Surface coatings that respond to external influences and change their physical properties upon application of external stimuli are of great interest, with light being a particularly desirable choice. Photoswitches such as azobenzenes have been employed in a range of photoresponsive coatings. One striking change in physical property of many photoresponsive coatings is their responsive wettability upon illumination. In this work, we present photoswitchable self-assembled monolayers based on arylazopyrazoles (AAPs). In solution, AAPs offer significant improvements in terms of the photostationary state, thermal stability, and fatigue resistance. The AAP photoswitch is coupled to triethoxysilanes for an easy, one-step functionalization of glass and silicon oxide surfaces. We show the synthesis of AAP-based silanes and the successful surface functionalization, and we confirm the excellent photoswitchability of the AAPs in a self-assembled monolayer upon alternating irradiation with UV (365 nm) and green (520 nm) light. The self-assembled monolayers are investigated by UV/vis spectroscopy, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and contact angle goniometry. We furthermore investigate the effect of substitution of the AAPs on the photoresponsive wetting behavior and compare this with density functional theory (DFT) calculations of the dipole moments of the AAPs.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is one of the most important techniques for chemical imaging of nanomaterials and biological samples with high lateral resolution. However, low ionization efficiency limits the detection of many molecules at low concentrations or in very small volumes. One promising approach to increasing the sensitivity of the technique is by the addition of a matrix that promotes ionization and desorption of important analyte molecules. This approach is known as matrix-enhanced secondary-ion mass spectrometry (ME-SIMS). We have investigated the effect of matrix acidity on molecular ion formation in three different biomolecules. A series of cinnamic acid based matrixes that vary in acidity was employed to systematically investigate the influence of matrix acidity on analyte ion formation. The positive ion signal for all three biomolecules showed a strong increase for more acidic matrixes. The most acidic matrix was then vapor-deposited onto mouse brain sections. This led to significant enhancement of lipid signals from the brain. This work indicates that proton donation plays an important role in the formation of molecular ions in ME-SIMS.

Missions to planetary bodies require innovative techniques for the in situ investigation of their surfaces, especially when landings are planned. Therefore, Raman spectroscopy as an excellent laboratory tool for rapid mineralogical analysis of both terrestrial and extraterrestrial rocks has been successfully proposed for the investigation of planetary surfaces. Examples are the Raman laser spectrometer (RLS) of the joint ESA and Roscosmos mission ExoMars 2022 as well as Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) and SuperCam onboard NASA's Mars2020 Perseverance Rover; another is the Raman spectrometer for Martian Moons eXploration (MMX) (RAX), which is being developed for the in situ exploration of the Mars' moon Phobos. When preparing such space missions, it is essential to be prepared for all possible outcomes, such as samples exhibiting space weathering (SW). In this work, we study the influence of micrometeorite bombardment on bodies without atmosphere as one trigger of SW. This type of SW effect is simulated with an excimer laser irradiating the investigated samples with an energy density of $2.5 J/cm 2 for each pulse. As possible components on Phobos, we investigated the silicates olivine (Fo 91 ) and pyroxene (En 87 ) and their mixtures with Raman spectroscopy before and after laser irradiation. Surprisingly, the characteristic Raman bands of the individual minerals in the spectra are not influenced by this kind of SW. On the other hand, the fluorescence-dominated background signal induced by laser irradiation is reduced, possibly due to the formation of nanophase Fe, which then facilitates a better interpretation of the individual mineral peaks.

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Photoswitches have long been employed in coatings for surfaces and substrates to harness light as a versatile stimulus to induce responsive behavior. We previously demonstrated the viability of arylazopyrazole (AAP) as a photoswitch in self-assembled monolayers (SAMs) on silicon and glass surfaces for photoresponsive wetting applications. We now aim to transfer the excellent photophysical properties of AAPs to polymer brush coatings. Compared to SAMs, polymer brushes offer enhanced stability and an increase of the thickness and density of the functional organic layer. In this work, we present thiolactone acrylate copolymer brushes which can be post-modified with AAP amines as well as hydrophobic acrylates, making use of the unique chemistry of the thiolactones. This strategy enables photoresponsive wetting with a tuneable range of contact angle change on glass substrates. We show the successful synthesis of thiolactone hydroxyethyl acrylate copolymer brushes by means of surface-initiated atom-transfer radical polymerization with the option to either prepare homogeneous brushes or to prepare micrometer-sized brush patterns by microcontact printing. The polymer brushes were analyzed by atomic force microscopy, time-of-flight secondary ion spectrometry, and X-ray photoelectron spectroscopy. Photoresponsive behavior imparted to the brushes by means of post-modification with AAP is monitored by UV/vis spectroscopy, and wetting behavior of homogeneous brushes is measured by static and dynamic contact angle measurements. The brushes show an average change in static contact angle of around 13° between E and Z isomer of the AAP photoswitch for at least five cycles, while the range of contact angle change can be fine-tuned between 53.5°/66.5° (E/Z) and 81.5°/94.8° (E/Z) by post-modification with hydrophobic acrylates.