Listening with Curiosity - Tracking the Acoustic Response of Portable Laser Ablation.

Nowadays, one of the methods of choice for minimal invasive sampling of solid matter is laser ablation (LA). Routine LA sampling is performed commonly in the laboratory and the amount of ablated mass can directly be monitored and analysed. By contrast laser-based sampling in the field, using a portable laser ablation system (pLA), still remains challenging concerning low-absorbing or NIR-transparent samples. The current hardware is limited in regards to photon energy and density resulting in unsteady ablation. But as the actual amount of collected mass is the major crux of on-site sampling, with this performance it is often unknown and estimates can only be made based on the experience from prior method development and the experience of the user. In the following work an easy-to-use method to monitor the amount of ablated material collected during laser-based sampling by measuring the acoustic response is presented. The pLA-system was coupled to inductively coupled plasma mass spectrometry (ICPMS) via a diffusion driven gas exchange device (GED) which allowed to monitor mass removal and acoustic response quasi-simultaneously. For the current instrumentation only actual mass removal leads to the formation of shockwaves (SW) and, thus, acoustic signals. These events can be used as indicator for executed LA events and counted on an individual basis. The intensity of acoustic signals has been shown to correlate with the LA mass, i.e., the amount of ablated material. This allows to perform re-adjustment of the laser focus during sampling for optimal ablation based on the intensity of the acoustic signal. Likewise, acoustic intensity together with counting allows the operator to make estimates about total mass sampled. Therefore, unsuccessful laser aerosol collection in the field shall become a thing of the past.

Dual isotope system analysis of lead white in artworks.

Isotopic studies are gaining much interest in heritage science, as they can provide insight into a material's age and provenance. Radiocarbon (14C) dating affords a time frame for the materials being studied, thus providing a historical context, whereas the specific pattern of lead isotope ratios may be used to set geographical constraints on the source of the original materials. Both methods require invasive sampling from the object, and henceforth limits their respective application. With the focus on lead white paint (2PbCO3·Pb(OH)2), in this study we extract the time of production of the pigment from the carbonate anion by radiocarbon dating while its origin is traced by lead isotope analysis on the cation. The methodology was applied to 12 British and 8 Swiss paintings from the 18th to 20th century, with known dates and provenance. The 14C analysis of the lead white in combination with the organic binder and canvas alone places all objects between the 17th and 20th centuries, which is in agreement with their signed date, wheras the lead isotope analysis of all samples are consistent with lead ores from European deposits. In most of the cases the combined results are consistent with the art historical data and prove that isotope analysis is intrinsic to the object. This feasibility study conducted on paintings of known age demonstrates the possibility to maximize the information output from lead white paint, thus increasing the benefits of a single sampling.

Synthesis and Characterization of Ion Pairs between Alkaline Metal Ions and Anionic Anti-Aromatic and Aromatic Hydrocarbons with π-Conjugated Central Seven- and Eight-Membered Rings.

The synthesis, isolation and full characterization of ion pairs between alkaline metal ions (Li+, Na+, K+) and mono-anions and dianions obtained from 5H-dibenzo[a,d]cycloheptenyl (C15H11 = trop) is reported. According to Nuclear Magnetic Resonance (NMR) spectroscopy, single crystal X-ray analysis and Density Functional Theory (DFT) calculations, the trop‒ and trop2-• anions show anti-aromatic properties which are dependent on the counter cation M+ and solvent molecules serving as co-ligands. For comparison, the disodium and dipotassium salt of the dianion of dibenzo[a,e]cyclooctatetraene (C16H12 = dbcot) were prepared, which show classical aromatic character. A d8-Rh(I) complex of trop- was prepared and the structure shows a distortion of the C15H11 ligand into a conjugated 10π -benzo pentadienide unit-to which the Rh(I) center is coordinated-and an aromatic 6π electron benzo group which is non-coordinated. Electron transfer reactions between neutral and anionic trop and dbcot species show that the anti-aromatic compounds obtained from trop are significantly stronger reductants.

Vibrational Changes Induced by Electron Transfer in Surface Bound Azurin Metalloprotein Studied by Tip-Enhanced Raman Spectroscopy and Scanning Tunneling Microscopy.

The copper protein azurin, due to the peculiar coupling of its optical and vibronic properties with electron transfer (ET) and its biorecognition capabilities, is a very promising candidate for bioelectronic, bio-optoelectronic and biosensor applications. However, a complete understanding of the fundamental processes relating azurin ET and its optical and vibronic characteristics with the charge transport mechanisms occurring in proteins bound to a conductive surface, the typical scenario for a biosensor or bioelectronic component, is still lacking. We studied azurin proteins bound to a gold electrode surface by scanning tunneling microscopy combined with tip-enhanced Raman spectroscopy (STM-TERS). Robust TER spectra were obtained, and the protein's vibronic response under optical excitation in resonance with its ligand-to-metal charge transfer band was found to be affected by the tunneling parameters, indicating a direct involvement of the active site vibrations in the electron transport process.