Comprehensive characterization of the structure and properties of human stratum corneum relating to barrier function and skin hydration: modulation by a moisturizer formulation.

The stratum corneum (SC) is key in the maintenance of the biomechanical barrier and hydration of skin. Our previous investigations showed beneficial effects of a combination of emollients on water capture and retention and protein and lipid organization, all of which are linked to dryness and dry skin damage. Here, we show how a formulation containing an emollient combination ("Trio") and its basal formulation (placebo) impacted the descriptors of SC hydration in SC layers. Only the Trio formulation-not its placebo formulation-modified SC biomechanical drying stress behaviour and imparted a high capacity to protect it from dehydration. This was in accordance with findings at the molecular level using Raman analyses and at the structural level using cryo-scanning electron microscopy (SEM). After topical application, only the Trio formulation profoundly increased lateral packing of lipids and their compactness. Cryo-SEM showed that, unlike the placebo formulation, the Trio formulation prevented the water loss when applied before the dehydration process. In conclusion, these studies demonstrate that stresses in the SC due to dehydration can be alleviated using a formulation containing emollients that interact with the SC lipid components.

Clusters of Hydroxyl-Functionalized Cations Stabilized by Cooperative Hydrogen Bonds: The Role of Polarizability and Alkyl Chain Length.

We explore quantum chemical calculations for studying clusters of hydroxyl-functionalized cations kinetically stabilized by hydrogen bonding despite strongly repulsive electrostatic forces. In a comprehensive study, we calculate clusters of ammonium, piperidinium, pyrrolidinium, imidazolium, pyridinium, and imidazolium cations, which are prominent constituents of ionic liquids. All cations are decorated with hydroxy-alkyl chains allowing H-bond formation between ions of like charge. The cluster topologies comprise linear and cyclic clusters up to the size of hexamers. The ring structures exhibit cooperative hydrogen bonds opposing the repulsive Coulomb forces and leading to kinetic stability of the clusters. We discuss the importance of hydrogen bonding and dispersion forces for the stability of the differently sized clusters. We find the largest clusters when hydrogen bonding is maximized in cyclic topologies and dispersion interaction is properly taken into account. The kinetic stability of the clusters with short-chained cations is studied for the different types of cations ranging from hard to polarizable or exhibiting additional functional groups such as the acidic C(2)-H position in the imidazolium-based cation. Increasing the alkyl chain length, the cation effect diminishes and the kinetic stability is exclusively governed by the alkyl chain tether increasing the distance between the positively charged rings of the cations. With adding the counterion tetrafluoroborate (BF4-) to the cationic clusters, the binding energies immediately switch from strongly positive to strongly negative. In the neutral clusters, the OH functional groups of the cations can interact either with other cations or with the anions. The hexamer cluster with the cyclic H-bond motive and "released" anions is almost as stable as the hexamer built by H-bonded ion pairs exclusively, which is in accord with recent IR spectra of similar ionic liquids detecting both types of hydrogen bonding. For the cationic and neutral clusters, we discuss geometric and spectroscopic properties as sensitive probes of opposite- and like-charge interaction. Finally, we show that NMR proton chemical shifts and deuteron quadrupole coupling constants can be related to each other, allowing to predict properties which are not easily accessible by experiment.

ATR-FTIR Characterization of Janus Nanoparticles-Part II: Follow-Up Skin Application.

Attenuated total reflection by Fourier transform infrared (ATR-FTIR) was used to implement reliable infrared descriptors over time of Janus nanoparticles (JNP), to follow their behavior before and after cutaneous application. In the last study, ATR-FTIR spectroscopic analysis allowed us to identify the evolution of intensity ratio of ν(C=O) at 1739 cm-1 and δ(H-O-H) at 1639 cm-1 as a spectroscopic descriptor, for JNP before cutaneous application (on the CaF2 window). This descriptor can be used to follow the physical stability (presence) of nanoparticles over time. The purpose of this study was to understand the behavior of JNP on the surface of the human skin. Therefore, a comparative study with the untreated skin and the skin after cutaneous application of lipophilic phase (Labrafil) of JNP was conducted using Franz cells. The suitability of the ATR-FTIR descriptor of JNP was evaluated, and a research of other descriptors was performed to understand the interaction that may exist between nanoparticles and the skin.

ATR-FTIR Characterization of Janus Nanoparticles. Part I: Implementation of Spectroscopic Descriptors.

The present work deals with original bicompartmental lipid Janus nanoparticles (JNPs), which are characterized by the presence of an oily compartment associated with an aqueous compartment delimited by a phospholipid-based bilayer. The size of JNP varies between 150 and 300 nm. As JNP are promising candidates for cutaneous application, the purpose of this study was to implement reliable infrared descriptors over time of JNP, to follow the physical stability of JNP in open air and over time. Therefore, a comparative study with the nanoemulsion and the physical mixture formulations was conducted by attenuated total reflection by FTIR spectroscopy. We defined herein spectroscopic descriptor reflecting the integrity of the JNP. Principal component analysis and orthogonal partial least square-discriminant analysis were used to validate the relevant descriptor and permitted to extract relevant and useful information from the spectral data. Dynamic light scattering measurements were also carried and gave supporting data for our conclusion on the fate of JNP over time.