In this experimental investigation the interaction of lithium with 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([OMIm]Tf2N) is shown. For this purpose thin films of lithium and [OMIm]Tf2N were successively vapor deposited on a copper substrate and analyzed by X-ray Photoelectron Spectroscopy (XPS) as well as by Ultraviolet Photoelectron Spectroscopy (UPS). When [OMIm]Tf2N is evaporated on top of a thin lithium film a chemical shift analysis of XPS spectra shows a variety of reaction products like LiF, Li2O and LixCHy which reveals the instability of the IL against lithium. Time resolved XPS spectra were discussed to distinguish cation reactions from beam damage effects. In a second step lithium is deposited on a [OMIm]Tf2N layer. The XPS spectra are in agreement with the results of the previous step, but show some differences concerning the [OMIm] cation. In a third step [OMIm]Tf2N has been deposited on a passivated lithium layer. XPS results show nearly unaffected [Tf2N](-) anions and partially decomposed [OMIm](+) cations. Interestingly the cation reactions show similarities when compared to the interaction of [C4C1Pyrr]Tf2N (1-butyl-1-methylpyrrolidinium bis[trifluoromethylsulfonyl]amide) and lithium.

We have measured the bulk and surface electronic structure of several ionic liquids of alkyl-imidazolium cations with different alkyl chains (EMIm, BMIm, HMIm, OMIm) and bis(trifluoromethylsulfonyl)imide anions (Tf2N) by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS He I and He II) as well as metastable induced electron spectroscopy (MIES). The results are compared with the densities of states (DOS) calculated by density functional theory (DFT). By XPS we found the stoichiometry of the respective ILs reproduced, and different carbon atom positions reflected by the splitting of the C(1s)-from the trifluor-methyl groups (CF3) of the anion with highest binding energy to the alkyl chains of the cation with the lowest one. Furthermore with increasing alkyl chain length the peak related to the alkyl group appears at slightly lower binding energy. The more bulk-sensitive XPS spectra reveal only minor differences in the valence band structure for the studied ionic liquids, whereas the more surface-sensitive methods UPS and especially MIES display distinct changes in the peakintensities for varying the alkyl chain length. This is a strong indication for either a non-stoichiometric composition of the upmost molecular layer of the IL-surface and/or a reorientation of the cations, probably turning the alkyl chains to the surface.

The lipids of the stratum corneum comprise the most important components of the skin barrier. In patients with ichthyoses or atopic dermatitis, the composition of the skin barrier lipids is disturbed resulting in dry, scaly, itching erythematous skin. Using the latest X-Ray Photoelectron Spectroscopy (XPS) technology, we investigated the physiological skin lipid composition of human skin and the effects of cold atmospheric plasma treatment on the lipid composition. Skin lipids were stripped off forearms of six healthy volunteers using the cyanoacrylate glue technique, plasma treated or not and then subjected to detailed XPS analysis. We found that the human lipid skin barrier consisted of 84.4% carbon (+1.3 SEM%), 10.8% oxygen (+1.0 SEM%) and 4.8% nitrogen (+0.3 SEM%). The composition of physiological skin lipids was not different in males and females. Plasma treatment resulted in significant changes in skin barrier lipid stoichiometry. The total carbon amount was reduced to 76.7%, and the oxygen amount increased to 16.5%. There was also a slight increase in nitrogen to 6.8%. These changes could be attributed to reduced C-C bonds and increased C-O, C=O, C-N and N-C-O bonds. The moderate increase in nitrogen was caused by an increase in C-N and N-C-O bonds. Our results show for the first time that plasma treatment leads to considerable changes in the human skin lipid barrier. Our proof of principle investigations established the technical means to analyse, if plasma-induced skin lipid barrier changes may be beneficial in the treatment of ichthyotic or eczematous skin.

"This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively." Keppler, Angela; Himmerlich, Marcel; Ikari, Tomonori; Marschewski, Marcel; Pachomow, Evgenij; Höfft, Oliver; Maus-Friedrichs, Wolfgang; Endres, Frank; Krischok, Stefan Radiation induced degradation effects are studied for a model ionic liquid (IL) - [EMIm]Tf 2 N -in order to distinguish in which way the results of X-ray based material analysis methods can be falsified by the radiation supplied by typical X-ray sources itself. Photoelectron spectroscopy is commonly used for determining the electronic structure of ionic liquids. Degradation effects, which often occur e.g. in organic materials during X-ray or electron irradiation, are potentially critical for the interpretation of data obtained from ionic liquids. The changes of the chemical composition as well as the radiation-induced desorption of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm]Tf 2 N) fragments are analysed by X-ray photoelectron spectroscopy (XPS) as well as quadrupole mass spectroscopy (QMS) upon exposure to monochromated or non-monochromated AlKa X-rays from typical laboratory sources. During the irradiation of [EMIm]Tf 2 N, an increasing carbon concentration is observed in both cases and especially the [Tf 2 N] À ion is strongly altered. This observation is supported by the results from the QMS analysis which revealed a variety of different IL fragments that are desorbed during X-ray irradiation. It is shown that the decomposition rate is directly linked to the photon flux on the sample and hence has to be considered when planning an XPS experiment. However, for typical experiments on this particular IL the measurements suggest that the changes are on a larger time scale as typically required for spectra acquisition, in particular if monochromated X-ray sources are used.

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