Detection of new biohints on lichens with Raman spectroscopy after space- and Mars like conditions exposure: Mission Ground Reference (MGR) samples.

The extremophile lichen Circinaria gyrosa (C. gyrosa) is one of the selected species within the BIOMEX (Biology and Mars Experiment) experiment. Here we present the Raman study of a biohint found in this lichen, called whewellite (calcium oxalate monohydrate), and other organic compounds and mineral products of the biological activity of the astrobiologically relevant model system C. gyrosa. Samples were exposed to space- and simulated Mars-like conditions during the EXPOSE-R2 mission parallel ground reference experiment MGR performed at the space- and planetary chambers of DLR-Cologne to study Mars' habitability and resistance to real space conditions. In this work, we complete the information of natural C. gyrosa about the process of diagenesis by the identification of carbonate crystals in the inner medulla together with the biomineral whewellite. The analysis by Raman spectroscopy of simulated Space and Mars exposed samples confirm alterations and damages of the photobiont part of the lichen and changes related to the molecular structure of whewellite. The conclusions of this work will be important to understand what are the effects to consider when biological systems are exposed to space or Mars-like conditions and to expand our knowledge of how life survives in most extreme conditions that is a prerequisite in future planetary exploration projects.

On the dual character of charged metal-molecule hybrids and the opposite behaviour of the forward and reverse CT processes.

DFT calculations predict two different electronic structures of metal-molecule hybrids which are selected depending on the surface charge. While the metal-to-molecule CT states are very sensitive to the charge, the energies of the reverse molecule-to-metal CT processes are surprisingly not modified at all by the charge of the metal.

Surface-enhanced Raman scattering of hydroxybenzoic acids adsorbed on silver nanoparticles.

Surface-enhanced Raman scattering (SERS) of hydroxybenzoic acids has been studied on silver sols in H(2)O and D(2)O solutions. The adsorption behavior of 4-hydroxybenzoic acid (4HBA) is different from that of salicylic (2HBA) and 3-hydroxybenzoic (3HBA) acids. It was concluded that 4HBA is adsorbed on silver nanoparticles (Ag(n)) as either oxidobenzoate (A(2-)) or hydroxybenzoate (A(-)), depending on the pH of the solution, given rise to a flat orientation. Both 2HBA and 3HBA acids are always adsorbed as hydroxybenzoates anions (A(-)) at pH >or=5 and link to the metal through the carboxylate group (Ag(n)--A(-)), standing more or less perpendicular to the metal surface. In the case of these monoanions, the selective enhancement of the bands is due mainly to a resonant electron or charge transfer process (ET or CT) from the metallic nanoparticles to the adsorbates, yielding the transient formation of the respective radical dianions (Ag(+)(n)--A(2-)). It is found that the enhanced bands, and especially the mode 8a;nu(ring), are related to the difference between the equilibrium structures of the adsorbate in its ground (A(-)) and CT-excited (A(2-)) states. In the SERS spectrum of 4HBA dianion, the contribution of CT mechanism is not observed.

Detecting photoinduced electron transfer processes in the SERS spectrum of salicylate anion adsorbed on silver nanoparticles.

The surface-enhanced Raman scattering (SERS) of salicylic acid (S) adsorbed on a silver sol in H(2)O and D(2)O has been investigated. At pH 5 or greater, the adsorbed species is the salicylate anion (2-hydroxybenzoate anion) (S(-)), which links to the metal nanoparticle (Ag(n)) through the carboxylate group (S(-)-Ag(n)). We demonstrate that the selective enhancement of the bands is due mainly to a resonant electron or charge transfer process (ET or CT) from the metallic nanoparticle to the adsorbate, yielding the transient formation of the respective radical dianion (S.(2-)-Ag(n) (+)). It is found that the enhanced bands, and especially mode 8a;nu(ring), are related to the differences between the equilibrium structures of the adsorbate in its ground (S(-)) and CT-excited states (S.(2-)).

Adsorption of mercaptoacetic acid on a colloidal silver surface as investigated by Raman spectroscopy.

The vibration nu(SH) has never been observed in the surface-enhanced Raman scattering of mercaptoacetic acid recorded in a wide range of pH. This behavior enables us to deduce that the -SH group is deprotonated and links to the metal forming an Ag-S bond as 1-alkanethiols do. On the contrary, the carboxylic or carboxylate groups do not link to the metal and the carboxylic group is preserved even at pH values under which it should be deprotonated. This fact enables the stabilization of the adsorbed monolayer by removing the electrostatic repulsions between -COO(-) groups and by the formation instead of hydrogen bonds between carboxylic groups. Only under rather basic conditions (pH > 8) does the carboxylic groups dissociate, but the nu(s)(OCO) band is neither enhanced nor shifted toward low frequencies.

Vibrational study of the metal-adsorbate interaction of phenylacetic acid and alpha-phenylglycine on silver surfaces.

Raman and SERS spectra of phenylacetic acid and alpha-phenylglycine on silver sols have been recorded at several concentrations and pH values. The alpha-phenylglycine has been also studied in D(2)O. The respective vibrational assignments have been proposed and the analysis of the SERS spectra has made it possible to conclude that phenylacetic acid links to the metal through its carboxylate group only, while alpha-phenylglycine links also through its amino group. In both cases the aromatic ring seems to be almost perpendicular to the metal surface. On the other hand, the contribution of the charge transfer (CT) mechanism to the enhancement of the SERS spectra has been calculated as well and it is found to be very important in both molecules. The band most enhanced by this mechanism is that of vibration 8a, mainly in alpha-phenylglycine.