changes of the aggregates' morphology. The anionic surfactant sodium dodecyl sulfate induces the formation of single-walled tubules of 15 nm diameter and 300−600 nm length, which completely transform after several days into thick multilamellar tubes of micrometer length. The cationic surfactant trimethyltetradecylammonium bromide first produces vesicles that later transform again into tubular aggregates of nanometer thickness and micrometer length.

A chemical mapping with high lateral resolution using an atomic force microscope in the pulsed force mode with chemically modified tips, introduced as "dynamic chemical force microscopy" (dCFM), was carried out to investigate the chemical properties of the cuticle of human hair and its changes following an oxidative treatment. Chemically modified atomic force microscopy (AFM) tips, CH3- and NH2-terminated, were applied to achieve a defined chemical contrast (hydrophobic and ionic) in aqueous medium. A comparative Fourier transform infrared spectroscopy-attenuated total reflection identified the dominant chemical groups of the surface vicinity of the hair fiber resulting from the bleaching process. The combined experimental results lead to the conclusion that the hydrophobic top layer is partially removed after bleaching, resulting mostly in hydrophilic SO3(-) end groups at the top of the surface of the hair, with a mean surface density "δ(mean)" of negatively charged groups of approximately 2.2 molecules/nm(2), corresponding to ∼600 μg/m(2) cysteic acid. This indicates that thioester bonds are disrupted and fatty acids are removed as a result of cysteine oxidation. At the molecular level, our results indicate a clustered "self-assembled monolayer" alignment of cysteic acid with a crystal-like structuring, reminiscent of the "fluid mosaic model of cell membranes", with a surface energy of approximately 0.04 N/m. Despite previous extensive works of AFM on human hair, this is, to our knowledge, the first time that the hydrophobic and ionic sites at the top surface of hair have been imaged at the nanoscale with dCFM.