The skin is the largest organ of the body, whose main function is to protect the body against the loss of physiologically important components as well as harmful environmental insults. From the inside to the outside, the skin comprises three major structural layers: the hypodermis, the dermis and the epidermis. The epidermis contains four different sublayers, the stratum corneum (SC), stratum granulosum, stratum spinosum and stratum basale, where the barrier function of the skin mainly lies in the outermost layer of the epidermis, the SC. The SC contains corneocytes that are embedded in a lipid matrix existing in the form of lipid bilayers. The lipid bilayers are formed mainly from ceramides, free fatty acids and cholesterol, constitute the only continuous pathway across the SC and are responsible for the barrier function of the skin. However, the depletion or disturbance of SC lipids in the SC leads to a perturbation of the barrier function of the skin, and, conversely, several skin diseases such as psoriasis and atopic dermatitis are associated with the depletion of these SC lipids. Therefore, it is of paramount importance to understand the interrelationship between the depletion of SC lipids and skin diseases as well as factors that affect the composition and organization of SC lipids in order to assess the potential benefit of a direct replacement of the missing SC lipids as a means of treating affected, aged or diseased skin. i 2014 S. Karger AG, Basel

The temperature-dependent self-assembly of the single-chain bolaamphiphile dotriacontan-1,1'-diyl-bis[2-(trimethylammonio)ethyl phosphate] (PC-C32-PC) was investigated by transmission electron microscopy (TEM), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), X-ray scattering, rheological measurements, and dynamic light scattering (DLS). At room temperature this compound, in which two phosphocholine headgroups are connected by a C(32) alkyl chain, proved to be capable of gelling water very efficiently by forming a dense network of nanofibers (Kohler et al. Angew. Chem., Int. Ed. 2004, 43, 245). A specific feature of this self-assembly process is that it is not driven by hydrogen bonds but solely by hydrophobic interactions of the long alkyl chains. The nanofibers have a thickness of roughly the molecular length and show a helical superstructure. A model for the molecular structure of the fibrils which considers the extreme constitution of the bolaamphiphile is proposed. Upon heating the suspensions three different phase transitions can be detected. Above 49 degrees C, the temperature of the main transition where the alkyl chains become "fluid", a clear low-viscosity solution is obtained due to a breakdown of the fibrils into smaller aggregates. Through mechanical stress the gel structure can be destroyed as well, indicating a low stability of these fibers. The gel formation is reversible, but as a drastic rearrangement of the molecules takes place, metastable states occur.

The formation of temperature-, concentration-, and pH-responsive hydrogels composed of the symmetric long-chain bolaamphiphile dotriacontane-1,1'-diyl bis[[2-(dimethylammonio)ethyl]phosphate] (Me(2)PE-C32-Me(2)PE) was investigated by rheological, scattering, and spectroscopic techniques. At pH 5, this bolaamphiphile is known to form a dense network of helically structured nanofibers (Köhler et al. Soft Matter 2006, 2, 77-86). Rheological measurements and dynamic light scattering were used to describe the macroscopic behavior of the hydrogels. Small-angle neutron scattering (SANS) and time-resolved static light scattering were applied to get information about the morphology of the self-assembled aggregates. Finally, solid-state 31P NMR spectroscopy was used to gain insight into the mobility of the bolaamphiphile molecules within the fiber aggregates. In comparison with the previously examined trimethylammonio analogue PC-C32-PC, which forms temperature-dependent hydrogels, Me(2)PE-C32-Me(2)PE exhibits additional concentration- and pH-dependent gelling properties. The significantly higher stability of the Me(2)PE-C32-Me(2)PE hydrogel is supported by the SANS data, which indicate the presence of fiber aggregates up to 50 degrees C.

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