Effects of Oscillatory Shear on the Orientation of the Inverse Bicontinuous Cubic Phase in a Nonionic Surfactant/Water System.

The bicontinuous inverse cubic phase (V2 phase) formed in amphiphilic systems consists of bilayer networks with a long-range order. We have investigated effects of oscillatory shear on the orientation of the V2 phase with space group Ia3d formed in a nonionic surfactant (C12E2)/water system by using simultaneous measurements of rheology/small-angle X-ray scattering. It is shown that grain refining occurs by applying the large amplitude oscillatory shear (LAOS) with a strain amplitude (γ0) of ∼20, which gives the ratio of the loss modulus (G″) to the storage modulus (G') (G″/G' = tan δ) of ∼100. On the other hand, orientation of the cubic lattice occurs when the small amplitude (γ0 ≈ 0.0004) oscillatory shear (SAOS) in the linear regime is applied to the sample just after the LAOS. Interestingly, the orientation is strongly enhanced by the "medium amplitude" (γ0 ≈ 0.05) oscillatory shear ("MAOS") after the SAOS. When the MAOS is applied before applying the LAOS, orientation to a particular direction is not observed, indicating that the grain refining process by the LAOS is necessary for the orientation during the MAOS. The results of additional experiments show that the shear sequence "LAOS-MAOS" is effective for the orientation of the cubic lattice. When the LAOS and MAOS are applied to the sample alternatively, grain refining and orientation occur during the LAOS and MAOS, respectively, indicating reversibility of the orientation. It is shown that (i) the degree of the orientation is dependent on γ0 and the frequency (ω) of the MAOS and (ii) relatively higher orientation can be obtained for the combination of γ0 and ω, which gives tan δ = 2-3. The lattice constant does not change throughout all the shearing processes and is equal to that before shearing within the experimental errors, indicating that the shear melting does not occur. These results suggest a possibility to control the orientation of the cubic lattice only by changing the conditions of oscillatory shear without using the epitaxial transition from other anisotropic phases, such as the hexagonal and lamellar phases.

The human vermilion surface contains a rich amount of cholesterol sulfate than the skin.

BACKGROUND: The vermilion of the human lip presents characteristic features and undergoes aging faster than the skin. Therefore, knowledge of the vermilion surface-specific functional molecules is important to understand lip aging and formulate lip care products. Previously, we analyzed the free fatty acids distributions and showed that docosahexaenoic acid highly accumulated in the vermilion's epithelium than in the skin. OBJECTIVE: We aimed to explore the functional molecules other than the free fatty acids on the vermilion's surface. METHODS: Human lip tissues from children and tape-stripped samples from smooth and rough lips of adults were measured by desorption electrospray ionization-mass spectrometry imaging (DESI-MSI). RESULTS: DESI-MSI of children's lip sections revealed a major distribution of five phospholipid species in the viable layer, but not in the superficial area, of both the vermilion and the skin than that in the underlying tissue. Interestingly, a remarkably higher distribution of cholesterol sulfate was observed in the vermilion's superficial area compared to that in the skin in all subjects under this study. Furthermore, DESI-MSI of tape-stripped lip samples showed an overall higher accumulation of cholesterol sulfate in the stratum corneum of the rough lips than that in the smooth lips. CONCLUSION: Our study concluded that cholesterol sulfate has a characteristic distribution to the vermilion's surface and showed an association with the roughness of the lip.